C ch hnh thnh v k thut x l SO2

MC LC
BNG1.4: LNG KH C HI DO T THI RA QUY CHO 1 TN NHIN LIU TIU TH 11.............................................................................................................2 BNG 1.5: LNG KH C HI DO T THI RA TRN 1 KM ON NG 11. . . .2 BNG1.4: LNG KH C HI DO T THI RA QUY CHO 1 TN NHIN LIU TIU TH ................................................................................................................10 BNG 1.5: LNG KH C HI DO T THI RA TRN 1 KM ON NG........10 2.1. C cu t chc v lin kt: .....................................................................................12 BNG 3.7: C TNH CA SO2.....................................................................15
4.2.1. Dung dch hp th:.......................................................................................................... 20 4.2.2. Thit b hp th: ............................................................................................................. 21 4.2.3. Hp th SO2 bng nc:.................................................................................................. 25

BNG 4.8: LNG NC L THUYT TNH BNG M3 CN HP TH 1 TN SO2 N TRNG THI BO HA NG VI NHIT V NNG SO2 KHC NHAU TRONG KH THI ..............................................................................................26
4.2.4 X l SO2 bng vi (CaCO3) hoc vi nung (CaO):...................................................... 27 4.2.5 X l SO2 bng Amoniac:................................................................................................. 29 4.2.6. X l SO2 bng MgO:...................................................................................................... 35 4.2.7 X l kh SO2 bng km oxit ZnO:................................................................................ 41 4.2.8. X l kh SO2 bng cc cht hp th hu c................................................................... 44

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MC LC BNG

Bng 1.1: Cc sn phm t ni la, nng phn trm khi lng..............................4 Bng1.2: So snh lng pht thi c hi do t nhin liu, kg/tn nhin liu ................7 Bng1.3: Mt s s liu pht thi cc cht kh nhim ch yu t cc qu trnh cng ngh khc nhau .................................................................................................................8 Bng1.4: Lng kh c hi do t thi ra quy cho 1 tn nhin liu tiu th .................11
Bng 1.5: Lng kh c hi do t thi ra trn 1 km on ng ............................................11

Bng 3.7: c tnh ca SO2 ............................................................................................16 Bng 4.8: Lng nc l thuyt tnh bng m3 cn hp th 1 tn SO2 n trng thi bo ha ng vi nhit v nng SO2 khc nhau trong kh thi ................................26

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A.

MC TIU TI
Ngy nay, song song vi nn kinh t pht trin v x hi vn minh, nn khoa hc k

thut hin i nng cuc sng ca con ngi ln mc tin nghi, thoi mi hn. Nhng mt iu m con ngi khng ng n l p ng c nhu cu cuc sng, s khai thc qu mc ti nguyn thin nhin hoc kt qu ca s tin b ca khoa hc k thut nh con dao hai li, va lm cho cuc sng thm phn tin nghi va lm cho mi trng xung cp n mc bo ng. Nhng nh my, x nghip, bnh vin thi ra cc ct khi, bi, nc thi cha y cc cht nhim nh:SO2, NOx, CO e do n cuc sng ca con ngi v h sinh thi t nhin. Chnh v th x l cc tc nhn nhim nh SO2 c bu khng kh ta th hng ngy c trong lnh hn, gim cc bnh v ng h hp, sng khoi tinh thn lm vic hiu qu hn ang l mt vn c quan tm hin nay. ti ny tp trung tm hiu r v kh nhim SO2 vi mc tiu:
Tm hiu ngun gc hnh thnh cht nhim SO2 Hiu r hn c ch v cc phng php x l SO2

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C ch hnh thnh v k thut x l SO2

B. I. 1.1.

NI DUNG THC HIN

NGUN GC PHT SINH: Ngun gc t nhin:

1.1.1. Hot ng ca ni la: Cc kh ph bin nht thng gii phng vo kh quyn t cc h thng ni la l hi nc (H2O), tip theo l kh CO2 v SO2. Bng 1.1: Cc sn phm t ni la, nng phn trm khi lng Ni la Kilauea summit Erta Ale Divergent Plate 1130 C 77.2 11.3 8.34 Erta Ale Convergent Plate 820 C 97.1 1.44 0.50

Phong cch kin to Hot Spot Nhit H 20 CO2 SO2 1170 C 37.1 48.9 11.8

Ngun: T Symonds v cng s. Al., 1994

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C ch hnh thnh v k thut x l SO2 Tc ng mi trng ca cc t phun tro ni la l rt nng n v lu di. T l pht thi SO 2 t mt lot cc ni la hot ng t <20 tn / ngy n > 10 triu tn/ ngy theo cch ca hot ng ni la v cc loi, khi lng ca macma c lin quan. V d, n ln phun tro ca ni la Pinatubo ngy 15 thng su nm 1991 tim khong 20 triu tn SO2 vo tng bnh lu. Cc sol kh lu hunh kt qu trong mt gii nhit 0,5-0,6 C ca b mt tri t Bc bn cu. Cc sol kh sulfate cng tng tc phn ng ha hc, cng vi cc cp chlorine tng bnh lu tng t nhim nhn to (CFC) chlorofluorocarbon, ph hy tng ozone v dn n mt s cc mc zn thp nht bao gi quan st thy trong kh quyn.

1.1.2. Chy rng

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1.2.

Ngun gc nhn to:

1.2.1. t nhin liu:

Trong nhin liu rn v lng lun lun c cha lu hunh vi hm lng khc nhau, c th c ti 6% trng lng trong than v 4,5 % trong du. Khi chy thnh phn lu hunh trong thin nhin phn ng vi oxy v to thnh vi oxit lu hunh, trong khong 99% l kh SO2 v t 0,5 2% l kh SO3
1.2.2. Do cc nh my nhit in:

Cc cht c hi thi ra kh quyn do t nhin liu cc nh my nhit in cng tng t nh cc qu trnh t nhin liu ni chung. im khc bit y l lng nhin liu tiu th cc trung tm nhit in thng rt ln, do lng khi thi cng nh cc cht c hi thi vo mi trng hng ngy l rt ln. V d nh my nhit in Ph Li I, cng sut 440MW tiu th hng ngy l 4500 tn than v thi vo kh quyn lng khi l 3 triu m3/ h, trong c cha 3 tn kh SO2, 400 tn kh CO2 v 8 tn bi.

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C ch hnh thnh v k thut x l SO2 Khi xem xt vn nhim khng kh do t nhin liu, iu quan trng l cn bit c tng quan ca lng cht nhim t cc ngun thi khc nhau: ngun t trong (ng c t) v ngun t ngoi (l nung, l nhit in). Cc ngun t trong ch yu l ng c t thng gy nhim khng kh mt cch trc tip v nguy him v khi thi ngay trn mt t trong khu ng ngi cc thnh ph. Cn cc ngun t ngoi c cng sut ln (trung tm nhit in) thng nm xa khu dn c v thi khi cao cn thit m bo an ton cho con ngi v sinh vt sinh sng trn mt t. Bng: lng kh c hi v bi do t chy 1 tn nhin liu t cc ngun khc nhau theo s liu ca W.Strauss Bng1.2: so snh lng pht thi c hi do t nhin liu, kg/tn nhin liu Cc ngun t trong Cht nhim Cc ngun t ngoi Nhin liu lng ng t c ng diezen c Sinh hot Nhit in v nghip CO NOX SO2 CH 395 20 1,55 34 9 3,3 6 20 0,005 14 20,8 SP 0,42 0,025 140 20,8 SP 0.26 0,25 10 19 SP 0,1 Than Sinh hot cng nghip 25 4 19SP 5

cng Nhit in v

Ghi ch: SP l t l phn trm trng lng ca thnh phn lu hunh v tro trong nhin liu. (Trn Ngc Chn, nhim khng kh v x l kh thi, tp 1, trang 15)
1.2.3. nhim trong cng nghip:

Bng1.3: mt s s liu pht thi cc cht kh nhim ch yu t cc qu trnh cng ngh khc nhau. Lp DH08MT Nhm 1 Trang 7

Th t 1

Ngun hoc qu trnh cng ngh

Lng pht thi SO2

Qu trnh t nhin hnh thnh v k thut x l SO2 C ch liu:

Than vi SP% lu hunh theo khi 19 SP g/kg NL (gi thit S liu v pht thi kh SO2 theo cc ngun c nh lng 5% lu hunh cn li trong

Kh t nhin liu Du vi SP% lu hunh theo khi

tro) 6,4 kg/106 m3 19,8 SP kg/103lt

lng

ng c chy gasolin (xng) loi 1,1 kg/103 lt (gi thit trong gasolin c 0,07 % S) 5 kg/103 lt (gi thit thnh phn S chim 0,3 %)

gasolin tiu biu c cng thc l C8H17) Diezen

Xng nu kim loi mu s ch. Phn ln cc loi qung kim loi u dng sunfua v khi nung chy to ra SO2 theo cc phn ng sau y: Cu2S + O2 = 2Cu + SO2 2PbS + 3O2 = 2PbO + 2SO2 Pht thi kh SO2 khi c kim sot mt cch va phi nng ln n 8000 ppm Nu qung ng - s luyn Nu qung ch s luyn Nu ch trong l ng Nu ch trong l phn x Nu qung km - s luyn 625 g/kg qung 330 g/kg qung 32 g/kg kim loi vo l 75 g/kg kim loi vo l

Lp DH08MT Nhm 1 3 Nh my axit sulfuric Axit sulfuric c sn xut ch yu bng

265 g/kg qung

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C ch hnh thnh v k thut x l SO2 Ghi ch: SP l t l phn trm trng lng ca thnh phn lu hunh v tro trong nhin liu. (Trn Ngc Chn, nhim khng kh v x l kh thi, tp 3, trang 27)

nhim kh SO2 trong mt s ngnh cng nghip:

Cng nghip gang thp: Ch yu cng on t chy hn hp th gia qung st v nhin liu

trn bng ti bng cch ht qua bng ti mt lu lng ln khng kh ( 6000 m3/ 1 tn qung cn thiu kt). Khng kh y cha nhiu bi (khong 5g/m3 TC) v kh SO2 (t 870 1440 mg/m3)

Cng ngh lc du: Kh thi vo kh quyn t nh my lc du chia lm 4 loi trong c 2

loi:
Kh thi t cc l nung, bp un, vi t s dng trong qu trnh

chng ct, trong c cha SO2 do t cc tp cht c cha lu hunh.

Kh c cha cc hp cht ca lu hunh nh H 2S v SO2 thot ra t

cc tng ca thp chng ct khi thi cc hp cht ca lu hunh t phn ct c.

Kh SO2 cn c thi nhiu cng nghip luyn kim mu, cng nghip

sn xut ximng( giai on sy v nung), sn xut giy.

1.2.4 Hot ng giao thng:

ng c xe tc hai loi; loi ng c my n v ng c diezen. Trong ng c my n bng tia la in rt kh m bo cho qu trnh chy c hon ton bi v n lun hot ng vi hn hp nhin liu v khng kh mi ch vn hnh. Cn trong Lp DH08MT Nhm 1 Trang 9

C ch hnh thnh v k thut x l SO2 ng c diezen th ch c khng kh c nn theo qu trnh on nhit khng cho thot nhit ra ngoi. cui giai on nn khng kh, nhin liu nhin liu c phun vo v khi tip xc vi khng kh nhit cao n bc chy. V th qu trnh chy trong ng c diezen nh c tha nhiu khng kh nn c hon ton hn. Lng kh c hi do t thi ra cn ty thuc vo ch vn hnh: lc khi ng, lc chy nhanh, lc hm li - u c s khc bit r rt.

Bng1.4: Lng kh c hi do t thi ra quy cho 1 tn nhin liu tiu th

Kh c hi Cacbon oxit CO Hydrocacbon Nit oxit NOx Sunfua dioxit SO2 Anehyt Tng cng Lng kh c hi, kg/tn nhin liu ng c my n chy xng 465,59 23,28 15,83 1,86 0,93 507,49 ng c diezen 20,81 4,16 13,01 7,80 0,78 46,56

Nu quy lng kh c hi do t thi ra v 1 km on ng chy:

Bng 1.5: Lng kh c hi do t thi ra trn 1 km on ng Cht c hi Cacbon oxit CO Hydrocacbon Nit oxit NOx Lng c hi g/kg ng i ng c my n chy xng 60,00 5,90 2,20 ng c diezen 0,69 2,57 0,14 2,07 0,68 1,02

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Sunfua dioxit SO2 0,17 0,47

((Trn Ngc Chn, nhim khng kh v x l kh thi, tp 1, trang 13)

2.

C CH HNH THNH: Trang 11

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2.1. C cu t chc v lin kt: SO2 l mt phn t C2V cong, nhm im i xng. V in t m formalisms, cc nguyn t lu hunh c trng thi xi ha ca +4, mt ph trch chnh thc ca 0. N c bao quanh bi 5 cp in t v c th c m t nh l mt phn t hypervalent T gc nhn ca l thuyt qu o phn t , hu ht cc in t ha tr c tham gia vo lin kt S-O.

2.2.

C ch hnh thnh:

2.2.1. t Sulfur Dioxide:

Sulfur dioxide l sn phm ca vic t lu hunh : S8 + 8 O2 8 SO2S8 + 8 O2 8 SO2 Cc t ca sulfua hydro v cc hp cht organosulfur tin tng t. 2 H 2S + 3 O2 2 H2O + 2 SO2 , 2 H2S + 3 O2 2 H2O + 2 SO2

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C ch hnh thnh v k thut x l SO2 Cc nung qung sulfua nh pyrit, sphalerit, v chu sa (thu ngn sunfua) cng pht hnh SO2: 4 FeS2 + 11 O2 2 Fe2O3 + 8 SO2 , 4 FeS2 + 11 O2 2 Fe2O3 + 8 SO2 2 ZnS + 3 O2 2 ZnO + 2 SO2 ,2 ZnS + 3 O2 2 ZnO + 2 SO2 HgS + O2 Hg + SO2 , HgS + O2 Hg + SO2 Mt s kt hp ca cc phn ng ny l chu trch nhim v ngun ln nht ca lu hunh dioxit, ni la phun. Nhng s kin ny c th pht hnh hng triu tn SO 2.
2.2.2. Gim bc t oxit lu hunh bc cao hn:

Sulfur dioxide l mt sn phm trong sn xut canxi silicat xi mng: CaSO4 c un nng vi than cc v ct trong qu trnh ny: 2 CaSO4 + 2 SiO2 + C 2 CaSiO3 + 2 SO2 + CO2 2 CaSO 4 + 2 SiO2 + C 2 Casio3 + 2 SO2 + CO2 Cc hnh ng ca nng axt sulfuric trn ng phoi tin sn xut ixt lu hunh. Cu + 2 H2SO 4 CuSO4 + SO2 + 2 H2O
2.2.3. T Sulfite:

Sulfite kt qu t phn ng ca cc c s dch nc v kh lu hunh. Cc phn ng ngc li lin quan n qu trnh axit ha ca metabisulfite natri : H2SO4 + Na2S2O 5 2 SO2 + Na2SO 4 + H2O H2SO4 + Na2S2O5 2 SO2 + Na2SO4 + H 2 O

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3.

