Chuyn : Cng ngh x l kh SO2 ThS.

inh Hi H

MC LC
Trang 1.1 Hp th kh SO2 bng nc 1.2 X l SO2 bng vi (CaCO3) hoc vi nung (CaO) 1.3 X l SO2 bng amoniac 1.3.1 H thng x l SO2 bng amoniac theo chu trnh 1.3.2 X l SO2 bng amoniac c chng p 1.3.3 X l SO2 bng amoniac v vi 1.4 X l SO2 bng cc cht hp th hu c 1.5 X l SO2 bng cc cht hp ph th rn 1.5.1 Hp ph kh SO2 bng than hot tnh 1.5.2 X l kh SO2 bng than hot tnh c ti ncqu trnh LURGI 1.5.3 X l SO2 bng nhm oxit kim ha 1.5.4 X l SO2 bng vi v dolomit trn vo than nghin 1.6 So snh kinh t k thut ca mt s phng php x l SO2 PH LC Lc khng kh bng lc sinh hc TI LIU THAM KHO 1 3 5 5 7 8 9 11 11 12 14 14 16 17

24

Chuyn : Cng ngh x l kh SO2 ThS. inh Hi H

C G GH X L KH SO2
SO2 l loi cht nhim bin nht trong sn xut cng nghip cng nh trong sinh hot ca con ngi. Ngun pht thi SO2 ch yu l t cc trung tm nhit in, cc loi l nung, l hi khi t nhin liu than, du kh t c cha S hay cc hp cht cha S.Ngoi ra mt s cng on sn xut trong cng nghip ho cht, luyn kim cng thi vo kh quyn lng kh SO2 ng k . Trn th gii hng nm tiu th gn 2 t tn than cc loi v gn 1 t tn du m. Khi thnh phn S trong nhin liu trung bnh chim 1% th lng kh SO2 thi vo kh quyn l 60 triu tn/nm. Vn nhim kh quyn bi kh SO2 t lu tr thnh mi him ho ca nhiu nc. Cng ngh x l SO2 trong cng nghip uc pht tin t rt lu. Ngoi tc dng lm sch kh quyn, bo v mi trng, cn c ngha kinh t l thu hi SO2 l ngun cung cp nhin liu cho sn xut H2SO4 v lu hunh nguyn cht. 1.1 Hp th kh SO2 bng nc Qu trnh x l SO2 bng nc din ra theo phn ng sau: SO2 + H2O H+ + HSO3-

S h thng hp th kh SO2 bao gm 2 giai on sau: Hp th kh SO2 bng cch phun nc vo dng kh hoc cho kh SO2 i qua lp vt liu m c ti nc. Gii thot kh SO2 ra khi cht hp th thu hi SO2 v nc sch. Mc ha tan ca kh SO2 trong nc gim khi nhit nc tng cao v ngc li gii thot kh SO2 ra khi nc th nhit ca nc phi cao. 1000C th SO2 bc ra han ton v trong kh thot ra c ln hi nc. Bng phng php ngng t ngi ta thu hi c kh SO2 vi m c gn 100% sn xut acid sunfuric. gii hp th cn phi un nng mt lng nc rt ln, l mt kh khn. Ngoi ra, s dng li nc cho qu trnh hp th phi lm ngui nc xung gn 10oC, tc phi cn n ngun cp lnh. cng l vn khng n gin v tn km. V vy, phng php ny ch nn p dng khi: -Nng SO2 trong kh thi tng i cao - C sn ngun cp nhit (hi nc) vi gi r - C sn ngun nc lnh

Chuyn : Cng ngh x l kh SO2 ThS. inh Hi H

Trong trng hp kh thi giu SO2 nh trong cng on nu qung sunfua kim loi ca cng nghip luyn kim mu, nng SO2 trong kh thi c th t 2-12%, ngi ta c th x l kh SO2 bng nc kt hp vi nc to thnh acid sunfuric. Qu trnh cng c thc hin thnh 2 giai on: giai on th nht kh SO2 kt hp vi oxy nh s c mt ca cht xc tc Vanadi bin thnh anhirit sunfuric v giai on th hai l dng nc ti trong lp vt liu m anhirit sunfuric kt hp vi nc to thnh acid H2 SO4 .
2O SO2 + OV5 SO3 2 SO3 + H2O

H2SO4

Trong giai on th nht, phn ng oxy ho kh SO2 c to nhit v phn ng xy ra cng mnh nhit cng thp, do cn thc hin qu trnh ny qua nhiu tng xc tc, sau mi tng u c lm ngui.
Kh sach thoat ra 1 2 4 3 SO2

6 Kh vao

Hi nc Xa

Chat tai lanh

6 5

1- Thap hap thu 2- Thap giai thoat kh SO2 3- Thiet b ngng tu 4,5- Thiet b trao oi nhiet 6-Bm Hnh 1 S hp th kh SO2 bng nc 1.2 X l SO2 bng vi (CaCO3) hoc vi nung (CaO) X l SO2 bng vi l phng php c p dng rt rng ri trong cng nghip v hiu qu x l rt cao, nguyn liu r tin v c sn mi ni.

