PH LC

M U
T xa xa con ngui bit du m v kh t nhin phc v cho cuc sng sinh hot mc d s hiu bit cn hn ch v rt lng ph nhng h cng coi l mt ngun ti nguyn v cng qu gi. Ngy nay cng vi s pht trin ca khoa hc k thut, con ngi nh gi v nhn thc c tm quan trng ca chng i vi s pht trin kinh t ca mi quc gia. l ngun nguyn nhin liu chnh pht trin cc ngnh cng nghip khc. Du m v kh t nhin l ngun khong sn khng phi l v tn nn cn bit cch khai thc, ch bin hp l chng lng ph ngun nguyn liu ny. Trc y lng du m c khai thc v ch bin gp nhiu ln kh t nhin khai thc, ngy nay khong cch c thu hp li bi lng du m cng ang dn cn kit cng vi s pht trin ca ngnh cng nghip ch bin du kh . Vit Nam ngnh cng nghip ch bin kh v ang trn pht trin . Chng ta khai thc, xy dng c nhng nh my ch bin ngun ti nguyn ny p ng c nhu cu s dng nng lng v c c nhiu thnh phm c gi tr kinh t cao. Tuy cn hn ch v cng ngh nhng n cng ng gp mt phn ln vo s pht trin kinh t ca t nc. Kh sau khi khai thc ngoi cc cu t chnh l cc hydrocacbon parafin cn cha cc tp cht nh: Bi, hi nc, kh tr, CO2, H2S v cc tp cht hu c ca lu hunh. y l cc thnh phn c th gy tn hi n sc kho con ngi cng nh n lm n mn ng ng thit b trong qu trnh khai thc v ch bin. c bit vi cc kh nh CO2 v H2S v vy trc khi a vo ch bin, kh cn phi qua cng on chun b, ti tin hnh loi b cc tp cht k trn bng cc qu trnh tch bi, tch hi nc v c bit l lm ngt kh. n Tnh ton cc thng s c bn ca thp lm ngt kh bng MEA. Em xin chn thnh cm n thy TS.Nguyn Danh Nhi ngi trc tip ging dy mn hc v hng dn em hon thnh n ny.

CHNG I: MT S PHNG PHP LM NGT KH

1.1. Tc hi ca kh Acid v s cn thit phi loi b kh Acid (H2S, CO2) Trong hn hp kh t nhin, kh ng hnh v kh ho du ngoi kh Hydrocacbon cn cha mt s kh khc nh: Kh chua (H2S, CO2), ng thi cn cha mt lng khng ln kh hu c khc nh: COS, CS2, Mecaptan S tn ti ca chng trong kh s gy cn tr trong s vn hnh v ch bin kh, chng gy n mn thit b, gy ng c cht xc tc trong ch bin, i vi ngi s dng n c nh hng khng tt n sc kho, gy nhim mi trng, kh cacbonic c phn t c hi hn. Nhng nu thnh phn ca chng qu ln th s lm gim nhit tr ca hn hp kh. Mt khc, Hydrosunfua (H2S) l kh d chy (gii hn chy n rng) l cht khng c mu trng thi rt kh chu. H2S rt c c th gy ng c dn n t vong cho con ngi khi tip xc lu vi n nng cao trong kh. Cho nn, trong qu trnh vn hnh kh chng ta phi ht sc quan tm n s an ton thit b, phng r r kh. T nhng vn phn tch trn chng ta nhn thy s bt li v tc hi ca kh chua H 2S, CO2 c mt trong kh t nhin, kh ng hnh. V th chng ta cn phi loi b chng trc khi a vo ch bin, ni mt cch khc chnh l lm ngt. Tuy vy, bn cnh s tc hi ca kh chua, th chng vn c li cn ng dng c trong cng nghip ch bin: + H2S l ngun nguyn liu quan trng sn xut Lu hunh nguyn cht v Acid Sunfuaric. + CO2 cng l nguyn nhin liu c dng trong cng nghip ch bin thc phm, trong cng nghip ho cht ho hc, trong nng nghip, trong cng nghip sn xut ung nc gii kht ... V vy, khi la chn cc quy trnh lm ngt kh cn phi tnh n mc loi cc cu t khng mong mun trn v tn dng chng sn xut ra cc sn phm chuyn dng cn thit. * Tiu chun cho php kh chua cn li trong kh sch - M: Hm lng H2S cho php 5,7 mgH2S/m3kh - Nga: Hm lng H2S cho php 20 mgH2S/m3kh
3

- Vit Nam : Hin nay cha c mt quy nh no c th no, v kh t nhin, kh ng hnh v kh ha du ca chng ta c hm lng CO 2 v H2S thp, (tr kh b Sng Hng c hm lng CO2 tng i cao) Ni chung, trong cc quy trnh cng ngh x l kh cn phi lm ngt kh nhm c mc ch: su. m bo an ton cho sc kho v nhim mi trng. Thu hi khi chua dng cho cc ngnh cng nghip khc, khi hm lng lu - p ng tiu chun v cc ch tiu k thut ca sn phm kh thng mi. hunh trong kh l ng k. 1.2. Gii thiu tng qut v cc phng php lm ngt kh: loi b kh chua (H2S, CO2) v cc hp cht khc cha lu hunh khng mong mun ra khi t nhin, kh ng hnh v kh ho du. Ngi ta s dng ch yu yu t l cc qu trnh hp th, tu thuc vo c im tng tc ca cc hp cht ny vi dung mi cht hp th chng c th hp thnh cc nhm sau. Phng php ha hc, phng php vt l, phng php kt hp vt l v ha hc. 1.2.1. Lm ngt kh bng phng php ha hc Lm ngt kh bng dung mi hp th ha hc l nhng dung dch nc Alkanol amin. Cc Alkanol amin thng c s dng l: mondo Etanol amin (MEA), di Etanol amin (DEA), Diglycol amin (DGA), TriEtanol amin (TEA), Di IzoPropanol amin (DIPA) Qu trnh lm ngt kh ca cc dung mi ny l qu trnh hp th, trong khi tip xc v phn ng ha hc vi kh chua. Qu trnh lm ngt kh bng Kalicacbonat cng thuc nhm ny. Phng php lm ngt ny m bo trit kh chua, vi hm lng Gim n mn ng ng, thit b trong qu trnh x l kh hay s dng kh. Gim thiu kh nng gy ng c cht xc tc trong cc cng on ch bin

