Làm ngọt khí

n tt nghip B mn : Lc ho du
Li ni 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 v khng c kh nng ti sinh 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 ngPhm Vn Thinh Lp: Lc ho du k46 1
i cng nh n lm n mn ng ng thit b trong qu trnh khai thc v ch bin. 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 cc kh axit. c s gip tn tnh ca cc thy c gio trong b mn lc ho du v s hng dn tn tnh ca Tin S Nguyn Th Bnh ti hon thnh n vi ti Tnh ton cc thng s k thut c bn ca thp lm ngt kh vi ngun nguyn liu kh t b Nam Cn Sn. Do kinh nghim thc t v kin thc ngnh ngh cn hn ch, n khng trnh khi nhng sai st, ti rt mong c s gp ca cc Thy, C gio trong b mn cng cc bn ng nghip. Ti xin chn thnh cm n !
Phm Vn Thinh Lp: Lc ho du k46
Phn I : Tng quan v kh t nhin

Chng I: Khi nim, ngun gc, phn loi v thnh phn kh t nhin 1. Khi nim v kh t nhin : { } Kh t nhin l tp hp nhng hydrocacbon kh CH4, C2H6, C3H8, C4H10... C trong lng t.Chng thng tn ti thnh nhng m kh ring r hoc tn ti trn cc lp du m. Trong ngha hp kh t nhin c hiu l kh trong cc m kh. Kh t nhin cng lun cha cc kh v c N2, H2S CO2, kh tr v hi nc. 2. Ngun gc du m v kh t nhin hiu r v thnh phn ho hc ca du m v kh t nhin cn tm hiu ngun gc, s hnh thnh chng.Mc d l vn cn tranh ci gia ngun gc v c v hu c .Nhng gi thuyt v ngun gc hu c c tnh thuyt phc hn 2.1. Ngun gc v c
Theo gi thuyt ny trong lng t cha cc Cacbua kim loi nh AL4C3,, CaC2 cc cht ny b phn hu bi H2O to ra CH4 v C2H2. AL 4C3 3CH4 CaC 2 C2H2 2 FeC C2H6 T cc cht khi u (CH4, C2H2) qua qu trnh bin i di tc dng ca nhit , p sut cao trong lng t v xc tc l cc khong st, to thnh nhng loi hydrocacbon c trong du kh. chng minh cho iu nm 1886 Berthelot M tng hp thnh cng hydrocacbon thm theo 3 giai on Kim loi kim + CO2 CO2 Cacbua kim loi C2H2 benzen + 3H 2O Fe2O3 + + 2H2O Ca(OH)2 + + 12H2O 4AL(OH)3 +
Cacbua kim loi + C2H2
Sabatir v Sendereus cng thc hin phn ng hydro ho axtylen trn xc tc Niken v St nhit trong khong 200-3000C thu c mt lot cc hydrocacbon tng ng nh trong thnh phn du m. V th gi thuyt v ngun gc v c c chp nhn trong thi gian kh di .
Trong nhng thp k gn y trnh khoa hc v k thut pht trin th ngi ta bt u hoi nghi v lun im trn v. + phn tch c (bng cc phng php hin i) trong du th c cha cc porphyrin c ngun gc t ng thc vt. + Trong v qu t,hm lng Cacbua kim loi la khng ng k. + Cc hydrocacbon thng gp trong cc lp trm tch, ti nhit t khi vt qu 150 2000C (v p sut rt cao ), nn khng nhit cn thit cho phn ng tng hp xy ra V nhng l do m gi thuyt v ngun gc v c ngy cng phai m. 2.2 Ngun gc hu c C l xc ng thc vt , m ch yu l cc loi to ph du sng trong bin lng ng, tch t cng vi cc lp t trm tch v c xung y bin t hng triu nm v trc bin thnh du m, sau thnh kh t nhin.C th qu trnh lu di xy ra theo 3 giai on :Bin i sinh hc bi vi khun, bin i ho hc di tc dng ca cc iu kin a ho thch hp v s di chuyn, tch t cc sn phm trong v tri t. Xc ng thc vt b phn hu bi cc vi khun a thch, sau b cc vi khun k kh trong qua trnh trm lng dn trong nc bin. Cc albumin b phn hu
