I HC QUC GIA H NI TRNG I HC KHOA HC T NHIN ----------------------------------------------

TRN HNG CN NG KIM LOAN

CNG NGH X L KH THI

ng khi

Thp m Bm hi lu Qut thi kh

Ca thi trn

B hi lu

h ni 2006

MC LC Trang DANH MC CC BNG DANH MC CC HNH CHNG 1. NHIM KHNG KH V CC GII PHP GIM THIU 1.1. nhim khng kh 1.2. Cc dng thi vo khng kh 1.3. Cc gii php gim thiu nhim khng kh 1.3.1. Cc gii php mang tnh v m 1.3.2. Cc gii php mang tnh cc b 1.3.2.1. p dng cng ngh sn xut sch 1.3.2.2. X l trit kh thi ti ngun 1.3.2.3. Duy tr trng thi t nhin ca khng kh 1.3.2.4. S dng cy xanh CHNG 2. TNH CHT V C TNH CA MT S CHT THI VO KHNG KH 2.1. Cc kh thi c hi 2.1.1. Halogen v cc dn xut 2.1.2. Cc hp cht dng kh ca lu hunh 2.1.3. Cc hp cht dng kh ca nit 2.1.4. Kh cacbon monoxit v dioxit 2.1.5. Asin (AsH3), Phosphin (PH3) v Stibin (SbH3) 2.2. Cc cht thi dng hi 2.2.1. Hi ca cc hp cht v c 2.2.2. Hi dung mi hu c 2.3. Bi 2.3.1. Khi nim v bi 2.3.2. Hnh vi ca cc ht bi trong khng kh 2.3.3. Bn cht v tc hi ca bi CHNG 3. CC PHNG PHP X L BI 3.1. Khi qut v x l bi 6 7 10 10 13 14 14 15 15 16 17 19 20 20 20 21 25 31 33 35 35 37 38 38 40 43 44 44

3.2. Phng php x l bi da vo lc trng trng 3.2.1. Nguyn l 3.2.2. Cu to v hot ng ca bung lng n 3.2.3. Cu to v hot ng ca bung lng nhiu tng 3.3. Phng php x l bi da vo lc ly tm 3.3.1. Nguyn l 3.3.2. Cu to v hot ng ca mt cyclone n 3.4. Phng phpas x l bi bng mng lc 3.4.1. Nguyn l 3.4.2. Cu to v vn hnh 3.5. Phng php x l bi bng dn ma 3.5.1. Nguyn l 3.5.2. Cu to v vn hnh ca thit b 3.6. Lc bi tnh in 3.6.1. Nguyn l 3.6.2. Cu to v vn hnh 3.7. Phng php sc kh qua cht lng 3.7.1. Nguyn l 3.7.2. Cu to v hot ng ca thit b 3.8. Phng php ra kh ly tm 3.8.1. Nguyn l 3.8.2. Cu to v hot ng 3.9. Phng php ra kh kiu Venturry 3.9.1. Nguyn l 3.9.2. Cu to v vn hnh 3.10. Ra kh kiu dng xoy 3.10.1. Nguyn l 3.10.2. Cu to v vn hnh 3.11. Ra kh kiu a quay 3.11.1. Nguyn l 3.11.2. Cu to v vn hnh
3

46 46 46 47 48 48 48 52 52 52 54 54 54 56 56 56 60 60 60 62 62 62 63 63 64 65 65 65 66 66 66

CHNG IV. CC PHNG PHP X L HI V KH C 4.1. Phng php tiu hy 4.2. Phng php ngng t 4.3. Phng php hp ph 4.3.1. Hin tng hp ph 4.3.2. X l hi v kh c bng phng php hp ph 4.3.2.1. Nguyn l ca phng php 4.3.2.2. Cc cht hp ph thng dng trong x l kh thi 4.3.3. Cc kiu tin hnh hp ph 4.3.4. Nhng u v nhc im ca phng php hp ph 4.4. X l kh thi bng phng php hp th 4.4.1. Nguyn l 4.4.2. Cc loi thit b hp ph CHNG V. CNG NGH X L MT S KH THI CNG NGHIP 5.1. X l kh lu hunh ioxit (SO2) 5.1.1. X l kh SO2 theo ng t 5.1.2. X l kh SO2 theo ng kh 5.2. X l kh nit oxit (NOx) 5.2.1. X l trung ha NOx bng ng t 5.2.2. X l NOx bng phng php kh nhit cao 5.2.3. X l NOx bng phng php xc tc chn lc 5.3. X l ng thi SO2 v NOx 5.3.1. Cng ngh x l trong l t 5.3.2. Cng ngh x l sau l t 5.4. X l ni tip NOx v SO2 5.5. X l kh H2S 5.5.1. Cng ngh x l H2S theo ng kh 5.5.2. Cng ngh x l H2S theo ng t 5.6. X l kh CO 5.7. X l kh CO2 CHNG VI. MT S S CNG NGH X L KH THI CNG
4

67 67 69 71 71 72 72 72 75 76 77 77 78 82 82 82 83 85 85 86 87 87 88 89 91 93 93 94 96 96

NGHIP C TRNG 6.1. Thit b x l bi bng lc ti 6.2. Thit b lc ti x l kh thi (kh l) cha SO2 6.3. H thng x l kh thi tng hp (SO2, NOx, HCl, HF) bng phng php lc ti kh 6.4. H thng x l kh l c trang b thp phn ng 6.5. H thng x l kh thi bng thp m t 6.6. H thng x l kh l cha SO2 bng huyn ph canxi cacbonat 6.7. H thng x l kh l cha SO2 s dng magie hydroxxit 6.8. Conng ngh x l trc tip SO2 v NOx trong l t 6.9. Cng ngh x l kh thi cha NOx s dng xc tc chn lc 6.10. S x l bi cng nghip bng cng ngh lng tnh in 6.11. H thng x l kh l kiu Ventury in ng 6.12. S cng ngh x l ng thi NOx v SO2 s dng chm tia in t 6.13. Cc h thng x l mi TI LIU THAM KHO

98 98 100 101 102 105 108 110 112 114 118 121 123 125 131

BNG DANH MC CC BNG Bng 1.1. Cc ngun v cc cht gy nhim khng kh ch yu Bng 1.2. Bng phn loi bi, hi v kh theo gii kch thc Bng 2.1. Ngng v thi gian tc ng ca H2S ln ngi Bng 2.2. Kch thc ht ca bi, khi v cc h phn tn ph bin Bng 2.3. T trng ca mt s cht dng khi v dng bt ri Bng 4.1. Cc phng php x l bi Bng 4.2. Vng kch thc ph hp v hiu qu x l ca cc phng php x l bi Bng 4.3. Nng sut lc bi ca xyclon n v xyclon t hp Bng 7.1. Kt qu s dng h thng x l 6 trn 31 c s Bng 7.2. Mt s lnh vc p dng h thng thp m t Kyowa Bng 7.3. So snh cng ngh x l trc tip ca Hitachi Zonsen kt hp SCR vi FGD Bng 7.4. Hiu qu x l vtui th ca thit b x l NOx loi nh Bng 7.5. Mt vi thng s x l NOx bng SCR ca cc c s ln Bng 7.6. Cc thng s quan trng ca hai phng php thiu hy

BNG DANH MC CC HNH Hnh 2.1. Chu trnh ca lu hunh trong t nhin Hnh 2.2. S ph thuc ca h s K0 vo chun s Raynon (Re) Hnh 4.1. Hiu qu x l bi ca cc loi thit bi Hnh 4.2A. Bung lng n Hnh 4.2B. Bung lng kp c vch cn tng hiu qu Hnh 4.3A. Mt ct ng v mt ct ngang ca mt xyclon n Hnh 4.3B. Cc kiu hng dng trong xyclon Hnh 4.3C. S h thng xyclon lc bi Hnh 4.4A. S ng i ca kh v bi qua mng lc Hnh 4.4B. S thit b lc bi bng mng hnh ng v hnh ti Hnh 4.4C. M hnh mt thit b lc ti trong cng nghip Hnh 4.5A. Thit b dp bi theo kiu dn ma Hnh 4.5B. Thit b dn ma c nhi vt liu m Hnh 4.6A. M hnh hot ng ca qu trnh lc bi tnh in Hnh 4.6B. S nguyn l ca qu trnh lc bi tnh in Hnh 4.6C. S thit b lc tnh in Hnh 4.7A. S thit b lc tnh in ng Hnh 4.7B. S thit b lc tm Hnh 4.8. S thit b ra kh kiu si bt Hnh 4.9. S hat ng ca mt xyclon t Hnh 4.10A. S nguyn l ca mt thit b kiu venturi Hnh 4.10B. Thit b ra kh kiu venturis Hnh 4.11. Cc cu tht ca venturi nc Hnh 4.12. S hot ng ca thit b dng xoy Hnh 4.13. M hnh thit b lc bi kiu a quay Hnh 5.1. S thit b tiu hy bng nhit Hnh 5.2. S thit b x l bng phng php nhit xc tc Hnh 5.3. Cu to ca ca t nhin liu Hnh 5.4. S X l NOx s dng phn ng c xc tc Hnh 5.5. S thit b ngng t b mt
7

Hnh 5.6. S thit b ngng t kiu tip xc Hnh 5.7. S tng tc gia cc phn t trong khi vt cht Hnh 5.8. ng cong hp ph ng nhit v ng p Hnh 5.9. ng cong hp ph ca hi t qua ct hp ph Hnh 5.10. M hnh thp hp ph hi v kh c Hnh 5.11. M hnh hp ph kiu tng quay Hnh 5.12. S mt h thng x l hp ph trong cng nghip Hnh 6.1. S CNXL kh thi cha SO2 theo ng t (FGD) Hnh 6.2. S CNXL SO2 theo ng kh sau l t Hnh 6.3. S CNXL SO theo ng kh trong l t Hnh 6.4. S CNXL NOx theo ng t Hnh 6.5. S CNXL NOx nhit cao Hnh 6.6. S CNXL NOx bng xc tc chn lc (SCR) Hnh 6.7. nh hng ca kch thc ht v phn tn canxi cacbonat n hiu qu x l SO2 Hnh 6.8. S CNXL ng thi SO2 v NOx trong l t Hnh 6.9. S nguyn l x l SO2 v NOx s dng chm tia in t Hnh 6.10. S CNXL ng thi SO2 v NOX s dng chm tia in t Hnh 6.11. S h thng x l NOx bng phng php xc tc chn lc kt hp x l SO2 Hnh 6.12. S CNXL H2S theo ng kh Hnh 6.13. S CNXL H2S theo ng kh Hnh 6.14. S CNXL H2S bng phng php st(III) theo ng t Hnh 7.1. Thit b lc ti x l bi kimloi nng ca hng NAVAC Hnh 7.2. H thng x l bi, kh SO2 v cc kh, hi axit khc bng con ng kh x dng thit b lc ti hiu sut cao Hnh 7.3. H thng x kh l bng thit b lc ti kh Hnh 7.4. nh hng ca nhit n hiu qu x l kh l Hnh 7.5. H thng x l kh c trong thit b thp phn ng Hnh 7.6. S ph thuc gia hiu sut x l kh HCl vo nhit v t l mol ca Ca(OH)2 v HCl Hnh 7.7. S thit b x l kh theo ng t s dng thp m

Hnh 7.8. S mt ct ca thit b thp m Hnh 7.9. H thng x l kh thi cha SO2 thu hi thch cao Hnh 7.10. S h thng x l kh thi cha SO2 s dng Mg(OH)2 Hnh 7.11. H thng x l trc tip SO2 v NOx trong kh thi c nhit cao s dng CaCO3 v ure Hnh 7.12. S nguyn l ca qu trnh x l NOx bng xc tc chn lc Hnh 7.13. S c trng ca mt thp SCR Hnh 7.14. S mt ct ng ca mt thp lc tnh in Hnh 7.15. S mt ct ngang ca mt thp lc tnh in Hnh 7.16. S h thng thp lc tnh in kiu kh Hnh 7.17. S h thng thp lc tnh in kiu t Hnh 7.18. S h thng x l kh l kiu venturi in ng (EDV) Hnh 7.19. S h thng x l kh l dng chm tia in t Hnh 7.20. S ba kiu x l mi bng phng php thiu hy Hnh 7.21. Hiu sut phn hy ph thuc vo nhit thiu hy ca mt s cht Hnh 7.22. S thit b kh mi kiu hp ph v gii hp lin tc

Chng I. nhim khng kh v cc giI php gim thiu nhim 1.1. nhim khng kh Th no l nhim khng kh? Mun tr li c cu hi ny th cn phi thng nht c khi nim v bu khng kh sch hay ni cch khc l thng nht quy nh v thnh phn nn ca mi trng khng kh. Trong bu kh quyn ca tri t th tng i lu l gn mt t nht - tng ca gi bo. Ti tng ny, cc cht nhim thng xuyn c ra sch bi ma v tuyt ri. Trn tng bnh lu th khc. Do s hp th ca lp zn, s n nh v s tng ca nhit theo chiu cao; cho nn cc cht nhim khi thm nhp vo tng ny c chiu hng tn ti lu di hn. Thc ra s nhim khng kh c hiu ch yu nh l s thay i bt thng thnh phn v nng ca cc cht trong tng khng kh gn mt t - tng i lu. Do vy ta c th chp nhn mt nh ngha v nhim khng kh nh sau [1, 2]: nhim khng kh c ngha l c mt mt hoc nhiu cht gy nhim trong bu khng kh ngoi tri nh bi, khi, hi, kh hay mi...vi khi lng, tnh cht v thi gian gy hi i vi s sng ca ngi hay ng, thc vt, hoc tc hi ti ca ci vt cht hoc cn tr qu mc i vi s tn ti bnh yn ca s sng v ca ci vt cht trn tri t. Trong lu v kim sot nhim mi trng khng kh ca bang t Arizna (M) cng a ra mt nh ngha tng t [1]: nhim khng kh c ngha l s c mt ca mt hay nhiu cht nhim hoc s phi hp ca chng trong khng kh ngoi tri vi khi lng v thi gian gy hi hoc c chiu hng gy hi i vi s sng ca ngi, ng, thc vt hoc ca ci vt cht. Nhng i km v i nh ngha ny c lit k cc cht nhim l khi, hi, than gi y, bi, m hng, cu gt, khi than, cc kh, m, mi, tia phng x, cc ha cht c hi hoc bt k vt cht no trong khng kh ngoi tri. ng thi nh ngha ny cn quan tm n xu th gy hi na. Nh vy trong thc t c hai ngun gy ra nhim khng kh, l ngun nhim t nhin v ngun nhim nhn to ngn lin vi cc hot ng ca con ngi [3, 4]. - Ngun nhim t nhin: Cc hot ng t nhin c th lm tng hm lng bi ti mt thi im v mt khng gian no nh gi lc, bo sa mc mang theo bi t ct trn mt t tung vo bu khng kh. Ni la hot ng c th phun vo bu kh quyn mt lng bi v kh khng l. Nhng hin tng nh trn xy ra khng lin tc, trong mt khong thi gian ngn v pht tn ra m vng rng ln lm gim nhanh hm lng c ht gy t nhim.

10

Cc hin tng phn hy, thi ra xc ng thc vt xy ra thng xuyn trong nhin a vo bu khng kh cc kh c hi. Nhng hin t tng ny ko di u n theo thi gian pht trin ca hnh tinh chng ta nn hm lng ca cc c ht c hi thng nm gii hn nn. Nhng nu hin tng trn xy ra sau mt thm ho no khng thng xuyn v cc b th n s thi vo khng kh mt lng kh c hi vt qu gii hn nn trong khong thi gian v khng gian gii hn trong v xung quanh khu vc xy ra thm ha s gy ra s nhim khng kh. Cc hin tng sm chp, my ma, bc x trong h mt tri v v tr, thng qua cc ph ng phn hy hoc kt hp cc cht tn ti trong khng n kh to ra cc cht c hi lm mt cn bng vn c ca bu khng kh cng c coi l s nhim. Nhn chung nhi m khng kh do thin nhin to ra v khi lng l rt ln song thng phn b trong mt khng gian rng v kh ng u nn t gy nguy hi. Mt khc cc sinh vt trn mt t, qua hng ngn vn nm quen vi nhng thay i ni trn v thch ng c. -Ngun nhim nhn to. Cc ngun nhim nhn to nguy him ch rt d xy ra hin tng cc b vi nng cao gy tc hi n con ngi, cc sinh vt v ca ci vt cht nm trong vng nhim. Cc ngun v cc cht gy nhim khng kh do nhn to c khi qut trn bng 1.1. Bng 1.1. Cc ngun v cc cht gy nhim khng kh ch yu Cht nhim 1 Ngun nhim 2

-Cc nh my nhit in -Cc ngnh cng nghip t nhin liu lm nng lng. Oxit cc bon (CO, -Giao thng vn ti. CO2) -Cc l t rc v dn dng -Phn hy, ln men ym kh -Cc c s khai thc v ch bin than , than g -t SP nng nghip sau thu hoch v dn dng. Bi than, tro -Cc nh my nhit in. -Cc c s sn xut gm, s -Ch ha qung v luyn kim. Bi Berili Bi uranium -Ch ha qung. -Cc c s luyn kim Hp cht cha -Cc c s sn xut ha cht cc kim loi c -Cc c s sn xut thuc tr dch hi c tnh cao -S dng cc sn phm thuc tr dch hi -Giao thng vn ti
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-Thuc tr su Cc hp cht c -Cc c s sn xut ha cht clo -Cc c s sn xut giy v bt giy -Kh trng bng clo v cc hp cht cha clo hot ng. -Cc c s sn xut v s dng halogen v ha cht cha Halogen v cc halogen hp cht c v -Cc c s sn xut phn ln t apatit c cha halogen -Cc c s luyn kim... -t nhin liu -Cng nghip sn v vt liu ph -Cc c s sn xut linh kin in t cn lm sch bng Hydrocacbon dung mi hu c -In n, sn, v -Cc c s sn xut ha cht hu c -Luyn cc... -t nhin liu Nit oxit -Cc nh my ha cht -Cc c s sn xut phn m, phn tng hp NPK -Cc c s sn xut ha cht -Cc nh my nhit in Lu hunh oxit -Luyn kim -Cc cng on t nhin liu khc Cc hp cht c -Cc c s sn xut thuc tr dch hi phot pho -S dng thuc tr dch hi -Cng nghip sn xut xi mng -Cng nghip khai khong Bi khong v c -Giao thng vn ti -Xy dng -Cc v th ht nhn Bi phng x -S d r ca cc c s nng lng ht nhn -Cc c s sn xut ha cht Hi kim, hi axit -X l b mt kim loi -Cc c s s dng axit v kim trong sn xut -Cc c s sn xut acquy Bi ch -Luyn kim mu -Giao thng vn ti -Cc c s m kim loi -Khai thc, trch chit vng, bc v cc kim loi qu him khc HCN v CN -Cc cng on t nhin liu -Sn xut ha cht
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1.2. CC DNG THI VO KHNG KH Cc cht thi vo khng kh nm di cc dng ch yu l bi, khi, hi, sol v kh. Ngi ta phn loi chng mt cch n gin nht l da vo kch thc ht ca chng (xem bng 1.2.) [5] Bng 1.2. Phn loi bi, hi v kh c theo di kch thc Loi Di kch thc (m) Ngun gc v c tnh Pht sinh trong qu trnh p, ph, n, mi khoan .. cc cht rn nh t , qung, than, kim loi .. Mt s bi c dng si c ngun gc nhn to, thc vt hoc khong. Cc bi ln, nh kh lng do lc trng trng. Cc bi nh c khuynh hng bay l lng trong khng kh. c to ra do ngng t cc phn t cht rn trong qu trnh t nhin liu, qu trnh lm nng chy kim loi hoc cc phn ng ho hc. c to ra do ngng t cc phn t cht rn trong qu trnh t chy nhin liu L sn phm ca qu trnh tp hp t nhin (ngng t) cc phn t cht lng trong khng kh. L phn th kh ca cc cht lng hoc rn trong iu kin bnh thng. S tn ti ca chng ph thuc vo iu kin c th ca mi trng. L dng vt cht m trong iu kin nhit v p sut thng thng chng khng tn ti di dng cc phn t th kh

Bi

0,1 - 75

Khi I

0,001 - 1,0

Khi II Sng Hi

0,1 - 1,0 0,01 - 10,0 0,0005 0,005

Kh

< 0,0005

- Cc cht dng kh: L nhng cht iu kin thng thng tn ti di dng kh nh: CO, CO2, NOx, SOx, Cl2... - Cc cht dng hi: L phn dng kh ca cc cht m iu kin nhit v p sut bnh thng chng dng rn hoc lng. - Cc cht dng sol kh: L tp hp cc phn t cht lng hoc cht rn th ri rc tn ti trng thi l lng cng khng kh vi khong thi gian khng hn nh. Kch thc nh nht ca sol c th ch bng kch thc ca
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mt phn t ln v cc ht sol ln c th dn vi m. Hm lng ca chng trong khng kh nm khong t 10 mg n 10 gam trn mt mt khi - Cc cht dng bi: L cc phn t cht rn th ri rc c to ra do cc hot ng ca t nhin hay con ngi c kch thc khc nhau (t 1/100 n hng trm micromet). Di tc dng ca cc dng kh hoc khng kh, trong nhng iu kin nht nh chng chuyn thnh trng thi l lng trong pha kh. Cc cht thi l kh, hi, bi hay sol c tc hi t hay nhiu s ph thuc vo bn thn tnh cht ca chng. Nhng nhn chung cc cht c hi dng kh thng l nguy him nht do tc ng trc tip v lin tc vo phi qua h hp. C nhiu cch phn loi bi, hi v kh . Di gc thu gom v tch lc, phn loi theo di kch thc c coi l ph hp v hu dng hn c. 1.3. CC BIN PHP GIM THIU NHIM KHNG KH [6] Gia thin nhin v con ngi trn hnh tinh ca chng ta lun c mt mi quan h mt thit. Nhng tc ng ngc li ca thin nhin i vi qu trnh gy nhim bu khng kh do nhng hot ng sng ca con ngi gy ra c quan h nhn qu vi nhau. Vic s dng cc kh lm hy hoi tng dn; vic s dng qu mc cc ngun nhin liu ha thch lm tng hm lng kh CO2 trong bu kh quyn tri t lm cho tri t nng ln do tc ng ca hiu ng nh knh. S nng ln ca tri t gy ra nhng hu qu nghim trng mang tnh ton cu nh mc nc bin dng ln s nhn chm nhng vng t thp, bo lc, hn hn, lt li, s sa mc ha... Chnh v th m Lin hp quc, nhiu t chc x hi v chnh ph nhiu nc ku gi mi ngi hy cu ly tri t. Nhng bin php gim thiu nhim bu khng kh l gii php hu hiu bo v tri t. Do tnh cht c th ca mi trng khng kh m s nhim t mang tnh cc b. S pht thi ni ny c th gy nhim nhng ni khc, tu thuc vo iu kin thi tit, kh hu hay s chuyn ng ni chung ca cc tng kh quyn. V vy cc gii php chng nhim khng kh cn phi mang tnh ton cu. Nhng bin php c th c th chia lm hai loi l cc bin php mang tnh v m v nhng bin php mang tnh cc b.
1.3.1. CC BIN PHP MANG TNH V M

Do nhn thc c nhng him ha ca s nhim khng kh nn hu ht cc nc trn th gii cng i ti mt tho hip mang tnh chin lc ton cu v ct gim cc kh thi gy tc ng nh knh v ph hoi tng

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zn - Ngh nh Kyoto. i vi tng quc gia, cn phi c nhng bin php hn ch tc ng ca con ngi vo thin nhin nh: + Kim sot v hn ch lng thi cc cht gy hiu ng nh knh, cc cht hy hoi tng zn v cc cht kh c hi khc. + Hn ch chy rng. Nhng t chy rng xy ra quanh nm trn th gii gy ra nhng tc ng ng thi lm suy thoi cht lng khng kh. Chy rng gy ra nhng lp khi bi trn din rng; sinh ra mt lng kh CO2 khng l v lm mt cn bng sinh thi. Hu qu ca n l nhng tc ng dy chuyn nh hng xu n mi trng tri t. Vic hn ch chy rng ngoi nhng bin php phng nga thin nhin, vic gio dc cng ng cng c tm quan trng khng km. + Hn ch khai thc rng, khai thc khong sn nhm gim thiu nh hng n s cn bng vn c ca kh quyn v b mt qu t. + Chng hoang ha, sa mc ha. Trng cy xanh, trng rng l bin php ly li s cn bng b mt i do hu qu ca chin tranh v khai thc qu mc ca con ngi i vi cc thm thc vt - l phi ca tri t. + Trng rng cy m ven b bin chng s xm ln ca ct, hi mui bin vo t lin; trng rng m chng sa mc ha.
1.3.2. CC BIN PHP MANG TNH CC B
1.3.2.1. P DNG CNG NGH SN XUT SCH

Gim thiu pht thi cc cht gy nhim ngay ti ngun l bin php hu hiu trnh gy nhim khng kh. Gii php u tin l pht trin cc qu trnh sn xut sch - khng thi hay ni cch khc l ti u ha mi iu kin sn xut v tn dng trit cc sn phm ph l xu th hin nay v cho thin nin k mi ny. Pht trin sn xut khng thi khng nhng gim c ti a gi thnh sn phm m cn c mt li ch rt ln khc ngoi phm vi ca c s sn xut l bo v mi trng v h sinh thi. y l li ch khng th ch tnh bng li nhun v sn phm do n mang li m n mang tnh cht x hi v ton cu. ng trn quan im v cng ngh, sn xut khng thi c th thc hin bng cc gii php tn dng v quay vng trit nguyn liu, nc v nng lng trong phm vi mt nh my v lin kt nhiu nh my tn dng tt c cc sn phm ph, thm ch ngay c cht thi ca nh my ny s dng lm nguyn liu cho nh my kia. Ngoi nhng iu trnh by trn, mt gii php quan trng pht trin sn xut khng thi l thay th nguyn liu u vo bng nguyn liu sch v s dng nng lng sch nh nng lng nguyn t, nng lng t nhin nh sc nc, sc gi v nng lng mt tri.
15

Vic vn hnh v qun l thit b my mc cng nh quy trnh cng ngh cng l mt bin php khng ch nhim khng kh. Nghim tc thc hin ch vn hnh, nh mc chnh xc nguyn vt liu, chp hnh ng quy trnh cng ngh s lm cho lng cht thi gim xung v c iu kin qun l cht ch ngun thi v lng cht thi. Hiu qu ca bin php qun l v vn hnh sn xut ph thuc rt ln vo nhn thc ca cc cp lnh o v cc nh qun l; sau l k lut lao ng v tnh t gic ca ngi lao ng. Cc ch ti phc v c lc cho cng tc ny hin nay ang c p dng rng ri trn th gii v c trong nc l cc tiu chu ca t chc tiu chun quc t vit tt l ISO (International n Standard Organization) p d ng cho cc qu trnh sn xut, vn hnh cng vic... Cho n nay, cc ISO c coi nh l nhng tiu chun c th nht nhm gim bt tiu hao nguyn, nhin, vt liu, nng cao cht lng sn phm lao ng v gim thiu pht thi.
1.3.2.2. X L TRIT KH THI TI NGUN

tin ti mt nn cng nghip sn xut sch cn cn mt khong thi gian di v m mt ngun ti ch nh khng l thay th nn cng nghip t hin ti. Hin nay do c tnh k tha v chm i mi, c bit l cc nc ang hoc km pht trin, nn sn xut cng nghip cn lc hu v pht thi lng ln cc cht gy nhim vo khng kh. i vi khu vc ny vic gim thiu nhim khng kh ph thuc ch yu vo trang thit b v cng ngh x l kh thi ti ngun. Vic x l trit cc ngun kh thi ti ngun s c kh nng gim thiu ti a nhim khng kh. X l kh thi ti ngun cho n nay, nhng nm u ca th k 21, vn l gii php quan trng, ph hp v hu hiu nht hn ch nhim khng kh v ci thin mi trng khng kh. Hin nay i vi mi quc gia v nhiu vn chung cho c th gii hu ht c cc tiu chun quy nh cho mi loi kh thi vi cc quy m v iu kin khc nhau. Da trn cc tiu chun , nu lm tt khu qun l, mi trng khng kh s c ci thin ng k. Trc y khi cc nh my v cc khu cng nghip cn tha tht th vic xy ng khi v tng chiu cao ca ng khi l mt gii php hiu qu gim thiu nhim cc b. Nhng khng gian ca kh quyn cng c gii hn v qu trnh lm sch t nhin cng ch c gii hn ca n. Do vic s dng ng khi ngy nay khng cn c khuyn co s dng nh l mt bin php gim thiu nhim khng kh na m u tin l x l trit kh thi ti ngun trc khi thi vo khng kh. X l kh thi bao gm cc phng php x l bi, sol kh; x l kh v x l hi thi c hi. Vi tng i tng c th s dng cc phng php
16

ring r hoc s dng t hp cc phng php nhm t hiu qu x l cao hn. Cc phng php v cc thi b x l kh thi s c trnh by mt t cch chi tit cc phn sau.
1.3.2.3. DUY TR TRNG THI T NHIN CA KHNG KH

S gim thiu nhim khng kh l lm trong sch hn bu khng kh ngoi tri. Nhng s nhim khng kh trong khng gian lao ng nh bn trong cc nh xng, hm l, phng lm vic hay khng gian ca mt x nghip, nh my... s gy tc hi trc tip ti ngi tham gia lao ng. y cng l mt vn cn c gii quyt. Mt bin php hu hiu duy tr trng thi t nhin ca bu khng kh cc b l thng gi. Nhim v ca thng gi l m bo trng thi khng kh cho con ngi sng v hot ng ph hp vi tiu chun v sinh quy nh trong cc khng gian khp kn. Ty theo tnh ch ca ngun gy nhim m la chn cc t phng php thng gi ph hp. a. Thng gi chung Mc ch ca thng gi chung l a khng kh t ngoi vo vi lu lng cn thit nhm pha long cng nhim bi khng kh nng, bi, hi hoc kh c... trong ton b khng gian nh xng, sau thi ra ngoi. Nhc im ca bin php ny l to ra mc khng ng u ca iu kin v sinh ti nhng im khc nhau trong khng gian nh xng; ng thi d a cc tc nhn c hi t vng ny sang vng khc. V vy, mt trong nhng yu cu cn thit khi p dng bin php ny l phi n nh c cc ngun pht thi c hi. Hin tn ti mt s s h thng trao i khng kh trong phng nh sau: + Thi trn ht di. + Thi di ht trn. + Thi trn ht trn. + Thi di ht di. Ty tng trng hp m p dng s ny hay s khc, nhng phi tun th theo nguyn tc l dng khng kh phi i theo trnh t: Khng kh sch Vng th Vng pht sinh kh c Ming ht Thi b. Thng gi cc b Mc ch ca thng gi cc b l ht kh, hi hay cc tc nhn gy c hi khc ngay ti ngun pht sinh. y l bin php hiu qu nht trong vic m bo trong sch khng kh cho vng lm vic.