Chuyn : Cng ngh x l kh SO2 ThS. inh Hi H

Cc phn ng: CaCO3 + SO2 = CaSO3 + CO2 CaO + SO2 = CaSO3 2CaSO3 + O2 = 2CaSO4 Khi thi sau khi c lc sch tro bi i vo scrub 1, trong xy ra qu trnh hp th kh SO2 bng dung dch sa vi ti trn lp m bng vt liu rng. Nc cha acid chy ra t scrub c cha nhiu sunfit v canxisunfat di dng tinh th CaSO3.0,5H2O, CaSO4.2H2O v mt t tro bi cn st li sau b lc tro bi, do cn tch cc tinh th ni trn bng b phn tch tinh th 2. Thit b 2 l mt bnh rng cho php dung dch lu li mt thi gian hnh thnh cc tinh th sunfit v sunfat canxi. Sau b phn tch tinh th 2, dung dch mt phn i vo ti cho scurb, phn cn li i qua bnh lc chn khng 3, cc tinh th c gi li di dng cn bn v c thi ra ngoi. vi c p vn v nghin thnh bt ri cho vo thng 6 pha trn vi dung dch long chy ra t b lc chn khng s 3 cng vi lng nc b sung hnh thnh dung dch sa vi mi. Cn bn t h thng x l thi ra c th s dng lm cht kt dnh trong xy dng khi chuyn sunfit thnh sunfat trong l nung.
Kh sach thoat ra

1 2 3 Nc 4

Kh vao 5

Voi

1- Thap hap thu 2- Bo phan tach tinh the 3- Bo loc chan khong 4,5- May bm 6- Thung tron sa voi Hnh 2 S h thng x l SO2 bng CaCO3 , CaO.

Chuyn : Cng ngh x l kh SO2 ThS. inh Hi H

1.3 X l SO2 bng amoniac Amoniac v kh SO2 trong dung dch nc c phn ng vi nhau v to ra mui trung gian amoni sunfit, sau mui amoni sunfit li tc dng tip vi SO2 v H2O to ra mui amoni bisunfit theo phn ng sau: SO2 + 2NH3 + H2O = (NH4)2SO3 (NH4)2SO3 + SO2 + H2O = 2NH4HSO3 Lng bisunfit tch t dn trong dung dch c th hon nguyn bng cch nung nng trong chn khng, kt qu thu c amoni sunfit v SO2. Amoni sunfit ny li c th s dng tip kh SO2 2NH4HSO3 Nung nng (NH4)2SO3 + SO2 + H2O

Ngoi ra trong dung dch cn c th xy ra s phn hy sunfit v bisunfit amoni thnh sunfat amoni v lu hunh n cht theo phn ng sau: 2NH4HSO3 + (NH4)2SO3 = 2(NH4)2SO4 + S + H2O Lu hunh n cht hnh thnh theo phn ng trn n lt ca mnh li tc dng vi amoni sunfit v to ra thiosunfat: (NH4)2SO3 + S = (NH4)2S2O3 Sau thiosunfat li kt hp vi amoni bisunfit v to ra lu hunh n cht nhiu gp 2 ln (NH4)2S2O3 + 2NH4HSO3 = 2(NH4)2SO4 + 2S + H2O Lu hunh n cht li tc dng vi sunfit. C nh vy tc phn ng phn hy dung dch lm vic tng dn v dung dch lm vic s hon ton bin thnh amoni sunfat v lu hunh n cht. 1.3.1 H thng x l SO2 bng amoniac theo chu trnh S h thng x l SO2 bng amoniac theo chu trnh c th hin hnh 3 Khi thi t l sau khi c lc sch tro bi i vo scrub 1 v c ti nc tun hon. Khi c lm ngui n 30oC, cn bi cn c thi ra ngoi. Trong nc tun hon dng cho qu trnh lm ngui khi trong scrub 1 c cha bi, SO2 v H2SO4. Lng kh SO2 kh c trong scrub 1 chim khong 10% lng SO2 chung trong khi thi khi nng ban u ca SO2 trong khi l 0,3%. Nhit cui ca nc t gn 50oC. nc tun hon c trong h thng n phi c lm ngui xung khong 27oC trong thit b lm ngui (thit b trao i nhit) s 2. Thit b 2 c th l thp lm mt, lc

Chuyn : Cng ngh x l kh SO2 ThS. inh Hi H

khng kh i qua thp phi c thi cao thch hp phng s lan ta kh SO2 t nc thot ra trong qu trnh lm ngui nc. ngn chn s tch t bi qu mc trong nc tun hon cn phi c b lng, mt b phn nc sau khi lng cn s thi ra ngoi sau khi trung ha axit v nc sch c b sung vo. T scrub 1 kh c lm ngui i vo thp hp th s 3, ti qu trnh hp th SO2 c thc hin trn nhiu tng, mi tng hp th c ti dung dch theo chu trnh kn, trong khi mt phn dung dch t tng trn c a xung ti mt cch lin tc cho tng di. Tng hp th trn cng c ti bng nc sch vi mc ch ngn cn s tht thot kh NH3 i theo khi thi ra ngoi. Dung dch hon nguyn c cp vo tng hp th k vi tng trn cng.

1.Thp hp th, 2,4.TB lm ngui, 3.thp hp th nhiu tng, 5.hon nguyn, 6.thp bc hi, 7.thng kt tinh, 8.my vt kh ly tm, 9.ni trng p. Hnh 3 S h thng x l SO2 bng amoniac Dung dch i ra tng hp th di cng c cha nhiu amoni bisunfit (NH4)2SO3 c trch mt phn a vo thp hon nguyn 5, trong c cp nhit bng hi nc bo ha kh (i trong dn ng xon) un nng dung dch. y xy ra phn ng 2NH4HSO3
Nung nng

(NH4)2SO3 + SO2 + H2O

Kh SO2 that ra t thp hon nguyn 5 t nng khong 94-97% v c s dng iu ch acid sunfuric. Dung dch sau khi hon nguyn xong (cha amoni sunfit) c lm ngui trong thit b trao i nhit 4 v a vo chu trnh ti. Nh vy dung dch hp th c tun hon theo chu trnh kn v do ngi ta gi l phng php theo chu trnh. Mt lng amoniac NH3 c b sung vo chu trnh ti b li lng NH3 tiu hao to thnh amoni sunfit theo phn ng 6