Phm Vn Thinh Lp: Lc ho du k46 5
nhanh nht, cc hydrat cacbon bi phn hu chm hn. Cc kh to ra nh N2, NH3, CO2, CH4... Ho tan trong nc ri thot ra ngoi, phn cht hu c cn li b chn vi ngy cng su trong cc lp t trm tch. Khng gian xy ra qu trnh phn hu sinh hc gi l vng vi khun. giai on ho hc tip theo, vt liu h c cn li, ch yu l cc cht lipid, nha, sp, terpen, axit bo, axit humic tham gia cc phn ng ho hc di tc dng xc tc ca vavt cht v c trong t iu kin p sut ln hng trm , thm ch hng nghn atmotphe, mt vi trm bch phn. cc cht v c khc nhau, c bit l cc aluminosilicat, c th ng vai tr cht sc tc. Qu trnh ho hc xy ra v cng chm. Cng sung su, thi gian cng ln, s bin i cng ch nn su xa theo chiu hng: Hp cht phc tp sinh vt gin hn Hp cht thm phc tp hp cht thm n gin, hyrocacbon n gin naphten, parafin Hyrocacbon phn t lng ln hyrocacbon phn t lng b Phn ng ch yu xy ra trong giai on ho hc l phn ng cracking, trong mch cacbon ca phn t cht hu c b t gy dn. Kt qu l to ra cc cht h c n gin hn, ch yu l hyrocacbon sinh ra ngy cng nhiu.
hp cht hu c n
ng thi vi vic xy ra cc phn ng cracking phn hu l qu trnh ngng t, kt hp mt s cc cht hu c tng i n gin va to thnh to ra cc cht hu c phc tp hn: cc cht nha, Asphalten .Cc cht nha, Asphalten tan km, nng hn, nn phn ln b kt ta, sa lng, phn t cn li l lng, phn tn trong khi cht lng hyrocacbon sinh ra bi qu trnh cracking. Tp hp cc phn ng ho hc bin dn cc vt liu hu c thnh du m v kh t nhin. Nh vy c th coi kh t nhin l sn phm ca qu trnh phn hu ho hc du m. Du m cng gi s cng nh i, cng cha nhiu cht t phc tp, cng bin nhiu thnh kh . Du m ang c to thnh dng hn hp lng c th b di c t ch ny sang ch khc di tc dng vn ng kin to ca v tri t. Chng thm thu, chui qua cc lp t xp, chng chy qua cc khe nt v c th b tp trung, b gi trong nhng tng c kht, to ra nhng ti du m ta thng gi l m du. Trong cc m du cc qu trnh ho hc vn tip tc xy ra, du vn lin tc bin thnh kh, to ra cc m kh. Khng gian xy ra cc phn ng ho hc gi l vng ho hc. Cn nh rng cc qu trnh xy ra rt chm, ko di hng chc, thm ch hng trm triu nm ri m vn ang xy ra, do tui ca du m, ca kh t nhin l rt ln.
Nh vy qu trnh hnh thnh du m v kh t nhin c th c biu din bng s tng qut sau:
(1) (2) C (3)
(2)
S hnh thnh du m v kh t nhin
(3)
(1): Qu trnh phn hu sinh hc;(2,2),(3,3): qu trnh ho hc. A: Cc vt liu hu c thc vt, ng vt B: Du m s khi. C: Du m. D: Kh t nhin.