17

Vic thit k hp l cc cc b phn thu cht gy nhim phi tho mn cc yu cu sau: + Khng cn tr thao tc cng ngh. + Khng cho khng kh cha cht nhim i qua vng th. + Vn tc thu kh ln c th ht trit cc cht c hi ra khi vng th ca ngi lao ng. c. Thng gi chng nng Trong qu trnh ho ng, con ngi lun c s trao i v nhit vi t mi trng. Mc trao i nhit tiu chun i vi ngi trong iu kin ngh ngi l 100 kcal/gi. V ma h, thi tit nng nn ch c con ng duy nht cn bng nhit l thot m hi. thu c hiu qu lm mt bng bc hi m hi th phi c cc iu kin sau: + m ca khng kh thp. + C go vi vn tc ph hp. Ti nc ta, m trung bnh tng i cao. Do vy tng hiu qu bc hi m hi phi dng gi c tc ln; v d: + i vi h iu ho khng kh: v = 0,25 - 0,38 m/giy. + i vi lao ng: v = 5,00 - 10,00 m/giy. Ty theo mc yu cu khc nhau v v sinh v cng nghip m p dng cc gii php thng gi chng nng khc nhau. C th chia lm hai loi: + Gii php thng gi t nhin. + Gii php thng gi cng bc. Thng gi t nhin l li dng cc yu t ca t nhin nh vn tc gi tri, chnh lch t trng ca khng kh to ra cc dng kh vo, ra mt cch hp l. Ti nc ta, thng gi t nhin ch yu l dng gi tri. Do vy vic m cc ca n gi, thot gi vi t l ln l vic lm rt quan trng. Theo cc nghin cu gn y cho thy t l m ca phi t 40 n 60% din tch tng mi m bo thng gi t nhin theo phng nm ngang c hiu qu. Mt vn na cng quan trng l vic hn ch bc x nhit mt tri truyn qua mi nh. V ma h, lng nhit truyn qua mi c th ln ti 110 - 120 kcal/m2. Nhng bin php c th p dng l phun nc ln mi nh, to tng cch nhit vi mi nh. Thng gi cng bc c s dng khi thng gi t nhin khng cn kh nng p ng c vn cn bng nhit. Thng gi cng bc nhm to ra vn tc gi thi thch hp, kt hp vi cc thng s nh nhit , m... a vi kh hu v trng thi t nhin d chu.
18

Trong cng nghip, ngoi yu t vn tc gi thi cn c th h nhit khng kh lm tng hiu qu lm mt. Mt trong nhng bin php n gin c th p dng l lm mt bng bc hi nc on nhit. Nguyn l chung ca bin php ny l cho dng khng kh i qua bung phun nc hoc lp mng t. Nhit ca khng kh lm nc bay hi v t n h nhit xung nhng m tng i tng ln. Bin php ny c p dng cho nhng vng c kh hu nng, kh nh min trung v min nam nc ta. Trong cc gii php thng gi cng bc th iu ha nhit khng kh l hnh thc cao nht ca k thut thng gi nhm p ng ch ng cc thng s vi kh hu trong nh m khng ph thuc vo kh hu ngoi tri.
1.3.2.4. S DNG CY XANH

Cy xanh c tc dng rt ln trong vic hn ch nhim khng kh nh chn gi bi, lc sch khng kh, gim ting n v che chn ting n, gim nhit khng kh v iu ha thnh phn ca khng kh. Mt s loi cy xanh rt nhy cm vi nhim khng kh, cho nn c th dng cy xanh lm vt ch th pht hin nhim. V th nn trng nhiu cy xanh trong khun vin v xung quanh cc nh my, dc cc ng giao th ng ni b, trong khu m gia cc khu cng nghip, cc khu thng mi. T l din tch cy xanh trn din tch khu cng nghip cn t t 15 n 20%.

19

CHNG II. TNH CHT V C TNH CA MT S CHT THI VO KHNG KH 2.1. CC KH THI C HI
2.1.1. HALOGEN V CC DN XUT [6, 7, 8]

1. S pht sinh. Cc halogen c hnh thnh ch yu trong cc qu trnh in phn cc mui halogenua (nh sn xut xt-clo, in phn sn xut kim loi kim, kim th) hoc di tc dng ca cc cht oxi ha mnh hn trong nhng iu kin c th (tr flo ch c th gii phng ra bng in phn). Ngoi ra chng cn c th sinh ra khi phn hy mt s hp cht halogenua nhit cao. Th d: 2X- - 2e = X2 (X l halogen) 4Cl- + MnO2 + 4H+ = MnCl2 + 2H2O + Cl2 2Br_ + Cl2 = 2Cl- + Br2 4I- + 2Cu2+ = 2CuI + I2 Ngoi ra mt lng khng nh cc halogen cng nh cc dn xut ca chng pht thi vo khng kh t cc ngun s dng halogen nguy n t lm nguyn liu cho qu trnh sn xut nh cng nghip sn xut plastic (PVC, PTFE...), clo ha cao su, sn xut thuc tr dch hi, st trng, thuc st trng v cng nghip ha cht ni chung. 2. Tnh cht c trng. Halogen nguyn t l nhng cht rt hot ng v c tnh oxi ha rt mnh. Tnh cht ny th hin gim dn t flo clo brom iot. Flo c th thc hin phn ng th y cc nguyn t nh oxi, clo... ra khi hp cht ca n: SiO2 + 4F2 = SiF4 + O2 Cc halogen tan trong nc, t oxi ha kh to thnh hai axit tng ng l hypocloric v clohydric. Cl2 + H2O = HOCl + HCl Trong dung dch 5.10 -3M Cl2 0oC c t i 89% lng clo chuyn thnh cc axit. Bn thn gc OCl- cng l cht oxi ha mnh, n c th ph hu cc cht mu hu c do n thng c s dng nh l tc nhn ty trng cho giy, vi si v my tre... HClO trong nc b phn hy t t thnh HCl v oxy theo phng trnh:
20

HClO = HCl + 1/2O2 Phn ng ny xy ra nhanh hn di tc ng ca nh sng, nht l di nh sng mt tri v khi c mt ca cht xc tc. Do c tnh oxi ha mnh cho nn cc halogen rt d phn ng ngay vi cc cht hu c (nht l trong iu kin m) bn ngoi da v bn trong c th ng thc vt v con ngi, gy tn thng rt nhanh v li hu qu nghim trng. i vi cc cht v c c tnh kh ngay c cc cht kh yu, cc halogen cng rt d phn ng to thnh cc halogenua tng ng kh bn vng v hu nh khng c hi (tr mt s hp cht ca flo). Halogen tc dng vi kim to thnh cc mui halogenua v hypohalit. Cl2 + Fe = FeCl2 Cl2 + 2FeCl2 = 2FeCl3 Cl2 + 2NaOH = NaCl + NaOCl Cl2 + Ca(OH)2 = CaOCl2 + H2O CaOCl2 = CaCl2 + 1/2O2 Cc halogen nguyn t thi vo khng kh u di dng cc phn t kh. Chng l nhng cht oxi ha rt mnh cho nn khi tip xc vi mt hm lng nh trong khng kh c th b tc ng ng k. Chng lm tn thng da, hy hoi cc nim mc mt, mi, ming v c bit nghim trng l gy n thng su i vi phi. Tu thuc vo thi gian v nng t halogen trong mi tr ng tip xc m nhng tn thng c th mc t vong, vim ph phi, hoi t cc nim mc hoc c th hi phc sau khi cch ly vi mi trng nhim c. Cc halogen bn thn n l nhng cht c hi i vi c th sng; cc dn xut ca chng, c bit l cc halogen hu c cng rt nguy him. Th d nh cc c clo (trong thuc tr su, dit nm, lm rng l cy, cht c ha hc...) l nhng cht c tc n g ln c th ng thc vt theo nhng c ch rt a dng. Cc kh hydrohalogenua (HF, HCl, HBr, HI) trong mi ng khan tr tng i l km hot ng. Nhng khi c mt ca nc hay hi nc th chng l nhng axit mnh; tc ng ln ng thc vt theo c ch phn ng ca cc axit. Ngoi ra m s hp cht th kh ca halogen v halogen vi cc t nguyn t khc cng l nhng cht rt c hi; th d nh ClF 3, fosgen, halogenua silan (SiHxXy)...
2.1.2. CC HP CHT DNG KH CA LU HUNH

Lu hunh hp cht tn ti nhng dng khc nhau tu thuc vo cc mc ha tr ca n. Th d nu xp theo ha tr t m n dng ta c dy:
21

H2S - SCN - S - SO2 - SO3 - H2SO4 - H2S2O8 kh kh rn kh kh lng lng Trong thc t thng gp nht l H2S v SO2 cn cc kh khc rt him khi thy xut hin trong cuc sng hng ngy. Kh H2S [6, 9] 1. S pht sinh. H2S c sinh ra ch yu t nhng qu trnh phn hy vi sinh ym kh nh cc c s x l cht thi: Cht hu c cha lu hunh
Vi sinh vt

CH4 + CO2 + H2S + ...

Hay t cc c s dt nhum s dng cc mui sunphua lm ph gia tr nhum hoc nh mu... Na2S + 2H2O H2S + 2NaOH FeS + 2H+ = H2S + Fe2+ 2.Tnh cht c trng b H2S l kh km n khi pht tn vo trong kh quyn. Ngi ta nghin cu v a ra gin v s bin i v thi gian tn ti ca n trong t nhin nh trn hnh 2.1. H2S + O O2 O3
Vi gi

SO2

h O O2
Nhiu gi hoc vi ngy

SO3 + H2O
Vi giy

H2SO4 + Me
Phn hy VS ym kh trong t, m ly, cc dng thy triu

MeSO4

Hnh 2.1. Chu trnh ca lu hunh trong t nhin

22

H2S trong dung dch nc th hin nh mt axit yu, tc dng c vi cc kim mnh, ng thi n cng rt d tc dng vi nhiu ion kim loi to thnh cc kt ta sunphua kh tan. H2S + NaOH Na2S + H2O H2S + Ca(OH)2 = CaS + 2H2O H2S + Pb2+ = PbS + 2H+ L mt cht c tnh kh yu cho nn H 2S cng d b oxi ha tr thnh lu hunh nguyn t hay cc gc sunpht tu theo cht oxi ha s dng l yu hay mnh. H2S + 2Fe3+ = S + 2Fe2+ + 2H+ 3H2S + 8MnO4- + 2H+ = 3SO42- + 8MnO2 + 4H2O H2S + 4Cl2 + 10NaOH = Na2SO4 + 8NaCl + 5H2O Hydrosunphua va l kh kch thch va l kh gy ngt. Nu tc ng trc tip ln cc nim mc mi v mt n s gy vim ni sn kt mc. Khi ht vo phi, H 2S s tc ng ln ton b ng h hp, nhng cu trc su hn s b ph hy su sc v hu qu c th li l bnh ph phi. Nu tip xc vi hm lng ln hn 1000 ppm (1500 mg/m 3), kh H2S s hp th vo phi rt nhanh, c biu hin th gp, sau l tru h hp v thng l dn ti t vong. Nhim c mn tnh i vi H2S nu thng xuyn tip xc vi hm lng khong 50 100 ppm. Ngng tc ng ca kh H 2S c th tham kho trn bng 2.1. Bng 2.1. Ngng v thi gian tc ng ca H2S ln ngi. Ngng tc ng Pht hin Chy nc mt Vim kt mc Mt cm gic mi Gy ngt Cht Nng (ppm) 0,0005 1,3 10,5 21,0 50 100 150 200 500 700 Trn 900 Thi gian tip xc Vi giy n 1 pht 6 7 gi Hn 1 gi 2 n 15 pht t hn 1 gi t hn 30 pht

Kh lu hunh dioxit [6, 10] 1. S pht sinh. Kh SO2 chim t trng ch yu trong cc kh c hi cha lu hunh thi vo khng kh. Phn ln SO2 sinh ra do qu trnht cc nhin liu ha thch c cha lu hunh nh than , du m. Nhng nhin liu loi ny c s dng vi khi lng rt ln cho cc nh my nhit in, luyn kim,
23

cho cc ng c chy bng xng, du v nhiu lnh vc khc s dng nhin liu ha thch. Bn cnh n cn cc ngun kh thi ca nhng qu trnh t lu hunh cng nh cc loi khong sun phua, phn hy khong sun pht nhit cao v cng nghip lc ha du. Tng lng SO2 thi vo khng kh hng nm c tnh vo khong 140 triu tn; trong khong 70% do t than, 16% do t nhin liu t du m v phn cn l i l do cng nghip lc ha du, luyn kim v cc hot ng khc. S + O2 = SO2 2CuS + 2O2 = 2CuO + SO2 2H2S + 3O2 = 2SO2 + 2H2O 4CaSO4 + 2C = 4CaO + 2CO2 + 4SO2 2.Tnh cht c trng Lu hunh dioxit nh ni trn, l anhydrit ca axit sunphur do n tan trong nc to thnh dung dich axit mnh, phn ng mnh lit vi cc baz, k c nhng baz yu to thnh cc mu tng ng. SO2 + H2O = H2SO3 H2SO3 + 2NaOH = Na2SO3 + 2H2O H2SO3 + Ca(OH)2 = CaSO3 + 2H2O Bn thn SO2 v g sunphit l nhng cht c tnh kh tng i c mnh. Nhng SO2 trong khng kh kh r t kh oxi ha thnh SO 3 m mun oxi ha n phi s dng xc tc thch hp v trong nhng iu kin nht nh. Ngc li gc SO32- hay cc mu sunphit li rt d dng b oxi ha bng i ngay oxi khng kh trong iu kin thng v qu trnh oxi ha xy ra nhanh hn khi tng nhit cho phn ng. SO2 + 2Fe3+ + 2H2O = SO42- + 2Fe2+ + 4H+ SO2 + H2O + CaCO3 + 1/2O2 = CaSO4 + CO2 + H2O MgSO3 + 1/2O2 = MgSO4 Kh SO2 c coi l kh thi nguy him v tnh c hi cng nh s pht thi lng ln v thng xuyn ca n. SO 2 c tc ng ln ng h hp bt u t nng 2,1 mg/m3 (0,75 ppm). Tip xc vi thi gian ngn (24 gi) nng 0,5 mg/m 3 c th gy ra chng ph phi nhng ngi gi v cc bnh nhn. Tip xc lu di nng 0,1 mg/m 3 c th gy ra cc triu chng v cc bnh v ng h hp. V vy ngng an ton cho tip xc ngn hn (24 gi) c hng dn l t 0,1 n 0,15 mg/m3 v cho tip xc di hn l t 0,04 n 0,06 mg/m3.

24

Kh lu hunh trioxit [6, 10] 1. S pht sinh. Kh SO3 thng ch thy trong khng kh ti cc xng np in cho c quy ch hay sn xut axit sunphuric. 2.Tnh cht c trng Kh SO3 khi hp nc s to ra axit sunphuric nhng thng dng m rt kh lng ng; v vy n vn c th tn ti trong kh quyn hoc trong cc vng vi kh hu m n hnh thnh. Mun hp th SO 3 sn xut axit ngi ta phi hp th n bng axit sunphuric c khong 98%. SO3 phn ng rt mnh vi cc baz, mui cacbonat to thnh cc mui sunpht tng ng. Ngng bt u gy tc ng phn ng ca ng h hp ca SO3 m l 0,35 mg/m3 v c th gy ra cc triu c hng cng nh cc bnh v ng h hp l 0,25 mg/m 3. Ngng ch dn an ton i vi SO 3 m l 0,04 n 0,06 mg/m3 cho tip xc di hn v 0,10 n 0,15 mg/m 3 cho tip xc ngn hn.
2.1.3. CC HP CHT KH CA NIT [6]

Nit cng l nguyn t a ho tr, n tn ti tng i bn di dng cc ha tr khc nhau. Ta c th th hin tnh cht ca nit theo dy di: HN3 (CN)2 NH3
Azidohydric dicyan amoniac

N2 N2O NO
nit dinitoxit nitoxit

NO2
nitdioxit

NO3
nittrioxit

Trong tt c cc hp cht k trn ca nit th ch c azidohydric th lng cn li u th kh. Cc kh ny u l cc kh quan trng trong cng nghip ha cht, cng nghip quc phng v mt s lnh vc khc. Amoniac [11] 1. S pht sinh Amonic l m ha cht cng nghip quan trng c sn xut vo t hng nhiu nht hng nm. Th d M, khi lng amoniac sn xut hng nm so vi cc ha cht khc ng th t ch sau axit sunphuric, vi v ox y (khong 25.106 tn vo nm 1990). Thng thng khong 80% sn lng amonic dng cho vic sn xut phn bn, 10% cho sn xut si nhn to v cht do, 5% cho sn xut cht n, 1,5% cho thc n gia sc, 0,6% cho cng nghip giy v bt giy, 0,5% cho cng nghip cao su v phn cn li dng cho cc lnh vc khc. Ring M, nhng hot ng cng nghip pht thi amonic vo khng kh ch yu t cc lnh vc nh: sn xut amoniac v phn bn, cng
25

nghip tinh lc du, luyn cc, sn xut soda v nhng s ri vi, d r khc ca ngi v cc c s s dng amoniac, hng nm ln ti khong 0,3 0,4.106 tn. Ngoi ra mt lng ln amonic pht thi vo khng kh qua cc qu trnh t chy nh t rc thi, t cc nhin liu ha thch v qu trnh d ha ca ngi v ng vt cng nh cc qu trnh thi ra, phn hy ym kh. 2. Tnh cht c trng Amoniac l cht kh c mi hc, khi tan trong nc to thnh dung dch kim yu. Amonic tan trong nc kh tt; song tan ca n ph thuc rt mnh vo nhit dung dch. OoC hm lng ca amoniac c th ln ti 50% trong nc, 20 oC gim xung cn khong 35% v 100 oC th tan ca amonic hu nh bng khng. NH3 + H2O (NH)4OH NH3 phn ng mnh vi cc axit to thnh cc mui tng ng, n cng c th phn ng vi cc oxit axit m ging nh vi cc axit. NH3 + HNO3 = NH4NO3 2NH3 + H2O + SO3 = (NH4)2SO4 Trong iu kin phn ng ph hp v c mt cht xc tc oxy khng kh c th oxi ha amonic thnh cc nit oxit; ngc li , s c mt ca nit oxit cng vi amonic trong iu kin thch hp (c hoc khng c mt ca cht xc tc) chng s phn ng v nhau to thnh nit v nc. 4NH3 + 5O2 = 4NO + 6H2O 4NH3 + 6NO = 5N2 + 6H2O 2NH3 + NO + NO2 = 4N2 + 3H2O Amonic thm nh vo c th ngi qua ng h hp, n ung v p thm thu qua da. Amoniac i qua cc lp m rt nhanh k c lp biu b ngoi da v r t linh ng trong cc nim mc v cc dch trong c th. Tc ng ca amonic trc ht l gy kch thch mnh v ph hy cc nim mc mi v mt v li hu qu. Khi hm lng amoni trong mu tng ln n mt mc no ngi ta nhn thy hm lng ca n trong no s t ngt tng ln; lc n s tc ng ln h thn kinh. Ngi ta ghi nhn c rng khi hm lng amoni trong no khong 50 mg/kg, xut hin hin tng co cng cc c v sau la i vo hn m. i vi h tun hon, khi hm lng amoni tng ln ti khong 100 mg/kg c th th thng li hu qu nghim trng. Cc con vt th nghim b cht v hi chng nhim c gy x va tm tht do amonic tc ng trc tip ln tim. Thng thng vi hm lng nh trong khng kh v tip xc khng thng xuyn th amonic hu nh vn hi.
26

Ngng nng nhn bit mi ca amonic sau nhiu th nghim cho thy vo khong 32 n 37 mg/m3. Song cng c cc kt qu a ra ngng thy mi ca amonic nh hn nhiu (0,5; 0,7 v 2,7 mg/m3). Khi tip xc vi nng amonic cao trong khng kh thng c biu hin nh sau: Gy kch thch cung hng ngay lp tc (280 mg/m3), gy ho (1200 mg/m3), e do s sng (1700 mg/m3), gy cht ngi (>3500 mg/m3). Azit v azidohydric 1. S pht sinh Cc hp cht ca N 3- c hnh thnh khi cho amit ca kim loi kim (NaNH2) tc dng vi N2O hoc Ag+ tc dng vi dung dch amoniac c. 2. Tnh cht c trng Azidohydric (azoimit) l cht lng khng mu c mi hc kh chu, si nhit 35,7oC. Hi HN3 c, ph hy nim mc mt, mi, lm dnh kt mc v l hp cht khng bn, rt d gy n do phn hy mnh lit, c bit khi tip xc vi cc vt th c nhit cao. 2HN3 ---> 3N2 + H2 + 141,8 kcal Trong dung dch, axit azidohydric kh bn v l mt axit yu (yu hn c axit acetic, ka = 1,2.10-5). Cc azit c kim loi chuyn tip hay c c kim lo nng nh azit ch a i hay bc cng d gy n khi nung nng hoc va p mnh; v vy m chng c s dng trong cng ngh lm ht n cho n. Azit ca kim loi kim nh NaN3 th tng i bn, ch phn hy v gy n khi nung nng mnh. Dixyan v xyanohydric [6, 12] 1. S pht sinh p c t ca kh ny gy ra bi ion cyanua (CN-). Cc h cht ca xyanua c mt s tnh cht rt c bit nn mc du chng rt c song vn c s dng nhiu trong cc lnh vc nh m in, mt s qu trnh x l nhit, ti thp, trong cng nghi ha cht (nh tng hp ultramarin...) v p trong sn xut mt vi cht hun hay xng khi. Hin nay c bit trong lnh vc khai thc v ch bin vng cng nh mt s kim loi qu trn th gii v ang s dng mt lng ln mui xyanua ca kim loi kim nh NaCN hay KCN. Dixyan sinh ra khi t mt s cht hu c nh bt xp c polyurethan, tc, da, sng. Trc tin hnh thnh gc CN sau kt hp li thnh (CN)2. Trong sn xut cng nh trong cc phng th nghim, nu ion
27

Cu2+ tc dng vi dung dch CN - hay CuCN tc d ng vi Fe 3+ s gii phng ra dixyan. 2Cu2+ + 4CN- = 2CuCN + (CN)2 CuCN + Fe3+ + Cl- = CuCl + Fe2+ + 1/2(CN)2 Trong thc t cuc sng chng ta thng thy hin tng HCN c sinh ra khi c m ng thi NH 3 v CO nhit 500 700oC (nh trong t iu kin t gch truyn thng). NH3 + CO = HCN + H2O Trong thin nhin, ti n cht ca HCN cn tn ti trong ht hnh nhn ng, l v cc b phn ca cy trc anh o v b c c sn cy (c m) a di dng hp cht c tn l amygdaline. Mt trong nhng c ch to ra HCN t cc vt liu ni trn c chp nhn l men emulsine c trong khi phn hy amygdaline s sinh ra HCN, glucoza v benzaldehyd. HCN cng tn ti trong kh than (0,1 n 0,3%) v kh t nhin. Trong cc phng th nghi m hay trong cc c s sn xut ha cht c s dng xyanua (c bit l xyanua ca kim loi kim v kim th), nu tip xc vi khng kh m, chng s gii phng ra HCN do tc dng ca nc v CO2; v HCN l axit rt yu (ka = 4,6.10-10). NaCN + H2O NaOH + HCN 2NaCN + H2O + CO2 Na2CO3 + 2HCN 2. Tnh cht c trng Xyanua (nhn ngn) l cht kch c, t xa xa n c xp vo hng u bng ca cc cht c Nht nhn ngn (CN -) nh thch tn (asen). Hi HCN gy ng c nhanh v mnh hn l cc mui xyanua tan. Ch cn khong 50 mg xyanua xm nhp vo c th c th gy cht ngi trong vng vi giy. Xyanua trong phc hay trong cc mui t tan t c hn mui tan ca n. C ch gy c ca xyanua l c ch cytochrome oxidaza, cn tr qu trnh oxi ha ca cc m. Xyanua cng tc ng ln h thng iu khin ca h thn kinh. Cc triu chng ca ng c xyanua xut hin rt nhanh sau khi c th tip nhn. Nu c th tip nhn mt lng ln xyanua, nhng triu chng b ng c th hin nh au u, chng mt, hn m v dn ti t vong ngay lp tc. Nu tip nhn mt lng nh xyanua, c th c th tiu hy v khng gy t vong. Nhng thng xuyn tip xc vi xyanua hm lng nh cha gy t vong th nhng hu qu li thng l thiu mu, suy nhc thn kinh, chy mu d dy v ph phi. Dixyan tan tt trong cn, ete v nc. Khi tan trong nc n d b phn hy thnh cc sn phm khc nhau, th d nh axit oxalic:
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NC CN + 4H2O = HOOC COOH + 2NH3 Trong nh ng iu kin nht nh, dixyan polyme ha to thnh paraxyan c mu nu en v khng tan trong nc cng nh trong cn. Ion xyanua c i lc to phc rt ln nht l i vi cc cation kim loi chuyn tip. Cc phc ny c bn cao nn gim ti a c tnh ca xyanua. Th d nh phc xyanua st: Fe2+ + 6CN- = [Fe(CN)6]44Fe3+ + 3[Fe(CN)6]4- = Fe4[Fe(CN)6]3 (mu xanh Berlin) Cc mu tan ca xyanua rt d tc dng vi cc axit to thnh i xyanhydric d bay hi. Ngc li cc kt ta xyanua nh AgCN, CuCN tan t trong axit, thm ch c axit mnh. Xyanua th hin nh l mt cht kh. N d dng b oxi ha bi cc cht oxi ha nh hydroperoxit, permanganat hay persunphat to thnh xyanat l sn phn hu nh khng c. Trong mi trng hp H 2O2 c coi l cht chng ch nh i vi xyanua. HCN + H2O2 = HCNO + H2O Hi xyanhydric tc dng tt vi kim mnh nh NaOH hoc KOH cho cc mui xyanua tng ng. HCN + NaOH = NaCN + H2O Cc nit oxit (NOx) [13] 1. S pht sinh N2O, NO, NO2 v N2O4 c sinh ra trong qu trnh oxi ha xc tc amoniac sn xut axit nitric. Trong qu trnh ny sn phm chnh l NO; bn cnh mt lng nh kh N2O khng hu ch cng c to thnh. 4NH3 + 5O2 = 4NO + 6H2O 2NO + O2 = 2NO2 4NH3 + 4O2 = 2N2O + 6H2O N2O cn c hnh thnh t vic nung phn hy hoc n phn hy cc vt liu c cha mui NH4NO3. Trong thc t, s nhim khng kh ca cc oxit nit ch yu do NO v NO2 gy ra. T l mol ca hai loi kh ny trong khng kh l khong 3 : 7 song tt nhin ph thuc nhiu vo nhit mi trng. Cc nit oxit cn c sinh ra khi axit nitric c tip xc vi khng kh, c bit l khi c s tham gia ca nh sng mt tri; khi t cc vt liu hu c c cha nit, khi n mn khai thc m. Khi tin hnh hn x hay to h quang in trong mi
29

trng khng kh c cha sn oxi v nit th trong nhng iu kin nhit cao nh vy, cc nit oxit cng c hnh thnh. Ngoi ngnh cng nghip sn xut axit nitric ra, cc lnh vc sn xut ha cht, phn bn, gia cng kim loi, x l b mt kim loi... cng sn sinh ra mt lng ln kh nit oxit. Trong cc phng th nghim, khi s dng axit nitric, c bit l axit nitric c phn hy mu hay nitro ha, rt cn ch ti s gii phng cc nit oxit. Trong nhng trng hp nh th tuy tnh v lng th nh song chng thng xy ra trong mt khng gian hp cho nn tnh ch nguy him ca n cn t c quan tm mt cch thch ng. 2. Tnh cht c trng ; N2O l kh c tnh kh song trong iu kin bnh thng, n khng b oxi khng kh oxi ha. Khi t chy vi oxi phn ng sinh ra mt nhit lng rt ln. Nhng khi c mt ngn la th N2O cng c phn ng chy vi hydro. N2O + H2 = N2 + H2O + 77,5 kcal. Hn hp N2O vi amonic em t cng s gy n rt mnh. 3N2O + 2NH3 = 4N2 + 3H2O + 210 kcal Kh N2O l cht kh khng mu, c mi d chu, c v hi ngt v tan kh tt trong nc v c bit l trong cn. Nu ht phi lng nh, N 2O to ra trng thi vui v (kh ci). Nhng nu ht phi mt lng ln, nn nhn c th b hn m v b ngt. NO l ch kh rt hot ng; n b oxi kh ng kh oxi ha t nhanh t r thnh NO2; khi tip xc vi clo to thnh nitrosylclorua. NO tan rt t trong nc v c i lc to phc rt mnh vi cc cation ca kim loi chuyn tip. 2NO + O2 = 2NO2 K3[Fe(CN)6] + NO = KCN + K2[Fe(CN)5NO] NO hn hp vi NO2 tc dng vi amoniac hoc ngay c vi ur, nht l trong iu kin c xc tc, s sinh ra nit v nc. NO + NO2 + 2NH3 = 2N2 + 3H2O NO2 tan trong nc to thnh axit nitric, mt axit mnh c tnh oxi ha. 3NO2 + H2O = 2HNO3 + NO NO2 m tc dng vi cc baz hay mui ccbonat mnh lit nh axit nitric. ng thi n cng tc dng mnh vi cc cht hu c v c th phn hy chng. Chnh v th m NO2 tc ng rt mnh ln da, cc nim mc mt, mi v phi; gy kch thch mnh v rt d li di chng nh ph phi... 2NO2 + 2NaOH = NaNO3 + NaNO2 + H2O 3NO2 + CaCO3 = Ca(NO3)2 + CO2 + NO
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Kh nit oxit r t nguy him v ranh gii gia nng gy kch thch nh v nng gy hu qu nguy him l rt hp. Ngi ta c th ht phi mt lng gy cht tim tng trong vng t 2 n 24 ting ng h m khng c bt c mt tc ng biu hin r rt no. Tip xc vi nng 100 n 500 ppm nit oxit trong khng kh c gy co tht t n gt ph qun v th cht do try h hp. Nu ht th thng xuyn vi nng thp cha gy cht th cc triu chng xy ra ln lt c th nh sau: kch thch nh, mt nhn bit, thy nga c, ho v xut hin cc cn co tht lng ngc. Hin tng ph phi tin trin, nn nhn thy kh th v ho ra m ln mu. Tip theo, mt vi trng hp c th b thiu mu, xanh xao, tun hon ngng tr v sau c th l t vong.
2.1.4. KH CACBON MONOXIT V DIOXIT