trung bnh v thp, ho tan Hydrocacbon trong dung mi hp th ny khng ng k. Thit b, cng ngh n gin v bn. Nhc im c bn ca qu trnh l khng tch c ton b lng kh chua H2S , CO2 , COS, CS2 v Mecaptan) kh c cha hm lng ln. V l hm lng cc hp cht cha lu hunh cn li tng tc vi dung mi to thnh cc hp cht ha hc bn ,kh ti sinh iu kin ca qu trnh. thc hin qu trnh cn phi c bc tun hon cht hp th cao v tiu hao nhit lng ln (chng tng ln khi nng cc cht khng mong mun tng ln). Cht hp th v sn phm tng tc ca chng vi cc tp cht cha trong kh nhin liu nhiu khi c hot tnh n mn cao. Cng vi s gia tng nng amin v mc bo ho dung mi bi kh chua cc tp cht khng mong mun th hot tnh n mn ha hc ca cc cht hp th Alkanol amin cng tng. V vy, kh nng hp th ca chng thng b hn ch khng phi bi iu kin cn bng nhit ng m l bi bo ho gii hn ca cc cht hp th bng cc kh Acid. 1.2.2. Cc qu trnh lm ngt kh bng phng php hp th vt l Phng php hp th ny dng bng dng mi hu c gm: Propylen cacbonat (C3H6CO3), Di Metyl Ete Polyetylenglycol (DMEPEG), N- Metyl Pirrolidon cc dung mi ny x l lng kh chua trong kh bng phng php hp th vt l. c im chung ca qu trnh: L cc dung mi ny c ho tan tt nhit thp, kh nng hp th cao cc kh chua (c bit l kh CO2, H2S) c th lm sch gn nh l trit ng thi chng c tnh u vit hn hp th ha hc ch: khi p sut ring phn ca mt kh chua ln hn iu kin hp th > 5 Mpa n vn lm vic c. Dung mi ny thng khng si bt, khng n mn thit b, nhiu cht c nhit hp th thp ( 700C) nhit c thp. y l iu kin quan trng trong trng hp p dng chng vng c kh hu lnh. Khi p sut ring phn ca cc tp cht cha Acid cao, qu trnh lm sch kh bng dung mi hu c (phng php hp th vt l) c yu cu kinh ph u t v chi ph vn hnh thp hn i vi vic thc hin bng phng php ha hc bng amin, do kh nng
5

hp th ca kh chua v cc hp cht khng mong mun khc. Vic ti sinh cht hp th vt l din ra ca nhiu trng hp khng cn cp nhit m nh gim p sut trong h thng. Nhc im ca qu trnh l: cc dung mi hp th c s dng hp th tng i cc Hydrocacbon, v lm sch trit kh trong nhiu trng hp ch tha mn sau khi x l b sung bng dung mi alkanolamin. 1.2.3. Lm ngt bng dung mi t hp Dung mi t hp gm Alkanol amin dung dch nc vi dung mi hu c nh Sunfolan, Metanol v da trn s hp th vt l ca cc hp cht khng mong mun bng dung mi hu c v tng tc ha hc vi Alkanol amin, l phn phn ng tch cc ca cht hp th. Cc qu trnh ny kt hp c nhiu u im ca cht hp th. Cc qu trnh ny kt hp c nhiu u im ca hp th vt l v ha hc. Chng c th c s dng lm sch trit khi nhng kh chua H2S , CO2 , COS, CS2 v Mecaptan. Qu trnh tuy c nhiu u im, c th b sung cho nhau mt cch hon ho, nhng n khng th khng c nhc im do cc dung mi c s dng, hp th ng k cc Hydrocacbon (c bit l cc Hydrocacbon vng thm tan tt). iu ny lm hn ch kh nng ng dng cc qu trnh hp th vt l v ha hc bi v loi tr s thp nhp s lng ln Hydrocacbon nng vo nguyn liu ca h thng sn xut lu hunh v trong thnh phn ca nh my ch bin kh cn phi c my v thit b tch Hydrocacbon nng khi kh nguyn liu hoc kh Acid trc khi n h thng sn xut lu hunh (trong cng ngh cn c giai on thu hi cc Hydrocacbon nng b cun theo bng cch cho Hydrocacbon khi sch quay vng li t di ln trn dung mi i t trn xung trong mt thp tip xc, cc Hydrocacbon s b cun theo dng kh, cn dung mi bo ho kh Acid, v cc hp cht cha lu hunh khc c a sang thp ti sinh). Tuy nhin iu ny khng phi lc no cng ng vai tr ch o lin quan n vic chn q trnh s l khi H2S v cc hp cht cha lu hunh v cht khng mong mun khc m km theo l chi ph u t v hot ng b sung trong qu trnh vn hnh. Cc qu trnh hp th vt l c th kinh t hn, l do cc dung mi hu c m bo thu
6

