K thut mi trng - Cng ngh x l H2S

CC CNG NGH X L KH H2S

Gii thiu
Kh thi H2S l vn c cp n trong nhiu cng trnh nghin cu, x l v ti liu. Kh thi H2S l kh c hi, khng mu sc nhng c mi kh chu( mi trng thi) c a vo kh quyn vi nhng lng rt ln c ngun gc t nhin v nhn to. Kh H2S xut hin trong kh thi ca cc qu trnh tinh ch du m, ti sinh si hoc khu vc ch bin thc phm, x l rc thi. Mt phn H2S pht sinh trong t nhin bi qu trnh thi ra ca cc cht hu c di tc dng ca vi khun t rc thi, cng rnh, b bin, ao t, h nc cn, k c t cc hm l khai thc than, cc vt ni la. Vn kh thi H2S thc s tr thnh vn mang tnh cp bch v cn c nhng gii php hiu qu nhm kim sot v x l trit trnh gy nh hng xu n sc kho con ngi v nhim mi trng . Vn pht thi kh H2S l mt trong nhng vn ang c quan tm hin nay khng ch Vit Nam m nhiu quc gia trn th gii. Di y nhm thc hin xin php c trnh by mt s phng php x l H2S c nghin cu v s dng. Trong khun kh ca mt bi bo co nhm thc hin c gng tm kim ti liu t cc ngun khc nhau v c bit l s gip v hng dn ca Thy gio TS. Phm Xun Ni lm vic ti B mn Lc Ho Du , Khoa Du Kh, Trng i hc M - a Cht H Ni. Tuy nhin chc chn s rt cn nhiu thiu st, rt mong Thy gio v cc bn s ginh nhiu thi gian c k bn tho v ng gp nhng kin, cho nhng nhn xt qu bu. Nhm thc hin xin chn thnh cm n!

H Ni thng 11 nm 2011

Nhm thc hin: Nhm 6

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K thut mi trng - Cng ngh x l H2S

MC LC:

CHNG I: TNG QUAN

Nhm thc hin: Nhm 6

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K thut mi trng - Cng ngh x l H2S A.Tng quan v H2S:

1.

Khi nim: Hydro sunfua (H2S) l mt cht kh khng mu,c mi thi kh chu (mi Cu trc phn t ca H2S tng t cu trc phn t nc, H2S b phn cc H2S t tan trong nc nhng li tan nhiu trong dung mi hu c. Cc cht H2S rt c, n c khng km g HCN. trng thi lng H2S b oxy ha H2S H2S => SH3 + SH-

trng thi) .

kh nng to thnh lin kt Hydro H2S yu hn H2O.

in li khng in li trong H2S lng.

mt phn. Trong nc H2S b oxy ha nhiu hn. H2S HOH => H3O+ + SH

Trong dung dch nc H2S l mt axit yu. Tnh cht ha hc : Hydro sunfua c tnh kh mnh v tnh axt yu (tan trong dung dch). Tnh kh:

2.

Kh H2S l mt hp cht khng bn lm d b phn hy cho lu hunh v Hydro 3000C H2S => H2 + S Dung dch H2S khng bn, trong khng kh vn c do c lu hunh kt ta.Qu trnh

trn cho php gii thch ti sao H2S khng tch t trong khng kh, mc d hng ngy c bit bao nhiu ngun pht sinh ra n (nh s phn hy anbumin trong cc ng vt,s phn hy mi th rc ri v b thi nh my )

H2S l mt cht kh mnh ngay dng kh hay trong dung dch Tnh axit :

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K thut mi trng - Cng ngh x l H2S

Trong dung dch H2S in li theo 2 nc: H2S ==> H+ HS- ==> H+ + HS+ S-

H2S cho hai loi mui: mui sunfua ( trung tnh ) ; mui bisunfua (mui axit). Trong H2S hai nguyn t Hydro cng c th ln lt b kim loi thay th cho Bisunfua v Na - S - H v Na - S - Na

Sunfua.

a s cc mui Sunfua t tan hoc khng tan.Mt s Sunfua khng tan thng c mu c Mui Bisunfua tan d dng khi c cc kim loi kim v kim th. Tnh cht vt l: H2S l cht khng mu,mi trng thi c trng,nng hn Khi lng ring .103( Kg/l) : 1,5392 Khi lng phn t (Kg/Kmol) : 34,08 Nhit nng chy Nhit si: -60,750C H2S c nht : 116 00C; 130 200C; 161 1000C ( nht .107Ns/m2) Kh nng to lin kt hydro ca H2S yu hn H2O H2S km bn, d phn hu, t tan trong nc, tan nhiu trong dung mi :-85,60C

trng ( CuS,Bi2,S3 mu en,Sb2S3 da cam )

3.