Cacbon monoxit (CO) [14,] 1. S pht sinh Kh CO c sinh ra t cc qu trnh t chy khng hon ton cc hp cht c cha cacbon. Nhng ngun ng k nht l kh thi ca cc ng c chy bng cc nhin liu ha thch; kh thi ca cc nh my nhit in, luyn kim, kh ha than v kh sinh ra sau cc v n ch cng nh cc v n hm l do metan v b than gy ra trong lng t. Bn cnh cn phi k n i kh sinh ra do un nu, si v cc hot ng khc na. Tng cng lng CO sinh ra t cc ngun ny c khong t 350 n 600 triu tn mi nm. Ngoi ra ngun CO t nhin hin ti khng xc nh c. 2. Tnh cht c trng CO l cht kh khng mu, khng mi, khng v v nh hn khng kh cht t. CO c th tip tc chy trong khng kh to thnh CO 2. Hn hp ti hn ca CO trong khng kh c th gy n, c bit l nhit cao hoc c mt ca tia la. C + 1/2O2 = CO + 26,64 kcal CO + 1/2O2 = CO2 + 67,75 kcal CO tc dng vi hi nc to thnh CO 2 v H2. Trong i kin u thng, cn bng khng c li cho vic hnh thnh sn phm; song khi c mt ca cht xc tc th phn ng xy ra hon ton. CO khng phi l anhydric ca bt k axit no song khi tan vi dung dch kim mnh, nng chng s kt hp vi nhau v to thnh mui focmit. CO + H2O --XT--> CO2 + H2 CO + NaOH = Na(CO2H) (natri focmit)

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CO kt hp c vi nhiu kim loi to thnh cc cacbonyl; trc ht nh l st, coban v niken. c bit ngi ta trnh cho clo tip xc vi CO, nht l c nh sng hoc cht xc tc, v chng kt hp vi nhau to thnh fosgen (COCl2) rt c 4CO + Ni = Ni(CO)4 CO + Cl2
h/XT

COCl2

Tc ng ng k nht ca CO i vi sc kho con ngi l kh nng to phc rt ln ca CO i v st trong t bo hng cu. i lc ca CO vi st trong phn t hemoglobin gp khong 240 ln so vi oxy. Khi ht th trong bu khng kh nhim bi CO, CO s thm thu rt nhanh qua ng phi v chim cc v tr phi tr ca oxy trong hemoglobin to thnh cacboxyhemoglobin lm suy gi m nhanh chng kh nng cp oxy ca mu cho cc bo trong c th. Nng cacboxyhemoglobin trong mu hon t ton ph thuc vo hm lng CO trong khng kh th, thi gian tip xc v nhp th ca nn nhn Ngoi ra CO cn c th lin kt vi myoglobin, cytochrom v mt s enzym na trong c th. Nng CO trong khng kh nn l 0,01 n 0,9 mg/m3. Tip xc vi nng ln hn s lm tng nng cacboxyhemoglobin trong mu (BCH). Khi BCH l n hn 2,5% bt u gy tc ng ln chc nng tun hon. 5% BCH khng an ton cho c kho, 10% BC H c th b e da v khi ti 60 s n 80% BCH s dn ti t vong. Mc du nn nhn cht do thiu oxi trong mu nhng t thi khng b tm ti m li c mu ta. Cacbon dioxit (CO2) [15] 1. S pht sinh CO2 sinh ra thng qua s t chy cc nguyn, nhi n liu c cha cc bon trong cc ngnh cng nghi p, dn dng, k c s t v chy rng. Bn cnh mt lng ln CO2 cn c sinh ra trong cc m than, cc b ln men, cc nh my sn xut ri, bia, nc ngt c ga, cc ni phn, thc n cho cy trng, vt nui. CO2 c mt khp ni v trong khng kh nn, n chim khong 0,3%. Hin nay theo s liu ca cc nh khoa hc, hm lng CO2 trong kh quyn ca tri t ngy mt tng. iu ny lm tng hiu ng nh knh ca tri t v hu qu l lm tng nhit trung bnh ca tri t; hu qu ca n l khn lng theo s cnh bo ca cc nh khoa hc. 2. Tnh cht c trng CO2 l kh khng mu, khng chy, c v hi chua v nng hn nhiu so vi khng kh . Chnh v vy m CO 2 thng tp trung li dy c hn nhng ch thp hay phn y ca khng gian ni n c sinh ra.

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CO2 tan tng i tt trong nc, nht l nhit thp. CO2 l anhydrit ca axit cacbonic. CO 2 d dng phn ng vi dung dch kim mnh nh NaOH hay Ca(OH)2 to thnh cc ccbonat tng ng. CO2 + H2O H2CO3 ; (k1 = 4,01.10-7; k2 = 5,2.10-11) CO2 + Ca(OH)2 = CaCO3 + H2O CO2 khi lm lnh p sut kh quyn s ng cng li v khi nhit xung quanh tng ln n thng hoa ( nhit 78,48 OC) m khng qua trng thi lng. CO2 rn ( kh) c th gy ra nhng vt bng rt kh lnh. CO2 hu nh khng c tc ng g ln ng tiu ha song n c tc ng sinh l mnh m khi thm nhp vo c th qua ng h hp; n lm tng nhp th thng qua tc ng ca n ln trung tm h hp trong ty sng. Khi hm lng ca CO 2 trong khng kh th vt qu gi tr 3% s gy kh th v iu ny cng tr nn r rt khi hm lng ca n vt qu 5%. Vi hm lng 10% s lm cho nn nhn bt tnh ch trong vng mt pht.
2.1.5. ASIN (AsH3), PHOTPHIN (PH3) V STIBIN (SbH3) [16, 17]

1. S pht sinh Mt lng ln acsin, photphin, stibin v c boran na c sn xut dng trong ngnh in t. Cc cht kh ni trn thng c tinh ch n siu tinh khit nhm thng hoa v phn h to ra nhng lp phim nguyn t y mng trong cc vi mch. Khi tinh ch v ngay c khi vn chuyn, s d r gy ra nhim nhng loi kh c ny. Mt trong nhng ngun pht sinh na l cc qu trnh v phn ng xy ra vi cc sn phm v x thi sau luyn kim ca cc kim loi hot ng nh nhm, thic, km... Trong qung ca cc kim loi ni trn lun lun c ln cc nguyn arsen, photpho hay antimon di dng cc sunphua ng t hnh hay khong tp. Trong qu trnh luyn kim, cc nguyn t ny to thnh cc hp cht khc nhau theo x ra ngoi cng vi cc kh oxit lu hunh v nit hp ph ty theo cc cng ngh c s dng. Ln trong x tt nhin cn c phn nh kim loi phn tn. Khi gp m hay nc, cc axit c to thnh t phn kh hp ph. Axit s ha tan cc ht kim loi to thnh mui tng ng v gii phng ra hydr. Hydr mi sinh s tin hnh kh cc hp cht ca arsen, photpho v antimon trong xto ra arsin, photphin v stibin thot ra khi lp x. Hin tng ny thng xy ra trong nh my, ti cc bi x v gy ra nhng mi nguy him cht ngi i vi cng nhn v nhng ngi sng ln cn. i vi photphin, n cn c hnh thnh khi lm ngui st thp bng nc hoc hi nc, trong sn xut acetylen (canxi photphua nh l tp cht trong cacbua canxi), thuc dit chut (km photphua), cht bo qun ht ng
33

cc (nhm photphua). Cc photphua kim loi hot ng khi gp nc s sinh ra photphin; ng li photphua ca kim loi nng th hu nh khng tc c dng vi nc v i khi ngay c vi dung dch axit long. S phn hy ym kh ca cc hp cht photpho hu c cng sinh ra photphin (ma tri). Stibin cn c pht hin vi nhng hm lng kh ln khi ch ha cc hp kim ca n vi cc kim loi hot ng bng axit. 2. Tnh cht c trng Asin l cht kh khng mu, nng hn khng kh khong 2,7 ln v c mi hnh nhn ng hay mi ti. Asin l cht kh mnh; d dng t chy trong khng kh to ra asen(III) oxit v nc, n cng b phn hy nhit cao khi khng c mt ca oxi to ra asen v hydro nguyn t. 2AsH3 + 3O2 = As2O3 + 3H2O + 44,2 kcal 10AsH3 + 16KMnO4 + 18H+ = 5Mn3(AsO4)2 + 24H2O + 16K+ + Mn2+ Asen (thch tn) l cht kch c song asin cn c hn nhiu do n thm nhp nhanh hn vo cc c quan trong c th vi asen thng qua so ng h hp. Asin l tc nhn hy hoi mu mnh lit. Cc biu hin v triu chng ca ng c asin u l hu qu tc ng ln mu ca n. Trong trng hp nhim c nh, khong mt ngy sau khi tip xc s c nhng triu chng nh bun nn, au u, run ry v au nhi vng thng v. Bnh vng da xt hin ngy th hai hoc ngy th ba. Hin tng vng da thng i km vi hin tng au v nhn gan. i khi ngi ta nhn thy thn b hy hoi. Phn ln cc trng hp t vong sau khi b trng c asin l do try tim mch. Nhng ngi may mn sng st c th bnh phc song mt vi trng hp, bnh thn kinh ngoi vi pht trin. Khi tip nhn mt lng ln asin (ng c cp tnh asin) th t vong l iu khng th trnh khi. Photphin l m kh c khng mu, c mi nh mi c n, t tan t trong n Bn cnh PH 3 (monophotphin) cn n ti mt dng na l c. t diphotphin (P2H4). Diphotphin thng l sn phm i km vi photphin v l cht lng d bay hi, t bc chy trong khng kh v cng d phn hy thnh photphin v P2H. P2H (photphohydro rn) l cht bt mu vng v bn trong khng kh, khng tan trong nc cng nh cc dung mi khc. Monophotphin tinh khit trong khng kh khng t bc chy nu nhit khng vt qu 150OC v n ch t bc chy khi c ln diphotphin. Khi chy s to thnh axit photphoric. PH3 + 2O2 = H3PO4 Khi nng photphin trong khng kh khong 0,2 ppm ta c th pht hin thy mi ca n (cng c ti liu cho thy ngng pht hin mi ca photphin cn thp hn na). Khi tip xc vi nng 20 ppm trong khng kh nn nhn c th t vong ngay lp tc. Trng hp nhim c photphin thng i km cc triu chng nh au bng, nn ma, mt cn bng, co git,
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hn m v c th dn ti t vong trong vng 24 gi. Trng hp nhim nh c th qua khi hon ton sau nhng hin tng ho v b kch thch trong ngf h hp. Nhim c mn tnh photphin xy ra khi thng xuyn tip xc vi nng rt thp v triu chng ni b t l cc tri chng v thn u kinh. Stibin c bit nh l mt cht kh khng mu, c mi kh chu v c c tnh cao. Ng c stibin rt ging ng c asin. Nhng trong chng mc no tc ng ca n c i phn nh hn. Song trong vic x l cc trng hp nhim c stibin vn cn rt quyt lit, thm ch phi truyn mu hay chy thn nhn to mi hy vng trnh c t vong. 2.2. CC CHT THI DNG HI [8, 18] Cc cht dng hi thi vo khng kh u c chung mt c tnh l c kh nng ngng t li trong nhng iu kin p sut v nhit ph hp. Do nhng tnh cht c th ca cht thi dng ny, chng ta chia chng thnh hai nhm chnh l nhm ch thi dng hi ca cc hp cht v c v cht thi t dng hi ca cc hp cht hu c thun tin cho vic nghin cu v x l.
2.2.1. HI CA CC HP CHT V C

Cc cht thi cng nghip nguy hi thuc nhm ny c quan tm nht l hi axit, hi kim, hi thy ngn v hi mt s oxit thng hoa nh As2O3, PbO. S d hi ca cc cht ni trn c t ln hng u trc ht do s xut hin thng xuyn ca chng trong nhng hot ng hng ngy ca chng ta vi khi lng ln; mt khc l do c tnh cng nh cc tc ng nguy him tim tng ca chng. 1. S pht sinh Hi axit v hi kim thng xut hin ti cc c s gia cng, x l kim loi, b mt kim loi; cc c s sn xut ha cht, vt liu c s dng axit v kim c bit iu kin nhit cao. Tt nhin phi k n cc nh my sn xut chnh cc axit hoc kim ni trn. Hi thy ngn thng c pht hin ti cc nh my sn xut xt - clo s dng in cc thy ngn, ti cc c s khai thc, gia cng, m cc kim loi qu nh vng, bc, bch kim... c bit trong cc tai nn hay ri ro trong sn xut, vn chuyn hay ch ha thy ngn kim loi. Trong nhng trng hp ny hm lng cc b thy ngn rt cao nhng may mn l thng ch trong khng gian c gii hn mt khc hi thy ngn nng nn pht tn km. Hi cc oxit thng hoa xu hin thng xuyn vi mt hm lng t ng k l ti cc khu vc c cc c s luyn kim, c bit l luyn kim mu, t pyrit, acsenopyrit v k c cc ni sn xut phn ln nung chy. Mt
35

lng ln na cng c pht hin ti cc c s sn xut thuc tr dch hi ngun gc v c nh thuc dit mi, dit chut, tr c... 2. Tnh cht c trng Cc cht dng hi c mt c tnh chung l chng u c th c ngng t li di dng cht gc ca n trong nhng iu kin nhit v p sut ph hp. Nhng thc cht nu dng sng sau ngng t m khng c thu gom v x l kp thi th vn khng th trnh c nhng tc ng nguy hi ca chng. Hi axit trong iu kin khan tc dng rt km vi kim cng nh vi cc mui cacbont. Nhng trong iu kin m hay sc vo dung dch th phn ng li xy ra bnh thng. i vi hi kim th cc phn ng trung ha cng din ra trong cc iu kin tng t. Hi axit v hi ki m thng gy kch thch rt mnh ln da. Cc triu chng cm nhn trn da l nga ngy kh chu; c bit hi HF khi thm qua da s gy ra cm gic nhc but ko di. nhng ngi tip xc thng xuyn vi hi axit v kim thng xut hin cc nt mn trn da. Mt ca chng ph thuc vo c a ca tng ngi v vo nng hi tip xc. Tip xc lu di c th gy ra vim da. K c hi kim v axit u tc ng ln cc nim m mt, mi v pha trn ca ng h hp. Cc triu chng c thng l chy nc mt, nga, rt trong mi v hng, ho. Trng hp nng c th gy nn hin tng c mt do kt mc b tn thng v ph phi. Hi thy ngn rt d ngng t; song ngay hi bo ha ca thy ngn trong iu kin bnh thng c th gy nguy him n sc kho v c tnh mng ca con ngi. Chnh v vy m thy ngn khng bao gi c php h mt tip xc vi khng kh. Hi thy ngn rt d hp th vo lu hunh to thnh thy ngn sunphua rt bn v hu nh khng c. N cng d b hp th vo dung dch st(III) clorua to thnh kt ta calomen (Hg2Cl2) bn vng. Hg + S = HgS 2Hg + 2FeCl3 = 2FeCl2 + Hg2Cl2 Hi thy ngn rt c (c hn gp nhiu ln cc dng khc ca thuey ngn) v n i d dng thm nhp vo c th bng ng h hp v thm l thu qua da rt nhanh. Thy ngn c kh nng tch lu sinh hc rt cao. C ti 80% lng thy ngn trong kh ht vo c gi li trn ng h hp. Hu qu ca ng c thy ngn thng l da xanh xao vng vt, thiu mu, run ry, hn m v t vong do suy nhc. Hi thng hoa c a acsen, ch oxit hay cc kim loi khc cng rt d ngng t. Cc oxit axit hay lng tnh chng c th hp th tt trong dung dch kim mnh v nng.
36

As2O3 + 6NaOH = 2Na3AsO3 + 3H2O Hi acsen tc ng ln ngi v ng vt cng ging nh acsin. Cc dng hi ca ch cng nh cc kim loi nng khc thm nhp vo trong c th ch yu cng qua ng h hp v i vo mu. Cc c ch tc ng ca n cng nh nhng triu chng nhim c c trnh by trong phn v kim loi nng.
2.2.2. HI DUNG MI HU C [19, 20, 21, 22]

Cc cht hu c cho ti nay ngi ta tnh c vo khong 10 triu cht khc nhau. Nhng s dng nhiu trong cuc sng ca chng ta ch vo khong vi nghn. Ngoi lnh vc thuc tr dch hi v cht do (plastic) ra th dung mi h u c chim mt t trng ng k (khng k xng du va dng lm dung mi va s dng chnh lm nhin liu). Nhn chung p sut hi bo ho ca cc cht hu c thng kh ln; v vy vic nghin cu tc ng dng hi ca cc cht hu c l rt quan trng. Trong khun kh ca gio trnh ny chng ta ch xem xt mt s dung mi hu c c hi quan trng, thng gp. 1. S pht sinh Hi dung mi thng c mt trong cc c s sn xut, gia cng cao su, sn xut dy dp, sn, v... Ti cc kho tng, cc c s sn xut, tinh ch dung mi do d r, thao tc; cc c s ch bin du m cng khng trnh khi nhng lng hi dung mi thot ra. Trong nhng khong khng gian hp khi s dng dung mi hay cc loi keo, sn ngi ta cng thng phi tip xc vi mt hm lng hi kh cao. 2. Tnh cht c trng Mt trong nhng c tnh quan trng nhng li l cc k nguy him ca cc dung mi h c l d chy. Mc du cc nh cng ngh c u gng tm cc dung mi kh bt chy s dng trong cng nghip nhng lun lun v l vn kh khn do nhng i hi kht khe ca cc cng n ngh. Cc dung mi v phn cc khc nhau kh i thm nhp vo trong c i th s tp trung vo nhng b phn khc nhau. Cc dung mi khng hoc t phn cc s tp trung vo cc c quan cha nhiu m, k c h thn kinh v ngc li cc dung mi phn cc s tp trung vo nhng ni cha nhiu nc v nh th c ngha l chng c kh nng phn b rng hn trong c th. Mt lng ln dung mi sau khi hp th vo trong c th s bc ra ngoi nguyn dng nh ban u nhng trong khong t 15 n 60% ty thuc loi dung mi v c a tng ngi, chng tham gia vo cc qu trnh bin i sinh hc.
37

Ng c cp tnh cng c th xy ra khi nn nhn tip xc vi nng hi cao. Cc triu chng thng thy l chng mt, chong vng, au u v nn ma. V d vi nng toluen khong 1000 ppm c th gy chng mt, mt thng bng v au u d di. Vi nng ln hn na c th gy hn m. Nu nn nhn khng c kp thi cch ly khi mi trng nhim th c th t vong. Cc dung mi hu c cng c th gy ra ng c mn tnh. Benzen l mt trng hp c theo di tng i h thng. V nguyn tc, benzen tc ng ln ty xng nu thng xuyn tip xc vi hm lng benzen trong mi trng vt qu nng cho php. Bc u nhng triu chng thng khng r rng. Tip theo thng thy mt mi, ri lon tiu ha, ch ng mt; sau xu hin hin tng chy mu mi v pht ban trn da. Bnh thiu t mu thng tm thy nhng ngi nhim c benzen mn. Giai don u ty xng vn pht trin sau th khng pht trin na v bt u s ph hy n cc t bo. Ngi ta cho rng benzen nh hng n qu trnh tng hp DNA. Cc chromosom l pht trin nhiu nhng ngi thng xuyn tip xc vi hi benzen v cc ng vt th nghim. Nhim c benzen thng km theo pht trin ca bnh mu trng cp. Qu trnh tip din ny s thng xy ra vi nm sau khi tip xc ln cui. Cc dung mi hu c t nhiu u c tc ng c hi ln c th ngi; do trnh cc tc ng xu, rt cn thit c cc bin php phng nga v x l thch ng i vi mi trng lm vic c s dng cc dung mi. 2.3. BI [23, 24, 25]
2.3.1. KHI NIM V BI

Ni n khi nim bi, ta lun lun phi hiu l s kt hp khng th tch ri nhau ca hai pha l pha kh (thng l khng kh) v pha rn tn ti dng ht th ri rc v phn b ngu nhin. Cc h cht rn phn tn t trong pha kh mi c gi l bi; cn nu cng nhng ht cht rn y c gom li, khng chuyn ng na th thng i vi khi nim l bt, tro hay b hng. Nh nh ngha v bi phn trn ta quan tm n dng tn ti v kch thc ht ca bi; hnh dung v di kch thc ca bi, ta c th tham kho bng 2.2. so snh gia chng vi di sng in t, vi khun v kch thc ca tc ngi di y. Kch thc ca ht bi (d) c biu din qua ng knh ca ht hnh cu, kch thc l ry m ht bi lt qua hoc kch thc ln nht ca hnh chiu ca ht. Ngi ta cng s dng khi nim ng knh tng ng (dt) cho loi ht bi c hnh dng bt k. d t c hiu l ng knh ca mt ht hnh cu c th tch bng th tch ca ht bi ang xt.
38

Nu ly tiu chun v kch thc ca ht bi phn loi th ta c th chia bi ra thnh cc loi nh sau: 1. Bi th (ct bi - grit): l cc ht bi cht rn c kch thc ln hn 75 m 2. Bi (dust): l cc ht bi cht rn coa kch thc t 5 - 75 m. 3. Khi (smoke): l cc t vt cht c th l rn hoc lng thng h c to ra (hoc ngng t) trong qu trnh t nhin liu c kch thc ht t 1 - 5 m. 4. Khi mn (fume): l nhng ht cng c ngun gc nh khi nhng rt mn; kch thc ht ca khi mn c quy c l nh hn 1 m. Bng 2.2. Kch thc ht ca bi, khi v h phn tn ph bin
0,0001 nh ngha k thut Ht / h phn tn tiu biu
i

0,001
i i i i i ii i

Kch thc / bc sng nh sng [m]

0,01 0,1 1,0 10 100
i i i i i ii i

1000
i i i i i i ii i

10000
i i i i i ii i i i i ii

Th rn Th lng

Khi mn Sng (mist)

i i i i i ii

i i i i i ii

Khi

i i i i i ii

i i i i i ii

Bi (dust) Bi nc

CO2 H2O

Khi nha thng Khi du t Tro bay Khi thuc l Bi than Bi v khi luyn kim Khi NH4Cl Bi xi mng Mui than Bi kh quyn Bi h hpVi khun Vi trng Hng ngoi gn Nhn thy Tc

Ct

ng vt Sng in t

Tia X

Tia cc tm

Hng ngoi xa

Sng cc ngn

V tnh cht c l, c s khc bit rt ln gia cc ht bi c kch thc ln v cc ht bi c kch thc cc nh. Cc ht bi c kch thc ln nh bi th chng hn th chng c kh nng lng ng nhanh nh trng lng ca chng v gia tc trng trng. Do chng thng b loi khi mi trng kh mt cch d dng. Ngc li, cc ht bi cc nh th tun theo mt cch cht ch s chuyn ng ca mi trng kh xung quanh; do chng tn ti kh lu. Khi lng n v (t trng) ca mt cht dng nguyn khi v dng bt vi kch thc ht khc nhau rt khc nhau. Nghin cu dng bt c th tr thnh bi ca mt s cht, cc tc gi nhn thy r iu ny nh trn bng 2.3.
39

Bi c tc hi ln nht n sc kho con ngi l loi bi d thm nhp v c th qua ng h hp ngi ta thng gi chung l bi h hp. Loi ny thng c kch thc nh hn 10 m. Bng 2.3. T trng ca mt s cht dng khi v dng bt ri. Cht Cadimi oxit Bc Vng Thy ngn HgCl2 Manh oxit T trng dng khi (g/cm3) 6,5 10,5 19,3 13,6 5,4 3,6 ng knh ht (m) 2,42 1,79 2,35 2,05 4,53 3,26 Dng bt T trng ng 3 (g/cm ) knh ht (m) 2,70 5,96 4,22 4,30 8,00 5,54 10,80 3,08 4,32 3,63 3,48 7,29 T trng (g/cm3) 0,51 0,94 1,24 1,70 1,27 0,35

2.3.2. HNH VI CA CC HT BI

Nh ta ni trn, bi l nhng ht cht rn hoc sol kh tn ti v chuyn ng trong pha kh (ch yu y s no n l trong khng kh). Bi c dng kh dung np v mang i. Cc ht bi c khi lng (kch thc) ln trn ng mang i ca dng kh s c xu hng lng xung mt t. Ngc li cc ht bi c khi lng rt nh, c bit l cc ht sol kh th c th tn ti trng thi l lng trong mt thi gian khng hn nh. Ht bi chuyn ng trong khng kh, trc tin ta xt ti lc cn ca dng kh. Trng hp n gin nht ta cho rng dng kh l ng nht, lin tc v v hn; ht bi l hnh cu chuyn ng vi vn tc (v) khng i th lc cn (F) ca dng kh ln ht bi s c tnh theo biu thc sau:
1 F = K 0 A dv 2 2

(2.1)

Trong :

1/2.v2 l ng nng ca dng kh chuyn ng vi vn tc v, A l din tch tit din trc i ca ht vi hng chuyn ng, K0 l h s t l hay h s sc cn, l t trng ca dng kh.

i vi ht hnh cu c ng knh l r th A = d2/4 v do ta c:

F= 1 K 0 .d 2 v 2 8 40

(2.2)

T ta c th rt ra biu thc tnh cho h s sc cn K0 nh sau:

K0 = 8F . .d 2 v 2

(2.3)

Thc nghim cho thy h s sc cn ph thuc vo chun s Raynon (Re).

Re = v.d = v.d .

(2.4)

Trong :

l nht ng ca dng kh: = /, v l nht ng lc v t trng ca dng kh.

Ko 104
103 102 101 1 10-1

10-3

10-2

10-1

101

102

103

104

105

106

Re Hnh 2.2. S ph thuc ca h s Ko vo chun s Raynon (Re) Khi chuyn ng vi vn tc nh, Re < 1, dng kh trc v sau ht hnh cu gn nh i xng nhau. Trong vng ny, nh trn hnh 2.2. ta thy s ph thuc ca Ko vo Re theo h logarit hon ton l mt ng thng v c biu din bng h thc:
K= 24 Re

(2.5)

T (2.3) v (2.4.) ta c cng thc Stokes (2.6) v vng ny c gi l vng chuyn ng c nht - vng Stokes:
F = 3. . . .v

(2.6)

Khi Re > 1, dng chuyn ng sau ht hnh cu bt u xut hin s ri dng cho n khi Re tng ln n khong 400. Vng ny c gi l vng chuyn tip. S ph thuc ca h s sc cn Ko vo chun Re c th hin bng biu thc Kljachko:
41

K0 =

24 4 + 1/ 3 Re Re

(2.7)

(Trong khong 3 < Re <400, Ko tnh theo biu thc trn c sai s khong 2%) Khi Re ln hn 500 v nh hn 1000, cc dng xoy cun vo tch ra khi vt cn v c hnh xon c. Lc ny h s sc cn trc i Ko hu nh khng i nm trong khong 0,38 n 0,50. Vng ny do Newton tm ra v n mang tn ng. Khi Re > 2.105 lp chuyn ng bin ca dng kh pha trc ht hnh cu tr nn khng n nh; nhng dng xon phn cch hnh thnh c pha trc chuyn ra pha sau vt cn lm cho h s sc cn trc i gim xung t ngt (n 0,1). Vn tc ri gii hn ca ht bi hnh cu t c khi lc cn ca khng kh cn bng vi lc trng trng ca n.
1 F = G = K o . A .v 2

(2.8) (2.9)

T ta c

vth =

2G K o . A.

V trong vng Stokes ta c:

1 G = 3 ( b ) g 6

(2.10)

Trong b l t trng ca ht bi v g l gia tc trng trng. T suy ra:

( b ) g 2 v gh = 18

(2.11)

Do t trng ca khng kh thng nh hn rt nhiu so vi t trng ca vt cht lm nn ht bi cho nn ta c th b qua v vn tc gii hn ca ht bi trong khng kh c th biu hin bng biu thc (2.12):
v gh =

b .g. 2 18

(2.12)

Biu thc (2.11) v (2.12) tnh vn tc treo l lng ca ht bi theo nh lut Stokes v ch p dng cho ht bi hnh cu c ng knh nh hn 70 m; v i vi ht bi c kch thc ln hn, cng thc Stokes cho sai s tng i ln so vi thc t.