hi chn H2S trong s c mt ca CO2 v cho php thu hi tt cho sn phm lu hunh khi t l H2S: CO2 .Trong nhng iu kin nht nh, cc qu trnh ny c mt s u im m ch c th pht hin trn c s phn tch kinh t k thut cao khi H 2S , CO2 , Mecaptan v cc hp cht khng mong mun khc da trn hp th ha hc v vt l. bng I.1 trnh by tm tt mt s quy trnh cng ngh lm ngt kh Hp th ha hc Quy trnh cng ngh Dung mi Hp th ha hc Quy trnh Dung mi cng ngh * lm sch bng Alkacol MEA Mon Etanol amin - Fluor - Selecsol Propylencacbonat DiMetyl Polyetlenglycol (DMEPEG), N MetylPi rrolidon (NMP) DEA ADIP Ekonamin Di Etanol amin Di Izopropanol Sun finol Hn hp dung dch nc Di Izopropanol amin v Sunfolan Kalycacbonat thng K2CO3 nng chy thng Assen ca kim Rectizol VeTrockk loi kim nng chy K3 ASO3 (*) Tn gi phn hot ng ca dung mi, dung mi l nc
7

ete

amin Di Glycol amin

Metanol ( nhit thp)

Cc tiu chun c bn trong vic chn chp hp th cng nh qu trnh hp th tng ng l:Nng u v nng cui ca cc t khng mong mun trong kh v p sut lm vic cho trc trong h thng hoc p sut ring phn u v cui ca chng trong iu kin lm sch. p sut ban u xc nh h thng tun hon ca cht th th (lu lng ring).p sut lin phn cui (mc lm sch) ph thuc trc ht vo mc ti sinh cht hp th v p sut cn bng ca kh c hp th trn b mt dung mi nhit xc nh ch yu da vo h s tun hon v iu kin ti sinh ca dung mi hp th. V vy, tnh kinh t ca qu trnh c xc nh trong kh nguyn liu (kh chua) v kh lm sch kh ngt. Trn c s nhng d liu ny ngi ta c th nh gi dung mi no trong cc dung mi hp th ha hc theo vt l c ng dng hp l nht i vi iu kin cho trc, sau phi xt n tnh c th ca cc tp cht cha trong kh v cc phng n tng tc c th c ca chng vi dung mi hp th, t mi c th chn la qu trnh thun li tin hnh kho st kinh t ,k thut. Tt c cc quy trnh cng ngh c nu trong bng I.1 ngoi tr quy trnh Vetrocokk, u da trn nguyn tc hp th ha hc hay vt l cc cht cha lu hunh, oxy khng mong mun v gii hp chng t cht hp th, a kh Acid cha H 2S n h thng sn xut lu hunh kiu Clase. Quy trnh Vetrocokk da trn nguyn tc hp th H2S bng dng mi hp th ha hc v xy ha trong thit b ti sinh thnh lu hunh nh s c mt ca ph gia hot tnh trong cht hp th v Oxy i vo y thp ti sinh cng vi khng. Quy trnh lm ngt kh Vetrocokk thng c s dng lm sch kh vi nng H2S thp. 1.3. Quy trnh lm ngt kh bng dung mi Alkanol amin Quy trnh cng ngh lm ngt kh bng cc dung mi Alkanol amin c s tha nhn v ng dng rng ri trong cng ngh ch bin kh t nhin kh ng hnh v kh trong nh my lc du. Khi p sut ring phn ca cc kh chua thp v trung bnh th kh nng hp th ca cc Alkanol amin tng theo t l H 2S v CO2. 1.3.1. Tnh cht chung v cc qa trnh lm ngt kh ca cc Alkanol amin * Tnh cht:
8

Cc Alkanol amin lun c s dng lm dung mi hp th ha hc lm ngt kh l: Mon Etanol amin (MEA), Di Etanol amin (DEA), Di Izopropanol amin (DIPA), Di Glycol amin (DGA). Nghin cu cu trc phn t ca cc Alkanol amin ta thy n c cu trc tng t vi NH3. V nguyn tc cng c th dng NH3 loi cc kh Acid ra khi Hydrocacbon nhng NH3 bay hi rt mnh. Do vy, gy kh khn cho qu trnh vn hnh v tn tht ln do s bay hi ca n. Bng I.2 cc amin dng hp th kh axt Tn ho cht Monoetanolamin MEA Dietanolamin DEA Trietanolamin TEA Disopropanolamin DIPA Cng thc H2N CH2 CH2 OH CH2 CH2 OH HN CH2 CH2 OH CH2 CH2 OH N CH2 CH2 OH CH2 CH2 OH CH2 CHOH CH3 HN CH2 CHOH CH3 CH2 CH2 OH H3C N Diglycolamin DGA CH2 CH2 OH H2N CH2 CH2 O CH2 CH2 OH

Metyldietanolamin MDEA

Bng I.3 Mt s tnh cht ha l c bn ca cc Alkanol amin MEA 61 1018 171 100 69 48 10.5 0.241 ( 200C)
9

Khi lng phn t Khi Lng ring, kg/m3 Nhit sI,0C p sut Pa 110 Pa 660 Pa 1320 Pa p sut hi bo ho 200C, Pa Nhit ng c,0C nht tuyt i, Pa.s