3. Phn loi 3.1. Phn loi theo ngun gc Ngi ta phn chng ra lm 2 loi da theo ngun gc ca m: + Kh thin nhin: l kh c khai thc t cc m kh ring bit trong t nhin, n c hm lng Metan rt cao, thng t 90 99% th tch, cn li l cc kh khc nh Etan, Propan v t Butan... + Kh ng hnh: L kh nm ln trong du m, c hnh thnh cng vi du cn gi l kh du m. V mt nh tnh kh ng hnh kh ging kh thin nhin nhng
v mt nh lng th kh ng hnh c hm lng Metan thp hn so vi kh t nhin, thng l 30 87% + Kh ngng t(condensat) : Thc cht l dng trung gian gia du m v kh ,bao gm cc hydrocacbon nh Propan, Butan v mt s hydrocacbon lng khc nh Pentan, Pexan,thm ch hydrocacbon Naphtenic v Aromatic n gin, iu kin thng kh ngng t dng lng 3.2. Phn loi theo thnh phn nh lng Da theo thnh phn ca kh Acid c trong kh
Hyrocacbon ngi ta phn n ra lm 2 loi : Kh chua v kh ngt. + Kh chua l kh ( kh t nhin hay kh ng hnh ) c hm lng H2S ln hn 5,8 mg/m3 kh iu khin 150C v 1 bar , hoc cha lng CO2 ln hn 2% th tch + Kh ngt l kh c hm lng H2S hoc (v) CO2 nh hn qui nh trn . Theo cch phn loi ny, cc kh t nhin v kh ng hnh Vit Nam phn ln l kh ngt, rt thun tin cho vic ch bin v s dng. Da vo hm lng cc kh Hyrocacbon nng (Propan, Butan, Pentan...) ngi ta phn loi kh thnh kh bo v kh gy. Theo cch phn loi ny: + + Nu hm lng C+3 cha ln hn 50g/m3 kh iu Tri li nu hm lng C+3 cha nh hn 50g/m3 kh, kin 150C v 1 bar gi l kh bo (kh giu). gi l kh gy (kh ngho). Kh bo c gi tr kinh tt cao
hn kh gy , v ngi ta c th ch bin thnh nhiu sn phm lng c gi tr kinh t cao hn nh : Kh u m ho lng (LPG), Condensat(C+5) pha xng. 4. Thnh phn c trng ch yu ca kh thin nhin v kh ng hnh bao gm hai phn : Hydrocacbon va phi hydrocacbon 4.1. Cc hp cht hydrocacbon Ch yu l cc kh metan v ng ng ca n nh:Etan , Propan, n-Butan,iso-Butan,ngoi ra cn mt lng t cc hp cht C5, C6 ..Hm lng cc cu t trn thay i tu theo ngun gc ca kh(khi thin nhin cha ch yu metan cc kh C3 C4 rt t,cn trong kh ng hnh hm lng C3 C4 cao hn). 4.2. Cc hp cht phi hydrocacbon Ngoi thnh phn chnh l cc hydrocacbon , trong kh thin nhin v kh du m cn cha cc tp cht nh:CO2,, N2,, H2S , H2 , He, Ar, Ne...trong cc loai kh trn thng N2 chim phn ln. Tu theo hm lng cc kh co trong cc m m ngi ta c phng php khc nhau thu hi chng. 5. S phn b ,tr lng v tim nng kh thin nhin ti Vit Nam Theo s liu ca trung tm nghin cu v pht trin ch bin du kh tim nng v tr lng kh thin nhin l 3000 t m3 ,Tr lng c thm lng v sn sng pht trin khai thc trong thi gian ti vo khong 400 t m3, ngun kh Vit Nam tp trung ch yu ti cc m kh ca
cc b :Sng Hng, Cu Long, Nam Cn Sn , v Malay-Th chu + B Cu Cong : Din tch 60 ngn km2 vi tr lng 50 t m3, sn phm ch yu du v kh ng hnh + B Nam Cn Sn :Din tch 160 ngn km2 vi tr lng 160 t m3 sn phm ch yu kh va condensat + B Malay-Th Chu :Nm pha ng vinh Thi Lan, tr lng 140 t m3 sn phm du v kh + B Sng Hng: Din tch khong 120 ngn km2 , tim nng kh l kh ln khong 2000 t m3 kh thin nhin nhng do b co hm lng CO2 ln nn vic khai thc v a vo s dng kh cc m ny l cha kh thi . Bng I.1 Thnh phn ca khi thin nhin (%V) trong cc m thuc B Nam Cn Sn M Cu t CO2 N2 Methane Ethane Propane i-Butane n-Butane i-Pentane nLan ty, Lan 1,92 0,36 89,65 4,30 2,39 0,56 0,49 0,14 0,08 Hi Thch 4,5 0,12 84,13 5,8 3,36 0,68 0,83 0,24 0,17
11
Mc Tinh 2,72 0,10 89,02 4,04 1,71 0,37 0,48 0,20 0,16
Rng i 5,64 0,08 81,41 5,25 3,06 0,71 0,76 0,32 0,23
Pentane Hexane Tng
0,10 100
0,17 100
0,12 100
2,54 100
Trung tm nghin cu v pht trin ch bin Du kh