42

2.3.3. BN CHT V TC HI CA BI

Bi v v phng din no ta c th xem xt ng thi c sol kh. Ngoi mt s tnh cht c l nh c trnh by phn trn th v mt ha hc, n mang y cc tnh cht ca cc cht ha hc to nn n. Tc ng ca bi ln sc kho con ngi chnh v th m cng phc tp hn. C hai kiu tc ng chnh ca bi l tc ng theo kiu c hc v theo kiu ha hc. Da trn c s ny ta c th chia bi ra lm hai loi; loi bi tr v loi bi tan (bi c th tan c trong mi trng nc hoc m). Bi tr tc ng ln c th con ngi theo kiu c hc. Th d nh bi bng thy tinh hay aming loi tinh th hnh kim. ng v phng din ha hc th c hai u l cc vt cht c trng rt tr v ha hc (silicat v aluminosilicat) nhng chng coi l loi bi nguy him c th dn n c ung th n b nhim. Bng ch ng l khi theo di cc nn nhn nhim bi u bng thy tinh hay aming dng hnh kim ngi ta thy nhng ht bi l nhng mnh gy nh nhn v sc. Khi chng thm nhp vo ti cc ph nang, khi phi h hp, chng s lin tc gy ra cc vt thng. Cc vt th ng khng c lnh ny s l mm mng cho cc tm gy ra ung th. Ngoi cc loi bi ni trn, bi than cng c ni n nhiu v n gy ra bnh bi phi cho nhng ngi tip xc nhiu nh cng nhn khai thc than, th l... Mc du nhng bi tr khng c tc ng v mt ha hc nhng hai hin tng gy tn thng ph nang v bnh bi phi cng lm chng ta quan tm. Bi tan c th thm nhp vo c th con ngi ch yu theo hai con ng l h hp v tip xc qua da. Khi vo trong c th, tng loi bi s gy ra cc tc ng theo c tnh ca n. Bn cnh hai loi bi k n trn, cn tn ti loi bi mang tnh cht cng hp; th d nh bi xi mng. Bi xi mng gm phn tr l cc silicat v phn tan l cc cht kim.

43

CHNG III. CC PHNG PHP X L BI [23,26,27,29] 3.1. KHI QUT V X L BI Nh ni n phn trn, bi l nhng ht cht rn c kch thc cng nh t trng khc nhau phn tn trong khng kh. x l lc sch bi trc khi thi kh ra mi trng ngi ta nghin cu v s dng nhiu cch khc nhau. Mi cch (phng php) ph hp vi cc loi bi v kch thc bi khc nhau v c nhng u nhc im ring. Chnh v vy m ty thuc vo i tng bi, ngi ta chn phng php x l ph hp. Cc phng php x l bi c th chia thnh cc nhm nh trn bng 3.1. Bng 3.1. Cc phng php x l bi
Lc -Bung lc gm -Lc c vt liu m -Lc ti (mng) X l bng cht lng -Dn ma -Sc kh -a quay -Lc tng kiu Venturi X l bng tnh in Lc tnh in X l da vo lc ly tm X l da vo trng lc

-Thit b s dng Bung lng bi lc qun tnh. -Thit b s dng lc ly tm (cyclon). -Thit b quay

Trn c s phn loi cc phng php x l, ta c th chia cc thit b x l bi lm 4 dng chnh nh sau:
1. Thit b lc c kh 2. Thit b lc mng 3. Thit b lc t 4. Thit b lc tnh in

Hai loi u (1 v 2) dng x l bi. Thit b lc t (3) c th dng x l bi hoc hi v kh c. Thit b lc tnh in (4) ch dng x l bi hoc sol kh. c trng v hiu qu x l bi ca cc kiu thit b c khi qut trn hnh 3.1. v bng 3.2.. Bng 4.2. v hnh 4.1. cho thy rng cc thit b x l bng lc qun tnh v cc cyclon rt tin tch cc ht bi tng i ln. Loi cyclon t hp c hiu sut ln nht. Dng cc thit b lc in, thit b lc ti v cc thit b lc t c th t c hiu qu lc kh cao. Thit b lc bi loi t ch dng khi cht kh cn x l chu c nhit thp v m. Trong trng hp ny cc thit b lc bi loi t c nhiu u
44

im hn so vi thit b lc tnh in ch thit b gin n v r tin. ng dng thit b lc bi loi t trong nh my c nhiu kh khn v y qu trnh tinh lc c lin quan ti vic thu gom v thi mt lng ln nc c tnh cht ha l cn phi x l trc khi thi. Thit b lc in l mt loi thit b lc sch bi c hiu sut cao; trong mun lc cc loi kh thi kh ta dng loi thit b lc in tm, cn lc sch bi v hi m kh hp th, cng nh lc sch c tt hn, ta dng loi thit b lc in ng v khi cn lc sch mt th tch kh ln th dng thit b lc in l hiu qu nht.
100 % 99,9 99 95 80 50

Lc ti
Lc tnh in

20 5
1 0,1 0,01

Venturi
Dng xoy

Xyclon

Dn ma 0,01 0,02 0,05 0,1 0,2 0,5 1 2 5 10 20 50 100

Kch thc ht bi, (m)

Hnh 3.1. Hiu qu x l bi ca cc thit b Bng 3.2. Vng kch thc ph hp v hiu qu x l ca cc phng php.
Stt Thit b x l 1 2 3 4 5 6 7 Bung lng bi Cyclon n Cyclon t hp Lc c vt m Thp lc t Lc ti (mng lc) Lc tnh in Kch thc ht ph hp Hiu qu x l 2000 - 100 100 - 5 100 - 5 100 - 10 100 - 0,1 10 - 2 10 - 0,005
45

40 - 70 % 45 - 85 65 - 95 Ti 99 % 85 - 99 85 - 99,5 85 - 99

C th ha bng 3.2. ta c th tham kho minh ho trn hnh 3.1. Ngoi ra, ngi ta cn dng cc thit b lc kiu si bt lc sch kh khi bi, khi v m (ti 90%). Nh vy mun chn c thit b tch bi v lc sch kh c hiu qu, phi xut pht t cc yu cu chnh:
1. Thnh phn ht bi v kch thc ht ca n 2. Trng thi v thnh phn ca kh 3. tinh lc kh cn thit 3.2. PHNG PHP X L BI DA VO LC TRNG TRNG 3.2.1. NGUYN TC

S lng bi bng bung lng l to ra iu kin trng lc tc dng ln ht bi thng lc y ngang ca dng kh. Trn c s ngi ta to ra s gim t ngt lc y ca dng kh bng cch tng t ngt mt ct ca dng kh chuyn ng. Trong thi im y, cc ht bi s lng xung. s lng c hiu qu hn, ngi ta cn a vo bung lng cc tm chn lng. Cc ht bi chuyn ng theo qun tnh s p vo vt chn v ri nhanh xung y.
3.2.2. CU TO CA BUNG LNG N

Mt bung lng n c cu to nh hnh 3.2A v bu ng lng kp trong cng nghip c m hnh nh trn hinh 3.2B.

Kh Khi x l x l

Khi cha x Kh vl bi

Hnh 3.2A. Bung lng n

Hnh 3.2B. Bung lng kp c vch cn tng hiu qu

46

B mt ct ngang ca bung lng c tnh theo cng thc:

S = a.h = V w

(m2)

Trong : a l chiu rng ca bung lng h l chiu cao ca bung lng V l lu lng kh qua bung lng w l vn tc dng kh qua bung lng. Nh vy, khi thit din ca bung lng cng tng th vn tc dng kh cng gim; bi c th lng tt hn. B mt lng cn thit (F) tnh theo cng thc:
F= V w1

(m2)

y w1 l vn tc lng bi, V l lu lng dng kh v bi. Thi gian lng ca ht bi c tnh theo cng thc:
t= h w1

(s)

Th tch lm vic ca bung lng (VLV):

VLV = V .t

(m3)

Chiu di cn thit ca bung lng (l):

l= S VLV = a a.h

3.2.3. CU TO V HOT NG CA BUNG LNG NHIU TNG

Bung lng nhiu tng l mt dy cc bung lng n l ni tip nhau. Tng tng n l hot ng ging nh bung lng n. Nh vy chiu dy tng cng:
H = n.h

Trong n l s tng. Hiu sut x l tng cng s l:

P = Pi

Trong Pi l hiu sut x l ring phn ca tng bung lng n.

47

3.3. PHNG PHP X L BI DA VO LC LY TM

3.3.1. NGUYN L

Khi dng kh v bi chuyn ng theo mt qu o trn (dng xoy) th cc ht bi c khi lng ln hn cc phn t kh s chu tc dng ca lc ly tm vng ra pha xa trc hn, phn gn trc xoy lng bi s rt nh. Nu ta gii hn dng xoy trong mt v hnh tr th bi s va vo thnh v v ri xung y. Khi ta t tm dng xoy mt ng dn kh ra, ta s thu c kh khng c bi hoc lng bi gim i kh nhiu.
3.3.2. CU TO CA MT XYCLON N

S mt xyclon n v h thng xyclon lc bi c m t nh trn hnh 3.3A, 3.3B v 3.3C.

Dc h L1 D L3 Kch thc tng qut ca mt xyclon thng thng

-ng knh ng v: D -ng knh ng ra: Dc=1/2 D -ng knh ng y: Dd=1/4 D -Chiu cao ng v: L1 = 2 D -Chiu cao phn nn: L2= 2 D -Chiu cao sa vo: h = 1/2 D -Chiu rng ca vo: b = 1/4 D -Chiu cao ng ra: L3= 1/3 D

L2

Dc D

Dd

Hnh 3.3A. Mt ct ng v mt ct ngang ca mt xyclon n. + Tc lng ca ht bi trong xyclon c tnh theo cng thc:
w0 = d 2 .( P .P2 ).U 2 1 9.P2 .v2 .D

Trong : d l ng knh ht bi (m). P1 l khi lng ring ca ht, P2 l khi lng ring ca kh mang,
48

2 l h s nht ng hc ca kh, u l tc vng ca dng kh trong xyclon (m2/s), D l ng knh phn hnh tr ca xyclon.
Kh bn vo Kh sch ra Kh bn vo
Cnh hng gi

Bi ra Kiu dng tip tuyn

Bi ra Kiu dng ng trc

Hnh 3.3B. Cc kiu dng trong xyclon + ng knh phn hnh tr ca xyclon c tnh theo cng thc:
D = 2.( R1 + 1 + R)

(m) ng knh gia ng ra v thn (m)

Trong : R1 l bn knh ng dn kh ra (ng trong hnh tr), R l khong cch tnh theo xyclon,
R1 = 4V .wt

Trong : V l lu lng kh qua hay nng sut ca xyclon, wr l vn tc dng kh i ra khi xyclon, (trong cng nghip th w 1 thng ly t 4 n 8 m/s). + Kch thc ca ng vo: ng vo thng l hnh ch nht c chiu cao h v chiu rng b. Thng thng t l h/b bng k v bng t 2 n 4. Trong :
49

b=

V k .wv

Wv l vn tc dng kh trong ng xyclon (thng bng 18 - 20 m/s)

Kh x l l Kh x
Kh x x Kh l

ngthot ng thot
Kh v bi Kh cha x l

Kh cha x Kh v bi l Cc cnh hng Cnh hng gi

Thu bi Ca thu bi Van

Hnh 3.3C. S h thng xyclon lc bi + Th tch lm vic ca xyclon:

VLV = V .t

(m3)

Trong t l thi gian lu ca dng kh trong xyclon.

4,06.102 R2 t= 2 2 log d .w . k . b R + R1

(s)

Trong w l tc gc ca dng kh trong xyclon,

w= wRtb Rtb

k l t trng ca kh v b l gc vo ca dng kh. R 2 l bn knh v phn hnh tr, Rtb l bn knh trung bnh ca phn hnh tr ca xyclon. + Chiu cao ca phn hnh tr Ht:
H= Vh VLV = k. 2 ( R2 R1 ).wtb .[ R2 ( R1 + 1 ) 2 ]

50

+ Chiu cao phn hnh nn:

H n = ( R2 Ro ).tg o

Trong Ro l bn knh l thot bi ( thng l 0,2 n 0,5 m), o l gc nghing gia bn knh v ng sinh (thng l 50 - 60o) Trong thc t ngi ta thng lp thnh t hp nhiu xyclon n li tng cng hiu qu x l kh thi. Nng sut lc ca xyclon (m3/h) c th tham kho bng 4.3. Bng 4.3. Nng sut lc bi ca xyclon n v xyclon t hp.
Loi xyclon 400 n Kp Ba Bn 1450-1690 5800-6760 500 2270-2640 4540-5290 9080-10600 Nng sut lm vic theo ng knh ca xyclon [mm] 600 3260-3810 6520-7620 1300015200 700 4400-5180 8800-10400 1320015500 1760020700 800 5800-6760 1160013500 1740020300 2320027000

+ Hiu sut lm sch bi ca xyclon:

=
G Gc G .100 = d .100 Gd Gd Gd rp Gc rp Gd rp
. .

Hiu sut lm sch ring phn:

rp =
n

Grp Gd rp

.100 =
1 rp .1

.100

= rp =
i =1

100

2 rp . 2

100

+ ...

Trong : i l thnh phn ca cc loi (kch thc) bi. G, G, G c l khi lng bi c x l, khi lng bi ban u, khi lng bi cn sau khi x l GRP l khi lng bi ring phn.
51

3.4. PHNG PHP X L BI BNG MNG LC, TI LC

3.4.1. NGUYN L

Dng kh v bi c chn li bi mng hoc ti lc; ti (mng) ny c cc khe (l) nh cho cc phn t kh i qua d dng nhng gi li cc ht bi. Cc ht bi b gi li trn mng l do c kch thc ln h n l (khe) ca mng hoc dnh li trn b mt ca vt liu do va p, do tip xc trc tip v do lc tnh in. Chnh v vy m mng lc gi li c c nhng ht bi c kch thc nh hn l (khe) trng ca mng lc (hnh 3.4.A). Khi lp bi dy ngn cn lng kh i qua th ngi ta tin hnh rung hoc thi ngc thu hi bi v lm sch mng. S mt thit b lc ti c m t trn hnh 3.4.B.
3.4.2. CU TO V VN HNH

Thit b lc l nhng tm vi (n) hnh ng hay hnh tm c t trn nhng gi cng bng nha hoc kim loi c cc l thong (an t si hoc ch to t tm lin c c l).
ng i ca Trng hp 3 bi

ng i ca kh

ng i ca kh

ng i ca bi

Khuch tn Trng hp 1

Trng Ht bi hp 2

Tit din si Tit din si

Hnh 3.4A. S d ng i ca kh v bi qua mng lc

Trng hp 1: Ht bi b gi li do tip xc, Trng hp 2: Do va p, Trng hp 3: Do lc tnh in

Ti lc bng vi, n c dng ng mt u h kh i vo cn u kia khu kn. ti c bn hn ngi ta thng t trong mt khung cng bng li kim loi hoc nha. Nng sut lc ca thit b ph thuc vo b mt lc, loi bi v bn cht, tnh nng ca vt liu lm ti (mng).
52

+ Din tch lc c tnh theo cng thc

S= V .3600 v.

- i vi ti lc: Trong :

S .D.l + .D2/ 4

- i vi mng lc: S = a.b V l lu lng kh (Nng sut lc) qua ti (mng),[m3/s]. v l cng lc ca mt m 2 b mt [m3/m2.h]. Thng thng v c chn t 15 n 200 m3/ m2.h. l hiu sut lm vic ca b mt lc. Thng thng c ly khong 85 %. D l ng knh ng lc. l l chiu di ng lc; a l chiu rng ca ti; b l chiu di ca ti.
Kh sch

Kh sch Kh sch

Kh cha bi Kh sch c bi

ng Ti

Kh Kh cha bibi c

Ti Mng

Bi Bi

Thit b lc ti

Bi Bi

Thit b lc mng

Hnh 3.4B. S thit b lc bi bng mng hnh ti v hnh tm .

53

+ Lc cn ca ti (mng) c tnh theo cng thc:

P = A.V n

[N/m2].

Trong A l h s thc nghim ph thuc vo nguyn liu lm ti (mng), c k n bo mn v cn bn. A thng giao ng t 0,25 n 25,00. n l h s thc nghim thng thng bng 1,25 n 1,30.
B phn chuyn ng c kh kh B phn chuyn ng c

Kh x x l Kh l

Ti lc ng ng Ti lc hnh

Kh x x l Kh l
Kh cha l Kh cha x x l

Kh x l l Kh x

Kh cha x Kh cha x l l

Hnh 3. 4C. M hnh mt thit b lc ti trong cng nghip 3.5. PHNG PHP X L BI BNG DN MA
3.5.1.. NGUYN L

Dng kh c ch bi i qua mn cht lng (thng l nc). Cc ht a bi gp nc s b thm t v b dm xung hoc cun bm theo, cn dng kh sch s c i qua. Nc thng c i t trn xung, cn dng kh i t di ln.
3.5.2. CU TO V VN HNH CA THIT B.

Dn ma l thit b n gin nht dp bi nhng li c hiu qu cao. Lng nc phun vo c th quay vng tr li sau khi lng bn bi. Thit b ny thng dng trong cc nh my xi mng hay cc x nghip nghin qung. S mt thit b dp bi bng dn ma c m t trn hnh 3.5.
54

Kh sau x l
Kh x l

B chn sol Thit b thi nc

H thng phun nc Nc a vo

Kh cha x l

Kh cha x l

Huyn ph bi

Nc nhim bn ra

Hnh 3.5A. Thit b dp bi theo kiu dn ma

Kh xx l Khis sau l

Nc cp

Ca phun Nc phun ra nc Vt liu Vt liu nnm

Kh cha Kh cha x lx l

Cht lng v bi Huyn ph cht nhim

Hnh 3.5B. Thit b dn ma c nhi vt liu n

55

3.6. LC BI TNH IN
3.6.1. NGUYN L

Trong mt in trng u, c s phng in ca cc in t t cc m sang cc dng. Trn ng i, n c th va phi cc phn t kh v ion ha chng hoc c th gp phi cc ht bi lm cho chng tch in m v chng s chuyn ng v pha cc dng. Ti y chng c trung ha v in tr li. M hnh hot ng ca nguyn l dp bi tnh in c m phng trn hnh 3.6A v 3.6B. Ngi ta s thu c bi t cc tm in cc dng; kh i ra l kh sch bi.
3.6.2. CU TO V HOT NG

Cu to ca mt thit b lc bi tnh in c m ta nh trn hnh 3.6C. Thng thng trong thit b lc bi tnh in kiu in c c tm (hnh 3.7A), ngi ta lm nhiu tng in cc m v dng lin tip nhau. Trong thit b lc hnh ng (hnh 3.7B), in cc dng l mt ng rng; in cc m thng l mt dy dn trn, khi hot ng xung quanh dy dn thng c qung sng do in t ion ho cc phn t kh khi n chuyn ng qua in cc dng. i vi kiu in cc tm ta c cc thng s: + Khong cch gia hai in cc khc du l L thng t 10; 15 - 20 cm. Khong cch ny ph thuc vo in th, cch in ca mi trng v cng dng in khi s dng.
Gi in Vng hot ng Catot M MMMM Anot

e+ Vng th ng Gi in

Hnh 3.6A. M hnh hot ng ca qu trnh lc bi tnh in

56

Lc y ca dng kh

Lc y ca dng kh

Kh v bi

Kh + Bi vo

Kh + Kh Bi ra ra

Lc tng hp

Lc trng trng

Lc in trng v trng lc

Lc tng hp

Hnh 3.6B. S nguyn l ca qu trnh lc bi tnh in + S in cc dng (in cc lng) c hnh tm hoc li c tnh theo cng thc:
Zd = b +1 2L

Trong :

b l chiu rng ca bung lc L l khong cch gia hai in cc

+ S in cc m l:
Zc = b = ( Z a 1) 2.l

+ Th tch lm vic ca thit b:

V1 = V .t

(m),

Trong V l nng sut lm vic ca thit b, t l thi gian lng ca bi. + Tc ca dng kh:
w= h t

Trong h l chiu cao lm vic ca thit b, i vi kiu thit b lc in hnh ng: + Th tch ng:
V0 = 1.

.D 2
4

57

Trong l l chiu di ng, D l ng knh ng.

Catt Kh sch ra Kh sch ra ( ) Catot

Kh c bi Kh c bi Bi
S mt ng lc tnh in

(+) Ant Bi

(+) Anot

S lc tnh in tm

Hnh 3.6C. S thit b lc tnh in + S ng c tnh theo biu thc

n = Vl /V0

Trong Vl l th tch lm vic. + Tnh in th v cng dng ti cc in cc:

U = E.l

Trong E l gradien in th ( kV/ cm) v s c chn nh sau: - i vi kh lnh: E t 4,3 n 4,5 kV/cm. - i vi kh nng: E t 3,8 n 4,0 kV/cm.
I = i.l

Trong i l mt dng theo chiu di (A/m) l l chiu di hot ng ca in cc m.

58

Kh v bi Kh c bi

Kh sch

Kh sch
ng knh ng : 100 - 300 ( mm ) ng knh ng Chiu di ng : 2 - 3 ( m )

Bi Bi

Hnh 3.7A. S thit b lc tnh in ng

Kh v bi
Kh c bi

Kh sch Kh sch

Bi Bi

Bi Bi

Bi Bi

Hnh 4.7B. S thit b lc tnh in tm

59

S ph thuc ca mt dng vo khong cch gia cc din cc c th tham kho bng sau: Khong cch gia cc in cc L ([cm]) Mt dng ( i [A/m]) < 10 0,3 - 0,4 < 15 0,5 < 20 0,6 - 0,7

S nhm in cc trong bung lc in minh ho trn hnh 7. Cng sut tiu tn cho ton b h lc tnh theo biu thc:
P= U .I .k . cos 1,41.

Trong :

U v I l in p v dng cn cho qu trnh lc, k l h s chnh lu dng, l h s hu ch ( = 0,8 v cos = 0,7 - 0,75) P1 l cng sut tiu tn cho cc hot ng ph nh rung bi... 1/1,41 l h s bin in p hiu dng.

3.7. PHNG PHP SC KH QUA CHT LNG (NC) PHNG PHP SI BT y l mt trong cc kiu lm sch kh thi khi bi bng phng php t c hiu qu cao (vi bu c ng knh ln hn 5 um, hiu sut lm sch kh t ti 99 %).
3.7.1. NGUYN L

Kh cha bi i qua mng c l ri qua lp cht lng di dng cc bt kh. Bi trong cc bt kh b thm t v b ko vo pha nc to thnh cc huyn ph ri c thi ra ngoi. Kh sau khi c lm sch s thi ra mi trng. Thit b lm sch kh kiu ny ph hp vi nng bi khong 200 n 300 mg/m3; cng sut c th ln ti 50.000 m3/h.
3.7.2. CU TO V HOT NG

Cu to n gin ca mt thit b ra kh kiu si bt c m t trn hnh 3.8.

60

Kh c i t di ln thng qua mt mng phn phi, li qua nc, qua mang (li) ra ri ra ngoi. Nc c cp lin tc vo ca nc v ly ra y cng vi huyn ph bi.
Kh l Kh xx l

Cht lng (nc) Cht lng

(nc)
Cht cht lng vo a lng

Tm chn Tm chn Kh vnhim bi Kh

Kh cha x l

Kh v bi

Cht lng thi ra Huyn ph bi

Hnh 3.8. S thit b ra kh kiu si bt + Din tch mng ( li ) c tnh theo bi thc:
S =V /w

Trong V l lu lng kh qua thit b, w l vn tc kh. Vn tc kh thng t 0,7 n 3,5 m/s. Nu w qu nh s khng to c bt si ln; Khi w ln qu s ph v lp bt (thnh phun). Vn tc w qua b mt t do ca mng (li) tng i n nh khong 2m/s. + ng knh l li khong t 2 n 8 mm. + Chiu cao ca lp bt trn li ( mng) tnh theo biu thc:
H = k1 .w.( H o + k 2 ) + 2 H o

Trong w l vn tc kh i qua li. k1 v k2 l h s thc nghim ( k 1 = 0,35 v k2 = 0,075 - khi din tch t do ca l li nh hn 18% v k1 = 0,65; k2 = 0,015 - khi din tch ca l li ln hn 18% v nh hn 30%). H0 l chiu cao ca lp cht lng ban u. + Hiu sut lm sch tnh theo cng thc:
61

P=

Go G .100 Go

Trong :

G0 l hm lng bi ban u, G l hm l ng bi cn li trong dng kh sau khi i qua thit b.

Trong thc t, thp lc thng c lm nhiu tng lc bi c sch hn. 3.8. PHNG PHP RA KH LY TM
3.8.1. NGUYN L

nc.

Thc t y l thit b kt hp lc ly tm ca cyclon vi s dp bi ca

Nc c phun p vo thnh hoc t trn xung theo thnh hnh tr ca thit b, ng thi kh c thi theo dng xoy t di i ln. Bi vng ra pha thnh b nc cun theo i xung ca thot di y.
3.8.2. CU TO V HOT NG.

Cu to ca thit b c m t nh trn hnh 3.9. Kh sch ra

Kh thi vo

Nc + bn ra

Nc vo

Hnh 3.9. S hot ng ca mt xyclon t

62

3.9. PHNG PHP RA KH KIU VENTURI

3.9.1. NGUYN L

Dng kh c dn qua mt ng tht, ti y tc dng kh tng ln cao (50 - 150 m/s). Khi vt qua u cp cht lng ng s ko theo dng sol. Nhng ht cht lng nh b s lm t bi cun theo v ngng li thnh dng bn i ra theo c di v dng kh ra s l kh sch.
Kh sau x l ra 5 Tch git Cht lng Kh cha x l vo 3 1 2 6 Dch sau x l 4

Hnh 3.10A. S nguyn l ca mt thit b kiu Venturi

Kh x l Kh sch KhKh bn v bi

Kh vobi v Kh

Tia Tia nc

Ca nc Nc vo

C hng C hng

Bung n nh

Nc v hi ra Ca thot hi v nc

Huyn ph bi

Hnh 3.10B. Thit b ra kh kiu venture

63

3.9.2. CU TO V VN HNH

Thit b ra kh kiu Venturi c m t trn hnh 3.10A v 3.10B. Kh c dn vo theo ca vo 1 qua c tht 2, ti y c t ca cp nc. Sau khi dn qua ca 3 kh i vo bung lc sol 4; ti y c trang b h thng tch sol l nhng tm li t xin so vi thnh bung. Sol nc ln bi t tch t li phn y v c thi ra ngoi theo ca 6. Kh sau khi tch sol v bi c thot ra ngoi theo ca 5. Ngc li vi kiu Venturi kh, ngi ta cn dng dng nc thay v dng kh thit b ra kh kiu ny gi l Venturi nc (hnh 3.11). Dng cht lng c vn tc ln i qua ca tht s to mt p sut m khong khng gian gia dng nc v thnh ca tht (nh kiu bm chn khng dng sc nc); kh thi s b cun vo qua ca tht, tip xc vi dng phun ca cht lng v qu trnh tch bi xy ra ging nh nguyn l trong thit b Venturi kh. Nc (cht lng) sau khi tch phn ln huyn ph bi cc ngn b ti phn y c thit b c s dng tun hon tr li. Kh i ra l kh sch. a i vi thit b kiu ny, vn tc ca cht lng thng vo khong t 20 n 30 m/s; tc dng kh vo t 10 n 20 m/s. Thit b ra kh ny c th lp lin tip nhau qua nhiu bc tu theo yu cu sch ca kh ra.

Kh c bi Kh c bi

Kh c bi Cht lng ra Cht lng ra

Thp ra Ringspait

Thp ra Radialstrom

Hnh 3.11. Cc ca tht ca Venturi nc.

64

3.10. RA KH KIU DNG XOY

3.10.1. NGUYN L

Dng kh c tc ln thi trc tip vo b mt cht lng theo mt gc xin; di p lc ca dng kh, cht lng s b tung ln, kh v lng tip xc vi nhau; bi b thm t s gi li trong cht lng v kh sch i ra ngoi.
3.10.2. CU TO V VN HNH

Cc kiu thit b ra kh dng xoy c m t nh trn hnh 3.12. i vi kiu 1 v 2 tuy c to c khc nhau nhng qu trnh vn hnh tng t u nhau. Dng kh v i c dn qua ca 1 vo bung ra ( vi vn tc b thng t 10 n 15 m/s) do cu to c tm chn nh hng 2 nn dng kh tip xc vi b mt cht lng di mt gc xin. Dng kh v cht lng c tip xc vi nhau trong vng tip xc 3. Hu ht bi s dc gi li trong lng cht lng; dng kh cha sol c i qua mng tch sol v i ra ngoi theo ca 4. Huyn ph bi c thng xuyn ly ra theo ca 5. Kiu thit b 3 c trang b cnh hng dng hnh xon c nn lm tng thi gian tip xc gia dng kh bn v sol nc nn hiu qu lm sch c tng ln. Mt khc do thi gian dng kh v sol i trong cnh nh hng di hn nn hu ht cc sol c lng li nn khng c trang b n thm mng tch sol. Kh n i vo ca 1 theo mt ng lp xin vi thnh b thit b; sau khi tip xc vi b mt cht lng s i vo cnh hng dng 2. Kh sch i ra theo ca 3. Huyn ph bi c nh k ly ra theo ca 4.
Kh sch ra Kh thi vo Kh sch ra

Kh sch ra

4
Kh thi vo

1 3 2 3 2 3 2 3 1
Kh thi vo

3 5

Huyn ph bi

Hnh 3.12. S hot ng ca thit b dng xoy

65

3.11. RA KH KIU A QUAY

3.11.1. NGUYN L

Bi trong dng kh i qua h thng kh bi gm nhiu tm c l hay li bng kim loi. Nhng tm li ny lun lun c thm t bng mt cht lng thch hp v quay trn u trong mt khng gian hnh tr. Nhng ht bi trong dng kh gp b mt cht lng s b lm t v b gi li ri tri theo nhng got nc ri xung y.
3.11.2. CU TO V VN HNH

Thit b ra kh kiu a quay c minh ho trn hnh 3.13. Kh thi c dn vo thit b theo ca kh vo 1 pha di; sau khi i qua h thng a quay 5 s i ra ngoi theo ca thot 2 pha trn. Cht lng c phun vo a trn cngbng h thng phun 3 gn trc quay v phn b u trn my cc a ng thi chy xung pha di. Bi b thm t s chy theo dng cht lng i xung pha di y thp v c thng xuyn tho ra theo ca thot 4.