Chuyn : Cng ngh x l kh SO2 ThS. inh Hi H

2NH4HSO3 + (NH4)2SO3 = 2(NH4)2SO4 + S + H2O tch amoni sunfat hnh thnh trong qu trnh hp th ra khi dung dch, mt phn dung dch sau khi hon nguyn c a sang thit b 6, ti y ngi ta cp nhit cho nc bc hi, phn cn li c lm ngui v kt tinh trong thng 7. Cc tinh th sunfat c vt kh trong my quay ly tm 8 cn phn dung dch th quay v chu trnh ti. Ngoi amoni sunfat, trong dd ra khi thp hp th 3 cn c th c thiosunfat. Do mt phn dd ra khi thp hp th 3 c a sang x l ni chng p 9. y di p sut v nhit =140oC sunfit, bisunfit v thiosunfat amoni phn hy thnh amonisunfat v lu hynh n cht theo phn ng (NH4)2S2O3 + 2NH4HSO3 = 2(NH4)2SO4 + 2S + H2O Dung dch amoni sunfat c tch khi lu hynh bng phng php lng v i vo thp bc hi 6, cn lu hynh n cht c ra khun. 1.3.2 X l SO2 bng amoniac c chng p

Hnh 4 S h thng x l SO2 bng amoniac c chng p Kh thi sau khi c lc sch bi i vo thp hp th 1, dung dch hp th c ti theo chu trnh tun han. Nng mui amoni trong dd hp th t khang 45%. Ngi ta b sung vo dd ti mt lng dd nc amoniac m c (30%). Mt phn dd ti tng ng vi lng dd mi b sung vo lun lun c tch ra sau thp hp th a vo b lc p 2, sau i vo thung chng p 3. y ngi ta cho mt lng nh axit sunfuric vo dd v un nng n nhit 180oC vi p sut d 14 atm. Di iu kin nhit v p sut nu trn qu trnh oxy ha t ng xy ra to thnh amoni sunfat v lu hynh n cht. Sau khi han thnh phn ng oxyha, cc cht trong thng 7

Chuyn : Cng ngh x l kh SO2 ThS. inh Hi H

chng p ngui dn, p sut d gim xung n 3.5atm, lu hynh n cht lng xung y ri a ra thnh khun. Phn dd ni bn trn c a sang thit b bc hi chn khng 4 ri i qua my lc ly tm 5 tch amoni sunfat. c im ca phng php x l SO2 bng amoni c chng p l sn phNm cui cng thu c ch yu gm amoni sunfat. 1.3.3 X l SO2 bng amoniac v vi Phng php ny c mt s hng cng nghip ca Php nghin cu v p dng ti trung tm cng nghip Saint Ouen gn th Pari ca Php. Hn hp hi nc v amoniac c phun trc tip vo khi thi trn ng ng dn vo h thng hai scrub lp ni tip 1 v 2. Kh SO2 trong khi thi kt hp vi amoniac to thnh sunfit v bisunfit amoni. Trong scrub 1 phn ln tro bi v cc sn phNm sunfit, bisunfit c lai ra khi dng kh v theo dung dch ti chy xung thng cha 7. Ti y nhit kh cng h xung cn khang 60oC. Tip theo kh i vo scrub 2 v cc sn phNm to thnh t SO2 v amoniac cn st li tip tc b tch ra khi dng kh v theo dung dch chy xung thng cha 8. Mt phn dung dch ti t scrub 2 chy xung thng cha 8 c a sang ti cho scrub 1 v mt lng dung dch mi c b sung vo thng 8.

1,2.thp hp th, 3.thng phn ng, 4.lm ngui, 5.my lc ly tm, 6.thng pha ch sa vi, 7,8.thng cha dung dch ti Hnh 5 S h thng x l SO2 bng amoniac v vi Dung dch bo ha thng cha 7 c a sang thng phn ng 3, ti sa vi v hi nc c cp vo kt hp vi sunfit v bisunfit amoni to thnh sunfit v sunnfat canxi theo cc phn ng sau: 8

Chuyn : Cng ngh x l kh SO2 ThS. inh Hi H

(N H4)2SO4 + Ca(OH)2 = CaSO4 + 2N H3 + 2H2O N H4HSO3 + Ca(OH)2 = CaSO3 + N H3 + 2H2O (N H4)2SO3 + Ca(OH)2 = CaSO3 + 2N H3 + 2H2O Amoniac v hi nc bc ln t thng phn ng 3 c ht v phun vo ng ng dn khi thi, cn bn nho lng y c a sang lm ngui trong thit b trao i nhit 4, sau cn c tch ra my lc ly tm 5 khng cha canxi bisunfit c tnh cht ha tan nn c th lai b hoc c s dng nh vt liu san lp, lm nn ng Hiu qu kh SO2 ca phng php amoniac vi c th t 95%, nng N H3 theo kh sch that ra khang 0.001%. u im ca phng php ny so vi phng php amoniac n thun l rt t tn amoniac v c th p dng kh SO2 trong khi thi c cha nhiu bi v nhit cao. H thng c th lm vic vi lu lng khi thi rt ln. N hc im ch yu ca phng php ny l lng ph thi nhiu. 1.4 X l SO2 bng cc cht hp th hu c Qu trnh x l kh SO2 trong kh thi bng cc cht hp th hu c c p dng nhiu trong cng nghip luyn kim mu. Cht hp th kh SO2 c ph bin l cc amin thm nh anilin C6H5N H2, toluiin CH3C6H4N H2, xyliin (CH3)2C6H3N H2 v imetyl-anilin C6H5N (CH3)2 Thc t cho thy dung dch xyliin trong nc c nhiu u im khi s dng kh SO2 trong khi thi vi nng thp, cn khi nng SO2 trong khi thi tng i cao (trn 2%) th imetyl-anilin c u th hn. Qu trnh sunfidin Qu trnh ny c cc hng cng nghip ha cht v luyn kim ca c nghin cu v p dng nh my Luyn Kim Hamburg kh kh SO2 trong khi thi ca l thi luyn ng. N ng kh SO2 trong khi thi dao ng trong phm vi 0,5-8%, trung bnh l 3,6%. Cht hp th c s dng l hn hp xyliin v nc t l = 1:1 Kh thi s b c lm ngui v lc sch bi trong thit b lc bng in, sau cho qua cc thp hp th 2 v 3 t ni tip nhau. Cc thp hp th c ti hn hp xyliin-nc theo s chuyn ng ngc chiu ca dng kh v dung dch hp th. Trong qu trnh hp th SO2 bng xiliin c ta ra mt lngnhit ng k, do cn lm ngui bng cc thit b trao i nhit 1. Kh sch i ra khi thp hp th c cha hi xyliin cn cho qua srcub 4 thu hi xyliin bng acid sunfuric long.