DEA 105.1 1090 187 150 1.33 28 0.38 ( 300C)

DIPA 133.2 989 248.7 167 133 1.33 42 0.198 ( 450C)

DGA 105.1 1055 221 1.33 9.5 0.026 ( 240C)

 ho tan trong nc 200C, Hon ton %kl Nhit ho hi 1.105Pa,j/kg 1486.4

96.4 1205.9

87 722.5

Hon ton 917.4

Mono etanolamin (MEA) l amin c tnh baz mnh nht trong cc Alkanol amin dng lm dung mi hp th trong cc quy trnh lm ngt kh. nhit thp n c th phn ng rt nhy vi cc Acid, n phn ng c c vi H2S v CO2. MEA c khi lng phn t nh nht trong cc Alkanol amin nn nhit ta ra trong phn ng hp th cc khi axit l ln nht trong cc Alkanol amin khc. ng thi MEA bn v mt ha hc, dung dch MEA t b phn hu, MEA phn ng khng thun nghch vi cc Cacbonyl Sunfua (COS) v Cacbondisunfua CS2 to thnh cc sn phm bn khng ti sinh c hoc kh ti sinh. V vy, gy tn tht mt lng ln dung mi hp th (nu kh nguyn liu c cha nhiu COS, CS2). Mt khc, MEA c p sut hi bo ho cao nht trong cc Alkanol amin, p sut hi bo ho ca MEA ln hn gp 30 ln so vi p sut hi bo ho ca DEA v 300 ln so vi TEA. Do , trong qu trnh vn hnh thng b tn hao mt lng dung dch MEA ng k do bay hi. DiEtanol (DEA) l mt baz yu hn so vi MEA, cng bn v mt ha hc. DEA phn ng c vi H2S v CO2 nhng phn ng ca n km hn so vi MEA. DEA cng phn ng vi COS, CS2 nhng cc phn ng ny xy ra chm hn so vi MEA. * Cc quy trnh lm ngot: - Qu trnh lm ngt kh bng dung dch MonoEtanolamin; qu trnh ny c ng dng rng ri lm sch kh t nhin v kh ng hnh Qu trnh lm ngt kh bng dung dch Di Etanol amin (DEA), qu trnh ny trc y c ng dng ch yu lm ngt kh nh my lc du nhng hin n cng c ng dng lm ngt kh t nhin. - Qu trnh lm ngt kh bng dung dch Di Glycoly amin (DGA), qu trnh ny c ng dng loi b trit H2S v CO2, nu dng DGA thay th cho MEA s cho php gim lu lng ring ca cht hp th v chi ph nng lng l 25 40%.

10

- Qu trnh kt hp ng thi va lm ngt va lm kh kh, dng dung mi l dung dch MEA hoc DEA vi Glycol. Qu trnh lm ngt kh bng dung dch TriEtanol (TEA), qu trinh ny c gii chuyn mn nh gi l khng hiu qu v hin nay c thay th bi qu trnh MEA v DEA. - Qu trnh lm ngt kh bng dung dch Di IzoPropanol amin (ADIP), qu trnh c ng dng lm ngt kh t nhin v kh du m, v n c chi ph vn hnh thp hn so vi qu trnh MEA. - Qu trnh lm ngt kh bng dung dch Metyl Dietanol amin (MDEA), qu trnh c bit c ch , do tnh chn lc ca n cao, khi phn ng vi H2S trong s c mt ca CO2. Trong qu trnh lm ngt kh ca cc Alkanol amin nu trn, th cc qu trnh MEA, DEA v ADIP th c ng dng nhiu nht lm ngt kh t nhin v kh ng hnh. 1.3.2. Quy trnh lm ngt kh bng MEA. S tng tc ca MEA vi H2S, CO2 theo phn ng sau: - Vi H2S: 2RNH + H2S (RNH3)2 + H2S - Vi Cacbonic: CO2 + 2RNH2 + H2O (RNH3)2CO3 2RNH3HCO3 (I.3) (I.4) CO2 + (RNH3)2CO3 + H2O Vi R nhm HOCH2CH2 (RNH3)2S 2RNH3HS (I.2) (I.1)

II
2
6

8
4

VI

11

IV III
3

V 9

1 0

11 7
5

VII

S nguyn l cng ngh hp th bng MEA 1. thp hp th; 2,3,4. thit b phn ly; 5,6. thit b lm ngui bng khng kh; 7,8. thit b lm lnh bng nc; 9. thit b trao i nhit; 10. thp nh hp th; 11. B phn un nng; I. kh nguyn liu; II. kh sch(kh ngt); III. Dung mi bo ho; IV. kh phn ly; V. Dung mi nh hp th mt phn; VI. kh axit; VII. Dung mi ti sinh tun ho tr li thp hp th. Trong cc phn ng trn th tc d phn ng ca MEA vi CO2 chm hn so vi phn ng ca n vi H2S nhit thp cc phn ng xy ra theo chiu t tri sang phi, nhit cao th cc phn ng xy ra theo chiu ngc li (t phi sang tri). Trong trng hp u xy ra qu trnh hp th ho hc, H2S, CO2 lin kt vi cht hp th theo phn ng ho hc (chiu t tri sang phi). Trong trng hp th hai din ra s gii hp (ti sinh cht hp th v tch cc kh Acid: H2H v CO2 c hp th). Nh phn ng hp th ca cc mui MEA v cc Acid nhit cao. Cc phn ng hp th ho hc l cc phn ng to nhit rt mnh, ngc li phn ng ti sinh (phn ng phn hu cc mui) l phn ng thu nhit. Dung mi hp th ho hc dng trong qu trnh lm ngt kh bng MEA l dung dch nc Mono Etanol amin, nng MEA trong dung dch khng vt qu 15 20% khi lng, v khi c nng cao th vn tc n mn kim loi ca n cang mnh do hp th hm lng kh axit ln (dung dch Alkanol amin tinh khit khng c tnh n mn). Nng dung dch cng cao th tnh n mn kim loi cng mnh, nn lm hn ch kh nng tng hiu qu ca qu trnh hp th bng Alkanol amin (v khng th dng cc dung dch Alkanol amin c nng cao). Gn y ngi ta thm mt s cht c ch qu trnh
12