Kh sch ra Trc quay Cp cht lng Cc a quay

Kh bn vo

Huyn ph bi

Hnh 3.13. M hnh thit b lc bi kiu a quay

66

CHNG IV. CC PHNG PHP L HI V KH C X [23,29,31] 4.1. X L KH V HI BNG PHNG PHP TIU HU phn hy mt cht dng kh hoc hi c hi cho mi trng thnh mt hay nhiu cht khc t hoc khng c hi c th thc hin bng ngun nhit - phn hy nhit; hoc phn hy nhit c xc tc hay thng qua cc phn ng ha hc; hoc kt hp c hai nh phng php t. + t v phn hu bng nhit. Phng php ny ph h vi kh thi ch a cc hp cht hu c nh p cc hi dung mi, hi cc ho than, hi t... vi iu kin nhit cao, l cc cht hu c s b phn hu thnh than, kh v hi nc. Nu phn hy t do, nhit phn hy i hi s cao v tc phn hy thng chm. V vy ngi ta thng tin hnh vi s c mt ca cc cht xc tc. Mt khc c th tin hnh t vi khng kh. Th d nh t kh ng hnh trong khai thc du m.

Kh bn Kh bn Nhin liu v khng kh Nhin liu v khng kh

Nhit TB Trao i Kh x l Kh x l

nhit
Kh bn Kh bn

Hnh 4.1. S thit b tiu hy bng nhit + Tiu hy bng ha hc. y l phng php c s dng kh ph bin i vi cc kh c hi. i vi cc cht hu c c hi nh thuc tr dch hi, ngi ta thng s dng cc phn ng oxy ha kh thay i cu trc phn t hay dng tn ti ca chng tr thnh cc sn phm t hoc khng c hi i vi ngi v ng thc vt. Th d: + Phn ng vi ozn vi s c mt ca tia cc tm. zn ha kt hp vi chiu tia cc tm l phng php rt c hiu qu i vi cht thi hu c hoc dung mi. Cht tr dch hi + O3
UV

CO2 + H2O + Cc cht khng c

+ xy ha bng cc cht xy ha mnh khc:

67

Cht hu c + KMnO4

Mn2+ + CO2 + H2O + ... MnO2 + cc sn phm khng c

Mingt Ca t Nhin liubn Kh 315 - 480 C

o

Cht xc tc Lp xc tc

425 - 600 C Kh x l Kh x l

Khng kh Khng kh
Kh cha x l Kh bn

Hnh 4.2. S thit b x l bng phng php nhit xc tc

nh ngn la nh ngn la u phun hi Tia hi (kh)
La trc nh bc chy La cp chy Dng cp gas ng cpgas u iu khin u iu khin nh bc chy nh bc chy

nh iu khin nh iu khin

ng mi la ng mi la
ng cp gas ng cp gas Hn hp Hn hp

To pilot 2 Ra pilot

2 Rapilot 3 3 To pilot

Ni kh u ni kh

To Ra pilot pilot 1

3-way plug valves Van 3 chiu

Hnh 4.3. Cu to ca ca t nhin liu Thng thng trong thc t, ngi ta s dng tng hp cc phng php ni trn t c hiu qu x l cao hn. Th d nh x l NO x bng NH3 vi xc tc ph hp chng ta s thu c sn phm l N2 v nc. S ca qu trnh x l c m t nh trn hnh 5.4.

68

NH3 NOx Kh thi NOx NOx NOx NH3 NH3 NH3 NH3

Lp xc tc N2 N2 N2 N2 H2 O H2 O H2 O H2 O Kh sch

Hnh 4.4. S x l NOx s dng phn ng c xc tc 4.2. PHNG PHP NGNG T Nguyn t c ca phng php l da trn s h thp nhit mi trng xung mt gi tr nht nh th hu nh cc cht th hi s ngng t li v sau c thu hi hoc x l tiu hy.
Cht lm lnh vo Dung mi lnh vo Khbn ra ra Kh sch Kh bn vo Kh bn vo

Cht ng t ra ra Cht ngng t

Dung mi lnh Cht lm lnh rara

Dung lm lnh Cht mi lnh (nc hay khng kh) (Kh hoc lng)

Hnh 4.5. S thit b ngng t b mt iu kin lm lnh bnh thng, ta c th x l bng ngng t thng ch thu hi c hi cc dung mi hu c, hi axit. Tt nhin phng php ny ch ph hp vi nhng trng hp kh thi c nng hi tng i cao. Trong trng hp nng nh, ngi ta thng dng cc phng php hp ph hay hp th.

69

Kh x ll Kh x

ng dn Nc a vonc Kh cha x l Kh cha x l

Ncv cht ngng t thi ra Nc v cht ngng t

Hnh 4.6. S thit b ngng t kiu tip xc. Hiu sut ngng t (gi tr tng i) c tnh theo cng thc:
=
Co C R .100 Co

Trong : CR l nng hi u ra, Co l nng hi ban u. Gi tr tuyt i ca hiu sut ngng t tnh theo cng thc:
P= (C C R ).VR m .100 = o .100 C o .V .M i C o .Vo

Trong : mi l khi lng ca cht i c ngng t, Mi l phn t lng ca cht i, VR l lu lng kh u ra, Vo l lu lng kh u vo.

70

4.3. X L HI V KH THI BNG PHNG PHP HP PH

4.3.1. KHI QUT V HIN TNG HP PH

Hp ph l mt qu trnh xy ra trn b mt tip xc gia hai pha d th (rn - kh, rn - lng, lng - kh). Nhng phn t ca cng mt cht nm b mt v bn trong khi cht c cc trng thi khc nhau dn n hnh vi ca chng cng khc nhau.

Hnh 4.7. S tng tc gia cc phn t trong khi vt cht Chng hn nh v trng lc, cc phn t bn trong khi vt cht chu lc tc dng mi pha ng u v nh nhau; cn cc phn t trn b mt th chu lc tc dng khng u nhau m lun lun c xu th b ko vo bn trong khi vt cht lm cho b mt khi vt cht c xu hng lun b co li nh minh ha hnh 5.7. Khi b mt khi v t cht tip xc vi cc phn t ca pha khc, cc phn t trn b mt khi vt cht tc dng ln cc phn t ca pha khc nhng lc hng v pha mnh nhm cn bng v lc theo mi hng. y chnh l nguyn nhn ca s hp ph cht trn b mt cht khc. Mt khc, nhiu trng hp t\ng tc gi a b mt cht rn vi cc phn t kh hoc lng khi chung tip xc vi nhau m s tng tc mnh tng t nh tng tc trong mt phn ng ha hc, chng s to nn mt hp cht mi trn b mt tip gip - hp cht b mt. Nh vy thc cht c th chia hp ph lm hai loi: Hp ph vt l v hp ph ha hc. + Hp ph vt l : L lo hp ph gy ra do tng tc yu gia cc i phn t; n ging nh tng tc trong hin tng ngng t. Lc tng tc l lc van Der wall. + Hp phu ha hc: L loi hp ph gy ra do tng tc mnh gia cc phn t v to ra hp cht b mt gia b mt cht hp ph v cc phn t b hp ph. i vi cht hp ph l cht kh, qu trnh hp ph ph thuc vo nhit v p sut. Lng kh hp ph l mt hm ph thuc vo hai bin T v P.
71

a = f (T , P)

Nu gi nhit khng i ta c ng ng nhit:

a = f ' ( P)

Nu gi p sut khng i ta c ng ng p:
a = f ' (T )

Nhit tng lm gim qu trnh hp ph. Ngc li, p sut cng tng th s hp ph cng tt. Ni cch khc, vic h nhit hoc tng p sut u c li cho qu trng hp ph.
4.3.2. X L HI V KH THI BNG PHNG PHP HP PH [28]

4.3.2.1. Nguyn l ca phng php Hi v kh khi i qua lp cht hp ph, chng b gi li nh hin c tng hp ph. Nu ta chn c cc cht hp ph chn lc, th c th loi b c cc cht c hi m khng nh hng n thnh phn cc kh khng c hi khc. Trong trng hp chung, ta c phng trnh cho lng cht b hp ph nh sau:
a = am . h.k (1 h).[1 + h(k + 1)]

Trong :

a l lng cht b hp ph trn mt n v khi lng cht hp ph, [mol/gam. am l lng cht b hp ph ng vi s lp y lp n phn t. h = P/PS vi P l p sut ring phn ca kh b hp ph PS l p sut hi bo ho ca n. k l h s v s tng tc ca cht hp ph v cht b hp ph.

Trn b mt phng s ngng t mt cht xy ra khi P/P S > 1. trong cc vng mao qu ca cht hp ph xy ra qu trnh h ph; ngha l cc n p cht kh hoc hi b gi li (c ngng t) mc du p sut hi ring phn nh hn p sut hi bo ho ( khi t l P/PS nh hn 1). 4.3.2.2. Cc cht hp ph s dng trong cng ngh x l kh thi - Than hot tnh. Than hot tnh l mt cht hp ph rn, xp, khng phn cc v c b mt ring rt ln. V bn cht nguyn t, n thuc nhm graphit - mt dng th hnh ca cacbon- gm cc tinh th nh c cu trc bt trt t; nhng khc vi graphit l trong tinh th ca than hot tnh cc vng sau nguyn t cacbon sp xp km trt t hn. V vy than hot tnh c cu to xp v to nn nhiu l hng nh khng ng u v rt phc tp.
72

Cu trc l xp phc tp v b mt ring khc nhau ty thuc vo cch sn xut. Cc l xp c bn knh hiu dng t vi chc n hng chc nghn anstron. V mt cu to, n c cu to kiu t ong gm mt h l xp mao qun thng nhau v thng vi mi trng bn ngoa vi cu trc khng gian ba chiu. C th chia kch thc l xp thnh ba loi sau: (1) Dng vi mao qun, bn knh hiu dng c 10 A, c b mt ring ln nht (350 - 1000 m2/gam) v chim phn ch yu trong than hot tnh. (2) Dng mao qun trung gian c bn knh hiu dng trong khong 100 n 250 A. B mt ring khng ln lm, khong 100 m2/gam. (3) D ng mao qun ln c bn knh hiu dng khong 1.000 n 10.000 A; dng ny c b mt ring rt nh, khng qu 2 m2/gam. Than hot tnh c tc dng hp ph tt i vi cc cht khng phn cc dng kh v dng lng. T lu than hot tnh c s dng lm mt n phng c, lm sch mu v kh mu cc sn phm du m. Ngy nay trn th gii than hot tnh c coi nh l mt cht hp ph ch yu trong cng ngh x l lm sch mi trng bao gm cc lnh vc: (1) Lm sch nc ung, x l nc sinh hot hoc x l nc thi ca cc cng trnh t nhim bn. Trong nhng trng hp ny than hot tnh s gi li cc hp cht hu c ho tan, nht l cc cht gy mi, gy mu v c vt nhng kim loi nng. Than hot tnh c bit c hiu qu x l cao i vi nc c b nhim nh cc cht dit tr dch hi. (2) X l nc thi cng nghip. Ngi ta s dng than hot tnh trong nhng trng hp hp ph cc cht km hoc khng b vi sinh vt phn hy, cc cht gy c hi i vi cc vi sinh vt. Trong trng hp ny x l chn lc bng than hot tnh ng vai tr nh l qu trinh tin x l cho cc bc x l sinh hc tip theo. (3) X l cp ba nc thi cng nghip v th. Khi than hp ph no, n khng cn kh nng h p ph tip tc na. i vi than hot tnh, trong trng hp ny khng phi b i m c th ti sinh v s dng li c. i a s cc cht hp ph trn than hot tnh u c th gii hp bng nhit. Khi trong mi trng nhit cao (di nhit bt chy ca than), cc cht hu c cng nh cc phn t axit bay hi v tch khi b mt ca than. i vi mi mt cht s c mt nhit x l ph hp. Vi cc hp cht ca kim loi th thng thng phi gii hp bng axit sau ra bng nc v sy ti sinh. - Silicagel. Silicagel l gel c a anhydrit axit silisic c cu trc l xp rt pht trin. Mng li ca gel bao gm cc nguyn t Si nm gia khi chp tam gic ni vi nhau thng qua cc nguyn t O phn b ti cc nh. B mt ca gel thay v cc nguyn t oxy c thay bng cc nhm hydroxyl (OH-); iu quyt nh tnh cht hp ph ca silicagel.
73

Silicagel d dng hp ph cc cht phn cc cng nh cc cht c th to vi nhm hydroxyl cc lin kt kiu cu hydr. i vi cc cht khng phn cc, s hp ph trn silicagel ch yu do tc dng ca lc mao dn trong cc l xp nh. Cng nh cc cht hp ph c th ti sinh khc, ch ti sinh c mt ngha rt quan trng. Ring i vi silicagel, trng thi ha hc ca b mt gel quyt nh tnh hp ph mnh cc cht phn cc. Trng tha ny ch c bo ton nhit di 200oC; nu gii hp c tin hnh bng kh kh. Nu ti sinh silicagel nhit cao hn s dn n s thay i bt thun nghch ca cu trc v b mt lm mt kh nng hot ng ca silicagel. Do cu to ca silicagel, c bit l lp lin kt ca nhm OH-, nu tin hnh gii hp bng kh nng m hay bng hi nc vi thi gian ko di s lm gim hot tnh hp ph ca chng do nguyn nhn ch yu l gim b mt ring. Do vy vic gii hp i vi silicagel cn phi lu hn so vi vic gii hp than haat tnh. - Zeolit. Zeolit l cc h cht alumosilicat c cu trc tinh th. Trong p mng li tinh th ca zeolit, mt phn ion Si4+ c thay th bi cc ion Al3+ gy ra s thiu ht v in tch dng do zeolit c th tip nhn cc cation nht nh ca cc kim loi khc. Mt khc n lm ph v cu trc u n ca tinh th n cht, gy ra nhng khong khng gian trng v cc lc in trng khc nhau trong zeolit. Tnh cht ca zeolit ph thuc vo t l Si v Al v mc to tinh th ca sn phm cui cng; ng thi n cn chu nh hng ca cc cation kim loi khc c nhn thm vo trong qu trnh hnh thnh sn phm. V vy ngi ta c th to ra nhng kiu zeolit khc nhau bng cch iu ch chng vi cc t l khc nhau ca Si v Al, vi cc iu kin hnh thnh tinh th zeolit. Trong cng nghip ph bin nht l cc zeolit A v zeolit X. Cc zeolit ny c tinh hp ph kh tt v tng i chn lc. Cc zeolit th hin tnh nhy cm rt r i vi nhit . Th d nh zeolit cha Ca ch b mt tnh hp ph khi nhit ln ti 800oC, cha Na b mt hot nhit 700oC cn zeolit cha Li th 640oC. - Cc cht hp ph t nhin. Trong t nhin c nhiu khong cht c tnh hp ph nh st, bentonit, diatomit... song kh nng hp ph ca chng thng c lm tng ln nhiu sau khi x l bng cc bin php ph hp. Tnh u vit nht ca cc c cht hp ph t nhin l chng c gi thnh rt thp so vi cc cht hap ph nhn to.

74

4.3.3. CC KIU TIN HNH HP PH [26,27]

Trong thc t tin hnh hp ph, ngi ta c th tin hnh theo hai phng php: phng php h ph tnh v phng php ng. Do phng p php hp ph ng c hiu sut cao hn v ph hp hn i vi thc tin sn xut cho nn thng c s dng trong x l kh thi cng nghip. Qu trnh h ph thng thng c tin hnh trong cc bung hp p ph c cha cc cht c kh nng hp ph. Kh thi cha cc cht cn hp ph c dn qua lp cht hp ph. Cc cht cn hp ph s c gi li cn kh sch s c thi ra ngoi. Nu cht hp ph c hot cn bng l a, chiu dy ca lp hp ph l L, din tch tit din ngang ca thit b hp ph l S, kh thi c nng cht cn hp ph l Co v tc dng trong thit b hp ph l w th lng cht c hp ph s c tnh theo biu thc:
m = a.S .L

hay

m = w.C o .S .

Trong l thi gian dng kh i qua thit b hp ph. Ta gi thit rng tc hp ph y l ln v cng, qu rtrnh hp ph t ti cn bng ngay lp tc khi cht cn hp ph tip xc vi cht hp ph th ta c th rt ra thi gian cn thit hp ph ht mt lng m cht thi l:
=
a .L w.C o

ng biu din qu trnh hp ph trong thp (ct) s c dng nh hnh 5.9.

Kh sch ra

C
V ct

dy lp hp ph

Lp vt liu hp Dn phn phi kh

C 0 V V
Ca kh b

Hnh 4.8. ng cong hp ph ca hi c qua ct hp ph

Hnh 4.9. M hnh thp hp ph

75

4.3.4. NHNG U V NHC IM CA PHNG PHP X LBNG HP PH.

Phng php hp ph c kh nng lm sch cao. Cht hp ph sau khi s dng u c kh nng ti sinh; iu ny d lm h gi thnh x l v y cng l u im ln nht ca phng php.
My hp ph quay My ht quay
Kh v hihi dung vo Kh v dung mi mi Than hot tnh Than hottnh ng kh ra ng kh ra

M t M t Qut Qut

Lp lc Lc Hi vo ng hi vo Lm lnh B lm lnh Than hot tnh Than hot tnh Kh vKh vdung mi hi hi dung mi

Hnh 4.10. M hnh thit b hp ph kiu trng quay

Nc ra Nc ra Nc vo Nc vo
Kh cha Kh cha xx l l Lc B lc My thi Qut Kh sch Kh sch

Dng hi Dng hi

Thu hi cht Thu hi nhim cht nhim

Cht nhim Cht nhim thu hi thu hi

Than hot tnh

Than hot

Than hot tnh

Than hot

Kh x Kh x l Dngp thp cho quayvng Dng p thp quay vng

Hnh 4.11. S mt h thng hp ph trong cng nghip

76

4.4. X L KH THI BNG PHNG PHP HP TH [26,30]

4.4.1. NGUYN L

Nguyn l ca phng php l da trn s tng tc gia cht cn hp th (kh hoc hi) vi cht hp th l cht lng hoc cc cht khc l cht rn hoc cht ha tan trong cht lng. Da vo bn cht ca s tng tc ni trn m ngi ta chia thnh s hp th vt l hay s hp th ha hc. - Hp th vt l: L qu trnh da trn s tng tc vt l thun ty; ngha l ch bao gm s khuch tn, ha tan cc cht cn hp th vo trong lng cht lng v s phn b ca chng gia cc phn t cht lng. ha tan ca mt cht cn hp th trong lng cht lng lun lun l mt hm ca nhiu bin s. Nu gi D l tan th ta c th biu din n nh sau: D = f (x1, x2... xj, T, S, P, kD,...) Trong : xi l nng ca cc cht kh hoc hi trong cht lng. T l nhit lm vic, S l din tch tip xc gia hai pha, P l p sut ring phn ca hi hoc kh trong pha kh, kD l h s khuch tn ca cht c hp th trong pha lng. Thc t qu trnh hp th tng khi din tch tip xc hai pha tng, v nhit lm vic gim; ring hiu sut x l th cn ph thuc mnh vo p sut ring phn ca kh hoc hi v nng ca chng trong pha lng. tng hiu qu x l, ngi ta thng dng cc kiu thit b lm tng din tch tip xc ti a, truyn nhit tt v hn ch s tng ca cht ho tan trong pha lng. Cc kiu thit b thng dng nh: thp hp th c tng m, thp hp th si bt, thp phun... -Hp th ha hc. Hp th ha hc l qu trnh hp th lun i km vi mt hay nhiu phn ng ha hc. Sau qu trnh khuch tn l qu trnh xy ra cc phn ng ha hc. Nh vy s hp th ha hc khng nhng ph thuc vo tc khuch tan ca cht kh vo trong chat lng m cn ph thuc vo tc chun ho cc cht - tc phn ng ca cc cht. Trong hp th ha hc, cht c hp th c th phn ng ngay vi cc phn t ca chnh cht hp th. Th d nh: amoniac hay kh sunphur hp th vo nc: NH3 + H2O -----> NH4OH SO2 + H2O -----> H2SO3
77

Cht cn hp th phn ng vi cc thnh phn hot ng trong cht hp th ( thng thng l dung dch ca cc cht hot ng). Th d nh hp th CO2, SO2 trong dung dch NaOH. CO2 + 2NaOH = Na2CO3 + H2O Na2CO3 + H2O +CO2 = 2NaHCO3 Vi SO2 cng c phn ng tng t. Trong trng hp chung ta c th biu din mt cch tng qut nh sau: aA + bB + cC -----> mM + nN + ... Khi t ti cn bng, hng s cn bng phn ng c dng [M]m.[N]n.... Kcb = [A]a.[B]b.[C]c... Kcb cng ln bao nhiu th qu trnh hp th xy ra cng thun li by nhiu. Gi tr [A] l nng t do ca cht A trong dung dch cha tham gia vo phn ng.
4.4.2. CC LOI THIT B HP TH

(1) Thit b hp th kiu mng cht lng. Mng cht lng trong thit b hnh thp c to t hnh khi cho ch lng chy thnh mng theo cc ng, t tm tnh hay a quay b tr hp l trong thp. Cht lng theo mng c th chuyn ng t trn xung di v kh i t di ln trn; rt t khi s dng ch chuyn ng cng chiu t di ln trn (ch lm vic ny ch s dng khi tc ca dng kh thi cao - trn 15 - 20 m/s). Vi thit b mng ng v mng tm, ngi ta thng p dng cho kh thi c tc trung bnh t 4 n 5 m/s. Thit b hp th kiu mng cht lng c u im l to c din tch tip xc pha kh ln v c kh nng tch, thot nhit tt ng thi vi qu trnh hp th. Ngy nay ngi ta t cn dng cc thit b hp th kiu mng ng v mng tm. Duy cn ph bin hn c t trong trng hp hp th mt s kh ho tan tt, c nng cao t hn hp kh m c ng thi c s to nhit mnh nh HCl, NH3.
78

(2) Thit b mng a quay c cu to ging nh thit b a quay trong x l bi v sol. Cht lng hp th c phn b u trn cc tng a, chuyn ng t trn xung v c quay trn lin tc trong sut qu trnh x l. Thc nghim cho thy tc chuyn khi tng khi tng s vng quay ca a. Trong thit b mng quay, sc cn thy lc nh v c th lm vic vi mc tiu hao cht hp th thp. Trong cng nghip, thit b ny vn c s s dng th d nh hp th HCl hay SO2 bng Na2S trong n xut natrithiosunphat (Na2S2O3). Thit b c 11 a vi ng knh 800 mm, tc quay l 150 vng/pht lm vic c vi nng sut l 1.700 m3/h. (3) Thp hp th m c dng ph bin nht. Trong thp, ngi ta thng nhi cc vt th lng cng nh c snh s, l so kim loi, vn than cc... lm tng din tch tip xc hai pha. Khi vn hnh, kh thi c i t di ln trn cn cht lng th i t trn xung di. Lu lng ca hai pha lun c tnh ton trc thit b t hiu qu cao nht. Khi cht lng chy trn b mt cc vt th lm m, v c bn chng c c trng ca mng cht lng. Tuy nhin v bn cht ca qu trnh vn hnh, gia thit b hp th mng v thi t b hp th m c s khac nhau. thit b hp th mng th mng cht lng chuyn ng lin tc theo chiu cao ca thp hp th; cn trong thit b hp th m th khi mng cht lng chuyn ng t n nguyn ca vt m ny sang n nguyn khc th mng c b ph v v mng mi ddc hnh thnh. Qu trnh ny c lp i lp li trong sut chiu di ca thp. Thc t trong thp hp th m, cc mng cht lng khi chuyn t n nguyn m ny sang n nguyn m khc thng b ph v bi s chuyn ng ngc chiu ca dng kh. Do vy m thp m phn no cn mang tnh cht nh mt thp hp th si bt. S chuyn ng thun dng trong thp m i khi cng c s dng. l nhng trng hp khi tc kh thi kh ln (khong 10m/s), khng hoc kh thc hin c i vi kiu ngc dng. S b tr thun dng s lm tng qu tr nh trao i cht, gim tr lc thy ng v gim kch thc ca thit b. Trong trng hp s hp th i km vi cc phn ng thy phn hoc to kt ta th ngi ta thng dng loi thp hp th m ni. Cc lp m ni (nhng mnh bt xp polyme hay cc qu cu rng lm bng cht do) c treo l lng bi dng kh trong thp v bi cc tm li . Gia cc lp m l nhng khong trng m bo cho cc kt ta khng lm tc nghn s lu thng ca dng kh qua cc lp m. Tt nhin y cht hp th lng cng c chuyn ng t trn i xung. Cc nghin cu thy ng hc v chuyn khi trong cc thit b hp th m ni cho thy, thp hp th kiu ny c th lm vic vi tc dng kh ln m khng b tc nghn. Nhc im ca thp hp th m ni l kh

79

thot nhit trong qu trnh hp th. Mun tch nhit, ngi ta thng phi s dng lm lnh tun hon. Trong cng nghi p sn xut axit phosphoric t qung ngi ta s dng kiu thp hp th m ni hp th kh SiF4 hay SiCl4 vo nc; v chng to thnh axit silicic khng tan trong nc. Hay dng huyn ph vi hp th cc kh nh CO2, SO2... (4) Thp h p th si bt (ging nh thp si bt trong x l bi) thng c s dng trong trng hp ti lng cao, p sut kh thi ln v qu trnh hp th c s to nhit, cn c lm lnh. Cc kiu thp hp th si bt chnh gm (1) si bt qua li (hay vt xp), (2) si bt qua cc a chp xen k v (3) trn c hc kh v cht lng. Hp th kiu si bt c nhc im ln nht l lun c lp bt chim th tch kh ln trong thit b. Vic chuyn ng ca cht lng gp phi tr lc ln. Cc nh thit k c nhiu cng trnh lm gim bt nhng nhc im trn c th s dng ki hp th ny trong cng nghip v n c h s chuyn khi rt cao. Chiu cao lp cht lng tng s lm tng kh nng hp th song ng thi cng tng tr lc ca thit b. Thng thng ngi ta khng tng lp cht lng qu 50 mm. (5) Thp hp th kiu a chp to ra s chuyn ng i dng ca kh v cht lng qua tng bc mt. Cht lng i t pha trn a xung y, ri vo y ca a phi di ri tip tc chy xung pha trn ca a tip theo. Cn kh th len li cng theo con ng y nhng ngc chiu vi cht lng. S minh ho n gin c th tham kho trn cc hnh trong phn ph lc. (6) Thp phun l loi thit b hp th n gin. Trong thp phun, cht lng c phun thnh bi (sng) t pha trn xung, kh thng i t di ln nhm lm tng din tch tip xc v nng thc t cht cn hp th trong pha kh gi m dn theo chiu t di i ln v nng cht b hp th trong pha lng c tng dn theo chiu t trn i xung. Qu trnh ny rt c li cho vic tng hiu qu x l. Thp hp th phun c th chia ra lm ba kiu khc nhau: (1) thit b hp th phun kiu thng rng, (2) thit b hp th phun thun dng tc cao v (3) thit b hp th phun sng kiu c kh. i vi kiu thng rng, vi phun sng thng c t pha trn phun xung. Trong trng hp thp hp th c chiu cao ln, ngi ta thng t cc vi phun chia ra cc tng khc nhau. Nhc im ca thit b thng rng l kh thng phn b khng u trong ton b thp dn n lm gim hiu sut x l. Tuy nhin kh phn b u ngi ta to ra cc b phn phn phi kh nh phn phi kh qua ming tht, phn phi kh thng qua mng phn phi xp hay phn phi kh theo dng xoy kiu cyclon...
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Thit b hp th thng rng c u im l n gin, u t thp, lc cn thy ng nh v c th s dng i vi kh thi c nhim bn cao; cht lng dng hp th c th quay vng cho ti khi hp th no mi thi cho nn tit kim c cht hp th. Nhc im ch yu ca loi thit b kiu ny l hiu qu x l khng cao do h s chuyn khi thp v tc dng kh khng c qu ln (nh hn 1 m/s) trnh hin tng cht lng b cun theo kh ra ngoi. Thit b phun thun dng tc cao. Thit b kiu ny ph hp vi dng kh thi c vn tc ln (khong t 20 - 30 m/s); khi vn hnh cht lng b cun theo cng dng kh, sau c tch ra bi mt thit b km theo. Thit b phun thun dng tc cao c dng nh kiu thit b Venturi (ging nh trong x l bi). Kh thi vi tc cao i qua n g tht, cun theo cht lng t ca ch di dng bi sng v cng i vo vng khuch tn ri ti b phnj tch cht lng. Trong vng khuch tan, ng nng ca dng kh chuyn thnh p lc vi mc hao ht l cc tiu. Thit b Venturi c s dng kh ph bin trong x l kh thi. (7) Thit b phun sng kiu c kh t c s dng, n ch ph hp trong nhng trng hp c bit.

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CHNG V. CNG NGH X L MT S KH THI CNG NGHIP [26,27,28,2931] 5.1. X L KH LU HUNH IOXIT (SO2) Kh lu hunh ioxit c nhng tnh cht ha hc rt c trng thun li cho vic x l. SO 2 hp nc s to thnh mt axit mnh d thc hin phn ng trung ha vi cc dung dch kim hay cc oxit kim loi mang tnh kim. Mt c trng thun li na ca kh SO 2 l khi hp nc, n chuyn thnh dng SO32- d dng b oxi khng kh oxi ha thnh SO42- ngay trong iu kin nhit v p sut thng; mc d trong mi trng khng kh kh, SO2 gn nh khng phn ng vi oxi. Cc mui sunph it v sunpht c cc kim loi a kim v amni u tan tt trong nc; nhng ngc li, mui ca chng vi cc kim loi kim th th li rt t tan. y cng l mt c trng m i khi l thun li nhng i khi li l bt li cho qu trnh la chn quy trnh x l. Da vo cc tnh cht c trng trn, trong cng nghip, thng s dng hai cch x l l x l theo ng t v x l theo ng kh.
5.1.1. X L SO2 THEO NG T (Fuel gas desulfurization - FGD)

Theo cch ny, SO2 thng c hp th vo dung dch kim nh NaOH, NH4OH, Ca(OH)2 hay Mg(OH)2. Cc ki u thit b hp th c s dng y thng dng nht l thit b dn ma, thp m v thp si bt. Vic la chn cht kim no cho qu trnh x l thng ph thuc vo hai yu t l yu t kinh t v tnh kh thi ca cc gii php cng ngh. Th d: Ca(OH)2 c gi bn trn th trng l r nht trong bn cht kim nu ra trn, cho nn v mt kinh t n c u th nht. Nhng sn phm ca qu trnh x l l CaSO3 hay CaSO4 u l cc cht t tan nn khng th s dng cc thit b c hiu qu cao nh thp m hay thp si bt c, do kt ta bm trn vt liu m hay trn cc l to bt kh m ch c th dng thit b dn ma. Cc phn ng ha hc xy ra trong qu trnh x l ln lt nh sau: - Qu trnh hp nc ca SO2 to ra axit sunphur, SO2 + H2O <==> H2SO3 <==> 2H+ + SO32- Qu trnh trung ha bng kim v oxi ha thnh sunpht c th xy ra tun t hoc ng thi. H2SO3 + 2NaOH + 1/2O2 = Na2SO4 + 2H2O H2SO3 + Ca(OH)2 = CaSO3 + 2H2O CaSO3 + 1/2O2 = CaSO4 H2SO3 + MgSO3 = Mg2+ + SO32- + H2O
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SO32- + 1/2O2 = SO42S cng ngh ca qu trnh x l SO 2 theo con ng t c m t nh trn hnh 6.1. v c th tm tt nh sau: SO2 t ngun thi (thng l cc l t sau qu trnh trao i nhit tn dng tip) trc ht c lm ngui bng nc lnh va h nhit ca lung kh thi va lm m kh SO2. Sau kh thi c dn qua thp hp th. Kh sch qua h thng chn sol ri c thi ra ngoi. Kt ta c qua h thng lng lc, oxi ha ri em ti s dng hoc thi an ton.