4.

Ngun gc:

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K thut mi trng - Cng ngh x l H2S

a.

Trong thin nhin: H2S sinh ra do cht hu c thi ra m thnh, c bit l ni nc cn, b bin v song h

nng cn, cc vt nt ni la, cc sui, cng rnh, hm l khai thc than. c lng t mt bin pht ra 30 triu tn H2S mi nm, v t mt t pht ra khong 50-60 triu tn mi nm. b.

Trong sn xut cng nghip: H2S sinh ra l do qu trnh s dng nhin liu c cha lu hunh. c lng kh H2S sinh ra

t sn xut cng nghip l 3 triu mi nm.

5.

Tc hi ca H2S: Trong cc khu th nng kh H2S trong khng kh thng di 0.001 ppm, nhng gn cc khu cng nghip nng kh H2S c th ln n 0.13 ppm. Ngng nhn bit ca H2S dao ng trong khong 0.0005-0.13 ppm. a.Tc hi i vi thc vt:

Thng tn l cy Rng l Gim sinh trng b.i vi con ngi: Nng thp Gy nhc u. Tinh thn mt mi. Nng cao Gy hn m , t vong. nng 150 ppm hoc ln hn gy t lit c quan khu gic, ng h hp, nim mc v

gic mc.

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K thut mi trng - Cng ngh x l H2S

Bng phn loi cc nh hng ca kh H2S theo nng .

Gi tr gii hn ca kh H2S l 10 ppm. Cc hot ng khi c s tn ti ca kh H2S vi hm lng

cao hn khng c php ko di qu 8 gi.

Hu ht nhng thng bo ch dn u nhn mnh 6 - 7 ppm l hm lng ti a m kh H2S

c php tn ti, nhng khng qu 12 gi.

Trong ngnh du kh , kh H2S nh hng rt nhiu n cng tc khoan. c.Tc hi i vi vt liu: Do c tnh axit nn H2S l nguyn nhn gy n mn nhanh chng cc loi my mc v

ng ng dn, nh n mn ng ng trong h thng cp thot nc.

Nhm thc hin: Nhm 6

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K thut mi trng - Cng ngh x l H2S

Chng II : CC PHNG PHP X L H2S HIN NAY

Trc kia h thng x l v thu hi kh H2S ch yu phc v cho vic lc sch kh cng nghip nh kh t thin nhin. Ngy nay cc h thng ny cn c pht trin mnh cho nhu cu gim thiu nhim bu kh quyn, bo v mi trng. Kh H2S thu hi t cc h thng x l c th trc tip bin i thnh sn phm lu hunh n cht hoc kh S02 cung cp nguyn liu cho cng on sn xut axit sunfuaric ni tip theo. I. X L H2S BNG NATRI CARBONAT, AMONI CACBONAT HOC KALI PHOTPHAT. Qu trnh x l H2S bng Na2CO3 c da trn c s cc phn ng sau: H2S + Na2CO3 = NaHS + NaHCO3 (1)

Tip theo l phn ng thu hi lu hunh c s tham gia ca Natri Vanadat NaVO3 2NaHS + H2S + 4 NaVO3+ O2 = Na2V4O9 (2) hon nguyn Vanadat ngi ta dung cht xc tc ADA ( Natri Amoni Vanadat v Disunfonat) Na2V4O9 + 2 NaOH + O2 + 2 ADA = 4 NaVO3 + 2 ADA (3) Phn ng trn xy ra trong thp hp th ca 1 h thng x l, dung dch bo ho t thp hp th 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 SEBURO 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 Vanadat theo cc phn ng trn. Phng n thay th cho Natri cacbonat l ngi ta dng photphat K3PO4 v phn ng kh H2S s l: K3PO4 + H2S = K2HPO4 + KHS(4) + NaOH + 3 S

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K thut mi trng - Cng ngh x l H2S

S x l H2S bng Na2CO3:

Trong :

1. Thp hp th 2. Thp gii hp th 3. Qut 4. Sy nng khng kh 5.iu chnh nc dung dch 6. iu chnh lu lng dung dch ti

Nhm thc hin: Nhm 6

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K thut mi trng - Cng ngh x l H2S

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 dung hi nc lm bay hi v thu hi H2S. Ngoi ra ,ngi ta cn c th Amoni Cacbonat v Kali Cacbonat lm dung dch hp th i vi kh H2S.