n mn cho php tng nng dung dch MEA ln 30% l tng hiu qu ca qu trnh. Mc bo ho kh Acid ca MEA thng t 0,3 0,4 mol/molDEA. Qu trnh lm ngt kh bng MEA thng c dng lm ngt kh chua H2S v CO2 khi p sut ring phn ca chng khng cao hn 0,6 0,7 Mpa. * nh gi u nhc ca qu trnh lm ngt kh bng MEA. - u im: + MEA c kh nng phn ng cao, n nh v d ti sinh, cng ngh v thit b n gin. + Qu trnh lm ngt kh bng MEA bo m c th tch trit H2S v CO2 ra khi kh trong khon p sut ring phn ca H2S v CO2 kh rng, c th vn hng qu trnh hp th p sut khng cao lm. Dung dch Mono Etanol amin tng i kh hp th Hydrocacbon, cn kh nng hp th i vi H2S v CO2 th rt cao. - Nhc im: Mc bo ho kh Acid ca dung dch Etanol amin thp, lu lng ring v chi ph vn hnh cao. Mt vi tp cht (CO2, COS, CS2) cha trong kh nguyn liu, khi tng tc vi dung mi to thnh cc hp cht khng ti sinh hoc kh ti sinh c. Do vy lm tn hao mt lng ng k dung mi, lm mt hot tnh cht hp th, lm tng tnh to bt ca dung mi, ngoi ra quy trnh lm ngt kh ca MEA cn nng lng cho vic ti snh dung mi hp th ln hn cc quy trnh khc. 1.3.3. Quy trnh lm ngt kh bng DEA Nhng phn ng chnh xy ra (trong qu trnh lm ngt kh) gia DEA vi H 2S v CO2; - Vi H2S 2R2NH + H2S (R2NH2)2S + H2S Vi CO2: CO2 + 2R2NH + H2O CO2 + (R2NH2)2CO3 + H2O (R2NH2)2CO3 2R2NH2HCO3
13

(R2NH2)2S 2R2NH2HS

(I.5) (I.6) (I.7)

 y R nhm C2H4OH Tng t nh qu trnh lm ngt bng MEA (s nguyn l cng ngh hp th cng khng khc nhiu), cc phn ng trn cng l phn ng thun nghch, chng xy ra theo chiu thun (t tri sang phi) nhit thp, v xy ra theo chiu nghch (t phi sang tri) nhit cao. Dung mi hp th s dng trong qu trnh lm ngt kh bng DEA l dung dch nc. Nng ca n trong dung dch dng lm dung mi hp th ph thuc vo nng kh Acid trong nguyn liu ban u v thng thay i t 20 35% khi lng. bo ho ca dung dch DEA trong qu trnh SNPA DEA c th t t 1 1,3 mol/mol DEA (ln hn qa trnh MEA). Tuy bo ho ca dung mi DEA trong qu trnh SNPA DEA cao, nhng kh nng hp th ca dung mi DEA km hn MEA, do MEA c khi lng phn t nh hn, nn cng mt nng % khi lng MEA c mt nng mol ln hn nn c kh nng hp th ln hn. - u im ca qu trnh : Bo m lm sch trit kh khi cc kh H2S, CO2 vi s c mt ca COS v CS2 (sn phm phn ng gia DEA vi COS v CS2 b thu phn trong iu kin ti sinh dung mi cho ra H2S v CO2). Dung dch DEA bn v mt ho hc, d ti sinh trong iu kin vn hnh ca qu trnh, c p sut hi bo ho thp hn nhiu so vi MEA, s hp th xy ra nhit 10 200C (cao hn so vi qu trnh MEA) nn cho php loi tr s to bt mnh lit ca dung mi lm ngt kh c nng Hydrocacbon nng cao (hoc c Hydrocacbon lng trong dung dch). - Nhc im: Kh nng hp th dung mi thp, lu lng ring ca cht hp th cao v chi ph vn hnh ln, mt s tp cht cha trong kh nguyn liu, mt phn CO2 tng tc vi dung mi to thnh cc hp cht khng ti sinh c, kh nng hp th ca Mecaptan v cc hp cht hu c cha lu hunh khc thp. 1.3.4. Quy trnh lm ngt bng ADIP:

