CC PHNG PHP X L H2S 2.

1 X L KH H2S BNG NATRI CARBONAT, AMONI CACBONAT HOC KALIN PHOPHAT Qu trnh x l H2S bng Na2CO3 c da trn c s cc phn ng sau: H2S + Na2 CO3 = NaHS + NaHCO3 (1) Tip theo l phn ng thu hi lu hunh c s tham gia ca natri vanadat NaVO3 2NaHS + H2S + 4NaVO3 + O2 = Na2V4O9 + 4NaOH + 3S (2) hon nguyn natri vanadat NaVO3 ngi ta dng cht xc tc ADA (ADA: natri amoni vanadat v disunfonat) Na2V4O9 + 2NaOH + O2 + 2ADA = 4NaVO3 + 2ADA (3) Phn ng (1) trn xy ra trong thp hp th Scruber Dung dch bo ha t thp hp th Scruber 1 chy ra c lm bc hi bng khng kh nng trong thp gii hp th 2 thu hi li Na2CO3 v chu trnh lm vic ca thp hp th Scruber 1 c th tip din. Kh H2S thu c t thp 2 s c a sang cng on tip theo thu hi sn phm cui cng l lu hunh n cht ng thi hon nguyn natri vandadat theo cc phn ng trn (2) v (3). Phng n thay th cho natri cacbonat l ngi ta dng kali photphat K3PO4 v phn ng kh H2S s l: K3PO4 + H2S = K2HPO4 + KHS (4) u im: Tnh cht bn vng ca n ng thi phn ng ca n vi H2S mang tnh cht chn la khi c mt ca kh SO2 trong kh thi. Trong trng hp ny c th dng hi nc lm bay hi v thu hi H2S. Ngoi ra, ngi ta cn c th dng amoni cacbonat v kali cacbonat lm dng dch hp thu i vi kh H2S. Vi amin cacbonat, phn ng xy ra nh sau: (NH4)2CO3 + H2S = (NH4)2S + H2O + CO2 (5) Amoni sunfua (NH4)2S thu c trong dung dch ra khi thp hp th s c phn hy thnh NH3 v H2S. Dung dch NH3 quay tr li chu trnh kt hp vi CO2 v H2O c trong kh thi to thnh amin cacbonat v phn ng trn tip tc xy ra theo S h thng x l kh H2S bng amoni cacbonat 2.2 X L H2S BNG XT NaOH C s ca phng php ny l kh H2S kt hp vi NaOH theo phn ng sau y: H2S + 2NaOH = Na2S + 2H2O (6) Na2S + H2S 2NaHS (7) Na2S + H2O NaHS + NaOH (8) Song song vi phn ng trn, NaOH cn tc dng vi CO2 CO2 + NaOH = NaHCO3 (9) NaHCO3 + NaOH = Na2CO3 + H2O (10) Ngoi ra phn ng kh H2S trong dch cn xy ra trong qu trnh oxy ha natri sufua Na2S thu c t phn ng t phn ng (15.6) to thnh natri hydrosunfua v hyposunfit. Na2S + H2O = NaHS + NaOH (11) 2NaHS + 2O2 = Na2S2O3 + H2O (12)

V mt bo v mi trng, cc phn ng ph (11), (12) l c li v chng gp phn lm gim nh khu x l dung dch dng xong trc khi thi ra h thng thot nc. Ngoi dung dch NaOH ra ngi ta cn c th dng sa vi thay th. Lc kt qu thu c ca qu trnh kh H2S, mt cch tng t nh trng hp dng NaOH, l cht cn nho c cha canxi sunfua CaS m cht ny cng cn x l trc khi thi ra ngoi. Dung dch NaOH s dng cng nh cht bn nho thu c khi dng sa vi thay th c th c x l bng cch dng vi clorua (hn hp cc cht Ca(ClO)2, CaCl2 v Ca(OH)2 oxy ha cc lin kt sunfit. Lng vi cloruaa dng vo mc ch ny l 6,3 kg quy v cho 1kg lu hunh (vi nng clo trong vi l 35%). Kh thi c x l trong scruber 1 vi lp m l khu s Raschig. H thng c thit k vi mt lng dung dch a s dng c thi lin tc ra ngoi sau khi x l bng vi clorua. Nng cht kim trong dung dch hp th i vo serub c khng ch mc 7 g/l. Vn tc kh trong scrub 0,6 m/s. Lng NaOH