Bng I.2 Thnh phn kh ng hnh B Cu Long M Cu t CO2 N2 Methane Ethane Bch H 0.07 0.25 74 12.35 S t Rng ng 0.04 0.26 79.20 10.87 6.14 1.04 1.46 0.35 0.35 0.29 100 Ruby 0.079 0.640 78.02 6 10.67 9 6.705 1.305 1.741 0.308 0.382 0.135 100
en 0.05 1.69 75.08 11.24 6.75 1.87 1.85 0.51 0.45 0.69 100
Propane 13.33 i-Butane 0.00 n0.00 Butane iPentane nPentane Hexane Tng 0.00 0.00 0.00 100
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Bng I.3 biu d kin khai thc n nm 2025

18 16 14 12 10 8 6 4 2 0 1 2 3 4 5 Series3 Series2 Series1
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Chng II: Mt s tnh cht quan trng ca kh hydrocacbon

1. Khi lng trung bnh v t khi s b nh gi c kh nng hay nh, ngi ta c th da vo khi lng phn t trung bnh v t khi ca kh : + Khi lng phn t trung bnh ca mt t hp kh tnh theo cng thc sau: MTB =
n
Mj Yj
j =1
(2.1)
Trong : Mj khi lng phn t trung bnh ca phn t j Yj Phn mol ca cu t j trong t hp Nu gi d l t khi ca t hp kh so vi khng kh ta c: dhh = Mtb/29 2. Nhit ti hn v p sut ti hn Mi mt cht hi c mt nhit m cao hn nhit n khng th ho lng bt kh p sut no gi l nhit ti hn Tc , gi tr p sut tng ng vi n gi l p sut t hn Pc , th tch tng ng l th tch ti hn Vc, p sut ti hn v nhit ti hn ph thuc vo tng loi Hyrocabon , cng mt nhit si nh nhau nhng cc
Hyrocacbon thm bao gi cng c nhit ti hn cao hn cc Hyrocacbon Parafin.
Trn bng 2.1 trnh by thng s ti hn ca mt s kh thng thng: Hyrocacbo n CH4 C2H6 C3H8 I C4H10 N C4H10 N C5H12 I C5H12 N C6H14 Nhit ti hn p (k) 190.55 305.43 369.82 408.43 425.46 469.60 460.39 507.40 sut ti
hn(atm) 45.44 48.16 41.94 36.00 37.47 33.25 33.37 29.73
Nhit v p sut ti hn ca Hydrocacbon n cht t C1 n C15 c th sch inh mt cnh gn ng theo cng thc Tc =391.7(n-1)/[2.645+(n-1)0.785] (2.2) n:la s ngyn t cacbon trong phn t +190,7
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Ap sut tt hn ca hidrocacbon t C 1 n C15 co th xc nh vi chnh xc 0,05Mpa theo cng thc: Pc (2.3) n l s nguyn t cacbon xc nh th tch ti hn ca cc hydrocacbon t C3 - C16 (vi chnh xc n 4 cm3/mol) c th s dng phng trnh: Vc (2.4) i vi mt hn hp hydrocacbon nhit ti hn v p sut ti hn ph thuc vo thnh phn nh tnh v thnh phn nh lng ca cc phn t . ng vi mi thnh phn s c mt nhit ti hn, n ch c trng cho thnh phn khi thnh phn bin thin th nhit ti hn v p sut ti hn cng thay i . Chnh v vy, i vi hn hp kh ngi ta quan tm ti nhit gi ti hn v p sut gi ti hn. Chng tnh ton theo cng thc sau: Tgth = V: Pgth =
n
495,1/(7,977+n1,2)
58n
22
T
i =1
ci
.C i
(2.5)
P .C
i =1 ci
(2.6)
Trong : Tci: Nhit ti hn ca cu t i Pci: p sut ti hn ca cu t i

Ci: Phn mol ca i trong hn hp 3. Gii hn chy n Mt hn hp kh ch c th bt chy khi gp ngun la nu nng ca n trong khng kh t n mt lng xc nh no . c trng cho kh nng chy n ca kh ngi ta nghin cu v a ra khi nim gii hn chy n: L phn trm th tch ca nhin liu trong hn hp vi khng kh hoc vi Oxy nguyn cht c th chy khi gp ngun la. + Hm lng phn trm th tch (hay % mol) ca mt kh trong liu trong khng kh hoc Oxy nguyn cht t gi tr nh nht c th bt chy khi gp ngn la gi l gii hn chy n di. + Lng % ln nht theo th tch (hay % mol) ca kh trong khng kh hoc Oxy nguyn cht m c th chy khi gp ngun la gi l gii hn chy n trn.Vi hm lng kh t gii hn chy n di n gii hn chy n trn, kh s bt chy khi c ngun la, l vng chy n. Hm lng kh nh hn gii hn chy n di v ln hn gii hn chy n trn c xem l vng an ton. T bng 2.2 ta nhn xt c khi lm vic vi kh chua l nguy him rt cao so vi kh ngt v phm vi chy n ca H2S trong khng kh l rt rng ngi ta thng quan tm n chy n di hn (bi v chy n di thng to ra do nhng s c r r t nhng thit b dn cha kh ra ngoi).