14

Dung mi c dng l dung dch nc diizopropanolamin (DIPA); hm lng cht hot ng trong c th t n 40%. Nh dung mi ny, vic lm sch trit kh khi H2S (n 1.5mg/m3) c bo m, diizopropanolamin c th ng thi lm sch kh khi CO2, COS v RSR. Hot tnh ca dung dch DIPA theo CO2 thp hn so vi dung dich MEA. Trong qu trnh lm sch c n 40 50% COS v RSR c hp th. Diizopropanolamin tng tc vi COS, CO2 v RSR to thnh cc hp cht d ti sinh, v vy s phn hu ca DIPA do tng tc vi cc hp cht cha lu hunh v oxy t hn nhiu so vi qu trnh MEA (chi ph hi cho ti sinhdung dich DIPA 2 ln nh hn trong qu trnh MEA vo khong 1kg/m3 kh axit). ho tan cc hydrocacbon trong qu trnh ADIP khng ln, v vy nng ca chng khng ln 0.5% th tch. Trong trng hp ng dng DIPA thit b lm sch kh c th c ch to t thp cacbon. S cng ngh lm sch bng MEA v qu trnh ADIP thc t khng khc nhau, v vy h thng lm sch bng Monoetanolamin c th d dng chuyn i cho hot ng vi diizopropanolamin. Qu trnh ADIP ng dng rng ri nc ngoi x l kh thin nhin v du m cng nh kh ca qu trnh xc tc ca cc nh my ch bin m.

CHNG 2: TNH TON CC THNG S C BN CA THP HP TH LM NGT KH S DNG DUNG MI MEA

Tnh ton cc thng s c bn ca thp hp th lm ngt kh bng amin I.D liu ban u %V M C1 80,0 C2 5,0 C3 3,5 n-C4 2,5 n-C5 2,0 H2 S 1,0 CO2 2,5 44,010 N2 3,5 28,010

16,043 30,070 44,097 58,124 72,151 34,080 +Lu lng kh nguyn liu: 4,5.106 Std.m3/ngy m +Nhit kh nguyn liu: 37oC +Hm lng kh H2S ra: 85 ppm (V)
15

+Hm lng kh CO2 ra: 0,5 % V +Nng MEA ngho: 15,3 %KL +T l mol H2S/mol MEA : 0,02/1 +T l mol CO2/mol MEA : 0,20/1 +Nhit dng MEA vo : 40oC +p sut nguyn liu l 1atm II.Cc gi tr cn tnh +p sut v nhit lm vic ca thp +Tnh lu lng amin vo y thp (amin giu) +S a ca thp hp th +ng knh thp +Chiu cao thp +Nhit ca dng amin III.Cc bc tnh ton Bc 1: C th ha cc thng s u vo bao gm
8

Nhit gi ti hn v p sut gi ti hn ca kh nguyn liu l:

j =1

pTc = TC j Y j = 190,55.0,8+305,43.0,05+369,82.0,035+425,16.0,025+469,65.0,02+3

73,6.0,01+304,20.0,025+126,26.0,035= 216,4373 [K]

p P = PYi = 4,61.0.8+4,88.0,05+4,25.0,035+3,8.0,025+3,37.0,02+9,01.0,01+7,38 c i i =1 8

.0,025+3,4.0,035= 4.63675 [Mpa]

T khi ca hn hp kh so vi khng kh l = M /29 =0,7293

22, 4.1.288, 6 = 23, 63[lit / mol ] 273.1

V=

Th tch 1mol kh nguyn liu iu kin (15,60C, 1at )

Vo .Po .T15,6 To .P 15,6 =

16

Vy s mol kh chua vo thp trong 1 gi ( ktc) l :

4,5.10 6 nkc = = 7934,83[ kmol /h ] 24.23,63

Khi lng phn t trung bnh ca kh : = Mi.yi =0,8.16,043+ 0,05.30,07+0,035.44,097+ 0,025.58,124+ 0,02.72,151+ 0,01.34,080+ 0,025.44,01+ 0,035.28,01= 20,218465 dvc Khi lng phn t trung bnh ca HC
M tbHC = 0,8.16, 043 + 0, 05.30, 07 + 0, 035.44, 097 + 0, 025.58,124 + 0, 02.72,151 = 0,93

20,19076882 = 20,1908 dvc Bc 2: Tnh ton p sut lm vic ca thp hp th

P PH 2 S b

P : p sut lm vic ca thp

PH 2 S : p sut hi ca H2S trn dung dch MEA ngho 15,3%KL nhit lm

vic ca thp (37oC) b : Hm lng H2S trong kh ngt A, B l hng s Theo phng trnh Antoine : lg PH S =
2

T n v oC P n v mmHg
A +B T

p sut hi ring phn ca H2S/MEA(15,3%) 40oC v 100oC Ti nhit 40oC (313K) c P=2,78477 mmHg Ti nhit 100oC (373K) c P=3.19469 mmHg (nhit tnh theo K v p tnh theo mmHg) Thay cc gi tr P 40oC (313K) v 100oC (373K) vo phng trnh Antoine xc nh c cc gi tr A v B nh sau : A = 5350,8 B = 17,54 o Ti nhit 37 C (313K) p sut hi ring phn ca H2S/MEA

17

lgPH2S =

5350,8 + 17,54 = 0,279248 37 + 273

Vy PH2S = 0.279248 mmHg = 37,23 pa Plv

PH 2 S b

37, 23 = 4380000 Pa= 4,38 Mpa 85.106

(Plv phi nh hn p sut ti hn <4.6 Mpa) b l hm lng H2S (ppm) cn st li trong kh u ra. Vy Plv ca thp l: 4,38 Mpa Bc 3: Tnh lng dung dch amin ngho vo thp (tnh cho 1h) 2 (HO-CH2-CH2)2NH + H2S ((HO-CH2-CH2)2NH2)2S
H R = 1905 kJ/kg H2S