Nc lnh Thit b lm ngui Kh thi vo Nc thi

Ca(OH)2/Mg(OH)2

Kh sch ra Khng kh Lng, lc Sy oxi ha Sn phm CaSO4/MgSO4

Thp hp th Nc lc

Hnh 5.1. S cng ngh x l kh thi cha SO2 theo ng t(FGD)

5.1.2. X L SO2 THEO DNG KH

Nguyn l ca cng ngh x l l da vo phn ng gia SO 2 m vi Ca(OH)2 khan hay CaO to thnh mui canxi sunphit hay sunphat di dng bi v tch chng ra khi dng kh bng cc thit b lc mng hay lc ti, kt hp cng x l bi. Cc phn ng ha hc xy ra cng ging nh phn trn, nhng ch khc l chng xy ra trong pha kh ch khng phi trong dung dch. SO2 + Ca(OH)2 = CaSO3 + H2O SO2 + H2O = H2SO3 H2SO3 + CaO = CaSO3 + H2O X l SO2 bng ng kh c th thc hin theo hai cch. Cch th nht l x l sau l t v cch th hai l x l trong l t. X l sau l t Cng ngh x l SO2 sau l t c th tm tt nh sau: Kh thi i ra t l t c dn i qua thp lm ngui bng nc lnh. Ti y kh thi ng thi c lm m chuyn ha SO2 thnh H2SO3 tng ng. Nu trong iu kin c oxi, H2SO3 c th c chuyn thnh H 2SO4. Kh m tip tuch c
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i vo thp ph n ng. Ti y, Ca(OH) 2 bt khan hay CaO dng bt c phun vo v trn u nhm to iu kin cho phn ng trung ha xy ra hon ton. Tip theo, kh v bi c chuyn qua bung lc ti. y bi v bi mui c gi li, kh sch c thi ra ngoi. Bi mui c tinh ch s dng hoc dng lm ph gia cho xi mng. S cng ngh x l sau l t c m t trn hnh 6.2.
Ca(OH)2/CaO

Nc CN

Thp lm ngui / m

Thp phn ng

Bung lc ti

Kh sch

Kh thi

Bi ln

Bi, mui

Hnh 5.2. S cng ngh x l SO2 theo ng kh sau l t

X l trong l t y l mt cng ngh xut kh to bo v thu c kt qu tng i tt. Theo cng ngh ny, bt CaCO3 c phun thng vo l t. nhit cao trn 1000oC CaCO3 s chuyn thnh CaO. Khi bi CaO i ra khi l cng vi SO 2 v hi nc, chng s phn ng vi nhau to thnh mui i ra cng bi v kh thi. Trong cng ngh ny, kch thc ht ca CaCO 3 v s phn b ng u trong khng gian l ng vai tr quyt nh hiu sut x l. Cng on lc ti loi bi v bi mui ging nh cng ngh x l sau l t. Hnh 6.3. m t lu trnh x l trong l.

Bt CaCO3

L t
Nhin liu t l

Xyclon loi bui s b

Bi ln

Thp lm ngui

Kh sch

Bung lc ti

Nc CN

Bui, bi mui

Hnh 5.3. S cng ngh x l SO2 theo ng kh trong l t

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5.2. X L KH NIT OXIT (NOX) Kh NOx (ch yu l NO2) va c tnh cht ca mt oxit axit c th chuyn ha thnh mui nitrat bng phn ng trung ha, va c tnh oxi ha tham gia nhng phn ng oxi ha kh. Nh trong phn tnh cht ca cc kh thi trnh by, nu c mt ca cht kh l NH3 hay ure, NO2 hoc hn hp ca NO v NO2 s phn ng chuyn thnh N2 v nc nhit trn 9000C hoc trn 2000C nu c mt ca cht xc tc. Da trn nhng tnh cht ny hai hng cng ngh x l c hnh thnh. l cng ngh x l bng phng php trung ha vi s c mt ca oxi khng kh chuyn hon ton NO v NO2 thnh mui nitrat. Th hai l cng ngh x l bng phng php oxi ha kh khng xc tc v c s dng xc tc.
5.2.1. X L TRUNG HA NOX BNG NG T

NO2 tc dng vi dung dch kim mnh to thnh ng thi hai mui nitrat v nitrit theo phng trnh phn ng: 2NO2 + 2NaOH = NaNO2 + NaNO3 + H2O nhng trong dung dch kim long hay trong nc, NO 2 ch to thnh mui nitrat hay axit nitric v kh NO. NO lt kh khng bn, n d dng tc m dng vi oxi khng kh oxi ha thnh kh NO2. 3NO2 + H2O = 2HNO3 + NO Kh NO2 va hnh thnh li tip tc phn ng cho n khi nng NO v NO2 gim xung ti gi tr cn bng trong nhng iu kin c th.

Oxi khng kh Lm ngui, to m, cung cp oxi Kh thi

Ca(OH)2 dd

Kh sch

Mui thu hi Thu hi mui

Trung ha

Nc CN

Nc quay vng

Nc thi

Hnh 5.4. S cng ngh x l NOx theo ng t

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NO trong iu kin thng, hu nh khng tan trong nc, khng tc dng vi dung dch kim long. Do x l NO, lun lun cn c s tham gia ca oxi oxi ha n thnh NO2. Quy trnh x l thng thng gm ba cng on. Cng on mt l lm ngui, ng thi to m v cp oxi. Cng on hai l trung ha bng kim vi trong thp phn ng kiu dn ma c trang b lp vt liu m . Cng on ba l x l thu hi mui v tun hon nc t dung dch thi ra t thp trung ha. S cng ngh m t nh trn hnh 6.4.
5.2.2. X L NOX BNG PHNG PHP KH NHIT CAO

nhit cao trn 8000C nu thm dung dch ure vo hn hp kh thi, NOx sinh ra qua qu trnh t s b kh v N 2, CO2 v nc theo cc phng trnh phn ng sau: NO + NO2 + (NH2)2CO = 2N2 + CO2 + 2H2O (NH2)2CO + H2O => 2NH3 + CO2 2NO + 2NH3 + 1/2O2 = 2N2 + 3H2O 6NO2 + 8NH3 = 7N2 + 12H2O Cng ngh kh NOx bng ure nhit cao chnh l li dng nhit cao ca kh thi hoc nhit ngay trong l t gim thiu pht thi kh NOx. Cng ngh x l ny tuy hiu qu khng cao, nhng i li, chi ph u t v vn hnh rt thp. Ton b cng ngh x l kh thi theo cng ngh ny bao gm cc bc: (1) Kh NOx nhit cao, (2) Trao i nhit, (3) Tch bi th v (4) x l cui cng tch nt bi nh v kh c khc. S cng ngh m t s lc trn hnh 6.5.
Dung dch Ure Nhit nng Kh sch

L t

Trao i nhit

Tch bi s b

X l cui cng

Nhin liu

Thi

Hnh 5.5. S cng ngh x l NOx nhit cao

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5.2.3. X L KH NO X BNG PHNG PHP XC TC CHN LC (SELECTIVE CATALYTIC REMOVAL - SCR)

NO v NO2 l nhng cht kh c tnh oxi ha tng i mnh; bn cnh nhng hp cht, trong nit mang ha tr m th li c tnh kh, nh NH3, (NH2)2CO, cc amin... Chnh v th m nhng hp cht mang ha tr m v ha tr dng ca nit kt hp vi nhau, nhng iu kin nht nh nit n s chuyn tr v nit phn t (N2). Nh trn ph 6.2.2 xt qu trnh oxi ha kh ny ca cc hp cht nit nhit cao. Khi c mt ca cht xc tc th nhit yu cu phn ng xy ra thp hn nhiu, trong khong t 180 n 4500C. Cng ngh kh NO x c xc tc thng th ng bao gm cc bc: (1) trao i v n nh nhit, (2) trn u hn hp kh, (3) oxi ha kh c xc tc v (4) thi, nh s trn hnh 6.6.
Nhit nng Trao i v n nh nhit Kh thi Ur / NH3 Thp trn kh Thp xc tc chn lc iu ha v thi Kh sch

Hnh 5.6. S x l NOx bng xc tc chn lc (SCR) Xc tc trong cng ngh ny c nhiu loi khc nhau nh V 2O5, hn hp oxit kim loi chuyn tip, zeolit mang kim lai, hp kim platin - rhodi... Trong thc t, V2O5 c thm TiO2 mang trn nn gm hay li kim loi c s dng nhiu nht, do xc tc loi ny gi r hn nhng li cho hiu qu x l cao v d to hnh, lp t. 5.3. X L NG THI SO2 V NOX Khi x l SO 2 bng phng php trung ha theo ng kh hoc t, lun lun c m phn kh NO x c x l, c bit l khi co cp thm oxi. t Trong trng hp cp oxi (oxi khng kh) ngay t u vo cng ngun thi nhm oxi ha sunpht thnh sunpht th NOx c x l cng SO2 nhiu hn. Nu qu trnh oxi ha sunpht l cng cn cui cng th lng NO x c x l khng nhiu. Nh vy, trong mi trng hp x l kh thi cha c SO 2 v NOx th NOx khng c x l trit , c bit l phn kh NO. Hin nay ang tn ti hai cng ngh x l ng thi SO2 v NOx c chp nhn l cng ngh x l trong l t v cng ngh x l s dng chm
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tia in t nng lng cao. Cng ngh x l trong l t cho hiu qu khng cao nhng n gi n v chi ph thp; cn cng ngh x l s dng chm tia in t nng lng cao c th x l trit c SO2 v NOx, song cng ngh phc tp hn v chi ph cao.
5.3.1. CNG NGH X L TRONG L T

y l cng ngh kt hp x l SO 2 trong l t theo ng kh v x l NOx bng ure nhit cao. Li dng nhit cao trong l t nhin liu ha thch, ni ang sinh ra cc kh NO x v SO2, nu phun ng thi bi CaCO3 v dung d ure v hi nc th ngay ti trong l xy ra cc phn ch ng: CaCO3 CaO + CO2, SO2 + H2O = H2SO3 CaO + H2SO3 = CaSO3 + H2O NO + NO2 + (NH2)2CO = 2N2 + CO2 + 2H2O (NH2)2CO + H2O => 2NH3 + CO2 2NO + 2NH3 + 1/2O2 = 2N2 + 3H2O 6NO2 + 8NH3 = 7N2 + 12H2O

15m CaO SO2 (Ti / thng) SO2

2m CaO (Ti)

SO2

SO2

2m CaO

(Tt)

2m CaO

(Tt)

Hnh 5.7. nh hng ca kch thc ht v phn tn canxi cacbont n hiu qu x l SO2

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Trong cng ngh ni trn, c ht ca canxi cacbonat phun vo l v phn tn ng u ca n nh hng rt mnh ti hiu qu x l SO 2. Nhng kt qu nghin cu minh ho trn hnh 6.7. cho thy; nu c ht l 15 m hay mc du c ht l 2 m nhng vn li vi kch thc tng t th hiu qu x l km v cng vi c ht 2 m nhng phn tn th hiu qu x l rt cao. Sn phm sau x l ca SO2 l CaSO3 hoc CaSO4 dng bi v ca NOx l kh N2, CO2 v hi nc. Do cng on x l cui cng s dng k thut lc ti hay lc tnh in l ph hp.

Bt CaCO3

Dung dch U r

Nc CN

Kh sch

L t

Lm ngui, Lm m Bi ln

Lc ti

Nhin liu

Bi v bi thch cao

Hnh 5.8. S cng ngh x l ng thi SO2 v NOx trong l t Cng ngh x l ny cho hiu sut x l cc kh khng cao (ti a khong 90% i vi SO2 v 80% i vi NO x), nhng n gin, u t thp v d lp ghp. Chnh v nhng l do m n rt ph hp vi vic x l cho nhng c s s dng l t nh l hay nhng ni hi nh n va s dng nhin liu ha thch.
5.3.2. CNG NGH X L SAU L T

Cng ngh x l trong l t nh trnh by trn cho hiu qu khng cao v tt nhin l khng th x l c hon tan kh SO 2 v NOx. x l trit NOx cng vi SO 2, cng c nhiu phng php c cng b. Trong phn ny xin gii thiu mt cng ngh tin tin c p dng nhiu mt s nc nh Nht bn v M; l cng ngh s dng chm tia in t nng lng cao. Nguyn l ca cng ngh x l ny l dng nhng chm tia in t c nng lng cao chiu trc tip vo dng kh thi c cha kh SO2, NOx v hi nc. Trong iu kin nh th, cc in t s p vo cc phn t kh v H2O
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to ra cc radical. Nhng radical va hnh thnh s tc dng vi kh SO2 to thnh cc phn axit sunphuric v vi NO x to thnh cc phn t axit t nitric. Nu ng thi hi amoniac c cp vo bung phn ng th amoniac s tc dng vi cc axit va hnh thnh to ra cc mui amoni tng ng. Ton b nguyn l ca cng ngh c m t trn hnh 6.9. S cng ngh x l ng thi SO2 v NOx sau l t s dng chm tia in t c nng lng cao c m t nh trn hnh 6.10. SO2, NOx, H2O Kh amoniac

O2, H2O

OH*, O*, HO2*

Phn ng vi SO2 v NOx SO2 NOx

OH*, O*, HO2* OH*, O*, HO2*

H2SO4 HNO3

ng phng e

Trung ha bng amoniac H2SO4 + NH3 = (NH4)2SO4 HNO3 + NH3 = NH4NO3

B pht cao p Hnh 5.9. S nguyn l x l SO2 v NOx s dng chm tia in t

Nc lnh

Kh amoniac Bung x l kh thi B to tia e

Kh sch

Thp lm ngui v lm m kh thi Kh thi Bi th

Thit b lc ti / lc tnh in Bi v mui

Hnh 5.10. S cng ngh x l ng thi SO2 v NOx s dng chm tia in t
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Trc tin kh thi c dn vo thp lm ngui v lm m bng nc cng nghip c nhit thp. Ti y mt phn bi c kch thc ln c tch ra v nhi t m bo gim xung di nhit ph n hy ca cc axit v cc mui, c bit l axit nitric v mui amoni nitrat. Kh thi ti p tc qua bung x l. Do bung x l c chiu bi nhng chm tia in t c nng lng cao nn cc phn ng ha hc c xy ra y. dn n sn phm cui cng, trong bung phn ng trc tin phi din ra qu trnh to ra cc radical do cc i n t bn ph cc phn t kh v hi. Tip theo l phn ng gia cc radical vi cc phn t kh SO2 v NOx hnh thnh cc phn t axit tng ng. Khi aminiac c cp vo bung phn ng, cc phn t axit va hnh thnh s tc dng vi amoniac to ra c c phn mui t amoni. Bc cui cng l cc phn t mui dng rn s kt hp li vi nhau to ra cc ht bi mui c kch thc ln hn i vo bung lc. Cc qu trnh trn xy ra rt nhanh, nhng cng cn mt khong thi gian hon thnh cc phn ng. Do bung x l cn phi c kch thc ph hp c thi gian lu cho cc phn ng xy ra hon ton. Cui cng bi mui v bi l c tch khi dng kh thi bng lc tnh in hoc lc ti hoc s dng c hai. Cng ngh x l ny ngoi mc ch x l kh c trong kh thi cn thu c hn hp mui nitrat lm phn bn rt tt hoc tinh ch cc mui phc v mc ch khc. 5.4. X L NI TIP NOX V SO2 Trong thc t, kh thi t l t nhin liu ha thch hay tuc bin kh thng lun cha c kh SO2 v NOx. Nu dng phng php trung ha x l th mt phn NO2 cng c x l cng vi SO2. Hin tng ny lun lun c c tnh n khi thit k cng ngh x l SO2; nhng khng xem l cng ngh x l NO x. Ngoi cc cng ngh x l ng th i SO2 v NOx nh trnh by trn th cng c th s dng cc cng ngh x l ring bit cho SO2 v NOx nhng c b tr ni tip nhau x l trit c hai. Hnh 6.11 m t s cng ngh x l ni tip kh NO x v SO2. S 1 minh ho lu trnh x l NOx bng cng ngh SCR trc, x l bi v SO2 bng cng ngh FGD sau. Theo lu trnh ny th kh l cn nhit 400 500oC c tn dng dn ngay vo thp SCR. Trn ng i ca n, amoniac c phun vo theo t lng c tnh ton trc. Trong thp SCR h u ht NOx s c chuyn thnh N2 v nc. Sau khi NOx c x l, kh l c dn tip sang thp trao i nhit sy nng khng kh cp cho l t ri qua thp lc tnh in loi phn ln lng bi c trong dng kh. Kh thi t bung lc tnh in i ra tng i sch v ch cn cha SO2. Vic x l SO2 c tin hnh trong h thng thp m FGD. Ti y ngi ta c th thu c sn phm thch cao hay magi sunpht sch hn. Vi s ny vic x l NOx bng cng ngh SCR tn dng c nhit ca kh l; nhng do
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kh l cha c x l g nn bi v SO 2 nh hng rt nhiu n kh nng hot ng v tui th ca cc tng xc tc trong thp SCR.
S 1

NH3

ng khi

L hi SCR AH EP FGD

S 2
NH3 L hi AH EP FGD GGH L SCR

ng khi

Hnh 5.11. S h thng x l NOx bng phng php xc tc chn lc (Selective t mt lu trnh khc trong x l x l bng cng ngh S 2 mCatalytic Removal - SCR) kt hp kh l SO2 (Fuel Gas Desulfurization FGD)
Ghi ch: AH: t nng khng kh, EP: Lc tnh in, GGH: Sy khng kh bng kh l.

FGD v SCR. Theo lu trnh ny, kh l trc ht c dn qua b trao i nhit sy nng khng kh cho l t, sau qua lc tnh in, qua h thng x l SOx bng thp m FGD ri mi i vo thp x l NOx bng cng ngh SCR. Nh vy khi tin hnh x l NOx kh l c x l kh sch khi cc thnh phn khc c bit l bi v SOx. Trong iu kin ny cc tng xc tc c bo v kh tt nn tui th ca chng tng ln ng k. Nhng c iu sau khi qua thp m, nhit ca kh l b h xun g qu thp khng cho thp SCR hot ng, do trc khi vo thp SCR, kh l phi c t nng tr li bng mt l ph t ti nhit cn thit cho SCR hot ng. Kh thi i ra t thp SCR c nhit cn cao s dng sy nng s b kh thi trc khi vo l sy ph ng thi lm ng nng cho n thot ra theo ng khi.
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5.5. X L KH H2S Khc vi cc kh SO2 v NOx, kh H2S khng phi l kh thi sinh ra do t cc nhin liu ha thch, m n l mt trong cc thnh phn ca kh t nhin, kh ng hnh t cc m khai thc du kh. Ngoi ra, H2S cn c sinh ra trong cc qu trnh kh ha than, cc qu trnh phn h ym kh v y mt s qu trnh sn xut khc. Kh H2S c tnh n mn thit b cao v l tc nhn gy ng c mnh cc xc tc dng trong trong cng nghi p. Do vy vic la b an ton H2S ra khi kh cng nghip l nhu cu bt buc. loi kh H2S, thng th ng c hai cch l tch loi theo ng kh v theo ng t.
5.5.1. CNG NGH X L H2S THEO NG KH

Cng ngh x l H2S theo ng kh thng da trn nguyn l 2hp ph kt hp oxi ha a S v S nguyn t v c thu hi. Mt trong nhng phng php c dng sm nht l s dng Fe2O3 xp, c b mt ring ln lm tc nhn hp ph v trao i vi H2S nhit thng to ra Fe2S3 km n nh theo phn ng: Fe2O3 + 3H2S = Fe2S3 + 3H2O hon nguyn Fe2O3 v thu hi lu hunh sau khi lp vt liu hp ph no, ngi ta dng dng khng kh ngho oxi (2 - 3% O2) thi qua. Lng oxi c tnh ton sao cho lng oxi bng 1,5 ln so vi l thuyt theo phn ng: Fe2S3 + 3O2 = Fe2O3 + 6S Hoc em t vi khng kh thu hi SO2 cho qu trnh sn xut axit sunfuric. Phng php ny cho hiu qu khng cao, nay rt t c s dng. Phng php c s dng nhiu v cho hiu qu kh cao l hp ph oxi ha trn than hot tnh. Khi tin hnh hp ph H 2S trn than hot tnh, nu c mt ca oxi, phn ng oxi ha H 2S to thnh S v nc ngay trn b mt than. 2H2S + O2 = 2H2O + 2S nng cao hiu qu x l H2S, ngi ta cho thm NH 3 vo hn hp kh; khi H2S s cn tc dng vi NH3 to thnh amoni sunfua. 2NH3 + H2S = (NH4)2S Khi b mt than hp ph bo ha, ngi ta dng dung dch amoni sunfua ra lu hunh ra v ti sinh than hot tnh. 2(NH4)2S + 6S = 2(NH4)2S4

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Amoni polysunfua c em phn hy 125 - 130oC v p su 1,7 t 5 2,0.10 Pa s thu c lu hunh v amoni sunfua s dng cho nhng ln x l tip theo S cng ngh ca phng php kh c m t trn hnh 6.12.
Kh sch H2S Tc nhn gii hp ph

Thp hp ph oxi ha

Bung tch lu hunh

Bung ti sinh cht hp ph

Kh cha H2S

X l S/Hp cht ca S

Lu hunh thu hi

Hnh 5.12. S cng ngh x l H2S theo ng kh

5.5.2. CNG NGH X L H2S THEO NG T

X l H2S theo ng t c nhiu phng php khc nhau nh trung ha bng kim mnh, hp th bng metanol/etanol amin, sunfolan, hp th oxi ha... Trong khun kh ca cun sch ny, xin gii thiu hai phng php thng dng cho hiu qu cao nht l phng php ta nanh v phng php Fe3+. Phng php ta nanh Phng php ny d vo phn ng trung ha H 2S bng Na 2CO3, oxi a ha hydrosunfua bng NaVO 3 v kh nng vn chuyn oxi t khng kh ca ta nanh vo ph ng ti sinh NaVO3. Qu trnh x l H 2S xy ra khi dng n kh tip xc vi dung dch hot ng cha ta nanh (TQ - ta nanh dng quinon v THQ - ta nanh dng hydroquinon), Na 2CO3 v NaVO3 theo cc phn ng sau: 2Na2CO3 + 2H2S = 2NaHCO3 + 2NaHS Na2V4O9 + 2TQ + 2NaOH = 4NaVO3 + 2THQ 2NaHCO3 + 2NaOH = 2Na2CO3 + 2H2O -----------------------------------------------------------------------------2H2S + 2TQ = 2S + 2THQ + H2O
94

(1) (3) (4)

2NaHS + 4NaVO3 + H2O = Na2V4O9 + 4NaOH + 2S (2)

Ta nanh dang hydroquinon oxi ha bng oxi khng kh tr li c dng quinon. THQ + 2O2 = TQ + 2H2O (5)

Kh sch H2S

Dung dch hot ng

Ph gia ha cht

Thp hp th oxi ha H2 S Kh cha H2S

Thp oxi ha ti sing dng TQ My cp oxi

Thit b tch lu hunh

Thp iu ha

Lu hunh thu hi

Hnh 5.13. S cng ngh x l H2S bng phng php ta nanh theo ng t

Trong qu trnh x l sinh ra mt lng nc v cng xy ra cc phn ng ph sau: TQ + H2S = THQ + S Na2CO3 + CO2 + H2O = 2NaHCO3 2NaHS + 2O2 = Na2S2O3 + H2O Dung dch hot ng sau khi x l (thc hin t phng trnh (1) n phng trnh (4)) s c a qua thp ti sinh ta nanh dng quinon theo phng trnh (5). Dung dch hot ng tip tc c iu chnh ri a tr li thp hp th u. S cng ngh ca phng php c m t trn hnh 6.13. Phng php oxi ha bng st(III) Phng php ny a trn phn ng ca st(III) vi H 2S trong mi d trng axit yu (pH khong 3,0 n 4,5). Khi kh H2S tip xc vi dung dch st(III) s xy ra phn ng oxi ha H2S thnh S nguyn t. H2S + 2Fe(OH)2+ = 2Fe2+ + S + 2H2O

95

Sau phn ng huyn ph S s c tch ra, dung dch Fe2+ c oxi ha bng oxi khng kh tr v trng thi ban u v c quay vng tr li. 4Fe2+ + O2 + 4H+ = 4Fe3+ + 2H2O 4Fe3+ + 4OH- = 4Fe(OH)2+ ------------------------------------------------4Fe2+ + O2 + 2H2O = 4Fe(OH)2+ S cng ngh ca phng php c m t trn hnh 6.14.

Kh sch H2S

Dung dch Fe(OH)2+

Thp hp th oxi ha

Thit b tch lu hunh

Thp oxi ha ti sinh st(III)

Thp iu ha

Kh cha H2S

Lu hunh thu hi

My thi khng kh

Ph gia ha cht

Hnh 5.14. S cng ngh x l H2S bng phng php st(III) theo ng t

5.6. X L KH CO Kh CO x l ch yu bng con ng t tip chuyn ha c thnh kh CO2 t c hi hn. Trong mt s trng hp, c bit trong sn xut kh ha than th ngi ta s dng phng php oxi ha xc tc vi s c mt ca hi nc thu c sn phm l CO2 v H2. CO + H2O
xc tc

CO2 + H2

S dng mt thp xc tc nhiu tng c th chuyn ha gn nh hon ton CO thnh CO2 (xem phn kh ha than). 5.7. X L KH CO2 CO2 c th tan t rong nhiu dung mi khc nhau; nhng trong thc t ngi ta thng s dng nc, metanol, dung dch kim, amoniac cho qu trnh hp th thu hi CO2. Trong metanol CO2 hp th theo kiu vt l. Trong
96

nc, sau khi khuch tn vo nc, CO2 s hp vi nc to thnh cc s n phm H2CO3 v HCO3 . Nhng sn phm ny rt d phn hy tr li thnh CO2 v nc theo phn ng thun nghch: CO2 + H2O H2CO3 Nhit tng s thc y qu trnh gii hp. Do vy hp th CO2 tt nht l tin hnh nhit thp. Khi s dng dung dch kim hay amoniac th ng thi vi qu trnh hp th l cc phn ng trung ha to thnh cc mui tng ng. CO2 + 2NaOH = Na2CO3 + H2O CO2 + Na2CO3 + H2O = 2NaHCO3 Cc sn phm mui c gi tr th c th thu hi. Trong thc t, ngi ta thng s dng kim vi x l CO2 thu c sn phn bt nh c gi tr kinh t v an ton cho mi trng.

97

CHNG 6. M S S CNG NGH X L KH THI T CNG NGHIP C TRNG [26,28,29] Trong thc t, kh thi ca mt nh my nhit in, mt nh myt rc, mt l luyn kim hay mt nh my sn xut phn bn, lun lun l mt hn hp bi v cc loi kh thi. Chnh v vy m khi xy dng mt phng n x l c th cho mt i tng no , t tng ch o phi p ng c mt s tiu ch cn thit nh sau: 1.Phi la chn c cc cng ngh x l ph hp v ti u nht 2.Kt hp c cng nhiu cng tt cc i tng cn x l x l trn cng mt cng ngh hay/v cng mt thit b. 3.Chi ph xy dng v vn hnh l ti thiu. 4.Cc sn phm sau x l phi khng c hi v phi kim sot c. Nu ti s dng hoc s dng c vo vic khc th cng c u tin. 5.Dy chuyn hot ng phi c an ton v tin cy cao. T nhng l do trn, sau y s nghin cu mt s dy chuyn x l kh thi s dng cc cng ngh hin i, c tnh u vit cao v ang hot ng ti mt s nc pht trin nh Nht bn hay v M. 6.1. THIT B X L BI BNG LC TI Cu to ca thit b gm 3 phn chnh: 1. Bung lc, 2. H thng ng ng, 3. H thng qut ht v 3 b phn ph l h thng dn kh nn lm vic theo ch thi xung, h thng ng m ca dn kh thi vo ca hai ngn trong bung lc lm vic trn c s chnh lch p sut bn trong v bn ngoi ti lc v ca ly bi ra theo ch lin tc. Bung lc c chia lm hai ngn ging ht nhau v mi ngn u c chia lm 3 tng. Tng trn cng l khong khng gian ni vi h thng qut ht thng ra ng khi qua ca lm vic trn v b tr nhng u thi kh nn vo trong cc tic. Tng gia l ni b tr nhng ti lc c nh l trn nhng khung bng thp. Tng di l ni phn phi kh cha bi vo cc ngn thng qua ca lm vic di v sau i vo cc ti lc. Vn hnh thit b: Hai ngn ca bung lc lm vic thay i nhau. Kh thi v bi c dn vo theo ca di v trc ht i vo ngn th nht. Sau mt thi gian lm vic nht nh, khi cc ti lc ngn th nht b ph mt lp bi dy lm tn hao p ln th h thng ng m ca lm vic s t ng ng ca lm vic ca ngn ny li v m ca lm vic ca ngn th hai. Trong khi ngn th hai lm vic th h thng kh nn s thc hin nhng t thi xung kh vo ming ti y bi bm trn mt ngoi ca ti

98

ra. Khi cc ti c lm sch, chng sn sng lm vic trong chu k tip theo. H thng ng ng ni c bt u t bung lc ti, qua qut ht, ng gim thanh v x kh sau x l ra ngoi. Kh nn thng c duy tr p sut cao v lm vic theo ch thi xung nn t c hiu qu lm sch bi cao.