Chuyn : Cng ngh x l kh SO2 ThS. inh Hi H

Dung dch hp th bo ha t thp hp th u tin (s 2) i ra vi nng SO2 130-180g/l c a vo thp bc hi 5. N hit phn di ca thp bc hi c gi mc 45-100oC bng cht mang nhit l hi nc i bn trong ng xon. Cc loi kh, hi (gm SO2, xyliin v hi nc) bc ln trong thp bc hi c ngng t thit b trao i nhit 1 ri i tip vp srcub 7 ti bng nc lm gim nng xyliin trong kh SO2. T y kh SO2 c s dng cho cc cng on ch bin acid sunfuric hoc lu hunh n cht. Dung dch long xyliin SO2 cng vi nc ngng t thit b ngng t 1 li quay ln ti vo thp bc hi 5. Dung dch hp th c hon nguyn phn di ca thp bc hi chy vo b lng 6, nc tha c thi i v hn hp xyliin-nc theo t l thch hp c bm qua thit b lm ngui ri ti cho thp hp th s 3.

1.Thit b trao i nhit (lm ngui), 2.3. Thp hp th, 7. Scrub, 5. Thp bc hi, 6. B lng Hnh 6 S h thng x l SO2 theo qu trnh sunfiin Trong qu trnh hp th, mt phn sunfit xyliin b oxy ha. hn ch s tch t sunfat xyliin trong dung dch hp th, ngi ta cho natri cacbonat (N a2CO3) vo dung dch ti thp hp th 3. N atri cacbonat tc dng vi sunfat xyliin to thnh natri sunfat (N a2SO4) v cacbonic. Kh CO2 cng vi kh thi c kh SO2 thot ra kh quyn, cn natri sunfat tng ng vi lng natri cacbonat s dng s c thi ra ngoi b lng 6 di dng dung dch trong nc thi.

10

Chuyn : Cng ngh x l kh SO2 ThS. inh Hi H

1.5 X l SO2 bng cc cht hp ph th rn Cc qu trnh x l SO2 bng cc cht hp th theo phng php t c nhc im l nhit ca kh thi b h thp, Nm li tng cao gy hoen r cc loi my mc, h thng cng knh v chi ph u t ln. Vi nhng l do trn th x l kh thi bng phng php kh rt c trin vng, c bit trong cng nghip nng lng v luyn kim mu. Kinh ph u t cho vic xy dng lp t h thng x l kh thi theo phng php kh thp hn so vi phng php t, cn chi ph s dng vn hnh th theo phng php kh i lc li cao hn so vi phng php t. Do nhu cu hon nguyn vt liu hp ph v lm sch kh thi khi bi ca vt liu hp ph, vn kt hp gia qu trnh kh v t ngy cng tr nn thit thc. 1.5.1 Hp ph kh SO2 bng than hot tnh Trc y ngi ta cho rng x l kh SO2 theo phng php hp ph bng than hot tnh l t hiu qu. Tuy nhin, trong nhng nm gn y, ngi ta thy rng phng php ny c th p dng rt tt x l khi thi t cc nh my nhit in, nh my luyn kim v sn xut acid sunfuric vi hiu qu kinh t ng k. S dng than hot tnh hp ph kh SO2 c s h thng n gin c th p dng c cho mi qu trnh cng ngh c thi kh SO2 mt cch lin tc hay gin on. N goi ra, h thng x l cho php lm vic c vi kh thi c nhit cao, trn 100oC. N hc im ca phng php ny ty thuc vo qu trnh hon nguyn c th l tiu hao nhiu vt liu hp ph hoc l sn phNm thu hi c kh SO2 c nng thp, c ln nhiu acid sunfuric v tn dng kho khn, phi x l tip mi s dng c.

11

Chuyn : Cng ngh x l kh SO2 ThS. inh Hi H

1.phu cha vt liu hp ph. 2.TB nh lng. 3.Thp hp ph nhiu tng. 4.Xiclon 5.Bunke 6.Thp gii hp ph 7.TB cp nhit 8.Qut 9.My sng Hnh 7 S h thng x l SO2 bng PP hp ph than hot tnh.