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Trn bng 2.2: Trnh by gii hn chy n ca Hydrocacbon v H2S

Hn hp vi khng kh Cu t Gii hn chy n dCH4 C2H 6 C3H 8 N C4H10 I C4H10 N C5H12 i C5H12 N- C6H14 H2S C2H 4 C6H 6 i, %V 5,3 3,0 2,2 1,9 1,8 1,5 1,4 1,2 4,3 3,1 1,4 Gii hn chy n trn, %V 14,0 12,5 9,5 8,5 8,4 7,8 8,3 7,7 45,5 32,0 7,1 Hn hp vi Oxy nguyn cht Gii hn chy n di, %V 5,1 3,2 2,3 1,8 1,8 3,0 2,6 Gii hn chy n trn, %V 61 66 55 49 49 53 30
Trong thc t khai thc, vn chuyn, ch bin v s dng khi ng hnh v kh t nhin, lun lun phi lm vic vi hn hp kh, do phi bit cch xc nh gii hn chy n i vi hn hp. Mt trong cc cht l tnh gii hn chy n ca hn hp theo cng thc 2.7. Y = 100/( N )
i =1 i n
ni
(2.7)
Trong : Y : Gii hn chy n ca hn hp ni: Phn trm th tch (hoc % mol) ca cu t i trong hn hp kh
Ni: gii hn chy n ca cu t i. Bit c gii hn chy n ca 1 cht kh (hay ca hn hp kh) nm vai tr quan trng trong vic phng chy cho h thng ng dn, trong quy trnh cng ngh ch bin kh cng nh trong s dng. hn ch ri ro do chy n, trong qu trnh vn chuyn kh ngi ta thng cho thm cht to mi d pht hin r r, kp thi x l trnh xy ra nguy c chy. 4. Nhit tr Nhit tr cn gi l nhit chy ca mt cht l hiu ng nhit ca phn ng t chy cht bng oxy O2 to thnh cc oxyd cao nht v cc cht tng ng. Nhit tr thng c k hiu: Q, n v o trong cng nghip l : Kj/Kg kh, kj/m3 kh. Trong cng nghip du kh ngi ta dng khi nim phn bit: Nhit tr trn v nhit tr di chng thng c gi tr khc nhau: - Nhit tr trn (nhit tr cao) Qt: L hiu ng nhit ca phn ng t chy hon ton 1 n v khi lng hay th tch ca kh Hydrocacbon m nc sinh ra trong phn ng trng thi lng. - Nhit tr di (nhit tr thp) Qd: l hiu ng nhit ca phn ng t chy hon ton mt th tch hay khi lng ca kh Hydrocacbon m nc sinh ra trong phn ng trng thi hi.