Bung lc bi

Hnh 6.1. Thit b lc ti x l bi kim loi nng ca hng NAVEC (Matsushita Seiko Engineering Co., Ltd., Nht Bn) B phn gom v ly bi ra lm vic theo ch lin tc gm mt ng vn chuyn bi theo kiu vt v tn v mt ca tho bi. Ca tho bi c b tr mt trc cnh kh quay u nhm mc ch va cn bi ra va ng vai tr nh mt van kn gi khng cho kh t bn trong khng lt ra ngoi. Thit b ny lm vic rt hiu qu v c p dng rng ri c bit x l bi kim loi nng. Thit b lc p ng c yu cu kht khe v hm lng kim loi nng trong kh thi cng nh trong mi trng lm vic.

99

6.2. THIT B LC TI X L KH THI (KH L) CHA SO2. H thng x l kh l cha bi v SO2 kiu lc ti lm vic trn nguyn l bin kh SO 2 thnh CaSO3/CaSO4 dng bi v x l chng cng vi bi trong kh thi bng lc ti. Thit b gm ba b phn chnh: (1) B phn trao i nhit bng h thng phun nc lnh ng thi ha m kh SO2 v to phn ng gia SO2 m vi vi bt - Ca(OH)2 dng bt - to thnh CaSO3, (2) Bung lc ti v (3) B phn tn thu v ti s dng CaSO4.
ng kh ra Ca(OH)2 ng chia kh ng khi

Kh thi

H2O Bng ti B sy kh
Lc ti ph

Silo ximng

Silo tro

Phu m

B to vin My trn

Bm bi Bng ti Thng cha

Hnh 6.2. H thng x l bi, kh SOx, v cc kh, hi axit khc bng con ng kh s dng thit b lc ti hiu sut cao. (Nihon Spindle Mfg. Co. Ltd, Japan)

100

Hot ng ca h thng x l nh sau: Kh l trc tin c dn vo thp lng nhng bi ln, ng thi lm ngui v lm m kh l bng nhng tia nc lnh phun vo trong thp. Ti y mt phn bi c kch thc ln c lng xung y thp v c ly ra ngoi bng h thng bng chuyn dng vt v tn ti b phn thu gom. Kh m sau c dn sang bung lc ti. Trn ng i, vi bt c phun mt cch nh lng vo dng kh. Kh SO2 m (thc cht l nhng ht sol H2SO3) lp tc tc dng vi Ca(OH) 2 to thnh CaSO3 dng rn. Nu trong dng kh c mt O2 th canxi sunphit s chuyn thnh canxi snnphat (thch cao). Ti bung lc ti, bi (tro bay) v cc ht mui canxi va hnh thnh s c gi li; kh sau x l s c dn ra ng khi. B phn lc ti hot ng tng t nh h thng lc bi kim loi nng trn hnh 6. 2. Bi t bung lc ti v t thp lm ngui ban u c thu gom li v ti s dng trong sn xut xi mng. H thng x l c b tr cc ng chia kh nhm mc ch p ng cho nhng c s lm vic khng lin tc hoc kh l c hm lng kh thi c hi khng n nh, tng, gim theo chu k sn xut. Trc khi i ra ng khi kh b ngui khng th t bay ln theo ng khi; do n c t nng li hoc dng qut y y ra ngoi. 6.3. H THNG X L KH THI TNG HP (SO2, NOX, HCL, HF) BNG PHNG PHP LC TI KH M hnh dy chuyn x l trn hnh 6.3. c s dng x l kh thi t cc l t rc v t cc nhin liu ha thch Nht bn v cc nc chu u khc. Rc lun lun c thnh ph rt phc tp v khi t s sinh ra n cc loi kh c khc nhau nh SO x, NOx, HCl, HF...Tuy nhin cc kh ny u c th tc dng vi vi bt to thnh cc sn phm bi kh hu nh khng c v c th thu li bng phng php lc ti nh trn m hnh hnh 6. 3. Dy chuyn bao gm nm phn chnh: (1) l l t v b phn tn dng nhit sinh ra trong qu trnh t; (2) l b phn lm ngui v ha m kh l; (3) l bung lc ti thu bi, bi mui; (4) l b phn cp vi bt v ha cht ph tr v (5) l b phn qut y kh ln ng khi. Qu trnh vn hnh ca m hnh ny nh sau: Kh l c nhit trn 1000 C trc tin c tn dng to ra hi nc qu nhit s dng cho cc qu trnh sy, si m, quay tuc bin... Nhit ca kh l sau vn cn cao s c s dng sy nng khng kh trc khi thi vo l trong bung t trnh lm mt nhit, tit kim nng lng. Tuy vy trc khi i vo thit b lc ti, kh l vn tip tc c lm ngui bng cc tia nc lnh. Vic lm ngui bng nc lnh y cn c mt tc dng quan trng mang tnh quyt
o

101

nh i vi hiu qu ca qu trnh x l l bin cc kh c k trn thnh cc ht sol axit. Trn ng i n bung lc ti, kh thi c tip xc vi vi bt dng bi c phun vo bng bm thi t cc silo. Chnh nhng ht Ca(OH)2 dng kh c s tc dng vi cc sol axit mi hnh thnh to thnh cc ht bi mui. Bung lc ti hot ng nh trnh by trong mc 6.1. v thit b x l bi kim loi nng (hnh 6.1). Qua bung lc ti kh thi c lm sch; sn sng thi an ton ra ng oi; song do nhi ca t dng kh xung qu thp khng th t bay ln ng khi c cho nn cn c sy nng hoc dng qut y.
B ha hi nc Nc lnh B lc ti Thng cha vi/ho cht ng khi

Qut Tro thi

Bi thi Bm vi/ ho cht

L t

Hnh 6.3. H thng x l kh l bng thit b lc ti kh (X l SOx, NOx, HCl, HF) (Hitachi Zonsen Corporation, Osaka, Japan) Hiu qu x l i vi cc loi kh c t l t thi ra ph thuc rt nhiu vo nhit ca kh khi phn ng vi canxi hydroxit. Nhng kt qu nghin cu v nh hng ca nhit phn ng i vi hiu qu x l SO 2 v HCl cho thy nhit cng cao th hiu qu x l cng km. Vi nhit trn 200oC, hiu qu x l gim rt nhanh. Hiu qu x l t trn 95% khi nhit phn ng nh hn hoc bng 150oC. Hin tng ny c th chu nh hng ca nhiu yu t khc nhau nhng quan trng nht l cn bng ca phn ng hp nc to axit v phn hy ca sn phm axit va to thnh ti to cc phn t oxit axit khan. Cc oxit axit khan u nh khng phn ng h vi Ca(OH)2 kh. SO2 + H2O <=> H2SO3 <=> 2H+ + SO3HCl <=> H+ + Cl102

R (%)

R (%)

T l Ca(OH)2 : HCl

T l Ca(OH)2 : SO2

Hnh 6.4. nh hng ca nhit n hiu qu x l kh l Bn cnh t l mol gia Ca(OH) 2 v SO2 cng nh HCl cng nh hng n hiu qu x l. Lng Ca(OH)2 cung cp vo d so vi t lng s cho hiu qu cao hn; song n s phi x l tip theo cng vi qu trnh oxi ha canxi sunphit thnh canxi sunpht. nh hng ca nhit phn ng v t l mol ln hiu sut x l c minh ho trn hnh 6.4. Dy chuyn ny cng x l c nhng cht c khc pht sinh khi t rc nh dioxin, thy ngn... khi s dng nhng ha cht ph gia km theo. 6.4. H THNG X L KH L C TRANG B THP PHN NG Ba thit b x l kh l bng phng php lc ti k trn (6.1. n 6.3.); vi bt u c cp vo trn ng ng dn kh thi ti bung lc ti. Bin php ny tuy n gi hn song nu lu lng kh thi ln s dn n thi n gian tip xc gia cc cht tham gia phn ng qu ngn, c bit li din ra gia pha kh v pha rn, cho nn khng phn ng xy ra hon ton. Qu trnh x l kh kim sot v hiu qu khng cao v km n nh. khc phc nhng yu im ca ba h thng thit b ni trn, h thng m t trn hnh 6.5 ca NKK Corporation (Nht bn) cho trang b thm thp phn ng. Kt qu l hiu sut x l tng ln r rt. Cc kt qu th hin trn hnh 6.6. cho thy i vi kh HCl chng hn, khng nhng hiu sut x l cao m t l phn mol ca canxi hydroxit trn kh (HCl) cng gim ng k. Qu trnh vn hnh ca h thng x l c th tm tt nh sau: Kh thi cha kh HCl, SO2 hay kh l, sau khic lm ngui v lm m c dn
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vo thp ph ng theo ca di phn y thp v i ra theo ca trn n phn u thp. Bt Ca(OH)2 t silo c cp vo thp bng bm thi xung. Qua b phn phn phi, vi bt c trn u trong thp cng vi kh l. Thi gian lu trong thp ln to iu kin cho phn ng trung ha xy ra hon ton hn. D ng kh sau c dn vo bung lc ti. B phn lc ti v cc phn tip ni sau hot ng tng t nh trong cc h thng x l trnh by nhng phn trn.
ng khi Silo cha viv HC Thit b lc ti

Thp phn ng B iu ha tro

Qut b tr Thi Qut thi Kh thi Thng cha tro

Hnh 6.5. H thng x l kh c trang b thp phn ng (NKK LIMAR, Envir. Industries Engineering Division)
H% 140oC 160oC 96 170oC 94 180oC Ca(OH)2

98

92

190oC

90 0 1 2 3 Ca(OH)2 / HCl

Hnh 6.6. S ph thuc gia hiu sut x l kh HCl vo nhit v t l mol ca canxi hydroxit v HCl
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Bng 6.1. Kt qu s dng h thng x l 6 trn 31 c s p dng No. 1 2 3 4 5 6 Cng sut Lu lng kh x l (t/24h) thi (m3/h) 400 300 115 200 150 150 151.000 97.000 67.000 67.000 53.000 53.000 HCl u vo (ppm) 1100 800 1000 1000 800 1000 HCl u ra (ppm) <15 <100 <25 <50 <50 <20 Nm lp t 2001 1997 1995 1995 1994 1998

c im ca h thng ny l n gin v hiu qu; thch hp cho vic x l kh thi c cha kh HCl v SO2. i vi cc c s sn xut hay s dng HCl th h thng ny rt ph hp v hiu qu, v kh thi c nhit khng cao. Trong tr ng hp lung kh c cha oxi trn 12%, n u ch s dng vi bt, th ch c th gim nng HCl xung n 40 ppm. Nu mun gim nng kh HCl xung 25 ppm, th cn thit phi b sung thm cc ha cht ph gia khc. Bng 6.1. di y lit k mt s thng s ca cc c s s dng h thng x l ny. 6.5. H THNG X L KH THI BNG THP M T H thng x l ny do cng ty Kyowa Kako Nht bn sn xut v nm bn quyn. H thng c lp t gn nh v c nhiu kch c khc nhau ph hp vi cc c s sn xut ln, nh. Ty thuc vo mc ch x l loi kh thi no m ta c th chn ha cht dng hp th ph hp. Chnh v linh hot ca thit b m n c s dng khng nhng x l cc kh c nh SO2, NOx m cn p dng c cho qu trnh x l cc kh v hi kim, axit khc. Trong mt s trng hp, h thng ny cn c th s dng x l mi i vi mt s cht hu c. H thng x l bao gm ba phn chnh: (1) B phn ghp ni vi ngun pht thi. B phn ny gm cc ng ni mm, van iu chnh lu lng kh thi v qut thi kh (cc m t 7 n c 10). (2) Thp m gm cc phn y thp, thn thp v ming thp. y thp c ni lin vi b cha cht lng hon lu dng hp th cc cht kh cn x l, c b tr ca x (bn) v ca trn. Thn thp c b tr ca dn kh thi

105

vo pha di, sau n cc tng m tng kh nng tip xc. Pha trn cc tng m l dn phun cht lng lm nhim v hp th kh v hi c.
4

Kh thi

Nc thi Nc cp

Hnh 6.7. S thit b x l kh theo ng t s dng thp m

Ch thch: 1. Thp m, 2. B cha hi lu, 3. Bm hi lu, 4. ng khi, 5. Ca thi, 6. Ca chy trn, 7. Qut thi kh vo, 8. ng ni mm, 9. Van l, 10. Nm ly mu, 11. Thng cha ha cht, 12. Bm cp ha cht.

ng khi Thp m Bm hi lu Qut thi kh

Ca thi trn

B hi lu

S mt ct ngang

S mt ct dc

Hnh 6.8. S mt ct ca thit b thp m

106

Bng 6.2. Mt s lnh vc p dng h thng thp m t Kyowa.

Kiu p dng p dng v iu kin Loi kh thi -Khi v hi axit sunphuric -Hi axit clohydric -Hi axit cromic -Khi v hi xt, natri xyanua, amoniac... Loi nh my, x nghip Pht tinh t b mt cc -Cc c s m, ty bnh cha axit. ra bng axit, Nhit cht lng ln -Cc nh my sn ti 80oC. xut v s dng axit. Pht sinh t cc thng -C s m en, cha, bng ti cn ra -C s x l b mt axit... Nhit cht kim loi, lng ti 80oC. -Phng th nghim Pht sinh t cc thng cha, bng ti cn ra axit... Nhit cht lng ti 80oC. Pht sinh t cc thng cha, cc thng phn ng, cc l t ... -Cc nh my ha cht v thc phm, -Cc nh my si cng nghip, -Phng th nghim... -Cc nh my ha cht -Cc x nghip dc -Cc nh my thc phm, -Cc phng th nghim Ni pht sinh

p dng c iu kin

-Hi v kh H2S, -Khi v hi axit phot-phoric, axit acetic...

-Khi v hi axit sunphuric, -Hi axit clohydric, -Hi cromt

Hi axit nitric, kh NOx ho trn cng cc kh k trn Nhng i tng c bit Hn hp cc kh k c clo nguyn t, hi axit nitric, NOx v HF

-Cc c s nhng Pht sinh t b mt cc thng cha nhit nhum kim loi, -Cc c s ty trng thng. kim loi Pht sinh t b ty -Cc nh my ha ra, thng cha, cc l cht t... -Cc nh my sn xut kim loi nh, -Cng nghip thy tinh -Cc c s Nhng, nhum kim loi

Dn phun c ni vi bm hon lu bm cht lng t b hon lu v phn ha cht b sung t thng cha. Trn cng l b phn chn sol. Ming thp l ni cho lu ng kh x l i ra v c ni trc tip vi ng khi (gm cc mc t 1 n 6).
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(3) B phn cp ha cht gm thng cha ha cht (11), bm nh lng ha cht (12), cc van iu khin v h thng ng dn. Khi vn hnh, kh thi c qut thi vo ca di, i qua tng m, dn phun v ra ngoi theo ca (6). Ton b phn ng gia kh c v tc nhn hp th xy ra y khi kh thi gp dung dch ha cht do bm hon lu cp cho dn phun. Sau nhng khong thi gian nht nh, khi nng huyn ph t ti mt gi tr nht nh; hoc nng tc nhn hp th (ha cht) xung qu thp khng cn kh nng x l na th dung dch hon lu c x v a i x l tn thu. Phn nc (dung mi) chy trn hoc sau x l tch huyn ph c quay vng tr li thng cha pha ha cht hoc thi i. Bm ha cht c vn hnh bng mt h thng iu khin t ng ni vi b cha dung dch hon lu iu chnh nng ha cht ph hp cho tng cng on x l. H thng x l ny c p dng kh rng ri. Bng 6.2. thng k mt s ng dng c trin khai cho hiu qu tt. 6.6. H THNG X L KH L CHA SO 2 BNG HUYN PH CANXI CACBONAT Nguyn l lm vic ca h thng ny l cho huyn ph canxi cacbo nt tip xc vi kh thi cha SO2 trong thp hp th. Canxi sunphit to thnh s c oxi ha bng oxi khng kh tr thnh thch cao. Phng trnh phn ng ha hc tng th xy ra nh sau: CaCO3 + SO2 + 2H2O + 1/2O2 = CaSO4.2H2O + CO2 Kt ta thch cao hnh thnh ngm hai nc c tinh th tng i ln nn d tch khi nc. Sau khi tch nc, thch cao c s dng lm ph gia xi mng hoc trong xy dng. H thng x l ny c lp t cho cc khu cng nghip, c bit l cc nh my nhit in. Ngoi h thng tin x l nh lc bi v x l bng tnh in cng vi b phn trao i nhit lm ngui kh thi ra th h thng x l kh l y bao gm ba b phn chnh l b phn thp hp th - oxi ha, b phn cp huyn ph canxi cacbont v b phn thu hi thch cao. Thp hp th - oxi ha c phn y ng vai tr nh b cha dch hi lu c trang b cc my khuy trnh s sa lng ca huyn ph canxi cacbont v ca thi khng kh cp cho phn ng oxi ha canxi sunphit thnh canxi sunphat. Phn gia thp l vng hot ng. Ti y huyn ph canxi cacbont c phun t trn xung v kh thi cha SO 2 c thi t pha di ln chng c th tip xc vi nhau mt cch hon ho. Phn u thp c trang b b phn chn sol v ng ni ra ng khi. Nh ni phn trn, kh thi t l t i ra trc khi vo thp hp th - oxi ha, n c lm
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ngui bng trao i nhit vi kh i ra t thp hp th - oxi ha. Qu trnh ny lm cho kh sau x l i ra nng ln v t y c ra ngoi theo ng khi. Bm hi lu lm nhim v bm dch cn cha canxi cacbonat cha phn ng ht ln dn phun hoc bm huyn ph thch cao sang b phn thu hi.
EP Van iu ha

ng khi
Thng cha bt CaCO3

L t

Qut B trao i nhit B chn sol My ly tm

Khng kh

Bm hi lu B lng Thch cao

Thp phun hiu sut cao

H thng oxi ha v hp th

H thng thu hi thch cao

Kh sch ra B chn sol Dn phun Kh thi vo

Cc dng loa phun ma

Tm chn My khuy

Cu trc ca thp phun oxi ha - hp th

Hnh 6.9. H thng x l kh thi cha SO2 thu hi thch cao

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B phn cp huyn ph vi gm silo cha canxi cacbont; silo ny cp u n bt vi cho b to huyn ph v t bm cp cho thp phn ng. B phn thu hi thch cao gm my ly tm dng tch nc khi thch cao. Thch cao m c ly ra ti s dng, cn nc lc th thu hi quay vng tr li ho huyn ph vi. u im ca h thng x l ny l: 1. Nng SO2 khng i hi n nh m c th dao ng ln; nhng hiu qu x l SO2 vn t trn 90%. 2. Sn phm ph l thch cao c th ti s dng lm nguyn liu cho sn xut xi mng hoc dng trong xy dng. 3. vi l mt nguyn liu r tin, sn c c s dng nh mt tc nhn hp th rt hiu qu i vi SO2. 4. Thp hp th n gin, ng vai tr t hp ca thp m, hp th v oxi ha. Hn na n cng c th x l c c bi trong kh l vi hiu q u loi b cao. H thng x l ny c lp t cho cc nh my nhit in c cng sut t 100 MW n 1000 MW ti Anh, Trung quc v Tip khc. 6.7. H THNG X L KH L CHA SO2 S DNG MANH HYDROXIT Cng ngh x l SO 2 trong kh lt bng nhin liu ha thch s dng manh hydroxit c pht trin t hn 20 nm trc. Nguyn l ca cng ngh ny l phn ng ha hc gia SO 2 vi huyn ph manh hydroxit xy ra trong thp m. SO2 + Mg(OH)2 = MgSO3 + H2O MgSO3 + 1/2O2 = MgSO4 Trong nhng nm gn y cng ngh manh hydroxit rt thnh hnh trn th gii do hiu qu x l SO 2 ca n cao i vi kh thi ca cc l hi t bng diezen, du FO v than cm. Nhng kiu l hi ny cho nng lc pht in cao. Sn phm MgSO4 sau khi tinh ch c gi tr thng phm cao. Quy trnh hot ng c th tm tt nh sau: Kh l hi trc khi vo thp hp th c lm ngui trong thp tin x l bng cc tia nc mt cung cp t ngoi vo hoc tch mt phn t dng bm hi lu. Trong thp hp th, kh l c thi vo theo chiu t di ln; sau khi tip xc hon ho vi huyn ph manh hydroxit kh sch i qua thit b tch sol s i ra ngoi theo ng khi. Huyn ph manh hydroxit c cung cp t thng cha vo b iu ha, trn ln vi dch hi lu i ra t thp hp th. Ti y hn hp c
110

kim tra pH v nng kim ri c bm (P) bm vo h thng phn phi phn trn ca thp hp th. Dung dch hp th s chuyn ng theo chiu t trn xung. Manh sunphit hnh thnh sau phn ng vi SO2, mt phn c oxi ha thnh sunpht ngay trong thp hp th bng oxi khng kh thi vo t y thp. Dng khng kh ny thi vo va cp oxi ng thi va ng vai tr l ng lc khuy trn hn hp huyn ph. Hn hp ny nh k c bm sang thp oxi ha. Ti y lng HSO 3- hoc Mg(OH)2 d c trung ha, sunphit c oxi ha hon ton thnh sunpht. Qu trnh hiu kh thp oxi ha cng c tc dng lm gim gi tr COD xung mc an ton. Dung d sunpht sau c dn sang h thng lng, tch nc ch thu manh sunpht th. Nc ci c dn tr li thng cha pha Mg(OH)2 hoc thi an ton ra ngoi.
Kh sch

Mg(OH)2

Nc

Kh thi Thp lm lnh Khng kh Thp kh sunfua dioxit MgSO4 Thp oxi ha

Nc lc

Hnh 6.10. S h thng x l kh thi cha SO2 s dng Mg(OH)2

Ghi ch: P: Bm, PH: B iu chnh pH, LC: B kim tra thnh phn dung dch, M: My khuy, F1: Van phn dng, P1: Thit b tch nc.

Nhng c trng u vit ca cng ngh ny l: 1. Gi thnh ca h thng cp ha cht thp hn so vi cng ngh s d ng xt v ng lng mol ca phn ng thp lm gim chi ph vn hnh.

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2. H thng d iu khin v khng nguy him v ha cht s dng ch c kim nh t c hi v t n mn thit b hn so vi xt. 3. Nguyn liu s dng x l c nhiu trong nc t bin (ng mui) d dng ly c khi cho tc dng vi vi ti. Chnh v th m lun tho mn c ngi s dng vi gi c t bin ng v s cung cp n nh. 4. D bo dng, khng bm cn nh trong cng ngh s dng huyn ph vi v mui manh sunphit v sunpht ha tan tt hn nhiu so vi manh hydroxit cng nh canxi sunphit v sunpht. 5. Trnh c nhng tc ng kh chu do CO 2 ng cn (nh trong cng ngh s dng sa vi), v dung dch manh long phn ng vi SO2 trong mi trng gn nh trung tnh. Chnh v th m thp hp th c th vn hnh hiu qu hn theo kiu thp si bt. 6. Manh sunpht thu c qua tinh ch n gin s thu c manh sunpht sch c gi tr thng phm cao hn thch cao. Do nhng c im u vit k trn m cng ngh x l kh l hi bng manh hydroxit hin nay c a chung ti nhiu nc trn th gii. 6.8. CNG NGH X L TRC TIP SO2 V NOX TRONG L HI (CA HNG HITASHI ZONSEN) tng khi ngun cho nhiu nghin cu v cng ngh x l trc tip SO2 ngay trong l hi trong mt thi gian di l phun trc tip bt vi hay lmit vo trong l t loi tr kh SO2. nhit trn 1000oC trong l, v l thuyt m ni th s xy ra cc phn ng sau: CaCO3 CaO + CO2 CaO + SO2 CaSO3 CaSO3 + 1/2O2 CaSO4 (1) (2) (3)

Nhng qua nhi th nghim cho thy phn ng (2) v (3) xy ra u khng hon ton nhit cao nh vy. Hiu qu x l SO 2 ti a khng vt qu gii hn 60% mc du s dng t l mol Ca gp ba ln S. iu ny c l gii phn no trong cc cng ngh trnh by cc phn trn. Hng Hitachi Zonsen ng dng v nng cao cng ngh ny bng cch ng thi x l c NO x trong kh l v t c hiu qu c v cng ngh ln kinh t. x l NOx hng trang b thm h th ng phun dung dch ure (NH2-CO-NH2) vo trong l ng thi vi bt vi (nh m t trn hnh 6.11.). Phn ng kh NO x xy ra khi n tip xc vi ure nhit cao nh ni trn.
112

Dung dch ure

B lc ti

Kh nn

Nc Nhin liu t l Thp lm ngui

Tro bay

ng khi

Nc lm ngui Khng kh nn

Hnh 6.11. H thng x l trc tip SO2 v NOx trong kh thi c nhit cao s dng CaCO3 v ure NO + NO2 + (NH2)2CO 2N2 + CO2 + 2H2O (4)

Lng nc ca dung dch ure v lng nc gii phng ra t phng trnh (4) to iu kin cho phn ng (2) v (3) xy ra hon ton hn. Kt qu m hng ny thu c vt qu s mong i ca h. Bng cch ny SO2 x l c ti 90%, NO x c ti 80% mc du nng ca cc kh ny trong kh l khng cao. Mt khc cng ngh x l ng thi SO 2 v NOx cng h thp t l mol gia canxi v lu hunh xung ch cn l 2,0 v gia ure v nit xung cn 1,5. Qu trnh vn hnh ca cng ngh x l trc tip SO 2 v NOx c th tm tt nh sau: Bt vi hay lmit c kch thc mn 1-2 m v dung dch ure c phun trc tip vo trong l ti vng c nhit cao (1200 1250oC). Kh l i ra trc tin c dn qua h thng trao i nhit (GAH) sy nng khng kh; sau i vo thp lm ngui bng nhng tia nc lnh ri vo bung lc ti. Bi v cc mui canxi c gi li, thu hi ti s dng; cn kh sch sau x l th c qut tng cng y ra ngoi theo ng khi. Trc khi kh thi v bi i vo bung lc ti, chng c b sung thm oxi t khng kh oxi ha hon ton mui canxi thnh canxi sunpht. Bung lc ti hot ng tng t nh trnh by cc phn trn.
113

Cng ngh x l ca Hitachi Zonsen c nhng u im ni bt l: 1. Gi thnh thit b thp v tiu th in nng khng cao, 2. Khng c nc thi, 3. Khng c mui bm trn ng khi 4. D dng ghp ni vi cc l hi hin hnh. So snh vi cng ngh x l bng xc tc chn lc ghp ni vi thp m t ng thi x l NOx v SO2 th cng ngh ca Hitachi Zonsen hn hn v cng ngh v gi thnh tnh trn 1 kWh. Bng 6.3. So snh gia cng ngh x l trc tip ca Hitachi Zonsen vi cng ngh xc tc chn lc ghp ni vi thp m t (SCR-FGD).
Ch tiu

CN

Qu trnh cng ngh Hiu sut: -Loi SO2 -Loi NOx Gi thnh -Thit b -Vn hnh Ghi ch:

Cng ngh SCR - FGD hin hnh BSCRBFFGD S (EP) < 90%, (Ca/S=1,05) < 80%, (NH3/NO=0,85) 1,00 USD/kWh 1,00 USD/kWh B k hiu l l hi BF l lc ti S l ng khi

Cng ngh mi ca Hitachi Zonsen BCBFS

80%, (Ca/S=1,5) 85%, (Ure/NO=1,5) 0,14 USD/kWh 0,40 USD/kWh

90%, (Ca/S=2,0) 85%, (Ure/NO=1,5) 0,15 USD/kWh 0,45 USD/kWh

C k hiu l thp lm ngui EP l lc tnh in FGD l x l SO2 bng thp m t

SCR l x l NOx bng xc tc chn lc theo ng kh. 6.9. CNG NGH X L KH THI CHA NOX S DNG XC TC CHN LC (CNG NGH SCR) Trong kh thi t cc l t nhin liu ha thch, t rc..., lun lun cha mt lng kh nit oxit nht nh. Qu trnh x l ng thi lu hunh dioxit v nit oxit lun gp mt kh khn v hiu qu x l ring phn i vi NOx. ci thin vn ny, mt s cng trnh ra i ch yu da vo tnh cht oxi ha kh ca cc hp cht a ha tr ca nit. c bit l phn
114

ng ca nit oxit vi amoniac hay ure to ra kh nit, nc hay cacbonic nhit cao hay khi c mt ca cc cht xc tc chn lc. 4NO + 4NH3 + O2 = 4N2 + 6H2O NO + NO2 + 2NH3 = 2N2 + 6H2O Hay NO + NO2 + (NH2)2CO = 2N2 + CO2 + 2H2O (NH2)2CO + H2O => 2NH3 + CO2 2NH3 + 2NO + 1/2O2 = 2N2 + 3H2O
NH3

Tng xc tc

Kh l

Kh sch

Hnh 6.12. S nguyn l ca qu trnh x l NOx bng xc tc chn lc Trong thc t, s c mt ng thi ca NO x v amoniac hay ure trong mt khng gian nht nh, nu nhit ca hn hp cao trn 800oC hoc c bit nu c mt ca cht xc tc ph hp th phn ng kh NOx thnh N2 v nc xy ra. Phn ng kh nhit cao khng c mt xc tc thng l khng trit v rt kh kim sot (phn ng 1). Hiu sut kh NO x ch t klhong t 30 n 70%. Mt khc nu s dng ure nhit cao th ng thi cng xy ra phn ng phn hy ca ure. Nu qu trnh phn hy to thnh NH3 (phn ng 2, thng l nhit khong 800oC) th phn ng kh tip theo l thun li; cn sn phm phn hy nhit ch yu l nit (phn ng 3) th hiu sut x l s gim mnh, c bit khi nhit trn 1000oC. Trong dng kh thi t cc l hi lun lun cha bi. Chnh bi l mt yu t gy tr ngi rt ln i vi hot ng ca b mt xc tc. Vic x l bi trc khi x l NOx lm tng hiu qu x l ca SCR; song cu to ca cc tng xc tc s ng vai tr ch yu nng cao hiu sut x l v tui th ca thit b SCR.
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Cc tng xc tc trong thp x l (hnh 6.13) thng c cu to thnh nhng ng xp st nhau nh hnh t ong hoc nhng tm hnh sng xp xen k v i nhau. Cu trc kiu nh vy rt thng thong, bi t b gi li v gy ra gim p thp. Vi cu trc ny kt hp vi s iu chnh dng kh thi vo thp x l theo ch xung v vn tc ln th hu nh trnh c s bm bi trn cc tng xc tc.