Theo s trn, khi thi i vo thp hp ph 3 gm nhiu tng, kh SO2 b gi li trong lp than hot tnh ca cc tng hp ph, sau kh i qua xiclon 4 lc sch tro, bi trc khi thi ra kh quyn. Than hot tnh sau khi c hon nguyn cng vi mt lng than mi b sung c chuyn ln phu cha 1 cp vo thp hp ph qua mt b phn khng ch liu lng 2. Than ri t tng trn xung tng di ca thp nh h thng co - o. Sau khi bo ha kh SO2, than hot tnh t tng di cng ca thp chy xung bunke 5 i vo thit b gii hp ph (hon nguyn) 6. Ti y mt lng nhit c cp t bn ngoi nng nhit ca than ln 400450oC nh thit b cp nhit 7 v qut 8. thc Ny qu trnh hon nguyn ngi ta cn thi kh tr nng hoc hi nc vo thit b hon nguyn. Kh SO2 thot ra t qu trnh hon nguyn c nng 40-50% v t khong 9697% lng kh SO2 c trong khi thi trc khi i vo h thng lc. Sau khi hon nguyn, than hot tnh c sng chn li qua my sng 9 loi b phn than qu vn nt v b sung thm than mi a ln phu 1. 1.5.2 X l kh SO2 bng than hot tnh c ti nc qu trnh LURGI X l kh SO2 bng than hot tnh c ti thu acid sunfuric do cng ty Lurgi ca c ngin cu p dng. Theo phng php ny, kh thi c lm cho bo ha hi nc nhit di 100oC i qua lp than hot tnh c ti nc lm Nm trong thit b hp ph 3. Kh SO2 c gi li trong lp than hot tnh v oxy ha thnh SO3 nh c oxy trong kh thi. Tip theo SO3 kt hp vi H2O 12

Chuyn : Cng ngh x l kh SO2 ThS. inh Hi H

bin thnh acid sunfuric v theo nc chy vo thng cha 4. Acid sunfuric trong thng 4 vi nng 20-25% c trch mt phn lm ngui v lm Nm kh thi cn x l. Qu trnh ny c thc hin trong mt scrub Venturi 1, trong acid long c dng kh chuyn ng ri vi vn tc ln x nh thnh git mn, nhit ca kh gim xung nh c nc bc hi, cn acid long th tr nn m c hn. Sau srcub Venturi, tro bi v acid c tch ra khi dng kh trong xiclon 2 v chy xung b cha 4, cn kh i tip vo thit b hp ph. qu trnh x l c lin tc cn lp t t nht l hai bnh hp ph lun phin nhau hot ng, ci ny theo chu k hp ph, ci kia theo chu k hon nguyn. Vic s dng acid thu c t qu trnh ph thuc vo mc nhim bNn tro bi v m c ca n khi x l kh thi c lc sch bi, nng acid thu c c th t 65-70%. Acid b nhim bNn nng c th c phn gii theo cc phng php thng dng thu kh SO2 dng vo vic iu ch acid sunfuric sch hoc lu hunh n cht. H thng th nghim ban u vi lu lng khi thi 1000-1500m3/h. N ng ban u ca SO2 trong khi khi t nhin liu mazt l 0,1-0,15%. Hiu qu kh SO2 t 98-99%. Cht hp ph lm vic trong hn 3 nm lin tc m hot tnh khng b gim st.

1.Scrub venturi - 2.Xiclon - 3.Tb hp ph - 4.b cha axit sunfuric - 5.Bm 6.Than hot tnh. Hnh 8 S h thng x l kh SO2 bng than hot tnh c ti nc (qu trnh LURGI)

13

Chuyn : Cng ngh x l kh SO2 ThS. inh Hi H

1.5.3 X l SO2 bng nhm oxit kim ha Qu trnh x l SO2 bng nhm oxit kim ha c da trn tnh cht hp ph ca hn hp Al2O3 v N a2O vi thnh phn natri oxit chim 20% khi lng ca hn hp. Trong qu trnh hp ph, kh SO2 b oxy ha, sau tc dng vi cc oxit kim loi bin thnh sunfat. Cht hp ph bo ha c hon nguyn bng kh tr nhit 600-650oC. Khi thi sau khi c s b lc sch bi trong xiclon 1 i vo thp hp ph 2 theo chiu t di ln trn.Cht hp ph dng ht c cp vo t nh thp v ri t do xung di. Trong qu trnh ri trong dng kh chuyn ng ngc chiu, cht hp ph kh kh SO2 trong khi thi. Bi v cc ht cht hp ph c kch thc b b dng kh mang theo s c tch ra trong xiclon 3 v kh sch c thi ra kh quyn. Mt phn cht hp ph sau khi ra khi thp 2 c tun hon tr li cho n khi t mc bo ha nht nh, phn cn li qua b phn khng ch liu lng 5 i qua thit b hon nguyn 6. Sau khi hon nguyn s c lm ngui ti bung lm ngui 7 v c cp vo phu np 4 cng vi mt lng cht hp ph mi b sung lp li chu trnh lm vic.

1,3.xiclon 2.Thp hp th 4.phu np than 5.Tb nh lng 6.Tb gii hp ph 7.bung lm ngui 8.b mt trao i nhit Hnh 9 S h thng x l kh SO2 bng nhm oxt kim ha 14

