ࡱ> g Ubjbj 7zzL%$$~~vvv8N <ZZ"|||666v<x<x<x<x<x<x<$>gAL<v75677<~~||k<9997~|v|v<97v<99;hZ<|`9.T}8;b<<0< <A 9FA <Av<H6"6966666<<Q9d666<7777A666666666$ D:  C S CAC QUA TRNH X LY HOA HOC 3.1 QUA TRNH TRUNG HOA C s: Phan ng trung hoa: Acid + Baz ( Muoi + Nc ng dung - Nc thai acid + nc thai kiem ( c trung hoa en trung tnh - Nc thai acid + hoa chat kiem ( c trung hoa en trung tnh - Nc thai kiem + hoa chat acid ( c trung hoa en trung tnh 3.1.1 Trung Hoa Nc Thai Nc thai cha cac axt vo c hoac kiem can c trung hoa a pH ve khoang 6,5-8,5 trc khi thai vao nguon nhan. Qua trnh trung hoa nc thai co the thc hien bang nhieu cach khac nhau: Tron lan nc thai axt vi nc thai kiem; Bo sung tac nhan hoa hoc; Loc nc thai co tnh axt qua vat lieu co tac dung trung hoa; Trung hoa nc thai kiem bang cac kh axt. Viec la chon phng phap trung hoa tuy thuoc vao the tch va nong o nc thai, che o thai nc thai, kha nang san co va gia thanh cua cac tac nhan hoa hoc. Lng bun can sinh ra t qua trnh trung hoa phu thuoc vao nong o va thanh phan nc thai cung nh lieu lng va loai tac nhan s dung. Trung hoa bang cach bo sung tac nhan hoa hoc e trung hoa nc thai axt co the s dung cac tac nhan hoa hoc nh NaOH, KOH, Na2CO3, NaHCO3, NH4OH, CaCO3, MgCO3, olomt (CaCO3.MgCO3). Song tac nhan re tien nhat la sa voi 5%-10% Ca(OH)2, tiep en la soa va NaOH cong nghiep. Trong nc thai axt va kiem thng cha cac ion kim loai, v vay lieu lng tac nhan tham gia phan ng trung hoa can tnh en ca yeu to tao thanh can muoi cac kim loai nang. Trung hoa nc thai axt bang cach loc qua vat lieu co tac dung trung hoa Trong trng hp nay ngi ta thng dung cac vat lieu nh manhett (MgCO3), olomt, a voi, a phan, a hoa va cac chat thai ran nh x va x tro lam lp vat lieu loc. Cac vat lieu tren c s dung dang cuc vi kch thc 30 en 80 mm. Qua trnh co the c tien hanh trong thiet b loc at nam ngang hay thang ng. Khi loc nc thai cha HCl va HNO3 qua lp a voi, thng chon van toc loc t 0,5-1 m/h. Trong trng hp loc nc thai cha 0,5% H2SO4 qua lp olomt, toc o loc lay t 0,6-0,9 m/h, neu nong o 2% H2SO4 th toc o loc lay bang 0,35 m/h. Trung hoa nc thai kiem bang cac kh axt e trung hoa nc thai kiem, trong nhng nam gan ay ngi ta a s dung cac kh thai cha CO2, SO2, NO2, N2O, Viec s dung kh axt khong nhng cho phep trung hoa nc thai ma ong thi tang hieu suat lam sach chnh kh thai khoi cac cau t oc hai. 3.1.2 On nh Hoa Nc X ly on nh nc bang axt X ly on nh nc bang axt c ap dung e ngan nga qua trnh lang ong canxi cacbonat. Hp chat Ca(HCO3)2 la hp chat khong ben vung va do vay thng ton tai di dang phan ly: Ca(HCO3)2 ( Ca2+ + 2HCO3- Ca2+ + 2HCO3- ( CaCO3 + H2O + CO2 Neu ch so bao hoa I co gia tr dng, chng to lng CO2 t do trong nc nho hn ham lng can bang. e bu lai s thieu hut CO2 phan ng se chuyen dch sang pha phai, khi o ham lng HCO3- trong nc giam i, ham lng CaCO3 va CO2 tang len. Muon tang ham lng CO2 ma khong tao ra CaCO3, ngi ta phai them axt vao nc e co phan ng sau: HCO3- + H+ ( CO2 + H2O Lng axt can thiet cho qua trnh on nh nc noi tren c xac nh theo o pH0 ban au cua nc va gia tr pHs can bang sau kh bao hoa nc bang CaCO3. X ly on nh nc bang kiem X ly on nh nc