19
Nhit tr di bao gi cng nh h n nhit tr trn mt lng bng nhit ngng t hi nc sinh ra v chng c phng trnh lin h nh sau: Qt = Qd + 558(9. h + W) Trong : 558: l lng nhit lm ngng t 1 kg nc h : l s Kg H lin kt W: s Kg nc c mt trong 1kg nhin liu th hi Trong thc t th thng dng khi nim nhit tr di. V nhit l mt trong nhng ch tiu nh gi cht lng ca kh hoc hn hp kh thng phm. Ta c th tnh nhit tr ca hn hp kh theo cng thc: Qhh =
n
(2.8)
Q .Y
j =1 j
(2.9)
Trong : Qhh: Nhit tr ca hn hp Qj: Nhit tr ca cc t j Yj: Phn mol ca cc t j 5. m im sng ca kh - m ca kh: L lng hi nc c trong kh ti mt p sut v nhit xc nh. m ca kh ph thuc vo p sut v nhit , p sut cng tng, nhit cng gim th lng hi nc trong kh cng nh v ngc lai. Ngi ta hay dng hai khi nim v m:
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+ m tuyt i: L khi lng nc c trong mt n v th tch hay mt n v khi lng ca kh (o bng gam H2O/m3 kh, gam H2O/kg kh). + m tng i: l t s gia khi lng hi nc c trong hn hp kh so vi khi lng hi nc cc i trong kh, trong cng mt nhit . (Lng hi nc bo ho nhit no ). im sng ca kh l nhit m ti hi nc trong kh c ngng t thnh cc git lng nh sng m mt p sut nht nh. Kh c im sng cng thp th hm lng nc trong cng nh. 6. Nhit dung, nhit bay hi, Entalpy - Nhit dung: + Nhit dung ca mt cht (k hiu l C): Nhit dung l lng nhit cn thit lm tng nhit mt n v cht ln mt , thng c o bng Cal/Kg nhit v bn cht ca cht . + Nhit dung ca cc Hydrocacbon tng gn nh tuyn tnh vi nhit ,gim theo t khi, nhit dung ca cc Hydrocacbon nh tng nhanh hn theo nhit + i vi cc hn hp p sut kh quyn nhit dung ring c xc nh nh sau . C pth =
0
C. Nhit
dung l hm qu trnh c gi tr ph thuc vo p sut,
C
i
Pi
yi
(2.10)
21
y C pi : Nhit dung mol ca cu t th i nhit ca h; yi : phn mol ca cu t th i. + p sut cao hn nhit dung ring ca cc hydrocacbon kh v hn hp ca chng cng ph thuc vo p sut. Trong trng hp ny nhit dung ring cc hydrocacbon kh c xc nh theo phng trnh: Cp =
0 pi
y i - Cp
(2.11)
Cp: Nhit dung mol ca hn hp cc kh hydrocacbon nhit v p sut ca h; C p : Nhit dung mol ca cu t th I trng thi l tng
i
nhit ca h; Cp: i lng hiu chnh cho p sut. - Entalpy: Trong ngnh ch bin kh ngi ta thng dng Entalpy H, y khng phi l Etalpy tuyt i m l bin thin Entalpy t nhit gc quy c T0 n nhit ang xt T. n v o l Kcal/Kg hoc Kj/Kg. Entalpy ca cc Hydrocacbon th hi ph thuc v p sut, p sut cng ln th Entalpy cng nh. - Nhit bay hi: Nhit bay hi l nhit lng cn thit cung cp cho mt n v khi lng cht lng n chuyn t pha lng sang pha hi, thng c tnh bng n v Kcal/Kg hoc Kj/Kg. Nhit bay hi ph thuc vo p sut, nhit bay hi tng khi p sut tng.
Cng thc Trouton tnh gn ng nhit bay hi ca mt cht (cu t): L = KTtbm /Mtb Trong : Mtb: Phn t lng trung bnh K : H s bng 20 n 22 Ttbm: Nhit si trung bnh mol ( K) (2.12)
PHN II:
cc phng php lm ngt kh
2.1. 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 H2S, 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
24
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 - 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 CO2 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: Gim n mn ng ng, thit b trong qu trnh x Gim thiu kh nng gy ng c cht xc tc m bo an ton cho sc kho v nhim mi trng. p ng tiu chun v cc ch tiu k thut ca sn Thu hi khi chua dng cho cc ngnh cng nghip l kh hay s dng kh. trong cc cng on ch bin su.
phm kh thng mi. khc, khi hm lng lu hunh trong kh l ng k. 2.2. 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. 2.2.1. 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 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. 2.2.2. 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 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. 2.2.3. 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 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 H2S , CO2 , Mecaptan
29
v cc hp cht khng mong mun khc da trn hp th ha hc v vt l.
bng II.1 trnh by tm tt mt s quy trnh cng ngh lm ngt kh

Hp th ha hc Quy trnh cng Dung mi ngh Quy trnh cng ngh * lm sch bng Alkacol MEA Mon amin - Fluor Etanol 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 thng K2CO3 chy nng ete Hp th ha hc Dung mi
amin Di Glycol amin
30
n tt nghip B mn : Lc ho du Assen ca kim Rectizol VeTrockk loi kim nng chy K3 ASO3 Metanol ( nhit thp)
(*) Tn gi phn hot ng ca dung mi, dung mi l nc 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 II.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 H2S 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. 2.3. 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 H2S v CO2.