Chuyn : Cng ngh x l kh SO2 ThS. inh Hi H

Lng cht hp ph lu thng trong h thng khong 48-50kg cho 1000m3 kh thi cn x l vi nng ban u ca SO2 l 0,3%. Vn tc chuyn ng ca kh trong thp hp ph l 2-2,5m/s. Hiu qu kh SO2 trong kh thi t trn 90%. 1.5.4 X l SO2 bng vi v dolomit trn vo than nghin T lu ngi ta bit cc kim loi kim c phn ng vi SO2 to ra cc mui sunfat. Tuy nhin qu trnh t nhin liu than nghin c trn bt vi v olomit kh kh SO2 th mi c p dng trong nhng nm gn y v hin nay vn ang c tip tc nghin cu hon thin. Phn ng gia vi CaO v dolomit CaCO3.MgCO3 vi SO2 : 2CaO + 2SO2 + O2 =2CaSO4 2CaCO3.MgCO3 + 2SO2 + O2 = 2CaSO4 + 2MgO + 4CO2 Phn ng gia vi v SO2 xy ra mnh nht nhit 760-1040oC, cn phn ng gia dolomit v SO2 nhit 600-1200oC. C th ni phng php ny l s kt hp gia qu trnh chy vi qu trnh kh kh SO2 thnh mt qu trnh thng nht trong bung t ca l m khng i hi phi lp t thm nhiu thit b ph tr khc. Than nghin vi c ht kch thc trn 6mm c trn cng vi bt kch thc 1,6-6mm thnh lp dy bn trn a phn phi kh 1. Khng kh c thi t di ln vi vn tc 0,6-4,6m/s. Khng kh xuyn qua lp than chy nhit 760-1040oC lm cho cc ht nhin liu v vi chuyn ng, nhng ht to v nng bc ln ri ri xung, cn cc ht mn bay theo sn phNm chy. Lp than trong bung t si ng v do ngi ta gi l qu trnh t than gi ha lng hoc gi si. Bung t c bao quanh bng cc vch ng 2 hp thu nhit bc x, trong lu thng nc v hi. N goi ra, trong lp than gi ha lng cn c th b tr cc dy ng xon 3 nhn nhit trc tip t lp than chy. Bn trn lp than cn c bt tr dy ng nm ngang 4 va nhn nhit, va cn tr khng cho cc ht than bc ln cao v theo khi ra ngoi. Trn ng khi c b tr cc dn ng nhn nhit i lu 5 v dn ng 6 tn dng nhit trong khi thi hm nng nc trc khi cp vo dn ng chnh. Khi thi i ra khi l c cha tro, cc ht vi hoc olomit v than c lc bi cp th trong xiclon 7 thu hi than cha chy ht, tip theo c lc tinh b lc 8 ri thi ra kh quyn. Lp than ni bn trn phn ln l tro, cc cht tr, vi v sunfat c ln mt t than cha chy ht s c thi ra ngoi v nhin liu cng cht hp ph SO2 uc b sung vo bung t qua a phn phi kh hoc qua ca cp than trn vch l.

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Chuyn : Cng ngh x l kh SO2 ThS. inh Hi H

1.6 So sanh kinh te ky thuat cua mot so phng phap x ly SO2

STT PP X ly Nong o au au t ban Chi ph san Thu hoi san Chi ph X ly SO2 SO2 au xuat trong pham trong quy cho 1000 % T/tch 1000 c nam nam Kwh,c 1000 c/nam 1000 c/nam 1 PP a voi 0.5 162.36 48.86 23.2 2 3 PP voi 0.5 nung PP NH3 0.5 chu ky 133.3 231.3 47.32 20.1 65.6 22.5 9.6

c : ng Curon ca Tip Khc Chi ph san Chi ph au Hieu qua t cho 1KW X ly SO2 xuat cho 1 (o la) (%) tan nhien lieu (o la) PP nhom Axt 17.77 100 0.55 kiem hoa Lu huynh 10.64 100 0.61 21.25 100 0.4 PP voi bot Axt 90 1.13 Khong Thu 1.0 hoi san pham PP X ly SO2 San pham Thu hoi

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Chuyn : Cng ngh x l kh SO2 ThS. inh Hi H

PH LC LC KH G KH B G LC SI H HC

Lc sinh hc l g? Lc sinh hc l mt bin php x l nhim tng i mi. y l mt phng php hp dn x l cc cht kh c mi hi v cc hp cht hu c bay hi c nng thp. Hnh dng ph bin ca mt h thng lc sinh hc ging nh mt ci hp ln, mt vi h thng c th ln bng sn bng r, mt vi h thng c th nh mt yard khi (0,76 m3). N guyn tc chnh ca h thng x l l to iu kin cho vi khuNn tip xc vi cc cht nhim trong kh thi. H thng lc kh thi ny l ni cha cc nguyn liu lc v ni sinh sn cho cc vi sinh vt. Trong h thng ny, cc vi sinh vt s to thnh mt mng sinh hc (biofilm), y l mt mng mng v Nm bao quanh cc nguyn liu lc. Trong qu trnh lc, kh thi c bm chm xuyn qua h thng lc, cc cht nhim trong kh thi s b cc nguyn liu lc hp th. Cc cht kh gy nhim s b hp ph bi mng sinh hc, ti y, cc vi sinh vt s phn hy chng to nn nng lng v cc sn phNm ph l CO2 v H2O theo phng trnh sau: Cht hu c gy nhim + O2 ---> CO2 + H2O + nhit + sinh khi Lch s Trong khi vic s dng cc h thng lc sinh hc cha c ph bin M th hng trm h thng lc sinh hc c ng dng thnh cng v c hiu qu Chu u (H Lan, Tn Ty Lan, c) v N ht Bn. H thng lc sinh hc trc y thng c thit k x l mi ca cc h thng x l nc thi, cc nh my ti ch, qu trnh phn compost. Sau , n c ng dng ph bin trong vic x l cc hp cht hu c d bay hi v cc hp cht hu c khc. 17