hoc CaO tiu hao quy v mt kg lu hunh l 8 kg. Phng php ny m kh c 100% H2S trong kh thi. H thng x l khng i hi ch to bng vt liu chng axit 2.3 X L H2S BNG AMONIAC Dung dch amoniac kh H2S trong kh thi l qu trnh kh n gin v c p dng rng ri. Trong thp thp th, H2S trong kh thi tip xc vi dung dch amoniac v chng kt hp vi nhau theo phn ng. 2NH3 + H2S = (NH4)2 S (13) nhit v p sut thch hp amoniac sunfua (NH4)2S phn gii thnh NH3 v H2S. Amoniac quay li quy trnh lm vic, cn H2S c a sang cng on iu ch axit hoc lu hunh n cht. 2.4 X L KH H2S BNG DUNG DCH NATRI THIOASENAT Na4As2S5O2 Phn ng hp th kh H2S bng dung dch natri thioasenat xy ra nh sau: H2S + Na4As2S5O2 = Na4As2S6O + H2O (14) Tip theo, natri thioasenat c hon nguyn theo phn ng: 2Na4As2S6O + O2 = 2Na4As2S5O2 + 2S (15) Hai phn ng trn xy ra rt nhanh v l cc phn ng ch yu trong hu ht cc iu kin vn hnh. Trng khi nng ban u ca H2S trong kh thi rt cao hoc thi gian tip xc gia kh H2S v dung dch hp th ko di th cc phn ng ph chm hn sau y c th xy ra: Hp th: Na4As2S5O2 + 2H2S = Na4As2S7 + 2H2O Hon nguyn: 2Na4As2S7 + O2 = 2 Na4As2S6O + 4S (17) Dung dch hp th natri thioasenat chun b bng cch ha tan As2O3 v natri cacbonat Na2CO3 trong nc vi t l: 1 mol As2O3 : 2 mol Na2CO3. Trong dung dch s c natri cacbonat v bicacbonat, natri asenit v axit asenic, cc ch t trn s phn ng xen k vi H2S v oxy to thnh natri thioasenat Na4As2S5O2 Dung dch bo ha chy ra t y hp th 1 c bm qua thit b cp nhit 3 hm nng n hit 45oC ri i vo thp oxy ha 4, trong dung dch v khng kg chuyn ng cng chiu t di ln trn. Khng kh khng nhng lm cho lu hunh dng bt s ni ln trn b mt ca dung dch trong thp oxy ha ri trn qua vch ngn trong thng phn ly (16)

chy vo thng lng . Dung dch c hon nguyn t thng phn ly t chy vo nh thp hp th ti cho lp m rng trong thp. Hiu qu x l ca h thng c th t 80 - 95%. 2.5 X L KH H2S BNG CHT HP TH OXIT ST Fe2O3 y la phng php c in nht c da trn c s cc phn ng sau: Fe2O3 + 3H2S = Fe2S3 + 3 H2O (18) 2Fe2S3 + 3O2 = 2 Fe2O3 + 6S (19) Sau khi bo ha H2S oxit st c hon nguyn bng khng kh (cp oxy) thu lu hunh. Tc phn ng ph thuc H2S ca oxit st ph thuc vo mc tip xc gia kh v b mt vt liu hp ph. Do nng cao tc phn ng, rng ca vt liu hp ph phi ln. Thng rng ca oxit st khng nh hn 50%. iu kin tt nht cho qu trnh hp ph kh H2S bng oxit st l nhit nm trong khong 28 30oC v m, ca vt liu hp ph khong 30%. hon nguyn c th p dng cc phng php khc nhau: " Oxy ha nguyn liu hp th bng oxy khng kh. " Thi hn hp kh c cha 22 - 3% oxy qua lp vt liu hp ph. Nhit hon nguyn 600 - 800oC. " Hon nguyn lin tc khi vt liu hp th bng cch b sung vo dng kh cn x l mt th tch khng kh vi tnh ton sao cho lng oxy trong hn hp kh gp 1,5 ln lng oxy l thuyt cn cho qu trnh oxy ha. Nh vy qu trnh hon nguyn s xy ra song song vi qu trnh hp ph Ngoi oxit st ngi ta cn c th s dng qung bn c cha (III) hydroxit kh H2S theo phn ng sau: 3H2S + 2 Fe(OH)3 = Fe2S3 + 6 H2O + 62,5 KJ/mol (20) iu kin ti u cho phn ng trn l 28 - 30 oC, m vt liu khng di 30%. Qu trnh ny c p dng i vi kh thi c nng H2S di 0,5% tc di 7,5 g/m3 Sau khi bo ha, vt liu hp ph c hon nguyn bng oxy trong khng kh vi s tham gia ca hi nc. Kt qu thu dc l st s chuyn thnh hydroxit v lu hunh n cht c tch ra: 2Fe2S3 + 3O2 + 6H2O = 4Fe(OH)3 + 6S + 606 KJ/mol (21) Th tch khng kh cp cho qu trnh hon nguyn c iu chnh ty theo nhit v hm lng oxy trong hn hp kh i vo h thng lc. Vt liu hp ph c xem l ht tc dng khi hm lng ca lu hunh chim 50% khi lng vt liu. Lu hunh tch t trong vt liu dn dn bao bc cc ht Fe(OH)3 v gy cn tr cho s thm nhp ca kh H2S vo b mt ca vt liu hp ph. Lc phi thp lp vt liu mi, cn lp vt liu ht tc dng c hon nguyn bng phng php nhit. H thng lc rt n gin, thng bao gm nhiu bnh lc lp song song nhau theo chiu i ca kh , trong mi bnh c nhiu lp vt liu hp ph kh ln lt i qua ht lp ny n lp khc. B cao ca mi lp khong 0,3 - 0,5 m . H thng van trn ng ng dn kh cho php ct bt k bnh hp phu bo ha thay mi lp vt liu hp ph khc hoc tin hnh hon nguyn. Nu bnh hp ph c bn lp th hiu qu kh H2S c th t 90.0 - 90.9%. Ngoi h thng kiu nhiu bnh hp ph, ngi ta cn ch to thit b hp ph kiu thp Ngoi oxit st ngi ta c th dng oxit km lm cht hp ph kh H2S theo phn ng. ZnO + H2S = ZnS + H2O (22)

 thc hin qu trnh nu trn, trong cng nghip oxit km c sn xut di dng ht vin nh vin thuc ng knh 7 - 8 mm, khi lng n v ng 1000 kg/m3, ng lng hp ph khng di 15% khi lng bn thn. Khi loi vt dng hp ph ny ht tc dng ngi ta thay mi ch khng hon nguyn v qu trnh hon nguyn phc tp, khng kinh t. V vy phng php ny ch p dng x l mt lng kh thi nh vi nng ban u ca kh H2S khng ln lm. 2.6 X L KH H2S BNG THAN HOT TNH Qu trnh hp ph kh H2S bng than hot tnh xy ra nh hin tng oxy ha kh H2S trn b mt ca than theo phn ng: H2S + O2 = H2O + S + 222 KJ/mol (23) thc y qu trnh oxy ha ngi ta thm vo kh cn lc mt lng nh amoniac (0,2 g/m3) Lu hunh c gii phng ra trong phn ng oxy ha nu trn dn dn tch t trong lp than v lm cho vt liu hp ph tr nn bo ha, lc cn tin hnh hon nguyn vt liu hp ph bng qmoni sunfua (NH4)2S theo phn ng: 2(NH4)2S + 6S = 2(NH4)2S4 (24) (NH4)2S + (n-1)S = (NH4)2Sn (25) Sau dung dch c phn hy bng hi nhit 125 - 130 v p sut (1,7 - 2,0) Pa thu li amoni sunfua (NH4)2S 2 lu hunh n cht: (NH4)2Sn = (NH4)2S + (n-1) S (26) Lu hunh thu c c th tch ra khi dung dch nh s khc nhau v khui lng n v. tinh khit ca lu hunh c th t c 99.9%, cn hi ngng t li trong qu trnh phn hy dung dch l amoni sunfur sch. Sau khi txch lu hunh ra khi thn bo ha, ngi ta ra than bng nc cho ti khi khng cn SO2 trong nc mi thi, sau than c sy kh dng tr li Kt qu nghin cu thc t cho bit kch thc ht than hot tnh cng nh th ngm H2S ca than cng ln. Thng ngi ta sn xut than c c ht 1 = 2 mm. Ngoi ra qu trnh hp ph ca than hot tnh xy ra c trit , kh thi c lc sch bi a nng bi xung bi xung cn li l 2 = 3 mg/m3 trc khi a vo h thng hp ph.