TC HI: Kh SO2, SO3 gi chung l SOx, l nhng kh thuc loi c hi khng ch i vi

sc kho con ngi, ng thc vt, m cn tc ng ln cc vt liu xy dng, cc cng trnh kin trc, l mt trong nhng cht gy nhim mi trng. Trong kh quyn, kh SO2 khi gp cc cht oxy ha hay di tc ng ca nhit , nh sng chng chuyn thnh SO3 nh oxy c trong khng kh. Khi gp H2O, SO3 kt hp vi nc to thnh H2SO4. y chnh l nguyn nhn to ra cc cn ma acid ma axit n mn cc cng trnh, lm cho thc vt, ng vt b cht hoc chm pht trin, bin t ai thnh vng hoang mc. Kh SO2 gy ra cc bnh vim phi, mt, da. Nu H2SO4 c trong nc ma vi nng cao lm bng da ngi hay lm mc nt qun o.
3.1.

i vi con ngi: SO2 v hp cht ca SO2 l nhng cht c tnh kch thch, nng nht nh c

th gy co git c trn ca kh qun. nng ln hn s gy tng tit dch nim mc ng kh qun. Khi tip xc vi mt chng c th to thnh axit SOx c th xm nhp vo c th con ngi qua cc c quan h hp hoc cc c quan tiu ha sau khi c ha tan trong nc bt. V cui cng chng c th xm nhp vo h tun hon. Khi tip xc vi bi, SOx c th to ra cc ht axit nh, cc ht ny c th xm nhp vo cc huyt mch nu kch thc ca chng nh hn 2-3 m. SO2 c th xm nhp vo c th ngi qua da v cc bin i ha hc, kt qu ca n l hm lng kim trong mu gim, amoniac b thot qua ng tiu v c nh hng ti tuyn nc bt. Hu ht dn c sng quanh khu vc nh my c nng SO 2, SO3 cao u mc bnh ng h hp. Nu ht phi SO 2 nng cao c th gy t vong. Trong mu, SO2 tham gia nhiu phn ng ho hc lm gim d tr kim trong mu gy ri lon chuyn ho ng v protin, gy thiu vitamin B v C, to ra methemoglobine chuyn Fe2+ (ho tan) thnh Fe3+(kt ta) gy tc nghn mch mu cng nh lm gim kh nng vn chuyn xy ca hng cu, gy co hp dy thanh qun, kh th. Lp DH08MT Nhm 1 Trang 14

C ch hnh thnh v k thut x l SO2

Hnh 3.1: Tc hi ca SO2 i vi con ngi Bng 3.7: c tnh ca SO2 Theo Henderson Haggard Triu chng Cht nhanh trong 30 1h mg/m3 1.300 1.000 Ppm 500 400

Nguy him sau khi ht th 30 1h

260 130

100 50

3.2.

i vi thc vt: SOx b oxy ha ngoi khng kh v phn ng vi nc ma to thnh axit sulfuric

l tc nhn chnh gy hin tng ma axit, nh hng xu n s pht trin thc vt. Khi tip xc vi mi trng c cha hm lng SO2 t 1 - 2ppm trong vi gi c th gy tn thng l cy. i vi cc loi thc vt nhy cm nh nm, a y, hm lng 0,15 - 0,30 ppm c th gy c tnh cp.

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Hnh 3.2: ma axit tc ng rng

3.3.

i vi cng trnh kin trc: S c mt ca SOx trong khng kh m to thnh axit l tc nhn gy n mn kim

loi, b-tng v cc cng trnh kin trc. SOx lm h hng, lm thay i tnh nng vt l, lm thay i mu sc vt liu xy dng nh vi, hoa, cm thch; ph hoi cc tc phm iu khc, tng i. St, thp v cc kim loi khc trong mi trng kh m, nng v b nhim SOx th b han g rt nhanh. SOx cng lm h hng v gim tui th cc sn phm vi, nylon, t nhn to, bng da v giy

Hnh 3.3: Tc hi ca SO2 i vi kin trc Lp DH08MT Nhm 1 Trang 16

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4. 4.1.

PHNG PHP X L: Phng php hp ph:

4.1.1. Hp ph kh SO2 bng than hot tnh:

Khi thi i vo thp hp th gm nhiu tng, kh SO2 c gi li trong lp than hot tnh ca cc tng hp th, sau khi i qua cyclone lc sch tro bi trc khi thi ra kh quyn. Than hot tnh c hon nguyn bng cch nng nhit ln 400450OC. Kh SO2 thot ra t qu trnh hon nguyn c nng 40-50% v t khong 9697% lng kh SO2 c trong khi thi. Sau khi hon nguyn than hot tnh c sn chn li loi b phn than qu vn nt v b sung thm than mi a ln hp ph tr li. Kh thot ra t qu trnh hon nguyn ngoi SO2 cn c mt s loi kh khc nh: H2S l 2-4%, lu hunh l 0,1-0,3%.
4.1.2. Hp ph kh SO2 bng than hot tnh c ti nc qu trnh LURGI:

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 m trong thit b hp ph. Kh SO 2 b gi li trong lp than hot tnh v oxy ha thnh SO3 nh c oxy trong kh thi. Tip theo, SO3 kt hp vi nc bin thnh axit sunfuric H2SO4 v theo nc chy vo thng cha. Axit sunfuric thu c trong thng cha vi nng 20-25%. H thng th nghim ban u vi lu lng khi thi 1000-1500 m3/h. Nng ban u ca SO2 trong khi khi t nhin liu mazut 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 ca n khng h b gim st.
4.1.3. X l SO2 bng nhm oxit kim ha:

Qu trnh x l kh SO2 bng nhm oxit kim ha c da trn tnh cht hp ph ca hn hp nhm oxit (Al2O3) v natri oxit (Na2O) vi thnh phn natri oxit chim 20% khi lng 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. Lp DH08MT Nhm 1 Trang 17

C ch hnh thnh v k thut x l SO2

4.1.4. X l SO2 bng Mangan oxit:

C 2 phng php tiu biu ca qu trnh x l SO 2 bng Mangan oxit l qu trnh Mangan c nghin cu p dng M v qu trnh DAR Mangan do hng Mitsubishi ca Nht Bn xut. Trong qu trnh Mangan ca M, cht hp ph c s dng l Mangan oxit (Mn2O3) dng ht c lm kh trong khng kh v trong chn khng nhit 300 - 400OC. Qu trnh DAR-Mangan ca hng Mitsubishi s dng cht hp ph l hn hp ca mt s oxit c gi l oxit Mangan hot tnh. Cht hp ph thu c bng cch dng amoniac x l Mangan sunfat v tip theo l oxy ha hydrat bng oxy trong khng kh v hi nc: MnSO4 + 2NH4OH Mn(OH)2 + (NH4)2SO4 Mn(OH)2 + 0,5iO2 + n(n-1)H2O MnO2+ i.nH2O Trong : i = 0,5-0,8 v n = 0,1-1,0

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4.1.5. X l SO2 bng vi v dolomit trn vo than nghin:

Qu trnh t nhin liu than nghin c trn bt vi v dolomit kh kh SO 2 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 xy ra nh sau: 2CaO + 2 SO2 + O2 2CaSO4 2CaCO3.MgCO3 + 2SO2 + O2 2[CaSO4 + MgO] + 4CO2 Phn ng gia vi v SO2 xy ra mnh nht nhit 760-1040OC, cn phn ng gia dolomit v SO2 nhit 600-1200OC. Phng php ny l s kt hp gia qu trnh chy vi qu trnh kh kh SO2 thnh 1 qu trnh thng nht trong bung t ca l m khng i hi phi lp t thm nhiu thit b ph tr khc. Trong mt s trng hp khc, ngi ta cn dng vi di dng va (30% cht rn trong nc theo khi lng) v phun vo dng khi thi trong thit b gi l bung sy kh kiu phun t trn ng khi ca l. Kh SO2 trong khi thi kt hp vi Ca(OH)2 theo phn ng: SO2 + Ca(OH)2 CaSO3 + H2O, CaSO3 b oxy ha rt nhanh bng oxy c mt trong khi thi v to thnh CaSO4: CaSO3 + O2 CaSO4 C canxi sunfit v canxi sunfat u rt t ha tan trong nc. Khi cc git va c lm kh bng nhit ca khi thi, chng s tr thnh nhng ht rn c nhiu l rng v c tch ra khi khi thi trong thit b lc bi. Ngi ta gi l phng php ra kh t - kh hn hp bng vi.
4.2.

Phng php hp th: Nguyn tc c bn ca vic hp th kh l to ra mt s tip xc gia dng kh vi

cc cht nhim v cc ht dung dch hp th thng c phun ra vi kch thc nh v mt ln. Cc cht nhim c tch ra bng vic ho tan trong cht lng hp th hoc xy ra phn ng ha hc gia cht nhim v dung dch hp th .Trong k thut hp th ,dng kh thng c cho i ngc chiu vi cc ht dung dch hp th vi tc hp l, thng thng ngi ta thng chn vn tc ny trong khong 1,0 -2,5 m/s.