2 (HO-CH2-CH2)2NH + CO2 ((HO-CH2-CH2)2NH2)2CO2

H R = 1917, 6 kJ/kg CO2
R2 H N HS +2
(1 ) 2 H ( 2 2)R N (2)

(3a) (3b)

2 R2 NH + CO2 + H 2O ( R2 NH 2 ) 2 CO3
(1) (2)

Theo Zapffe hiu sut ca phn ng (1) 3a v 3b ch l 65% Theo Riesenfeld hiu sut ca phn ng (1) 3a v 3b ch t 75% Hiu sut trung bnh l 70%
2.

mola min 100 ; 3 t l = 3:1 molH 2 S 70

t hiu sut hp th ti a ta s dng t l S mol H2S trong kh chua S mol H2S trong kh ngt = 0,6745 [kmol]

nAmin:nH2S = nAmin:nCO2 =3:1

nH2S (chua) = %VH2S(chua). mol kh vo = 1%.7934,83= 79,3483 [kmol]

nH2S (ngt) = %VH2S (ngt). mol kh vo = 85.10-4%. 7934,83 Vy s mol H2S b hp th l

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nH2S = nH2S (chua) nH2S (ngt) = 79,3483- 0,6745= 78,6738 [kmol] nMEA dng hp th H2S = 3 nH2S b hp th = 3. 78,6738= 236,0214 [kmol]

S mol CO2 trong kh chua S mol CO2 trong kh ngt Vy s mol CO2 b hp th l:

nCO2 (chua) = %CO2 (chua). mol kh vo = 0,025. 7934,83= 198,37075 (kmol)

nCO2 (ngt) = %CO2 (ngt). mol kh vo = 0,005. 7934,83= 39,674 [kmol]

n CO2 = nCO2 (chua) nCO2 (ngt) = 198,37075- 39,674 = 158,697 [kmol] nMEA dng hp th CO2 = 3nCO2 b hp th = 3.158,697= 476,091 [kmol]

Tng s mol MEA nguyn cht cn dng:

nMEA = nMEA dng hp th H2S + nMEA dng hp th CO2 = 236,0214 + 476,091= 712,1124 [kmol] Vy Lng dung dch MEA 15,3% bm vo thp trong 1h l. = 284286,4405 [kg] Lu lng tnh theo kg/h ca dung dch amin ngho = 284286,4405+ 6268,0133+ 485,3755= 291039,8293 [kg] Vi: mCO2/MEA ngho = nCO2/MEA ngho .MCO2 =0,2. nMEA(nc). MCO2 =0,2. 712,1124.44,01 =6268,0133 [kg] mH2S/MEA ngho = nH2S/MEA ngho .MH2S =0,02. nMEA(nc). MH2S =0,02. 712,112.34,08=485.3755 [kg] Bc 4: Lu lng dung dch amin giu ra y thp mMEA (giu) = mMEA (ngho) + mH2S(ht) + mCO2(ht) +mHC(ht) ta chn s mol HC b hp th ti a l 0.5% th tch Khi lng HC b hp th : mMEA(ngho) = (namin.M amin/C% amin) + mCO2 ngho + mH2S ngho mMEA(ngho) = nMEA .MMEA /%MEA = 712,1124.61,08.100/15,3%

nHC = 0,5%.nkc. M = 0,005. 7934,83.20,1908= 801,0528 [kg]

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Khi lng H2S b hp th : Khi lng CO2 b hp th : mMEA (giu) = mMEA (ngho) + mH2S(ht) + mCO2(ht) +mHC(ht) = 291039,8293+ 801,0528+ 2681,2031+ 6984,2550 = 301506,3402 [kg]

mH2S(ht) =nH2S(ht)..MH2S= 78,6738.34,08= 2681,2031 [kg]

mCO2(ht) =nCO2(ht).MCO2= 158,697.44,01= 6984,2550 [kg]

Bc 5: Tnh lu lng kh ngt ra nh thp mkh ngt= m kh chua [ m(H2S, CO2, HC) b hp thu] mkc=nkc. M = 7934,83.20,1908= 160210,5656 [kg] mkn=mkc mCO2(ht) + mH2S(ht) +mHC(ht)) ( = 160210,5656- (6984,2550+2681,2031+2681,2031) = 147863,9044 [kg] bc 6: tnh nhit dng amin giu ra y thp c s tnh ton da trn nh lut bo ton nng lng Qthu = -Qta hay |Qthu| = |Qta|
a.

Nhit ta Q ta gm (mc ny T n v oC) Nhit phn ng gia H2S v MEA

Q1 =m H 2S(ht).q H2S = 2681,2031.(-1905)= -5107691,906 [kJ]

Nhit phn ng gia CO2 v MEA

Q2 = mCO2 ( ht ) .qCO2 = 6984,2550.(-1917)= -13388816,84 [kJ]

Nhit phn ng gia HC v MEA

Q3 = m HC( ht).q HC= 801,0528.(-4403)= -3527035,478 [kJ]

Vi nhit phn ng gia H2S, CO2 v HC vi MEA ln lt l

qH 2 S = 1905( kJ / kg ) qCO2 = 1917( kJ / kg ) qHC = 4403( kJ / kg )

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b.