2.3.1. Tnh cht chung v cc qa trnh lm ngt kh
ca cc Alkanol amin * Tnh cht: 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 II.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
33
Bng II.3 Mt s tnh cht ha l c bn ca cc Alkanol amin

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 MEA 61 1018 171 100 69 48 DEA 105.1 1090 DIPA 133.2 989 248.7 167 133 1.33 42 0.198 ( 450C) 87 722.5 DGA 105.1 1055 221 1.33 9.5 0.026 ( 240C) Hon ton 917.4
187 150 1.33 28 0.38 ( 300C) 96.4 1205.9
10.5 0.241 ( 200C) ho tan trong nc Hon 200C,%kl ton Nhit ho hi 1486.4 1.105Pa,j/kg
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%. Glycol. Qu trnh kt hp ng thi va lm ngt va lm kh kh, dng dung mi l dung dch MEA hoc DEA vi
35
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. 2.3.2. Quy trnh lm ngt kh bng MEA.
S tng tc ca MEA vi H2S, CO2 theo phn ng sau: - Vi H2S: 2RNH + (II.1) (RNH3)2 + H2S (II.2) - Vi Cacbonic: CO2 + 2RNH2 (II.3)
H2 S
(RNH3)2S 2RNH3HS
H 2O
(RNH 3)2CO3
CO2 + (RNH3)2CO3 + H2O (II.4) Vi R nhm HOCH2CH2
2RNH3HCO3
II VI 2
6
8 4
1
1 IV 0
III 3 7
5
V 11
9 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 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. 2.3.3. Quy trnh lm ngt kh bng DEA Nhng phn ng chnh xy ra (trong qu trnh lm ngt kh) gia DEA vi H2S v CO2; - Vi H2S 2R2NH + H2S
(R2NH2)2S
39
(II.5)
(R2NH2)2S + H2S Vi CO2: CO2 + 2R2NH + H2O
2R2NH2HS (R2NH2)2CO3
(II.6) (II.7)
CO2 + (R2NH2)2CO3 + H2O y R nhm C2H4OH Tng t nh qu trnh
2R2NH2HCO3 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. 2.3.4. Quy trnh lm ngt bng ADIP: 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
41
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. 2.4. Quy trnh lm ngt kh bng Kalicacbonat: Dng kalicacbonat lm dung mi hp th ho hc loi CO2 v H2S ra khi hn hp kh. Kalicacbonat nng chy s hp th CO2 v H2S theo cc phn ng sau: K2CO3 + CO2 + H2O K2CO3 + H2S theo hai bc: u tin l H2O phn ng vi K2CO3 H2O + K2CO3 thnh Kalicacbonat: KOH + CO2 Cn vi H2S:
2KHCO3 KHS + KHCO3
(II.9) (II.10)
Theo Ruziska th phn ng II.9 v II.10 thc t xy ra
KOH + KHCO3
(II.11)
Sau KaliHydrocit to thnh s phn ng vi CO2 to KHCO3 (II.12)
KOH + H2S
KHS + H2O
(II.13)
Qu trnh s dng vi kh t nhin c p sut ring phn kh Acid tng i cao. Do vy hin nay qu trnh lm ngt kh bng Kalicacbonat nng chy thng c s dng lm ngt kh t nhin c hm lng kh Acid trung bnh v cao. Qu trnh lm ngt kh ny c s cng ngh cng gn tng t vi cc qu trnh lm ngt bng dung mi Alkanol amin. Tuy nhin trong h thng lm ngt kh bng Kalicacbonat nng chy ny, cc thp hp th vn hnh nhit cao hn, do vy tit kim c mt lng nhit ng k cho vic trao i nhit v lm nng thit b, nhit cao cng lm tng kh nng ho tan ca Kalicabonat trong dung dch. iu ny cho php s dng dung dch Kalicacbonat nng chy c nng cao v tng kh nng hp th kh Acid ca dung mi hp th. T cc phn ng (II.9), v (II.10) cho ta thy nguyn nhn v sao m thp hp th phi vn hnh nhit cao l : v sn phm ca c hai phn ng c nng mui Kali cao hn so vi dung dch mui Kalicacbonat ban u. Phn ng gia Kalicacbonat v CO2, c mt phn t Kalicacbonat (K2CO3) cho hai phn t Kalicacbonat (KHCO3). Cn phn ng Kalicacbonat v H2S, c mt phn t Kalicacbonat cho mt phn t Kali Bisunfua (KHS) v mt phn t Kalicacbonat. V l do ny m hu ht cc qu trnh vn hnh lm ngt kh t nhin bng dung mi Kalicacbonat