bang kiem c ap dung e ngan nga qua trnh xam thc. Khi nc co d lng CO2 xam thc, can s dung kiem e kh CO2 t do theo phan ng sau: CO2 + OH- ( HCO3- Lng kiem can thiet c xac nh theo gia tr pH0 va pHs cua nc. 3.2 QUA TRNH TRAO OI C s: Phan ng trao oi: AB + CD ( AD + CB ng dung: Qua trnh lam mem nc bang phng phap hoa hoc C s cua phng phap hoa hoc la mem nc la a cac hoa chat co kha nang ket hp vi cac ion Ca2+, Mg2+ co trong nc tao thanh cac ket tua CaCO3, MgCO3, Mg(OH)2, va loai tr chung bang bien phap lang loc. Cac hoa chat s dung co the la Ca(OH)2, Na2CO3, NaOH, Lam mem nc bang voi ket hp vi so a: MgSO4 + Ca(OH)2 ( Mg(OH)2( + CaSO4 MgCl2 + Ca(OH)2 ( Mg(OH)2( + CaCl2 CaSO4 + Na2CO3 ( CaCO3( + Na2SO4 CaCl2 + Na2CO3 ( CaCO3( + 2NaCl Lam mem nc bang trinatriphophat (Na3PO4) 3CaCl2 + 2Na3PO4 ( Ca3(PO4)2( + 6NaCl 3MgSO4 + 2Na3PO4 ( Mg3(PO4)2( + 3Na2SO4 3Ca(HPO4)2 + 2Na3PO4 ( Ca3(PO4)2( + 6NaHCO3 3Mg(HCO)2 + 2Na3PO4 ( Mg3(PO4)2( + 6NaHCO3 3.3 QUA TRNH OXY HOA KH C s: Phan ng oxy hoa kh ng dung Kh sat trong nc ngam; X ly nc thai cha cac hp chat hoa hoc kho phan huy; Kh trung. 3.3.1 Qua Trnh Kh Trung (Disinfection) Qua trnh kh trung la qua trnh tieu huy cac vi sinh vat gay benh. Khac vi qua trnh tiet trung (sterilization) la qua trnh tieu diet toan bo vi sinh vat co trong nc hoac nc thai, qua trnh kh trung ch tieu diet mot cach co chon loc nhng vi sinh vat gay benh. Trong lnh vc x ly nc thai, ba nhom vi sinh vat gay benh quan trong nhat la vi khuan (bacteria), vi trung (virus) va amoebic cyst (nang bao). Nhng loai benh do vi khuan lan truyen qua moi trng nc bao gom benh thng han (typhoid), benh dch ta (cholera), benh pho thng han (paratyphoid), benh kiet l (bacillary dysentery). Nhng benh do vi trung lan truyen qua moi trng nc bao gom benh bai liet (poliomyeitis) va benh viem gan sieu vi (infectious hepatitis). Qua trnh kh trung hau het c thc hien bang cach s dung (1) hoa chat, (2) tac nhan vat ly, (3) phng phap c hoc va (4) phng phap bc xa. oi vi phng phap hoa hoc, cac tac nhan hoa hoc dung lam chat kh trung bao gom (1) Clo va cac hp chat cua clo, (2) Brom, (3) iot, (4) Ozone, (5) phenol va cac hp chat cua phenol, (6) ru, (7) cac kim loai nang va nhng hp chat tng ng, (8) mau, (8) xa phong va chat tay ra, (10) cac hp chat amonium, (11) H2O2, va (12) cac hp chat acid va kiem. Trong nhng hp chat nay, nhng chat kh trung thong dung nhat la cac hp chat hoa hoc co tnh oxy hoa va clo la mot trong nhng tac nhan c s dung thong dung nhat. Brom va iot cung c s dung trongkh trung nc thai. Ozone la tac nhan kh trung co hieu qua cao va ngay cang c s dung nhieu. Nc co o acid va o kiem cao cung c s dung e tieu huy vi sinh vat gay benh v nc co pH ln hn 11 hoac nho hn 3 kha oc oi vi vi khuan. ( Kh trung bang clo Cac hp chat clo thng dung cac tram x ly nc thai bao gom (Cl2), Calcium Hypochlorite [Ca(OCl)2], Sodium Hypochlorite [NaOCl] va Chlorine Dioxide [ClO2]. Khi kh Cl2 c hoa tan vao nc se co hai phan ng xay ra: phan ng thuy phan va phan ng ion hoa. Qua trnh thuy phan xay ra nh sau: Cl2 + H2O ( HOCl + H+ + Cl- Hang so ben cua phan ng nay la:  Qua trnh phan ly HOCl xay ra nh sau: HOCl ( H+ + OCl- Hang so phan ly HOCl:  Lng HOCl va OCl- ton tai trong nc c goi la clo t do (free available chlorine). S phan bo cua hai nhom nay co y ngha rat quan trong v hieu qua kh trung cua HOCl ln hn so vi OCl- khoang 40-80 lan. S phan bo HOCl c tnh toan theo phng trnh sau:  Gia tr hang so phan ly Hypochloric acid theo nhiet o c trnh bay trong Bang 3.1. Bang 3.1 Gia tr hang so phan ly Ki theo nhiet o Nhiet o (0C)Ki x 108 (mol/L)01,4951,75102,03152,32202,62252,90Clo t do trong nc cung co the c tao thanh bang cac muoi hypochlorite theo cac phng trnh phan ng sau: Ca(OCl)2 + 2H2O ( 2HOCl + Ca(OH)2 NaOCl + H2O ( HOCl + NaOH Kha nang diet trung cua clo phu thuoc vao s ton tai cua ion HOCl trong nc, ma qua trnh tao thanh va phan ly HOCl lai phu thuoc vao nong o ion H+, tc la gia tr pH cua dung dch: pH tang, nong o HOCl giam, nong o OCl- tang; pH = 7, nong o HOCl can bang vi nong o OCl-.  ` Hnh 3.1 Quan he gia thanh phan HOCl va OCl- theo gia tr pH. Ket qua thc nghiem cho thay qua trnh thuy phan Cl2 ch xay ra hoan toan khi pH > 4. Mc o phan ly HOCl phu thuoc vao pH 200C c trnh bay trong Bang 3.2. Bang 3.2 Mc o phan ly cua HOCl phu thuoc vao pH 200C pH567891011OCl- (%)0,050,502,5021,0097,0099,5099,99HOCl (%)99,9599,5097,5079,003,000,500,10 Thanh phan HOCl la thanh phankh trung chnh trong nc ch ton tao pH thap, do o qua trnh kh trung ch at hieu qua cao pH thap. Nc t nhien thng khong tinh khiet va cac phan ng vi cac tap chat cha trong nc se anh hng en s hnh thanh clo t do d. V du neu nc co cha cac chat hu c, ammonia, nitites, sat, mangan, th clo se phan ng vi cac thanh phan nay theo phng trnh phan ng nh sau: HOCl + NH3 ( NH2Cl + H2O Monocloramin HOCl + NH2Cl ( NHCl2 + H2O Dicloramin HOCl + NHCl2 ( NCl3 + H2O San pham monochloramin va dichloramin sinh ra tuy thuoc vao gia tr pH cua moi trng. pH cang cao, lng clo ket hp e tao thanh dichloramin cang thap va monocholoramin cang cao. Kha nang diet trung cua monochloramin thng thap hn so vi dichloramin khoang 3 en 5 lan. Kha nang diet trung cua chloramin thap hn Clo t 20 en 25 lan. o la ly do khien cho qua trnh kh trung vi clo xay ra hieu qua gia tr pH thap. Trong he thong kh trung cha ammonia va cac hp chat amonium. Lng clo tham gia phan ng e tao thanh cloramin c goi la clo ket hp, tong lng clo t do di dang Cl2, HOCl, va OCl- va lng clo ket hp c goi la clo hoat tnh kh trung. Do kha nang diet trung cua clo t do va clo ket hp khac nhau ma lng clo d can thiet e am bao kh trung triet e cung c anh gia cac mc khac nhau. Tong lng clo can thiet cho vao nc e am bao sau qua trnh kh trung co c lng clo d mong muon thng c xac nh trc tiep bang thc nghiem. ( Kh Clo (Dechlorination) Tnh oc hai cua clo d. Do trong nc thng cha nhieu loai hp chat hu c co the phan ng vi clo tao thanh nhng hp chat co tnh oc va gay tac hai lau dai. Do o, e giam en thap nhat tac hai cua cac hp chat nay en moi trng, can phai kh lng clo d vt qua yeu cau co trong nc thai c x ly bang clo theo mot trong nhng phng phap trnh bay di ay. Phan ng vi SO2. Kh SO2 co the kh clo t do, monocloramin (NH2Cl), dichloramin (NHCl2), trichloride nitrogen (NCl3) va cac hp chat