Vi Amoni 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 Amoni Cacbonat v phn ng trn tip tc xy ra theo s h thng x l kh H2S bng Amoni Cacbonat

Nhm thc hin: Nhm 6

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K thut mi trng - Cng ngh x l H2S

II. CNG NGH X L H2S BNG NaOH
Cng ngh ca phng php ny l kh H2S kt hp vi NaOH theo phn ng sau y: H2S + NaOH = = = Na2S + 2H2O 2NaHS NaHS +NaOH (6) (7) (8)

Na2S + H2S Na2S + H2O

Song phn ng trn ,NaOH c tc dng vi CO2 theo phng trnh sau: CO2 + NaOH = = NaHCO3 Na2CO3 + H2 O (9) (10)

NaHCO3 + NaOH

Ngoi ra phn ng kh H2S trong dung dch cn xy ra qu trnh oxy ha Natrisunfua thu c t phn ng (6) to thnh Natri Hydrosunfua v Hydrosunfit. Na2S 2NaHS + H2 O + 2O2 = NaOH + + NaHS H2 O (11) (12)

= Na2S2O3

V mt bo v mi trng, cc phn ng ph (11), (12) cng gp phn lm gim nh khu x l dung dch dng xong khi thi ra h thng thot nc. Ngoi dung dch NaOH ngi ta cn c th dng sa vi thay th.Lc kt ta thu c ca qu trnh x l 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 vi sa thay th c th c x l bng cch dng vi Clorua ( hn hp cc cht Ca(ClO)2 oxy ha c lin kt Sunfit). Lng vi Clorua dng vo mc ch ny l 6,3kg quy v 1kg lu hunh Nhm thc hin: Nhm 6

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K thut mi trng - Cng ngh x l H2S

( vi nng Clorua vi l 35%). S x l kh H2S bng NaOH v vi sa theo hnh sau:

c Trong : 1.Thp hp th 2.Thng cha dung dch 3.Thng x l dung dch s dng trc khi thi ra mi trng Nhm thc hin: Nhm 6

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K thut mi trng - Cng ngh x l H2S

4. Bnh cha dung dch mi ( xt hoc vi sa ) 5. Bnh cha vi clorua 6. Bm Kh thi c x l trong thp hp th vi lp m l khu s Raschig . H thng c thit k vi mt dung dch s dng c thi lin tc ra ngoi sau khi x l bng vi clorua . Nng cht kim trong dung dch hp ph i vo SCRUBO c khng ch mc 7 g/l .Vn tc kh trong SCRUBO 0,6 m/s .Lng NaOH hoc CaO tiu hao quy v mt kg lu hunh l 8kg .Phng php ny m bo kh c 100% H2S trong kh thi.H thng x l khng i hi ch to bng vt liu chng axit.

III.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 hp th , H2S trong kh thi tip xc vi dung dch amoniac v chng kt hp vi nhau theo phn ng : NH3 + H2 S = (NH4)2S (13)

nhit v p sut thch hp amoniac sunfua (NH4)2S phn hy 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.

Nhm thc hin: Nhm 6

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K thut mi trng - Cng ngh x l H2S

IV.X L KH H2S BNG DUNG DCH NATRI THIOASENAT Na2As2S5O2:

Phn ng hp th kh H2S bng dung dch Natri Thioasenat xy ra nh sau : H2S + Na2As2S5O2 = Na4As2S6O + H2O (14)

Tip theo ,Natri Thioasenat c ti sinh theo phng trnh phn ng sau : 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 hp 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 :

Nhm thc hin: Nhm 6

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K thut mi trng - Cng ngh x l H2S

2Na4As2S5O2 2Na4As2S7 + + H2S O2 = = Na4As2S7 + H2O 2S (16) (17)

2Na4As2S6O +

Dung dch hp th Natri Thiasenat c chun b bng cch ha tan As2O3 v Natricacbonat Na2CO3 trong nc vi t l 1: 2 . Trong dung dch s c Natri Cacbonat v Bicacbonat , Natri Asenit v Axit Asenic , cc cht trn s phn ng xen k vi H2S v oxy to thnh Natri Thioasenat Na4As2S5O2 .

Dung dch bo ha chy ra t y thp hp th 1 c bm chy qua thit b cp nhit 3 hm nng n nhit 450C i vo thp oxy ha 4 , trong dung dch v khng kh chuyn ng cng chiu t di ln trn.Khng kh lm cho lu hunh dng bt s ni ln Nhm thc hin: Nhm 6

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K thut mi trng - Cng ngh x l H2S

trn b mt ca dung dch trong thp oxy ha ri trn qua vch ngn trong thng phn ly 5 chy vo thng lng 6 .Dung dch c hon nguyn t thng phn ly 5 t chy vo nh thp hp th ti cho lp m rng trong thp. Hiu qu x l ca h thng c th t hiu sut 80 90%. V. X L H2S BNG CHT HP TH Fe2O3: y l phng php c in nht c da trn c s ca cc phn ng sau: Fe2O3 2Fe2S3 + + 3 H2 S 3O2 => => Fe2S3 2Fe2O3 + + 3H2O 6S ( 18 ) ( 19 )