Hiu qu ca cc qu trnh ph thuc vo din tch b mt tip xc gia dng kh v cc ht dung dung dch hp th, thi gian tip xc, dung dch hp th, nhit kh thi, hng chuyn ng tng i ca dng kh v dung mi, tc dng kh 4.2.1. Dung dch hp th: Trong cc yu t nu trn, dung dch hp th l mt trong cc yu t rt quan trng. Yu cu vi dung dch hp th cn phi t c: c kh nng hp th c cc cht nhim cn x l, r tin, d kim, d bay hi nhit v p sut thp, nht ng lc hc thp, t hoc khng gy n mn thit b. Tuy nhin kh c loi dung dch hp th no p ng c tt c cc yu cu trn, v th khi la chn dung dch ngi ta thng da vo kh nng c th hp th c cc loi cht nhim lm yu t quan trng nht. Dung dch hp th c th c phn loi nh tnh phn ng ca chng, nu chng l ha cht dng tch cht nhim. i vi sulful dioxit c th chuyn sang mu xanh nht do kt hp vi nc v oxit canxi (CaO), c th l do n kt hp vi hydroxyt canxi (Ca(OH)2),to ra dng mui sulfat canxi (CaSO4). Chnh phn ng ny c tc dng lm ty sch SO2 ra khi dng kh: SO2 + H2O +CaO = CaSO4 + H2O. Nu ch tch kh ra do ha tan m khng xy ra phn ng ha hc, cht hp th ny c coi nh l cht hp th khng phn ng. Nc hoc du cacbon nng l nhng v d cho dung dch hp th khng phn ng. Loi dung dch hp th khng th dng li c sau khi dng hp th ,ngha l sau hp th phi b i, do vy chng l loi dung dch hp th khng ti sinh. Nc l mt v d, vi nhng loi dung dch hp th m thu c lng kh nhim nh mt tc ng no nh thay nhit dung dch,thay i p sut th gi l dung dch hp th c th ti sinh c. Dung dch hp th c th ti sinh l nhng dung dch t tin hoc l nhng cht xc tc, c th l nhng cht dng trung ha cht nhim c th chuyn ha chng thnh dng rn hoc lng ri tch chng ra hoc l nhng cht a thm vo quy trnh sn sut tp trung cht nhim.

4.2.2. Thit b hp th: Thit b hp th l loi thit b m trong bn thn n c cha dung dch hp th, hp th kh i qua. Vic lp t, thit k sao cho c th tch ra c mt lng kh ln nht t dng kh. Sau y l mt vi kiu thit b hp th: Thp m Thp m c dng mt hnh tr ng thng, trong n cha y nhng ht vt liu thch hp, c th l ht polyetylen c dng xon c hoc hnh vnh khuyn, cc khu s l t t st nung vi cc kch thc khc nhau c xp ngu nhin trong thit b.

Hnh 4.1.Thp hp th kiu m Thp a

Hnh 4.2.Thp a Thp a c dng hnh tr ng thng , bn trong c cha mt s a ln hnh trn c c l. Dng kh i t di ln vi vn tc thch hp s to ra cc bt kh trong lp cht lng pha trn a, v th qu trnh tip xc ny thng gi l qu trnh tip xc dng bt. pha cnh a c nhng ng nc nhm cung cp nc t a ny sang a khc. Thp phun (thng ra kh rng) Thp phun c dng tr t thng ng, c s dng da trn nguyn tc to ra s tip xc trc tip gia cc cht nhim v cc ht dung dch hp th c phun ra di dng cc ht nh v mt ln. Dung dch hp th c phun ngc chiu vi dng kh bc ln, to ra mt s hn lon trong dng kh. Trong trng hp c bit khi mun ha tan vi tc cao cc thnh phn trong dng kh, ng thi phun dung dch hp th vo trong dng kh to ra mt tc ln tip xc gia dng kh v cht lng ln nht c th c.Thp phun cn c tc ng lm tch ra nhng ht cht lng c kch thc ln hn 10 v thp cn c th dng x l bi .u im ca loi thit b ny l cu to v vn hnh n gin, gi thnh thp hn thp m v thp a, hiu sut kh n nh nhng thng rt thp v tiu hao dung dch hp th ln hn cc loi thit b trn.

Hnh 4.3. Thng phun Lc bng phun ha cht Thit b gm hai n nguyn, dung dch hp th c a vo mt n nguyn t pha nh bng cch phun mnh xung dng kh, kh thi c i vo t pha hng thit b. Nhng ht dung dch hp th nh mn c phun vo lm gi li cc ht bi nh, bi vy lm tng thm hiu qu lc. Cc kh sch c thot ra cc n nguyn cn li.

Hnh 4.4.Thit b r kh bng phun nc Thng rung ng Trong thng c cha mt thit b khuy ng, khi a dung dch hp th vo s lm xo trn dng kh; trong thng cn c cc a ngn cng c tc dng lm xo trn dng kh. Chnh s chuyn ng xo trn ca dng kh ny to iu kin cho dung dch hp th tt cc kh cng nh bi nhim .

Hnh 4.5. Thng rung ng 4.2.3. Hp th SO2 bng nc: Hp th kh SO2 bng nc l phng php n gin c p dng sm nht loi b SO2 trong kh thi, nht l trong khi t cc loi l cng nghip. S h thng x l SO2 bng nc bao gm 2 giai on
1- Hp th kh SO2 bng cch phun nc vo dng kh thi hoc cho kh thi i qua

lp vt liu m (vt liu rng) c ti nc scrubo.

2- Gii thot kh SO2 ra khi cht hp th thu hi SO2 (nu cn) v nc sch

Mc ha tan ca kh SO2 trong nc gim khi nhit cng tng cao, do nhit nc cp vo h thng hp th kh SO2 phi thp. Cn gii thot kh SO2 khi nc th nhit ca nc phi cao. C th l nhit 1000C th SO2 bc ra mt cch hon ton v trong kh thot ra c ln c hi nc. Bng phng php ngng t ngi ta c th thu c kh SO2 vi m c axit sunfuric. 100% dng vo mc ch sn xut

 bng 4.8 l lng nc l thuyt cn hp th 1 tn kh SO2 trong kh thi cho n gii hn bo ha ng vi nhit v nng ban u khc nhau ca SO2 trong kh thi Bng 4.8: Lng nc l thuyt tnh bng m3 cn hp th 1 tn SO2 n trng thi bo ha ng vi nhit v nng SO2 khc nhau trong kh thi Nng SO2 Lng nc, m3, nhit trong kh thi, % khi lng 12 10 8 6 4 100C 48 57 70 92 140 150C 55 67 84,5 106 165 200C 66 78 96,2 123 200

Lng nc thc t phi ln hn mt t so vi lng nc l thuyt v nc sau khi ra khi khi thit b hp th khng th t mc bo ha kh SO2. gii hp th cn phi un nng mt lng nc rt ln tc phi c mt ngun cp nhit (hi nc) cng sut ln. l mt kh khn. Ngoi ra s dng li nc cho qu trnh hp th phi lm ngui nc xung gn 100C, tc phi cn n ngun cp lnh. cng l vn khng n gin v kh tn km T nhng nhc im ni trn, phng php hp th kh SO 2 bng nc ch p dng c khi:

Nng ban u ca kh SO2 trong kh thi tng i cao

C sn ngun cp nhit (hi nc) vi gi r C sn ngun nc lnh

 C th x c nc c cha t nhiu axit ra sng ngi Trng hp kh thi giu SO2 nh trong cng on nu qung sunfua kim loi ca cng nghip luyn kim mu chng hn, nng SO2 trong kh thi c th t 2 12% ngi ta c th x l SO2 bng nc kt hp vi qu trnh oxi ha SO2 bng cht xc tc Qu trnh cng c thc hin thnh 2 giai on. Giai on th nht kh SO2 kt hp vi oxi nh s c mt ca cht xc tc vanai (V) bin thnh anhirit sunfuric SO3 v giai on th hai l dng nc ti trong scrub anhirit sunfuric kt hp vi nc to thnh axit sunfuric H2SO4. Trong giai on th nht, phn ng oxi ha kh SO 2 c ta 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. S h thng x l SO2 bng nc kt hp vi oxi ha bng cht xc tc c th hin hnh 14.1b. 4.2.4 X l SO2 bng vi (CaCO3) hoc vi nung (CaO): X l SO2 bng vi l phng php c p dng rng ri trong cng nghip v hiu qu x l cao, nguyn liu r tin v sn c mi ni. Cc phn ng ha hc xy ra trong qu trnh x l: CaCO3 + SO2 = CaSO3 + CO2 CaO + SO2 = CaSO3 CaSO3 + O2 = 2CaSO4 S h thng x l kh SO2 trong khi thi bng sa vi:

Hnh 4.1: S h thng x l SO2 bng CaCO3 v CaO 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 chua cha axit chy ra t scrubo c b sung thng xuyn bng sa vi mi. Trong nc chy ra t scrubo c cha nhiu sunfit v caxi sunfat di dng tinh th :CaSO 3.0,5H2O, CaSO4.2H2O v mt t tro bi cn st li sau b lc tro bi, do cn tch cc tinh th ni trn ra khi dung dch bng b phn tch tinh th 2. Thit b s 2 l mt bnh rng cho php dung dch lu li mt thi gian d hnh thnh cc tinh th sunfit v sunfat caxi. Sau b phn tch tinh th 2, dung dich mt phn i vo ti cho scrubo, phn cn li i qua bnh lc chn khng 3, cc tinh th b gi li di dng cn bn v c thi ra ngoi. vi c p vn v nghin thnh bt cc thit b 7, 8 ri cho vo thng 6 pha trn vi dung dch long chy ra t b lc chn khng 3 cng vi mt lng nc b sung c dung dch sa vi mi. Hiu qu hp th SO2 bng sa vi t 98%. Sc cn kh ng ca h thng khng vt qu 20mm ct nc.

Nguyn liu vi dc s dng mt cch tun hon, cn bn t h thng x l thi ra c th c s dng lm cht kt dnh trong xy dng sau khi chuyn sunfit thnh sunfat trong l nung. Hiu qu hp th SO2 trong scrubo ph thuc vo vn tc kh v pH ca dung dch sa vi ti trn lp m Phng php x l SO2 bng dung dch vi sa c th dung nguyn liu l vi hoc vi nung. Dng vi th r tin hn nhng hiu qu x l khng bng vi nung u im ni bt ca phng php ny l cng ngh n gin, chi ph u t ban u khng ln, c th ch to thit b bng vt liu thng thng, khng cn n vt liu chng axit v khng chim nhiu din tch xy dng. 4.2.5 X l SO2 bng Amoniac: Amoniac v kh SO2 trong dung dch nc c phn ng vi nhau to ra mui trung gian amoni sunfit li tc dng tip vi SO2 v H2O to ra mui amoni bisunfit theo phn ng sau: SO2 + 2 NH3 + H2O = (NH4)2SO3 (NH4)2SO3 + SO2 + H2O = 2 NH4HSO3 Lng bisunfit tch t dn dn 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 tip tc s dng kh SO2 2 NH4HSO3 t0 (NH4)2SO3 + SO2 + H2O

Ngoi ra trong dung dch c th xy ra s phn hy sunfit v bisunfit amoni thnh sunfat amoni v lu hunh n cht theo phn ng sau y: 2 NH4HSO3 + (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 lu hunh n cht nhiu hn gp 2 ln (NH4)2S2O3 + 2 NH4HSO3 = 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 s hon ton bin thnh amoni sunfat v lu hunh n cht a/ H thng x l SO2 bng amoniac theo chu trnh S h thng x l SO2 bng ammoniac:

Hnh 4.2: S x l SO2 bng amoniac Kh thi t l sau khi c lc sch tro bi i vo scrubo 1 v c nc ti tun hon. Khi c lm ngui ti 300C, cn bi cn c thi ra ngoi. Trong nc tun hon cho qua trnh lm ngui khi trong scrubo 1 c cha bi, SO2 v H2SO4. Lng kh SO2 kh c trong scrubo 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 500C.

nc tun hon c trong h thng, n phi c lm ngui xung khong 270C trong

thit b lm ngui (thit b trao i nhit ) s 2. Thit b 2 c th l thp lm mt, lc 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 lin tc vo vng tun hon. T scrubo 1 kh c lm ngui v i vo thp hp th s 3, ti qu trnh hp th SO2 c thc hin trn nhiu tng, mt tng hp th c ti dung dch theo chu trnh kn, trong kh 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. Thnh phn dung dch ti mi tng hp th c gi khng i. Dung dch hon nguyn c cp vo tng hp th k vi tng trn cng. Dung dch i ra tng hp th di cng c cha nhiu bisunfit (NH4)2SO3 c tch th mt phn a vo thp hon nguyn 5, trong c cp nhit bng hi nc bo ha kh (i trong dn xon) un nng dung dch. y xy ra phn ng 2 NH4HSO3 t0 (NH4)2SO3 + SO2 + H2O

Kh SO2 thot ra t thp hon nguyn 5 t nng t 94 98% v c s dng iu ch axit 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 NH 3 tiu hao to thnh amoni sunfit theo phn ng: 2 NH4HSO3 + (NH4)2SO3 = 2 (NH4)2SO4 + S + H2O tch amoni sunfit hnh thnh trong qua 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 dung dch ra khi thp hp th 3 cn c th c thiosunfat. Do mt phn dung dch ra khi thp hp th 3 c a sang x l ni chng p 9. y di p sut v nhit 1400C sunfit, bisunfit v thiosunfat amoni

phn hy thnh amoni sunfat v lu hunh n cht theo phn ng: (NH4)2S2O3 + 2 NH4HSO3 = 2(NH4)2SO4 + 2S + H2O

Dung dch amoni sunfat c tch khi lu hunh bng phng php lng v i vo thp bc hi 6 , cn lu hunh n cht c ra khun. Tinh th amoni sunfat thu c t my ly tm 8 c th cc thnh phn sau: (NH4)2SO4 (NH4)2SO3 NH4HSO3 H2 O 92-93% 2-3% 0,5 1% 4-5%

Amoni sunfat l mt loi phn bn v mc d c ln mt t sunfit v bisunfit, cht lng ca n vn khng b nh hng my. Cng c th nng cao cht lng phn bn bng cch dng khng kh nng sy kh cc sunfit v bisunfit oxi ha v bin thnh amoni sunfat hon ton. b/ X l SO2 bng amoniac c chng p: S h thng x l SO2 bng amoniac c chng p:

Hnh 4.3: S x l SO2 bng aminoac 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 hon. Nng mui amoni trong dung dch hp th t khong 45%. Ngi ta b sung vo dung dch ti mt lng dung dch nc - amoniac m c (30%) . Mt phn dung dch ti tng ng vi lng dung dch mi b sung vo lun lun c tch ra sau thp hp th a vo b lc p 2, sau i vo thng chng p 3. y ngi ta tch mt lng nh axit sunfuric vo dung dch v un nng n nhit 180 0C vi p sut d 14 atm. Di iu kin nhit v p sut nu trn qu trnh oxi ha t ng xy ra to thnh amoni sunfat v lu hunh n cht. Sau khi hon thnh phn ng oxi ha, cc cht trong thng trng p ngui dn, p sut d gim xung n 3,5 atm, lu hunh n cht lng xung y ri a ra thnh khun. Phn dung dch ni bn trn c a sang thit b bc hi chn khng 4 ri a qua my lc ly tm 5 tch amoni sunfat. c im ca phng php x l SO2 bng amoniac c chng p l sn phm cui cng thu c ch yu gm amoni sunfat.

c/X l SO2 bng amoniac v vi

Hnh4.4: S h thng x l SO2 bng amoniac kt hp vi sa vi Hn hp hi nc v amoniac c phun trc tip vo khi thi trn ng ng dn vo h thng hai scrubo lp ni tip 1 v 2. Kh SO2 trong khi thi kt hp vi amoniac to thnh sunfit v bisunfit amoni. Trong scrubo 1 phn ln tro bi v cc sn phm sunfit, bisunfit c loi ra khi dng kh v theo dung dch ti chy xung thng cha 7. Ti y nhit d kh cng h xung cn khong 600C. Tip theo kh i vo scrubo 2 v cc sn phm 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 scrubo 2 chy xung thng cha 8 c a sang ti cho scrubo 1 v mt lng dung dch mi c b sung vo thng 8. 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 sunfat canxi theo phn ng sau y:

(NH4)2SO4 + Ca(OH)2 = CaSO4 + 2NH3 + 2H2O NH4HSO3 + Ca(OH)2 = CaCO3 + NH3 + 2H2O (NH4)2SO3 + Ca(OH)2 = CaCO3 + 2NH3 + 2H2O Amoniac v hi nc bc ln t thng phn ng 3 c ht v thu vo ng ng dn khi thi , cn bn nho lng y c a sang lm ngui trong thit b trao i nhit 4, sau c tch ra my lc ly tm 5 v dung dch trong mt phn a v thng 8 tham gia vo chu trnh ti cho scrubo 2, phn cn li chy vo thng 6 pha ch sa vi mi. Cn thu c my lc ly tm 5 khng ch canxi bisunfit c tnh cht ha tan nn c th loi b hoc c s dng nh vt liu san lp, lm nn ng Hiu qu x l SO2 ca phng php ammoniac - vi c th t 95%, nng NH3 theo kh sch thot ra khong 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 SO 2 trong khi thi c cha nhiu bi v nhit cao, h thng c th lm vic vi lu lng rt ln. Nhc im ca phng php ny l lng ph thi nhiu. 4.2.6. X l SO2 bng MgO: Kh nng s dng MgO kh SO2 trong kh thi c bit t lu nhng nghin cu ng dng trong cng nghip mi c thc hin gn y ch yu l cng ngh ca Lin X. Phng php ny da trn cc phn ng: MgO + SO2 = MgSO3 MgSO3 + SO2 + H2O = Mg(HSO3)2 2MgSO3 + O2 = 2MgSO4 Magie sunfat khng c hot tnh i vi SO2 do phn ng oxi ha sunfit l khng mong mun. Tuy nhin, khi nng MgSO4 trong dung dch lm vic t 120-160 g/l th qu trnh oxi ha sunfit s ngng li khng tip tc xy ra na.

Magie bsunfit c th b trung ha bng cch b sung thm MgO mi: Mg(HSO3)2 + MgO = 2MgSO3 + H2O ha tan ca magie sunfit trong nc rt hn ch nn MgSO3 s kt ta thnh MgSO3.6H2O v nhit 50oC tinh th ny bin thnh MgSO3.3H2O. Cc tinh th c tch ra khi dung dch huyn ph, sy kh v x l nhit 800-900oC thu hi MgO v SO2 MgO c quay tr li chu trnh lm vic cn SO2 m c c a sang cng on ch bin axit sunfuric hoc lu hunh n cht. a/ Phng php MgO kt tinh theo chu trnh: Kh thi cn x l SO2 a vo scrubo 1 trong c ti dung dch huyn ph MgSO3.6H2O v MgO. Kh SO2 trong kh thi s b kh theo phn ng: MgO + SO2 = MgSO3 v MgSO3 + SO2 + H2O = Mg(HSO3)2, kh sch thot ra ngoi. Sau khi ra khi scrubo 1, mt phn dung dch b oxi ha chy vo b cha 3, ti y c b phn o liu lng 4, MgO c b sung vo b cha. Lng MgO b sung ph thuc vo lng SO2 kh c. T b cha 3 dung dch vi t l rn-lng 0,1 c a ln ti cho scrubo sau khi c lc cc ht cng b lc 2. Mt phn dung dch ra khi scrubo 1 c a sang xiclon thy lc 5 v 6. Phn bn st lng y xiclon s chy xung my lc chn khng c bng ti s 8 tc cc tinh th MgSO 3.6H2O. Phn ni bn trn cc xiclo cng cn ln nhiu cn bn c a sang my lc p 7 loi b cn bn, phn dung dch cn li cc b lc 7 v 8 chy tr v b cha 3 chun b dung dch ti ln.

Hnh 4.5: S x l SO2 bng MgO kt tinh theo chu trnh pH ca dung dch ti ch vo scrubo nm trong khong 6,7-7,2 v t scrubo chy ra l 5,5-5,8. Cng ti dung dch trong scrubo l 18-20 m3/m2.h. b/ Phng php magie oxit khng kt tinh: khc phc tnh trng lp m ca scrubo b ng cn nhanh chng bi cc tinh th magie sunfit, ngi ta p dng phng php kh magie oxit khng kt tinh. Thc cht ca phng php ny l cc tinh th hnh thnh trong dung dch ti c tch ra trong thit b ring bit gi l b trung ha, trong magie bisunfit theo dung dch scrubo chy ra kt hp vi MgO: Mg(HSO3)2 + MgO = 2MgSO3 + H2O, nh lng magie sunfit cn li trong dung dch sau khi ti ch chim khong 2-3% v thit b hot ng c nh nhng hn. S x l:

Hnh 4.6: S x l SO2 bng MgO khng kt tinh Kh cn lc sch SO2 c a vo scrubo 1, c ti dung dch hp th t thng p lc 2. Sau khi hp th SO2 trong kh thi, dung dch c nng magie bisunfit 50 -70 g/l t scrubo chy vo b cha 3.T mt phn dung dch a v thng p lc 2 ti tr li cho scrubo, phn cn li i vo thng trung ha 4 tch cc tinh th MgSO3.6H2O. Mt lng MgO thu c t qu trnh hon nguyn c cp vo thng trung ha 4. cc phn ng xy ra mt cch trit , thng trung ha 4 cn c dung tch ln, m bo c 30-35 pht hot ng ca h thng v phi c khuy lin tc 5060 vg/ph. Qu trnh tch v nung magie sunfit ly ra t b trung ha 4 cng c thc hin thu MgO v SO2. Dung dch long v nc t my p 7 chy v b cha 10 c khuy, ti y ngi ta cng b sung mt lng nc b hao ht v mt na lng MgO thu c sau qu trnh hon nguyn l nung 8. Dung dch mi t b cha 10 c a b sung vo thng p lc 2 tham gia vo chu trnh ti cho srubo.

c/ Phng php magie oxit si bt:

Thit b hp th trong phng php magie oxit c th thay i khc nhau. Trong phng php gi l magie oxit si bt, thp hp th c kt hp vi thng kt tinh thnh mt khi thng nht. Kh thi cn lc sch SO2 i vo khoang trng bn trn ca thit b hp th 1 gm nhiu ng hnh tr thng ng, u di ca cc ng hnh tr nhng ngp 8-10 cm vo dung dch hp th cha phn di ca thit b hp th. Kh thi theo cc ng hnh tr sc qua lp dung dch hp th, lm si bt , ri qua b phn tch git nc 3 thot ra ngoi. Khi i qua lp dung dch si bt, kh SO2 trong kh thi cho phn ng vi dung dch hp th v b gi li trong dung dch di dng cc cht sunfit v bisunfit theo cc phn ng: MgO + SO2 = MgSO3 v MgSO3 + SO2 + H2O = Mg(HSO3)2 Thp hp th kt hp vi thng kt tinh lun lun c b sung dung dch mi c pha ch b cha 4. B phn khuy ca thng kt tinh lun lun hot ng v cht bn nho lng xung y thng. Sau cht bn nho c a sang cc cng on lc bng xiclon thy lc v my p c bng ti rroiof a sang l nung hon nguyn MgO. u im ca h thng ny l thp hp th khng cn lp m bng vt liu rng, do vn cn bn gy tc lp m khng xy ra. Tuy nhin do dng kh phi sc qua lp dung dch nn sc cn kh ng ca h thng tng i cao v v vy vn tc dng kh i qua tit din ngang ca thit b hp th phi hn ch mc thp nht. d/Phng php magie oxit kt hp vi potas (kalicacbonat): Nhc im ln nht ca phng php kh SO2 bng MgO l h thng thng b ng cn cc tinh th khng ha tan. V th, ngi ta tm ra phng php mi khc phc nhc im ny l phng php magie oxit-potas. Phng php ny dng dung dch kalicacbonat v kalisunfat ti cho thp hp th . Cc phn ng xy ra: K2CO3 + SO2 = K2SO3 + CO2 K2SO3 + SO2 + H2O = 2KHSO3 K2SO3 + O2 = 2K2SO4