clo cao phan t theo cac phng trnh phan ng sau: Cac phan ng vi clo: SO2 + H2O ( HSO3- + H+ HOCl + HSO3- ( Cl- + SO42- + 2H+ SO2 + HOCl + H2O ( Cl- + SO42- + 3H+ Cac phan ng vi cloramin: SO2 + H2O ( HSO3- + H+ NH2Cl + HSO3- + H2O ( Cl- + SO42- + NH4+ + H+ SO2 + NH2Cl +2H2O ( Cl- + SO42- + NH4+ +2H+ Lng SO2 s dung phai c khong che e tranh ton hoa chat va lam giam ham lng oxy hoa tan trong nc sau x ly do phan ng gia HSO3- vi O2: HSO3- + 0,5O2 ( SO42- + H+ Ham lng oxy hoa tan giam se keo theo giam pH va tang BOD va COD cua nc sau x ly. Phng phap dung than hoat tnh Qua trnh hap phu bang than hoat tnh co the kh hoan toan ca clo t do va clo ket hp theo cac phng trnh phan ng sau: Phan ng vi clo: C + 2Cl2 + 2H2O ( 4HCl + CO2 Phan ng vi cloramin: C + 2NH2Cl + 2H2O ( CO2 + 2NH4+ + 2Cl- C + 4NHCl2 + 2H2O ( CO2 +2N2 +8H+ + 8Cl- ( Kh trung bang ClO2 Kh ClO2 la kh khong ben va co kha nang chay no nen kh nay phai c tao ra tai tram x ly theo phng trnh phan ng sau: 2NaClO2 + Cl2 ( 2ClO2 + 2NaCl Hieu qua cua ClO2. Tac nhan kh trung hoat tnh trong he thong ClO2 la ClO2 t do. Tnh chat hoa hoc cua ClO2 trong moi trng nc cha c xac nh ro rang. Tuy nhien, do ClO2 la tac nhan oxy hoa rat manh do o co che diet khuan co the xay ra do kha nang lam mat hoat tnh cua he thong enzyme cua te bao vi sinh vat hoac lam mat kha nang tong hp protein cua te bao. S hnh thanh san pham phu. Mot so san pham phu la cac muoi chlorite va chlorate co the tao thanh trong qua trnh kh trung vi ClO2. Tuy nhien, cac hp chat nay co kha nang phan huy nhanh hn cac hp chat clo d do o mc o tac hai cua chung thap hn. Mot trong nhng u iem cua qua trnh kh trung bang ClO2 la ClO2 khong phan ng vi ammonia va cac hp chat ammonium nen khong tao thanh cac hp chat cloramne co tnh oc. Them vao o, cac phan ng tao thanh cac hp chat hu c clo hoa cung khong xay ra trong bat c ieu kien nao. Qua trnh kh ClO2. Lng ClO2 d vt qua yeu cau co the loai bo bang kh SO2 theo phng trnh phan ng sau: SO2 + H2O ( H2SO3 H2SO3 + 2ClO2 + H2O ( 5H2SO4 + 2HCl (Kh trung bang BrCl BrCl thuy phan tao thanh HOBr va HCl theo phng trnh phan ng sau: BRCl + H2O ( HOBr + HCl HOBr la acid yeu co the phan ly theo phng trnh phan ng sau: HBr ( H+ + OBr- Neu trong nc co mat NH3, HOBr cung phan ng vi NH3 tao ra cac bromamine theo cac phng trnh phan ng sau: NH3 + HOBr ( NH2Br + H2O NH2Br + HOBr ( NHBr2 + H2O NHBr2 + HOBr ( NBr3 + H2O Mac du can tien hanh nhng nghien cu bo sung e xac nh chnh xac c che kh trung bang cua BrCl, nhng gia thiet thch hp nhat la BrCl hap phu len te bao vi sinh vat va pha huy hoat tnh emzyme cua te bao. Cac hp chat bromamin the hien kha nang diet khuan tot hn so vi cac hp chat cloramine va ong thi co kha nang phan huy nhanh hn. S hnh thanh cac san pham phu. Cac hp chat hu c bromate hoa se hnh thanh trong qua trnh kh trung bang BrCl va nhng hp chat nay de dang b phan huy quang hoa va thuy phan. Mot so nhien cu cho thay cac hp chat hu c bromate co kha nang tch luy sinh hoc torng ca tiep xuc vi nc thai x ly bang BrCl. Tuy nhien, ham lng cac chat hu c bromate trong ca thap hn nhng hoa chat khac (nh PCBs va chlordane). Hien tai cha co nhieu