Chuyn : Cng ngh x l kh SO2 ThS. inh Hi H

Sau y l mt s mc lch s ca vic pht trin h thng lc sinh hc: 1923 Phng php x l sinh hc c ngh s dng x l cc cht kh c mi hi. 1955 Phng php x l sinh hc c p dng x l cc cht kh c mi hi nng thp c. 1960 H thng lc sinh hc c s dng x l cc cht kh nhim c v M. 1970 H thng lc sinh hc t c nhng thnh qu cao c. 1980 H thng lc sinh hc c s dng x l cc cht kh c v cc hp cht hu c bay hi ca cc ngnh cng nghip. 1990 Hin nay, hn 500 h thng lc sinh hc ang hot ng ti c, H Lan v ph bin rng M. Vic x l mi hi c tin hnh t nhng nm 1950 v lc ngi ta thng s dng h thng lc qua t, hay b lc sinh hc nh git. Cc cht kh c mi hi thng l hydrogen sulphite hay mercaptant v cc hp cht sulfur khc. Vic x l cc cht hu c bay hi mi c p dng gn y v tr nn ph bin trong thp k va qua v hin nay cn ang c tin hnh nghin cu su thm. V d, hin nay mt s nghin cu chng minh c l cc h thng lc sinh hc c th dng x l cc hp cht hu c c nhn thm v cc hp cht bo, cn, aldehydes, acid hu c, acrylate, acid carbolic, amines v ammoniac. M t qu trnh x l H thng lc sinh hc cung cp mi trng cho vi sinh vt pht trin v phn hy cc cht kh c mi hi v cc cht hu c gy nhim trong kh thi. H thng lc bao gm mt bung kn cha cc vi sinh vt v hp th hi nc, gi chng li trong nguyn liu lc. N guyn liu lc c thit k sau cho c kh nng hp th nc ln, bn cao, v t lm suy gim p lc lung kh i ngang qua n.

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Chuyn : Cng ngh x l kh SO2 ThS. inh Hi H

Hnh sau y l mt b lc sinh hc c mt lp nguyn liu lc (din tch 6000 ft2) nh my Monsanto

Cc h thng nh hn, ph bin hn vi nhiu lp nguyn liu lc c trnh by trong hnh sau:

Cc n v nguyn liu lc ny gi l "khi sinh hc" (Biocube) c thit k bi EG&G Corporation c kch thc cao khong 7 ft v ng knh khong 6 ft. Vic s dng nhiu lp nguyn liu lc kiu ny hn ch c vic cc nguyn liu lc b dn nn li v vic cc lung kh xuyn thnh nhng ng thot qua lp nguyn liu lc. Hn na, n cn to s thun li trong vic bo tr hay thay mi nguyn liu lc. Trong qu trnh lc sinh hc, cc cht kh gy nhim c lm Nm v sau c bm vo mt bung pha bn di nguyn liu lc. Khi cht kh i ngang

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Chuyn : Cng ngh x l kh SO2 ThS. inh Hi H

qua lp nguyn liu lc, cc cht nhim b hp th v phn hy. Kh thi sau khi lc sch c phng thch vo kh quyn t bn trn ca h thng lc. Hu ht nhng h thng lc sinh hc hin nay c cng sut x l mi v cc cht hu c bay hi ln hn 90%. Tuy nhin, hn ch ca phng php ny l ch x l c nhng kh thi c nng cht nhim thp (<1000ppm) v lu lng kh x l ch nm trong gii hn 300-500 ft3/ft2-gi. guyn liu lc Lp nguyn liu lc Nm to nn iu kin l hc v ha hc thun li cho vic chuyn i cc cht nhim t pha kh sang pha lng v qu trnh phn hy sinh hc cc cht nhim ny bi mng sinh hc. C ch ca qu trnh lc sinh hc bao gm qu trnh hp ph, hp th v phn hy bi cc vi sinh vt. Cc vi sinh vt trong mng sinh hc lin tc hp th v bin dng cc cht nhim, bin chng thnh cc sn phNm cui cng l nc, CO2 v cc loi mui. N guyn liu lc in hnh l hn hp ca cc cht nn phn compost, t, cy thch nam (heather), plastic v cc ph phNm g. Cc nguyn liu lc nhm cung cp din tch b mt ln hp th v hp ph cc cht nhim. N goi ra n cn lm nhim v cung cp cht dinh dng cho cc vi sinh vt. Mt vi loi nguyn liu lc khng p ng c v nhu cu dng cht cho vi sinh vt, do chng ta phi hiu chnh bng cch cho thm vo cc hp cht m v phospho. Cc nguyn liu lc thng c tui th t 5 - 7 nm trc khi phi thay mi. Cc im cn quan tm khi quyt nh chn nguyn liu lc: Kh nng gi Nm to lp mng sinh hc C din tch b mt ln to iu kin cho qu trnh hp th v pht trin ca vi sinh vt C cha cc dng cht cung cp cho cc vi sinh vt To lc cn khng kh thp (gim mc st p v nng lng cn s dng cho my bm) Cc tnh cht l hc khc nh n nh l hc v d dng thao tc. Mt s thng s thit k Din tch Din tch l mt thng s c quan tm hng u trong vic thit k h thng lc sinh hc. x l lu lng kh khong 30 ft3/pht, mt h thng lc sinh hc c th cn din tch 25 ft2. i vi nhng lu lng kh ln hn, chng ta cn nhng din tch ln hn v c th bng din tch mt sn bng r nh ni trn.