Nhit thu Qthu gm (mc ny T n v oC) Nhit cn thit un nng dung dch MEA ngho (khng tnh lng
nA min .M A min ].C A min .(T TA min ngho ) C % A min

H2S) t Tdd ti T vo:

Q4 = [

CAmin= 1,6927 [kJ/kg-C] Q4 = 284286,4405.1,6927.(T-40)= 481211,6578.(T-40) [kJ]

Nhit em H2S b hp th t Tkh chua n T

Q5= nH2S(hp th) . MH2S.CH2S.(T-Tkh chua) CH2S = 1,0165 [kJ/kg-C] Q5= 78,6738.34,08. 0,7724 (T 37) = 2070,9613(T-37) [kJ]

Nhit cn un nng H2S c sn trong dung dch amin ngho nH2S .MH2S.CH2S.(T-Tamin )= 0,02.7934,83.34,08.0,7171.(T-40)

CH2S = 1,0171[kJ/kg-C] Q6 =

(ngho) ngho

= 3878,3494.(T-40) [kJ] Nhit cn un nng CO2 b hp th

CCO2 = 0,8813 [kJ/kg-C] Q7 = nCO 2 ( ht ) .M CO2 .CCO2 .(T Tkc ) = 158,697.44,01.0,8813.(T-37)

=6155,2239.

(T-37) [kJ]

Nhit cn thit un nng CO2 c sn trong amin ngho

CCO2 = 0,8833[kJ/kg-C] Q8 = nCO2(ngho).MCO2.CCO2.(T-Tamin ngho) Q8 = 0,2.7934,83.44,01.(T-40)= 69842,3737[kJ]

Nhit cn thit un nng kh hydrocarbon b hp th l:

0,8.2, 2801 + 0, 05.1,8213.0, 025.1, 7712 + 0, 02.1, 7626 = 2,2114 [kJ/kg-C] 0,8 + 0, 05 + 0, 025 + 0, 02, +0,895

CHC (ht) =

C1 % th tch Nhit dung 2,2801

C2 0,8 1,8213

C3 0,05 1,7712
21

n-C4 0,025 1,7678

n-C5 0,02 1,7626

Tng 0,895

ring Q9=mHC b hp th.CHC.(T-Tamin)= 3540,519.2,2114.(T-40) =7829,5037.(T-40) [kJ]

Nhit lng tht tht bn ngoi ly ti a bng 5% tng nhit ta

Q10 = 0, 05 .Qta= 0,05.(Q1+Q2+Q3)= 0,05.( 5107691,906 +13388816,84

+3527035,478)

= 1101177,211 [kJ]

Vy tng lng nhit thu vo l:

QThu= (Q4+Q5+Q6 +Q7+Q8+Q9+Q10)= -0,05208.109+1672165.281.T [kJ] QThu = - Qta

10

Q
i=4

= (Q1 + Q2 + Q3 ) = 22023544,22 [kJ]

p dng phng trinh cn bng nhit trn ta tnh c nhit dng MEA giu ra khi y thp:

Nhit dng amin giu ra khi y thp T = 44,318oC

Bc 7: Tnh s a l thuyt ca thp Nlt = (*)

Trong A l yu t hp th, A =
q= nH 2 S ( kn ) nH 2 S ( kc ) = 85.106 = 85.10-4 =0,0085 0, 01

a : Phn mol H2S trong kh nguyn liu, a=0,01 R : t s mol Amin/s mol H2S, R =3:1 r : s mol H2S cn li trong amin ngho,
nH 2 S na min = 0, 02 1

p : p sut lm vic ca thp, p= 4,38 Mpa p1 : p sut ring phn ca H2S trong amin giu Tnh theo phng trnh Antoine
22

Trong dung dch amin ra ta c :

lg pH 2 S = A B = 0,1284 T +C => pH 2 S = 337,5278 [mmHg]= 0.045 [Mpa]

A 8,02401 T: nhit [oC]

B 1921,0

C 203,3

pH 2 S p sut ring phn ca H2S [mmHg]

Thay cc thng s trn vo (*) ta c A, A=1,02

1 ln Nlt= 0, 0085(1, 02 1) + 1 = 9,6995 ln1, 02

Bc 8: Tnh s a thc ca thp Nthc=

N lt trong hiu sut lm vic ca a vi kh 0, 25 0, 4

N thc=

9, 6995 = 24, 2488 ; 25 [a] 0, 4

Bc 9: Tnh ng knh thp hp th

D = 0, 0114 0,1.Q.T . p

Trong D: ng knh thp Q : Lu lng kh nguyn liu, Q= 4,5.106/24= 187500 [m3/h] T : Nhit lm vic ca kh nguyn liu, T= 310 [K]
: Vn tc tuyn tnh ca kh trong thp, chn = 0,13[m/s]= 468 [m/h]

P : p sut lm vic ca thp, p= 4,38 [Mpa] Vy ng knh thp D = 0.6071 [m] Bc 10: Tnh chiu cao ca thp H= Nthc .d + h d : Khong cch gia cc a chn d=0,50,6 [m] h : Chiu cao b tr gm chp trn v chp di thng ly h= 1,21,6 [m]
23

H = 25.0,5 + 1,2 = 13,7[m]

KT LUN
Vi dng kh nguyn liu c hm lng CO2 l 2,5% v H2S l 1% lm ngt dng kh ny phi dng thp hp th ti thiu p ng cc iu kin sau: +chiu cao 13,7 m +ng knh 0,6071 m +p sut lm vic 4.38 Mpa

TI LIU THAM KHO

[1] CNG NGH CH BIN KH THIN NHIN V KH DU M ngi dch: Hong Minh Nam- Nguyn Vn Phc- Nguyn nh Soa- Phan Minh Tn [2] TS. Trn Xoa, TS. nguyn Trng Khung, K s H L Vin. S tay qu trnh v thit b cng ngh ha cht tp 1

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