Sau khi ha tan H2S , oxit st c ti sinh li bng khng kh (cp oxy) thu lu hunh .Tc phn ng hp th H2S ca oxit st ph thuc vo mc tip xc gia kh v b mt vt liu hp th.Do nng cao tc phn ng , rng ca vt liu hp th phi ln. rng ca oxit st thng khng nh hn 50%. iu kin tt nht ca qu trnh hp th kh H2S ca oxit st l khong nhit nm trong khong 28 300C.

Nhm thc hin: Nhm 6

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K thut mi trng - Cng ngh x l H2S

H thng kiu nhiu bnh hp th

hon nguyn c th c cc phng php khc nhau : Oxy ha nguyn liu hp th bng oxy khng kh. Thi hn hp kh c cha 2 3% oxy qua lp vt liu hp th.Nhit hon 600 800 0C.

nguyn

Hon nguyn lin tc khi vt liu hp th bng cch b sung vo dng kh cn x

l mt th tch khng 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 th. Ngoi oxit st ngi ta cn c th s dng qung bn c cha (III) hydroxit kh H2S theo phn ng sau : Nhm thc hin: Nhm 6

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K thut mi trng - Cng ngh x l H2S

3H2S + 2 Fe(OH)3 = Fe2S3 + 6H2O + 62,5 KJ/mol (20)

iu kin ti u cho phn ng trn l 28 300C , m vt liu khng di 30%.Qu trnh ny c p dng vi kh thi c nng H2S di 0,5% tc l 7,5 g/m3. Sau khi bo ha,vt liu hp th c hon nguyn bng oxy ca khng kh vi s tham gia ca nc .Kt qu l st thu c s chuyn thnh dng hydroxit v lu hunh n cht c tch ra: 2Fe2S3 + 3O2 + 6H2O = 4Fe(OH)3 + 6S + 606KJ/mol ( 21)

Th tch khng kh c 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 th c coi l ht tc dng khi hm lng lu hunh chim 50% khi lng vt liu.Lu hunh tch t trong vt liu dn dn bao bc ly cc ht Fe(OH)3 v gy cn tr cho s thm nhp ca kh H2S v b mt ca vt liu hp th.Lc phi thay lp vt liu mi , cn lp vt liu ht tc dng c hon nguyn bng phng php nhit. H thng lc n gin,thng bao gm nhiu bnh lc lp song song nhau theo chiu i ca kh ,trong mi bnh c nhu lp vt liu hp th kh ln lt i qua ht lp ny ti 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 th bo ha thay mi lp vt liu hp th khc hoc tin hnh hon nguyn.Nu bnh hp th c 4 lp th hiu qu kh H2S c th t 90 -90,9 % ngoi h thng kiu nhiu bnh hp th ,ngi ta cn ch to thit b hp th kiu thp.

Nhm thc hin: Nhm 6

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K thut mi trng - Cng ngh x l H2S

H thng kiu nhiu thp gm nhiu tng hp th Ngoi oxit st ngi ta c th dng oxit km lm cht hp th kh H2S theo phn ng: ZnO + H2S = ZnSW + 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,dung lng hp th khng di 15% khi lng bn thn. Khi loi vt dng hp th ny ht tc dng ngi ta thay mi ch khng hon nguyn v qu trnh hoang nguyn phc tp,khng Nhm thc hin: Nhm 6

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K thut mi trng - Cng ngh x l H2S

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. VI.X L KH H2S BNG THAN HOT TNH: Qu trnh hp th kh H2S bng than hot tnh xy ra nh hin tng oxy ha kh H2S trn b mt ca than theo phn ng: H2 S +
1

/2O2

= H2 O

+ 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 th tr nn bo ha,lc cn tin hnh hon nguyn vt liu hp th bng Amoni sunfua (NH4)2S theo phn ng : 2(NH4)2S + 6S (NH4)2S + (n-1)S = 2(NH4)2S4 = (NH4)2Sn (24) (25)

Sau pha 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 khi 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 sunfua sch. Sau khi tch lu hunh ra khi than 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 Nhm thc hin: Nhm 6

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K thut mi trng - Cng ngh x l 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 cn 2 3 mg/m3 trc khi a vo h thng hp ph.

S h thng x l kh H2S bng than hot tnh.

Nhm thc hin: Nhm 6

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Nhm thc hin: Nhm 6

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