so lieu ve cac tac ong en moi trng do kh trung bang BrCl, do o van can nghien cu chi tiet hn. ( Kh trung bang ozone Kh trung bang ozone la phng phap kha tien tien va ngay cang c ng dung rong rai. C che kh trung s dung ozone la da tren kha nang phai huy enzyme va nguyen sinh chat cua te bao. Trong moi trng nc, ozone phan ly tao thanh cac goc t do co kha nang oxy hoa manh theo cac phng trnh phan ng sau: O3 + H2O ( HO3+ + OH- HO3+ + OH- ( 2HO2 O3 + HO2 ( HO +2O2 HO + HO2 ( H2O + O2 Cac goc t do HO2 va HO co tnh oxy hoa va la tac nhan kh trung. Cac goc t do nay cung tham gia phan ng vi cac tap chat co trong dung dch. Hieu qua kh trung bang ozone. Ozone co tnh oxy hoa manh va kha nang kh trung ln hn nhieu so vi clo. Qua trnh kh trung bang ozone khong tao thanh cac chat ran hoa tan va khong b anh hng cua cac ion ammonium cung nh pH. Them vao o, do kha nang phan huy nhanh tao thanh oxy, nen nong o oxy hoa tan trong nc sau khi x ly bang ozone at trang thai gan bao hoa nen khong can suc kh e am bao nong o DO theo tieu chuan xa thai. Ozone co kha nang phan huy nhanh nen cung khong can cac qua trnh phu e kh ozone tha nh oi vi cac tac nhan kh trung khac. Nhc iem cua phng phap kh trung bang ozone la chi ph x ly cao. ( Kh trung bang cac hoa chat khac Cac hoa chat khac co the s dung e kh trung nh iot, H2O2 va kim loai. Cac kim loai nang nong o rat thap co the tieu diet c mot so loai vi sinh vat va rong tao, tuy nhien, oi hoi thi gian tiep xuc lau, chi ph cao va de gay anh hng en sc khoe cua con ngi nen t c s dung. Bang 3.3 Nong o diet trung cua cac ion kim loai nang Kim loaiNong o diet trung (mg/L)E ColiReu, taoBac0,040,05ong0,080,15Cadimi0,150,10Crom0,700,70Kem1,041,40 3.3.2 Kh Cyanide KH CYANIDE BANG Cl2 Qua trnh oxy hoa kh Cyanide bang Clo c thc hien trong moi trng kiem. Khi cho Clo vao nc, hypocloric acid c tao thanh theo phng trnh phan ng sau: Cl2 + H2O ( HOCl + HCl Hypocloric acid phan ng vi ion CN- theo phng trnh phan ng sau: CN- + HOCl ( CNCl + OH- (1) CNCl + OH- ( Cl- + HOCl (2) Phan ng 1 xay ra khong phu thuoc vao pH, trong khi o phan ng 2 phai c thc hien pH ln hn 10. Acid cyanic tao thanh b phan huy thanh CO2 va N2 theo phng trnh phan ng sau: 2CNO- + 3OCl- + H2O ( 2CO2 + N2 + 3Cl- + 2OH- Phan ng nay xay ra cham hn pH cao hn, do o phai duy tr pH trong khoang t 7,5 8,0. V ly do nay viec khong che pH hai giai oan phai c thc hien chat che cung vi viec cung cap u lng chat oxy hoa. Hypoclorat natri cung co the c s dung thay the clo. KH CYANIDE BANG OZONE Cyanide cung co the b o xy hoa bang ozon va tao thanh cac san pham khong oc hai theo phng trnh phan ng sau: CN- + O3 ( CNO- + O2 2CNO- + 3/2O2 + H2O ( 2HCO3 + N2 Phan ng nay phu thuoc rat nhieu vao pH va c thc hien trong moi trng kiem pH t 11 en 12. 3.3.3 Kh Crom Cac phan ng kh thng c ap dung e loai bo Crom (VI) trong nc bang cac tac nhan sulfat sat (II), bisulfit natri, sulfua dioxit. Thong thng, khi s dung sulfat sat (II) phan ng vi Cr(VI) trong moi trng axt tao sulfat sat (III) va Crom (III). Ca hai thanh phan nay c ket tua di dang hydroxyt khi co mat nc voi. 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