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Chuyn : Cng ngh x l kh SO2 ThS. inh Hi H

Thnh phn ha hc v hm lng ca cht nhim trong kh thi Phn tch thnh phn ha hc v hm lng ca n trong kh thi cn thit xc nh xem bin php lc sinh hc c thch hp hay khng. Cc h thng lc sinh hc hot ng tt khi cc hp cht nhim (khng ho tan trong nc) c nng thp (<1000 ppm). Mt s hp cht phn hy sinh hc rt chm (nh cc hp cht chlor) do i hi h thng x l c kch thc ln. Thi gian lu tr Thi gian lu tr l khong thi gian vi sinh vt tip xc vi lung kh thi v c tnh bng cng thc sau: RT = Tng th tch cc l rng ca lp nguyn liu lc/lu lng kh thi Thi gian lu tr cng di s cho hiu sut x l cng cao. Tuy nhin, trong qu trnh thit k chng ta cn phi gim thiu thi gian lu tr h thng c th x l mt lu lng ln hn. Thng thng, thi gian lu tr ca cc h thng lc sinh hc bin ng trong khong 30 giy n 1 pht. m m ca lung kh thi cn phi x l rt quan trng v n gi Nm cn thit cho cc mng sinh hc. Do , lung kh thi thng c bm qua mt h thng lm Nm trc khi bm vo h thng lc sinh hc m bo Nm ca lung kh thi i vo h thng lc sinh hc phi ln hn 95%. Kim sot pH Cc sn phNm ph ca qu trnh phn hy sinh hc l cc acid hu c. duy tr pH ca h thng nm trong khong thch hp cho cc vi sinh vt hot ng, chng ta cn cho thm cc dung dch m pH. guyn liu lc N guyn liu lc c th bao gm than bn, cy thch nam, phn compost, than ht hoc cc nguyn liu thch hp khc. N i chung, cc nguyn liu ny phi c kh nng cung cp cht dinh dng cho vi sinh vt v khng gy gim p lung kh nhiu. Thm vo , Nm ca cc nguyn liu lc phi c duy tr mc 30 - 60% cho qun th cc vi sinh vt pht trin. Do , bn cnh thit b lm Nm kh thi, ngi ta thng lp t h thng phun nc cho cc lp nguyn liu lc. Gim p Vic gim p ca lung kh khi i ngang lp nguyn liu lc nn c hn ch ti a. N u lp nguyn liu lc gy tr lc ln cho ngun kh, ta cn tiu tn thm nng lng cho my thi kh, gy tng gi thnh x l. Kh nng gy tr

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Chuyn : Cng ngh x l kh SO2 ThS. inh Hi H

lc cho ngun kh ph thuc vo Nm v rng ca lp nguyn liu lc. Nm tng, rng lp nguyn liu gim l nguyn nhn gy tng tr lc cho ngun kh. i vi cc h thng in hnh mc gim p nm trong khong 1 -10 hPa. Bo tr Khi bt u a vo hot ng, h thng cn c chm nom mt ln/tun. Sau khi h thng hot ng n nh v gii quyt tt c cc vn c th xy ra. Tn s thm nom c th gim xung 1 ln/na thng hoc hng thng. u v khuyt im ca h thng lc sinh hc u im

u im chnh l gi thnh thp, gi vn hnh thp, t s dng ha cht. Thit k linh ng, do c th thch nghi vi mi loi hnh cng nghip v din tch ca x nghip. H thng lc sinh hc linh ng trong vic x l mi hi, cc hp cht hu c bay hi v cc cht c. Hiu sut x l thng ln hn 90% i vi cc kh thi c nng cc cht nhim < 1000 ppm. N hiu loi nguyn liu lc, vi sinh vt v iu kin vn hnh khc nhau c th p dng p ng nhu cu x l.

Khuyt im

H thng lc sinh hc khng th x l c cc cht nhim c kh nng hp ph thp v tc phn hy sinh hc chm v d nh cc hp cht hu c bay hi c cha chlor. Cc ngun nhim c nng ha cht cao cn cc h thng ln v din tch ln lp t h thng lc sinh hc. N gun gy nhim c mc phng thch cht nhim bin ng cao s gy nh hng n h vi sinh vt cng nh hiu sut x l ca chng. Thi gian cho cc vi sinh vt thch nghi vi mi trng v to thnh cc mng sinh hc (biofilm) c th ko di hng tun n hng thng, c bit l i vi vic x l cc cht hu c bay hi. Thng mi ha

c hn 50 h thng lc sinh hc s dng phn compost lm nguyn liu lc c lp t theo kiu thng mi Chu u v M trong vng 15 nm qua. Vic s dng h thng lc sinh hc x l cc cht hu c bay hi c p dng trong cc ngnh cng nghip sau:

22

Chuyn : Cng ngh x l kh SO2 ThS. inh Hi H

Cng ngh ha cht v ha du Cng ngh du kh Cng ngh nha tng hp Cng ngh sn xut sn v mc in Cng ngh dc phNm X l cht v nc thi X l t v nc ngm Vic s dng h thng lc sinh hc x l mi, cho ti nay p dng trong cc ngnh cng nghip sau: X l nc cng rnh X l cht v nc thi l m Cc cng ngh ti ch Cc nh my sn xut gelatin v keo dn Cng ngh ch bin tht v nng sn Cng ngh sn xut thuc l, ca cao, ng Cng ngh sn xut gia v, mi nhn to.

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Chuyn : Cng ngh x l kh SO2 ThS. inh Hi H

TI LIU THAM KHO

1.inh Xun Thng, N him Khng Kh, N h xut bn i Hc Quc Gia TP HCM, 2003. 2. inh Xun Thng v cng s, K Thut Mi Trng i Cng, N h xut bn Gio Dc, 2000. 3. Hendrik Harssema, N guyn nh Tun, Phm Th Anh, Gim st v m hnh ha cht lng khng kh, Centerma center. 4. Trn N gc Chn, N him Khng Kh V X L Kh Thi, N h xut bn Khoa Hc V K Thut,2004. 5. Bi vit ca tc gi L Hong Vit v L Hoa. 6. Stanley E. Manahan, Environmental chemistry, Lewis publishers.

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