Dung dch K2SO3 c trung ha bi MgO nhit 40 45oC to thnh cc tinh th hexahydrat magie sunfit kt ta v gii phng kalisunfit tham gia tr li vo chu trnh kh SO2: 2K2SO3 + MgO +6H2O = MgSO3.6H2O + K2SO3 + H2O Tip theo, qu trnh tch lc magiesunfit v nung hon nguyn MgO, thu hi SO2. S lm vic:

Hnh 4.7: S x l SO2 bng magioxit si bt Kh thi c nng SO2 t 0,15-0,6% i vo scrubo1 vi lp m bng vt liu rng xon, vn tc kh i qua tit din ngang ca scrubo c th t 15m/s, tn tht ct p tng i nh tng ng 14mm H2O cho 1m chiu cao ca lp m. Thp hp th c ti dung dch kalibisunfit nng 15-18%, cng ti 8-10m 3/m2.h. Dung dch ra khi scrubo c cha 150-300g/l, kalibisunfat thnh sunfat bng cch cho thm cht parafenylendiamin 0,01- 0,005% theo khi lng. Lc nng kalisunfat c th gim xung 15-20g/l.

Mt phn dung dch ng vi lng SO2 hp th c t scrubo chy ra c a vo bnh lc 3 tch cc cht rn, sau i vo thng phn ng 4 trung ha bisunfit. Hiu qu kh SO2 ca h thng t t 95-99% khi nng ban u ca SO2 trong kh thi i vo h thng t 0,15-0,6% theo th tch. y l phng php c tun hon theo chu trnh i vi c K2SO3 ln MgO, p dng cho c kh thi c nhit cao v cha nhiu bi m khng cn lm ngui hay lc bi trc khi vo h thng. 4.2.7 X l kh SO2 bng km oxit ZnO: X l kh SO2 bng km oxits (ZnO) cng tng t nh phng php oxit magie tc l dng phn ng gia SO2 vi km sunfit v bisunfit, sau dng nhit phn ly thnh SO2 v ZnO. u im chnh ca phng php ny l qu trnh phn ly km sunfit ZnSO3 thnh SO2 v ZnO xy ra nhit thp hn ng k so vi qu trnh phn ly bng nhit i vi MgSO3. p sut bo ha ca s trn MgSO3 bng 1 atm nhit 650oC, trong khi i vi ZnSO3 p sut bo ha nh trn c nhit ch bng 260 0C. iu cho php tin hnh phn ly ZnSO3 trong l mp v thu hi vi nng gn bng 100% trong lc MgSO3 c phn ly trong dng sn phm chy ca nhin liu nung v ch t nng khng vt qu 15-20%. a/ Phng php km oxit n thun: Theo phng php ny kh thi sau khi c lc tro bi khng cn lm ngui s b i vo scurb, trong ti dung dch huyn ph ZnO. Pnh ng xy ra trong scrcub nh sau: ZnO+ SO2=ZnSO3 (14.24)

Km sunfit hnh thnh t phn ng trn l loi mui km ha tan trong v kt ta di dng cc tinh th ZnSO3.25H2O trong b tun hon c khuy. Tinh th km sunfit c tch ra khi dung dch bng my lc hoc my ly tm. Dung dch long sau my lc c a v chun b sa km oxit mi, cn tinh th km sunfit th c sy kh v a vo l nung hon nguyn km oxit v thu hi SO 2 nng cao (gn bng 100% ).

Kh SO2 thu hi c th c ha lng hoc ch bin thnh axit sunfuric hoc lu hunh n cht. Trong qu trnh kh SO2 v trong kh thi c cha oxy nn km sunfit b oxi ha thnh sunfat - l cht c ha tan cao do c nng km sunfat trong dung dch dn dn tng cao. loi b km sunfat, mt phn dung dch sau khi tch lc cc tinh th km cn cho bc hi v b sung vo chu trnh mt lng km oxit tng ng. Nhc im ca phng php ny l i hi phi lc sch tro bi trong kh thi trc khi a vo h thng x l SO2 v tiu hao nhiu km oxit do c hin tng oxy ha km sunfit thnh sunfat. Ngoi ra, nu trong kh thi c cha cc cht nhim nh hydroclorua v oxit nit th lng tiu hao km oxit s nhiu hn do hnh thnh cc clorit v nitrit ha tan. b/ Phng php km oxit kt hp vi natri sunfit: S cng ngh ca phng php ny c th hin hnh 2.12. Kh thi sau khi qua b lc tro bi c a vo scrub 1 tip xc vi dung dch ti l sunfit v bisunfit natri. Kh SO2 b hp th bi dung dch ti l natri sunfit bin thnh bisunfit theo phn ng: Na2SO3 + SO2 + H2O = 2NaHSO3 (14.25)

Dung dch sau khi ti trong scrub c a v b lng 2, tro bi lng xung y b v dung dch trong i vo thng phn ng 7, km oxit sau khi c hon nguyn l nung 10 c a vo thng phn ng phc hi t l sunfit v bisunfit natri trong dung dch ti, cn km sunfit th kt ta thnh cn. Phn ng xy ra nh sau:

Hnh 4.8: S h thng x l SO2 bng km oxit kt hp vi natri sunfit 1-scrubo; 2,5-b lng ; 3,4,7 thng phn ng; 6,8-thit b lc chn khng; 9-my sy hnh trn;10-l nung hon nguyn ZnO v thu hi SO2 2NaHSO3+ZnO=ZnSO3+H2O (14.26) Tinh th km sunfit t thng phn ng 7 c tch ra my lc chn khng 8, qua my sy 9 ri i vo l nung 10. T l nung 10 km oxit quay tr li chu trnh cn kh SO2 thu hi c s lm kh v cung cp cho cc cng on ch bin axit sunfuric hoc lu hunh n cht. Phn dung dch sau my lc 8 c quay v ti cho scurb. Khi h thng lm vic, mt lng natri sunfit oxy ha thnh sunfat. Trong h thng ny sunfat c loi b bng cch chuyn thnh mui canxi nh x l dung dch bng vi cp vo thng phn ng 3 c khuy lin tc. Canxi sunfit khng ha tan c dng nho c b sung vo b lng 2, t y bn nho cha canxi sunfit v tro bi c a vo thng phn ng 4 kt hp vi mt lng nh kh SO2 trch ra t l nung 10, kt qu l canxi sunfit s chuyn thnh bi sunfit d ha tan hn theo phn ng : CaSO3+H2O+SO2==Ca(HSO3)2 (14.27)

ng thi cc ion ha tan trong thng phn ng 4 tc dng vi natri sunfit t ha tan. Canxi sunfat v tro bi c mt trong dung dch to thnh canxi sunfat t ha tan.

Canxi sunfat v tro bi s c lng trong b 5 v sau c tch ra my lc chn khng 6. Dung dch c loi b sunfat c cha canxi bisunfit ha tan li c x l bng vi trong thng phn ng 3 to ra cn nho mi b sung vo b lng 2. Lng vt liu tiu hao thu hi 1 tn kh SO2 nng 100% theo phng php ny nh sau: Vi: Km oxit : Natri sunfit : Mazut : Nc : 0.095 tn 0.015 tn 0.07 tn 0.28 tn 9.20 m3

Phng php ny cng nh phng php km oxit n thun khng i hi lm ngui s b khi thi, hiu qu kh SO2 t 96-98%. Nhng nhc im ch yu l h thng x l kh phc tp v tiu hao nhiu mui natri. 4.2.8. X l kh SO2 bng cc cht hp th hu c Qu trnh x l kh SO2 trong kh thi bng cc cht hp th hu c p dng nhiu trong cng nghip luyn kim mu.. Cht hp th kh SO2 c s dng ph bin l cc amin thm nh anilin C6H5NH2, toluidin CH3C6H4NH2, xylidin (CH3)2C6H3NH2 v imetyl-anilin C6H5N(CH3)2. Thc t cho thy dung dch xylidin trong nc c nhiu u im khi s dng kh SO2 trong khi thi vi nng thp, cn khi nng SO2 trong khi thi c nng tng i cao (trn 2%) th dimetyl-anilin c u th hn. Sau y ta xem xt cc s cng ngh x l SO2 theo cc qu trnh c s dng hai cht hp th hu c ch yu nu trn: xylidin v dimetyl anilin. Qu trnh sunfidin Qu trnh ny c cc hng cng nghip ho cht v luyn kim ca c nghin cu v p dng nh my luyn kim Hamburg kh SO 2 trong ng khi ca l thi

luyn ng . Nng 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 xylidin v nc t l = 1:1.