10

2 8 9

5 7 7

6 Hnh 6.13. S c trng ca mt thp SCR

Ghi ch: 1. ng kh l vo, 2. B phn phi kh l, 3. Ngun cp amoniac, 4. B iu khin lng cp amoniac, 5. B phn tch hm lng NOx, 6. ng kh sch ra, 7. Mt modul xc tc, 8. Qut thi kh, 9. Li phun amoniac, 10. u thi mui ra khi xc tc
116

Cng ngh x l NO x bng xc tc chn lc c trin khai p dng cho rt nhiu ngun kh thi t vic t cc nhin liu ha thch - than v du ho - c nng NO x kh cao. Th d nh l hi ca cc nh my nhit in, tuc bin kh, l nung xi mng, cc l t bng du diezen, du FO...Bng 6.4 v 6.5 di y cho bit mt s thng s v x l NO x bng cng ngh SCR ca mt vi loi kh l.
Bng 6.4. Hiu qu x l v tui th ca thit b x l NOx loi nh.
CC D LIU TUC BIN KH L T DIEZEN L T DU FO

Thnh phn kh thi -NOx (ppm) -O2 (%) -SOx (ppm) -H2O (%) Nng lc x l -Nhit kh thi (oC) -Lu lng (m3/h) -Hiu sut x l NOx (%) -Tui th xc tc (nm)

30 - 150 7 - 15 0 - 30 10 180 - 450 5000 - 20000 > 90 3-6

800 - 1500 10 - 13 20 - 500 10 300 - 480 5000 - 10000 > 90 2-3

100 - 200 1-4 100 - 1500 10 280 - 400 5000 - 10000 > 80 3-6

Bng 6.5. Mt vi thng s x l NOx bng SCR ca cc c s ln C s Thng s Nhin liu Lu lng kh thi (m3/h) Nhit , (oC) 420 Nng NOx 250 (ppm) Hiu qu x l, (%) > 80 Babcock Hitachi K. K. Than 3.029.000 Nhit in Tokyo Gas - du 1.240.000 410 50 > 80 Luyn kim Sumitomo Du 90.200 330 965 90 IHI - SCR Co., Ltd. Du - than 10.000 3.000.000 200 - 600 150 - 450 60 - 95

c im u vit ca cng ngh SCR: 1. D kt ni, lp t v vn hnh 2. Gi thnh x l thp do nguyn liu r v xc tc d kim. 3. Hiu qu x l chp nhn c. 4. Khng gy ra nhim th cp 5. Ph hp vi hu ht cc loi l t s dng nhin liu ha thch. 6. C th kt hp vi x l SOx v bi.
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6.10. S X L BI CNG NGHIP BNG CNG NGH LNG TNH IN S trn hnh 6.14 v 6.15 l cc m ct ca mt thp lng bi tnh t in ca hng Sumiko Engineering (SMEC), Nht bn lp t cho cc khu cng nghip x l kh thi cha bi l lng, m v sol kh kh lng. tng hiu qu x l, cc in cc c lp t vi khong cch rng hn (0,4 - 0,5 m so v thp lng thng thng l 0,2 - 0,3 m). Chnh i u ny c i th tng hiu in th ln 80 - 100 kV (so v 30 - 60 kV cc thp lng i thng thng). Bn cnh so vi thp lng thng thng, kiu thp lng ca SMEC c gi in mnh hn, mt dng cao hn, sc ht bi v dng cc mnh hn, c kh nng x l c cc ht bi c kch thc ti 0,01 m (so vi 0,05 m) v c th x l bi trong kh thi ti sch 0,005 g/m3 (so vi 0,01 g/m3). Khong cch in cc rng hn cn to iu kin cho vic lp t cng nh lm sch in cc d dng hn. SMEC lp t c hai loi thit b lng tnh in kh v loi lng tnh in t. H thng lng tnh in kh c p dng cho cc c s nh luyn kim v cc c s c thnh phn kh thi tng t (nh s trn hnh 6.16). Vi h thng lng kh, kh thi t l luyn kim c nhit ti 1000oC sau khi qua thp lm ngui kh, nhit s gim xung khong 300oC c dn ngay vo thp lng bi tnh in. Ti y bi s c tch loi hu nh hon ton. Kh thi sau x l c qut b tr (IDF) y ln ng khi. H thng lng tnh in t c minh ho trn hnh 6.17. X l bi, SO2, SO3 v m H2SO4 t cc nh my sn xut axit sunphuric bng cng ngh lng tnh in t ca SMEC rt hiu qu. Kh thi c thnh phn nh trn, theo cng ngh ca SMEC, trc ht c x l bng dung dch kim trong thp hp th m. Ti y hu ht SO 2 c loi. Kh thi ch cn mt lng bi c kch thc nh v m do SO3 sinh ra. Nhng thnh phn ny s c loi b gn nh hon ton khi i qua thp lng tnh in t. Huyn ph bi t thp lng tnh in v thp hp th m s c x l tch nc quay vng hoc thi an ton. Ngoi kiu lng tnh in ci tin nh ca SMEC k trn, cn xut hin nhiu kiu ci tin khc nhm nng cao hiu qu lng bi v m, ng thi tit kim in nng gip gim chi ph vn hnh. Trong s ng k nht l kiu b tr hai dn in cc qung (l in cc hnh dy) v dn in cc gp l in cc tm ring bit trong cng mt bung mang li nhng im u vit nh sau: 1. Hin tng ti hp ion sau qu trnh ion ha kh xy ra, ht bi nhim in c bn cao nn hiu qu lng cao hn.

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22

21

Hnh 6.14. S mt ct ng ca mt thp lc tnh in 1. Kt cu gi , 2. V, 3. in cc gp, 4. m cc, 5. Trng vt, 6. B n nh m cc, 7. Thanh trt, 8. Ca phun nc di, 9. Ca phun nc trn, 10. Ca phun thi, 11. Bng chnh lu, 12. cp in, 13. Cht gi 14. Thanh gi ngang, 15. Tm , 16. ng rng, 17. Bung , 18. Qut kh sch ra, 19. Qut kh nng, 20. B hi lu. 21. ng kh thi vo, 22. ng kh thi ra.

Hnh 6.15. S mt ct ngang ca thp lc

119

B iu khin to v m Nc CN Oxi Qut

L luyn kim

Thp lm ngui

B lc in kh

ng khi

Hnh 6.16. S h thng lc tnh in kiu kh

Nc CN

-Kh thi c cha bi, SO2 v c SO3 trong sn xut axit sunphuric, -L t qung sunphua trong cng nghip luyn kim mu
Dch kim

Nc thi ra ni x l ti s dng hoc thi b

Bm hi lu Thp m Thp lc in t

Hnh 6.17. S h thng lc tnh in kiu t

2. Do cu trc hai dn v lp t in cc qung hnh ng gim ti a hin tng bi qun v nhiu trong qu trnh lng bi tch in. 3. Qung phng in hot ng n nh, bi lun c np in. 4. Trng sc rng c th to ra do s phng in ca in cc ng. 5. S thu ht mnh cc ht bi mang in tch tri du v pha in cc gp hnh tm lm tng hiu qu x l bi.
120

6. H thng lng tnh in ny c th gia cng bng nha trnh s n mn ca mi trng x l nu cn. Kiu ci tin th hai l to cho bung lng tnh in lm vic lin tc trong iu kin n nh m khng cn ngng hoc rung in cc gp ly bi ra khi in cc. thc hin c ny ngi ta thit k in cc gp chuyn ng nh mt bng ti lin tc trn hai con ln t pha trn v pha di iu khin bng dy xch. Bi tch in trong vng hot ng s c gom li trn b mt in cc gp. Khi phn in cc gp chuyn ng xung ti pha con ln di, bi s c ly ra bng mt i chi qut t hai pha ca in cc. Cng vi b phn phi kh thi u vo hp l, hiu sut x l bi ca thit b tng r rt v thit b lm vic rt n nh. Kiu ci tin ng k th ba khng nhm vo vic ci tin thit b m nhm tng hiu qu ca vic s dng in nng. l to ra nhng dng chuyn ng xung bng nhng xung in mt chiu. in trng kiu xung to ra s chuyn ng c qun tnh ca ht bi mt mt tit kim c in nng (ch cn mt na n mt phn ba so vi lng tnh in thng), mt khc trnh c s phng in kn to ra nh trong in trng lin tc. Bn cnh ci tin ny cn thu hp khng gian ca bung lng xung ch cn t mt n hai phn ba so vi bung lng tnh in thng thng v nng cao hiu sut thu bi (lng bi u ra ch cn vi microgram trn mt khi). 6.11. H THNG X L KH L KIU VENTURI IN NG (EDV) H thng venturi in ng c gii thiu ln u tin Php nm 1988. y l h thng x l loi bi v hp th cc kh c ng thi vi hiu qu cao. H thng ny bao gm cc b phn nh sau: 1. Thp kh bi. Trong thp, kh l c dn vo ca t trn u thp. T y nhng ht bi tng i ln v cc kh gy nhi nh i m HCl,HF c loi khi kh l tip xc vi dung dch tun hon c cha sa vi. Dung dch huyn ph i ra t thp ny c x l tch phn cht rn ra, phn dung dch c s dng quay vng tr li. Sa vi c b sung; nhng dung dch quay vng vn c th hot ng hiu qu khi pH ca n xung ti 1,5 n 2,5. Kh l sau khi tip xc vi dung dch quay vng, nhit ca n c h xung rt nhanh. 2. Venturi thu bi. Ti ng vo v ng ra ca venturi u c b tr nhng nm phun nc. Nhng ht bi nh v m ca nc cha loi ht c thp kh bi th s c loi ht y. Bi c khng ch sut trong qu trnh on nhit trong venturi v dc tch loi bng nhng tia nc nh

121

t cc nm phun. Tng t nh thp kh bi, nc thi t venturi cng c x l v quay vng.

Thp hp th Ni hi Thp kh bi B tch sol

Venturi thu bi

Module lng tnh in

L t rc

Nc CN

ng khi

Ca(OH)2
Nc thi ra ni x l

B sy kh

NaOH

Hi nc

Qut

Hnh 6.18. S h thng x l kh l kiu Venturi in ng (EDV) 3. Thp h th. Dung dch hp th y l dung dch NaOH trong p nc lnh c phun t trn xung. Kh thi sau khi ra khi h thng venturi s c dn vo theo chiu t di i ln. Do nhit ca dung dch hp th tng i thp cho nm m trong dng kh s c gim i ng k. Mt khc dung dch hp th l dung dch kim mnh, cho nn hu ht cc kh v hi c sinh ra qua qu trnh t, c bit l t rc sinh hot, tc dng c vi kim mnh u b gi li. 4. Modul lc tnh in t. Qua ba cng on x l trn, kh thi ch cn cha cc ht bi nh c micromet ca cc kim loi nng c hi, cc phn t c clo, cc hp cht v c, hi v khi mn khc. Cc phn t nh b ny qua b lc tnh in t s b gi li hon ton bi nhng mn nc mnh chuyn ng trong in trng. 5. B phn cp ha cht. Vi bt c ha tan trong nc thnh dung dch sa vi c nng khong 5 n 10% cung cp cho thp kh bi v b sung cho dung dch quay vng ca thp ny. Dung dch xt c nng 10% c pha t xt k thut dng cp cho thp hp th v dung dch quay vng ca thp hp th.
122

H thng x l kiu venturi in ng c nhng u im l: 1. Vng chc, n gin v i hi khng gian khng ln. H thng bao hm c hai chc nng l kh bi l hp th kh v hi c nh NOx, SOx, HCl, HF... 2. Cc nm phun cht lng c ci tin c th phun c cht lng dng bn v khng gy ra s c tc nghn, khng b n mn v t hng hc. 3. Sa vi v huyn ph canxi cacbonat c s dng cho nn gim c chi ph v ha cht (ch bng mt phn ba so vi chi ph s dng hon ton bng NaOH) 4. X l c c cc ht bi vi c micromet, k c cc phn t c clo, mui clo v c v cc phn t nh nht cha cc kim loi nng. 5. Kh thi sau x l p ng c nhng tiu chun kht khe nht hin nay v k c trong tng lai gn. 6. Nc thi hu nh c quay vng li hon ton, khng c nc thi. 6.12. S CNG NGH X L NG THI NO X V SOX S DNG PHNG PHP CHM TIA IN T. Nhng kt qu nghin cu v th nghim ca Chubu Electric Power Co., Inc. v Japan Atomic Energy Research Institute vo nh ng nm u thp k 90 ca th k trc cho thy di tc dng ca nhng chm tia in t c vn tc chuyn ng ln cc phn t kh v hi nc s b ion ha hoc tch thnh cc radical. Nh ng radical ny rt hot ng v lp tc chng c th oxi ha SO2 v NOx ri cc sn phm sau oxi ha hp nc to thnh cc axit H2SO4 v HNO3 tng ng. Nu trong mi trng c mt amoniac th cc mu i amoni s c hnh thnh. Qu trnh va trnh by cng l nguyn l c bn ca phng php x l ng thi SO x v NOx bng phng php chm tia in t. Trong qu trnh x l kh l s dng phng php chm tia in t th cng on x l bng chm tia in t ch ng vai tr loi b SO x v NOx. Cc cng on x l khc c phi hp lm sch trit kh l trc khi thi ra mi trng. Qu trnh x l theo cng ngh ny c m t mt cch n gin trn s hnh 6.19. Theo s ny th kh thi t l hi trc tin c loi bi khi n c dn qua b lng tnh in kiu kh; sau c lm ngui xung khong 110 oC bng trao i nhit vi khng kh ly kh nng dng cho vi c sy nng li dng kh thi lm ng lc y n ln ng khi. Kh thi tip tc c dn vo thp lm ngui bng nc lnh nhit ca n gim xung khong 60 n 70oC. y l nhit ph hp cho qu trnh x l SO x v NOx bng chm tia in t. S chuyn ha ng thi SOx v NOx xy ra trong ng qu trnh. Trn thnh ca ng qu trnh c nhng ca
123

s v t cc u in cc phng ra cc chm tia in t. Khi cc in t phng qua dng kh trongng qu trnh, cc phn ng to radical v to ra cc axit xy ra. N2,O2,H2O SOx NOx
L t

e-

OH.,O.,HO2. H2SO4 HNO3

OH.,O.,HO2. OH.,O.,HO2.

EP

Trao i nhit

ng khi

Nc lnh

H thng to tia in t

t nng li kh

EP

Lc ti

ng qu trnh Thp lm ngui, lm m H thng cp NH3 X l sn phm ph

Hnh 6.19. S x l kh l dng chm tia in t

ng thi vi qu trnh hnh thnh cc hi axit, amoniac c cp vo trong ng qu trnh. Ngay lp tc cc mui amoni c to thnh. H2SO4 HNO3
NH3 NH3

(NH4)2SO4 NH4NO3

Nh vy kh thi sau khi ra khi ng qu trnh trn 80% lng kh SO x v NOx c x l thnh cc bi mui tng ng. Bi mui c thu gom bng h thng bung lng tnh in v bung lc ti lp ni tip nhau sau ng qu trnh.
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H thng x l theo kiu ny c nhng c tnh u vit nh sau: 1. X l ng thi c SOx v NOx trong cng mt h thng. 2. Qu trnh x l hon ton l qu trnh kh, khng c v khng phi nc thi. 3. Lp t v vn hnh n gin, khng i hi khng gian ln. 4. Khng i hi chi ph cho xc tc kh NO x v gii quyt nhng phc tp do cc h thng nh thp m hay cc thit b khc to ra. 5. Sn phm ph l cc mui amoni cng nghip c gi tr cao trong vic s dng lm phn bn ha hc. 6.13. CC H THNG KH MI TRONG CNG NGHIP Mi th ng gy ra bi cc hp cht hu c d bay hi (Volatile Organic Compound - VOC) nn cng ngh x l mi ch yu c tp trung gii quyt cho i tng ny. Cc cht v c gy mi thng l cc cht c nh H2S, SO2, NH3... hay mt s cc cht hu c c tnh cht hot ng hoc c tan tt khc c nghin cu x l bng cc cng ngh trnh by nhng phn trn nh hp th, trung ha, oxi ha kh... c th cho x l mi (cc VOC) l cc cng ngh thiu hy, hp ph v ngng t c ng dng nhiu nht hin nay. Cng ngh thiu hy. Cc hydrocacbon d hi thng c nhit ng o thiu hy nm trong khong t 650 n 815 C v thi gian lu cn thit c h vo khong mt phn hai giy (t 0,4 n 0,6 giy). Cc sn phm ca s thiu hy ch yu l nc v CO 2. Trong mt s trng hp c bit c th cn c cc sn phm khc c tnh cht c hi th sau thiu hy cn x l tip theo. Trong kh mi bng phng php thiu hy tn ti hai cng ngh. Mt l kh trc tip bng nhit th nhit hiu dng cho qu trnh thiu hy phi ln hn 750oC. Hai l kh mi s dng xc tc oxi ha th nhit cn thit ch nm trong khong t 100 n 280oC. V mt thit b v lu trnh x l th hai cng ngh ny dng nhau. Nu l cng ngh s dng xc tc oxi ha th sau bung t c b tr thm cc tng xc tc. Xc tc y cho hiu qu cao l platin dng li. Hnh 6.20 l cc s cng ngh kh mi bng phng ph p thiu hy. Nguyn tc ca qu trnh l dng nhit ca ngn la t bng kh t cung cp nhit cho vng thiu hy. Hi hu c cn thiu hy s c dn vo vng ny. Qua thi gian lu trong ng l, hi hu c s b x l gn nh hon ton. Dng kh ra khi l thiu c nhit cao s c tn dng vo cc mc ch sn xut hi nc qu la, sn xut kh nng, nc nng, cp nhit cho

125

mi trng cn nhit cao v sy nng kh thi c cha mi cn kh trc khi dn vo vng t. Cng ngh t trc tip c nhng u im sau: 1. Hiu qu kh mi tuyt vi. Mc d nng ca cht gy mi dao ng nhng hiu sut kh mi vn lun lun t trn 99%. S 1

Hi nc (10-20 kg/cm3) Trao i nhit I

Khng kh nng Trao i nhit II

Kh sch

M t Nhin liu
Ni hi Nc mm Bm B cha nc mm

Khng kh Kh thi kh

S 2
M t Nhin liu
Trao i nhit I L thu nhit

Khng kh nng Trao i nhit II

Kh sch

Kh thi kh Khng kh

S 3
M t
Trao i nhit I

Khng kh nng Trao i nhit II

Khng kh nng Trao i nhit III

Kh sch

Nhin liu

Kh thi kh

Khng kh

Khng kh

Hnh 6.20. S ba kiu x l mi bng phng php thiu hy

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2. Kh nng ng dng rng ri. Hu ht cc cht hu c dng hi u p dng cng ngh ny c, k c cc hp cht gy ng c cho xc tc. 3. H thng thu hi nhit thi a dng v hu dng. i vi cng ngh thiu hy s dng xc tc oxi ha, tuy nhit trong l thiu khng cao song hiu qu x l vn t trn 99% i vi hu ht cc cht hu c d bay hi s dng thng thng trong sn xut. Hnh 6.21 di y cho bit hiu sut x l ph thuc vo nhit thiu hy ca mt s cht hu c thng gp. Nhit sinh ra trong qu trnh thiu hy tuy khng ln song n v c tn dng nh i vi cng ngh thiu hy trc tip. Bn n cnh thiu hy s dng xc tc oxi ha cn phi k n cc im u vit sau: 1. Hiu qu x l cao. Tuy h thng c lp t thm tng xc tc nhng s tn hao p sut hu nh khng ng k. Do nhit thiu hy thp cho nn trnh c nhng ri ro gy ra bi cc tc ng ca mi trng nhit cao. 2. Tit kim nng lng v vt liu mt cch ng k. y mun k n s tiu hao kh thp v vt liu ch to thit b i hi khng cao so vi t cng ngh thiu hy trc tip. 3.
H% 100
1
80

4 5 2 3 6

60

40

20 50 100 150 200 250 300 Nhit trong tng xc tc

Hnh 6. 21. Hiu sut x l ph thuc vo nhit thiu hy ca mt s cht

Ghi ch: 1. Methanol, 2. Cacbon monoxit, 3. Acrolein, 4. MIBK 5. MEK, 6. Toluen, 7. n-Hexan, 8. Amoniac, 9. Etyl axetat
127

4. Thit k vng chc v n gin. 5. Khng to ra nhim th cp nh nc thi nhim bn, kh thi cha cc cht cn phi x l tip theo... 6. C th thu hi nhit thi sau x l ti a cung cp nhit cho cc mc ch khc rt thun tin. 7. Thi gian s dng xc tc ko di. Do xc tc lm vic trong iu kin nhit thp cho nn tn hao khng ng k v nu tng xc tc b bn th c th ra sch hoc i nhn ci mi. Bng 6. 6 d y a ra mt s thng s so snh gia hai cng i ngh thiu hy trc tip v thiu hy s dng xc tc oxi ha. Bng 6.6. Cc thng s quan trng ca hai phng php thiu hy.
CC THNG S THIU HY TRC TIP THIU HY C XC TC

Lu lng kh thi Nhit ca kh thi Nng VOC Th tch kh nng thu hi Nhit kh nng Th tch hi nc thu hi Nhit dng kh mi Nhit thu hi t kh nng Nhit thu hi t hi nc Tng cn bng nhit

100 m3/pht 130oC 1.000 ppm 70 m3/pht 172oC 0 kcal/h 231.100 kcal/h 307.900 kcal/h

100 m3/pht 70oC 2.500 ppm 90 m3/pht 120oC 1250 kg/h (P=15kG/cm2) 403.200 kcal/h 174.700 kcal/h 750.000 kcal/h 420.700 kcal/h

Th tch nc nng thu hi 960 kg/h

Nhit thu hi t nc nng 76.800 kcal/h

Cng ngh hp ph. Cng ngh ny cn gi l cng ngh lm giu cc cht hu c d bay hi trong kh thi. Qu trnh hp ph v gii hp thc cht mi l cng on tch cc cht hu c dng hi c nng rt thp ra khi kh thi v lm m c n trong mt th tch nh hn. x l trit cn thit phi i tip qua mt cng on na l ngng t hay thiu hy. Nhng cng ngh ny rt c a chung trong vic kh mi cho cc phng iu ha nhit v mi y khng gy c m ch gy kh chu. Thit b kh

128

mi kiu ny thng l gn nh v c th lp t bn trong my iu ha nhit rt thun tin. Nguyn l hot ng ca thit b kh mi theo phng php hp ph v gii hp lin tc c m t nh trn hnh 6. 22. B phn hot ng chnh l mt trng quay c np cht hp ph. Trng quay ny quay u nh mt giy curoa ni vi mt mt v mt b gim tc tc quay chm cho cc qu trnh hp th v gii hp thc hin hon ton. Hai mt ca trng quay c b tr ba ca hnh qut, chia thnh ba vng hp ph, gii hp v lm ngui cht hp ph. Kh c cha cht gy mi c thi qua tng hp ph vng hp ph. Ti y cc cht hu c gy mi c gi li hu nh hon ton v kh i ra l kh s ch. Khi tng hp ph hp ph mi s chuyn dn sang vng gii hp. Ti v ng ny ngi ta dng khng kh nng thi qua gii hp v thu hi hi gy mi c lm giu li x l tip tc hoc thi ra ngoi i vi trng hp kh mi cho cc phng iu ha nhit . Cht hp ph sau gii hp c nhit kh cao cho nn trc khi vo vng hp ph n c lm ngui bng dng khng kh lnh thi qua; y ng thi cng l dng khng kh dng gii hp sau khi c t nng thm khi qua thit b t nng khng kh. Thit b kh mi kiu hp ph v gii hp lin tc
Kh sch ra

Vng hp ph

Kh cn x l vo

Thit b t nng khng kh Vng lm mt

Vng gii hp Khng kh vo Mt v giy curoa VOC nng cao ra ni x l

Hnh 6. 22. S thit b kh mi kiu hp ph v gii hp lin tc

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Cht hp ph y thng c s dng l than hot tnh hoc cc zeolit k nc hoc hn hp c hai. Tui th ca tng hp ph tng i cao nu hot ng ng ch quy nh cho tng loi thit b. Cc thit b lm vic theo nguyn l ni trn c lnh vc ng dng rt rng nh kh mi cho cc c sn xut cao su, nha, cht do, sn, cc s phng v, cc kho xng du, dung mi hu c v cc phng iu ha nhit . Cng ngh ny c nhng u im sau: 1. Hi cc cht hu c c th c tch mt cch kh trit v c lm giu t nng rt nh trong khng kh th hay kh thi. 2. Hiu qu kh mi rt cao. Kh sau khi x l c sch v n nh cao. 3. Chi ph vnh hnh rt thp. 4. Tui th ca tng xc tc ni ring v ca thit b ni chung rt cao. 5. Thit b kh mi bng cng ngh hp ph kiu ny nu kt hp vi mt l thiu nh s dng xc tc th s tr thnh mt h thng kh mi l tng. So snh v cng ngh thiu hy n thun th s kt hp ny tit kim i c rt nhiu.

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TI LIU THAM KHO 1. Henry C. Perkins. Air Pollution, McGraw-Hill Kogakusha, Ltd., Tokyo, London, Sydney, New Delhi..., 1974 2. http://www.EPA.gov/air/criteria.html. updated June 4th 2007. 3. Noel de Nevers. Air Pollution Control Engineering, McGraw-Hill, Inc., New York, London, Tokyo, Toronto, Sydney..., 1995. 4. Daniel Vallero. Fundamrntals of Air Pollution, 4th Edition, Elsevier, 2007. 5. Air & Waste Management Association, Edited by W.T.Davis. Air Pollution Engineering Manual, John Wiley & Sons, 2000. 6. Josef Vejvoda, Pavel Macha, Petr Buryan. Technologie ovzdu a itn odpadnch plyn, ISBN 80-7080-X, Praha 2003. 7. ILO. UNEP, WHO. Fluorine and Fluorides - EHC 36, WHO Geneva 1984. 8. UNEP, ILO, WHO. Chlorine and hydrogen chloride, EHC 21, WHO, Geneva, 1982 9. UNEP, ILO, WHO. Hydrogen Sulfide - EHC 19, WHO Geneva 1981. 10.UN Environmental Programme, WHO. Sulfur Oxides and Suspended Particulate Matter, Envir. Health Criteria 8, WHO Geneva 1979. 11.UNEP, ILO, WHO. Ammonia - EHC 54, WHO Geneva 1986. 12.M. Ruchirawat, R. C. Shank. Environmental Toxicology, Vol. I, II, III. Chulabhorn Research Institute, Bangkok 1996. 13.UNEP, ILO, WHO. Nitrogen, oxides of nitrogen - EHC 4, WHO Geneva 1977 14.UNEP, ILO, WHO. Carbon Monoxide, EHC 13, WHO Geneva 1979. 15.UNEP, ILO, WHO. Carbon Disulfide, EHC 10, WHO Geneva 1979. 16.UNEP, ILO, WHO. Arsenic, EHC 18, WHO Geneva 1981. 17.UNEP, ILO, WHO. Phosphine and celective metal phosphides, EHC 73, WHO Geneva 1988 18.UNEP, ILO, WHO. Petroleum products, selected, EHC 96, WHO Geneva 1990. 19.UNEP, ILO, WHO. Toluene, EHC 52, WHO Geneva 1986. 20. UNEP, ILO, WHO. Formaldehyde, EHC 89, WHO Geneva 1989. 21.UNEP, ILO, WHO. Ethylene oxide, EHC 55, WHO Geneva 1985. 22.UNEP, ILO, WHO. Chlorophenols, EHC 93, WHO Geneva 1989.
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23.Trn Ngc Chn. nhim khng kh v x l kh thi, Tp I, II, III, NXB Khoa hc v k thut, H ni 2001. 24.UNIDO. Quan trc kh thi v cht thi cng nghip, H ni 1998. 25. Mark Z. Jacobson. Atmospheric Pollution (Histiry, Science and Regulation), Cambridge University Press, 2002. 26.Jorgensen S. E., Johnsen I.. Principles of Environmental Science and Technology, Elsevier, Amsterdam, Oxford, New York, Tokyo, 1989 27.Neal K. Ostler (Editor). Introduction to Environmental Technology, Prentice Hall, Englewood, New Jersey, Columbus, Ohio, 1996. 28.Noel de Nevers. Solutions Manual to Accompany. Air Pollution Control Engineering, McGraw - Hill, Inc. New York, London, Tokyo,...1994. 29.Commitee for Studying Transfer of Environmental Technoloty (CSTET). Air Pollution Control Technonogy in Japan, UNEP/IETC-Osaka, 1994. 30.Stanley E. Manahan. Environmental Chemistry, Lewis Publisher, Boca Raton, Ann Arbor, London, Tokyo, 1993. 31.Cc Mi trng, Vin Mi trng v Ti nguyn. Cng ngh Mi trng, NXB Nng nghip, H ni 1998 32.UNEP, ILO, WHO. Methylmercury - EHC 101, WHO Geneva 1990.

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