Hnh 4.9: S h thng x l kh SO2 theo qu trnh sunfidi 1-thit b trao i nhit(lm ngui);2;3-thp hp th; 4;7-scrubo;5-thp bc hi;6-b lng. Trn hnh 14.13 l s h thng x l kh SO2 theo qu trnh sunfidin . Kh thi s b c lm ngui v lc sch bi trong thit b lc bng in, sau cho qua cc cht hp th 2 v 3 t ni tip nhau. Cc thp hp th c ti hn hp xylidin nc theo s chuyn ng ngc chiu ca dng kh v dung dch hp th. Trong qu trnh hp th SO2 bng xilidin c ta ra mt lng nhit ng k, do cn lm ngui dung dch bng cc thit b trao i nhit 1. Kh sch i ra khi thp hp th c cha hi xylidin cn cho qua scrubo 4 thu hi hi xylidin bng axit sunfuric long. Dung dch hp th bo ha t thp hp th u tin (s 2) i ra vi nng SO 2 130-180 g/l c a vo thp bc hi 5. Nhit phn di ca thp bc hi c gi mc 455-1000C bng cht mang nhit l hi nc i bn trong ng xon. Cc loi kh, hi (gm SO2, xylidin v hi nc) bc ln trong thp bc hi c ngng t thit

b trao i nhit 1 ri i tip vo scrubo 7 ti bng nc gim nng xylidin trong kh SO2. T y kh SO2 c s dng cho cc cng on ch bin axit sunfuric hoc lu hnh n cht .Dung dch long xylidin 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 xylidin nc theo t l thch hp c bm qua thit b lm ngui ri ti cho thp hp th s 3. Trong qu trnh hp th, mt phn sunfit xylidin b oxy ha. hn ch s tch t sunfat xylidin trong dung dch hp th, ngi ta cho natri cacnonat (Na 2CO3) vo dung dch ti thp hp th 3. Natri cacbonat tc dng vi sunfat xylidin to thnh natri sunfat (Na2SO4) v cacbonic (CO2). 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. Hiu qu kh SO2 ca h thng t 96%-99%. Mt s s liu k thut ca h thng x l SO2 cng sut ln hot ng theo qu trnh sunfidin c th c nu ra sau y tham kho.

Nng xut thu hi SO2 ca h thng :70t/ngy. Nng trung bnh ca SO2 trong kh thi:

Nng ban u: 8% Nng cui :0,1%

Hiu qu kh SO2: 98,7% Mc bo ha SO2 ca dung dch hp th :150g/l. Lng vt liu tiu hao cho mt tn SO2:

Xylidin :7,3 kg. Hi nc :1,47 t.

Nc lm ngui :57 m3

 Chi ph in nng :98 kWh.

Qu trnh kh SO2 bng dimetylanilin Qu trnh ASARCO (American Smelting and refining Company). Qu trnh ny c nghin cu v p dng nhiu cc nh my luyn kim

thuc bang Washington ca M.

Hnh 4.10: S h thng x l kh SO2 theo qu trnh ASARCO . 1-thp hp th: 2,3,5-b cha; 4;7-b phn ly; 6-thit b lm ngui; 8-thp gii hp th; 9thng ngng t; 10- scrubo; 11-thit b cp nhit (un nng); 12-b mt trao i nhit. S h thng hp th kh SO2 bng dimetyl-anilin theo qu trnh ASRACO c gii thiu hnh trn.

Kh thi sau khi c lc sch bi v cc gt sng axit sunfuric bng b lc in v scrubo c a vo thp hp th 1 trong xy ra 3 qu trnh sau y:
Hp th kh SO2 bng dimetyl-anilin khan. Kh SO2 cn li trong kh bng dung dch natri cacbonat long thu sunfit v

bisunfit natri dng trong cc giai on tip theo. Hp th hi imetyl-anilin bng axit sunfuric long v thu c sunfat imetylanilin. Phn di ca thp hp th c chia thnh tm tng ti dung dch. Lng nhit ta ra trong qu trnh hp th SO2 bng imetyl-anilin c kh bng cc thit b lm ngui 6: dung dch sau khi ti tng trn chy ra c lm ngui ri a xung cho tng di; tng di cng c ti bng dung dch tun hon, dn dn hp th c bo ha bi kh SO2 v mu ca n chuyn t mu vng nht sang mu thm. Phn gia ca thp hp th gm hai tng c ti dung dch natri cacbonat long Phn trn cng ca thp c chia thnh 14 tng v dng axit sunfuric long ti. Cht hp th bo ha t thp hp th i ra c un nng trong b mt trao i nhit 12 nh lng nhit ca bn thn cht hp th c hon nguyn t thp gi hp th 8 i ra ti vo phn gia (phn bc hi) ca thp 8. Kh SO 2, hi imetyl-anilin v hi nc bc ln trong thp 8 c a vo thng ngng t 9, hi nc v hi imetyl-anilin s ngng t li, cn kh SO2 i tip sang thp ra cui cng s 10 dng nc kh sch hi imetyl-anilin to thnh sunfit dimetyl-anilin nh s c mt ca SO2. Dung dch c hnh thnh cng vi nc ngng t thng ngng t 9 c dng ti vo phn trn cng ca thp 8. Cht hp th c hon nguyn cng vi nc ngng i ra t pha di ca phn bc hi c lm ngui s b trong b mt trao i nhit 12 v tip tc c lm ngui su hn trong thit b 6 ri i vo b hn li 4, ti imetyl-anilin c tch ra khi nc v chy vo b cha 2 ti cho thp hp th 1. Mt phn nc c tch ra t thng phn li 4 i vo b cha 5 v c dng ti

vo phn di cng c gi l phn hon nguyn ca thp gii hp th 8 phc v cho vic hon nguyn imetyl-anilin. Phn nc cn li cng vi dung dch hp th chy ra t phn trn v phn gia ca thp hp th 1 i vo b cha 3. Dung dch trong b cha 3 c cha mt lng nh cht dimetyl-anilin di dng l lng c a vo b phn ly dung dch long s 7, sau phn nc chy vo b cha 5 cn cht l lng c m c hn i tip vo b phn ly 4. Phn nc trong b 5 c cha cc cht sau: Axit sunfuric long v dung dch sunfat imetyl-anilin t phn trn ca thp hp th. Dung dch natri cacbonat long c cha c sunfit v bisunfit natri. Dung dch sunfit imetylanilin long t phn bc hi ca thp gii hp th . T b cha 5 nc c dng ti vo phn di cng ca thp gii hp th 8
Ti y trong dng hi nc ,sunfit imetyl-anilin c phn gii thnh imetyl-

anilin v kh SO2 chng theo hi nc bc ln trn. Cng ti y, nhit hon nguyn, sunfat imetyl-anilin tc dng vi sunfit v bisunfit natri to thnh imetyl anilin t do, kh SO2 v natri sunfat. Hn hp kh SO2, hi imetyl-anilin v hi nc cng bc ln trn v thot ra khi thp gii hp th, cn dung dch natri sunfat th thi ra ngoi. pha di ca phn bc hi v phn hon nguyn ca thp 8 dung dch c un nng bng cc b t 11. Dung dch thi ra hu nh khng cha imetyl-anilin. pH ca dung dch thi c gi mc 5-6 bng cch iu chnh lng natri cacbonat ti vo phn gia ca thp hp th.