nng chy c iu khin bng kh nng ho tan ca Kalicacbonat hn l kh nng ho tan ca Kalicacbonat. Qu trnh lm ngt kh bng dung dch Kalicacbonat nng chy c ng dng loi mt lng ln CO2 trong s hn hp kh mt cch hiu qu. N cng c ng dng lm ngt kh t nhin cha c H2S v CO2 nu trong kh nguyn liu khng c CO2 th Kali Bisunfua rt kh ti sinh, v vy qa trnh lm ngt kh bng dung dch Kalicacbonat nng chy khng ph hp lm ngt cc hn hp kh cha t hoc khng c CO2. Qu trnh lm ngt kh bng Kalicacbonat nng chy c thun li l: n c th loi c COS v CS2 m khng lm mt hot tnh ca dung mi hp th. Cc Bonylsunfua s b thu phn theo phn ng sau: COS + H2O CO2 + H2S (II.14) Sau sn phm ca phn ng thu phn (II.14) s phn ng vi Kalicacbonat nh phn ng (II.9), (II.10) trnh by phn trn. C vi chng c cho rng iu kin lm vic ca thp hp th trong qu trnh lm ngt kh bng dung mi Kalicacbonat nng chy CO S khng b thu phn hon ton v hin nhin c th c vi nh hng ca CO2 v H2S n cn bng ca phn ng (II.14). Trong dung dch Kalicacbonat nng chy CS2 b thu phn to thnh COS v H2S. Vi phng trnh biu din:
44
CS2 + H2O (II.15)
COS
+ H2S
H2S to thnh trong phn ng (II.15) s phn ng trc tip vi dung dch Kalicacbonat nng chy theo phn ng (II.10), cn COS s b thu phn tip theo phn ng (II.14) to thnh CO2 v H2S, H2S v CO2 sinh ra s phn ng trc tip vi Kalicacbonat nng chy. Do hn 1 bc thu phn nn tc phn ng ca CS2 vi Kalicacbonat chm hn so vi COS. Theo Parrich v Neilson th cc Mecaptan phn ng vi dung dch Kalicacbonat to thnh cc Mecaptua: Phng trnh phn ng: K2CO3 + RSH (II.16) T (II.16) ta nhn thy tnh Acid ca cc Mecaptan gim theo chiu di ca Hydrocacbon tng, nn kh nng phn ng ca chng vi dung dch Kalicacbonat nng chy gim khi chiu di ca gc Hydrocacbon tng. Parrich v Neilson a ra nhng s liu v kh nng hp th tng i ca kh Acid v cc cu t khng mong mun, tc phn ng tng i gia Kalicacbonat vi cc kh Acid v cc cu t khng mong mun: Cu t CO2 H2S COS CS2
RSK +
KHCO3
Kh nng hp th 1,00 1,41 Thu phn Thu phn

45
Tc phn ng 1,00 3,60 0,36 0,01
CH3SH NH3
0,03 0,10
1,20 3,50
Bng II.3: Kh nng hp th v tc phn ng ca dung dch Kalicacbonat nng chy vi H2S, CO2 v cc cu t khng mong mun khc 2300F v 2Psia.
kh axit 3
kh ngt 1 kh chua 2 Bm dung mi ngho Dung mi giu Phm Vn Thinh Lp: Lc ho du k46 46
S nguyn tc ca qu trnh lm ngt kh bng dung dch Kalicacbonat nng chy. s dng kh chua qua thit b tch u vo (khng c trnh by trn s ) v tip n l trao i nhit vi dng kh ngt i ra nh thp hp th (1). Dng kh chua sau khi c lm nng i vo phn di ca thp hp th (1) v i t y thp ln tip xc vi dng Kalicacbonat nng chy (ngho) i t trn xung. Thp hp th qu trnh lm ngt kh bng dung dch Kalicacbonat nng chy thng vn hnh nhit c 2300F. Dng kh ngt i ra t nh thp hp th (c hm lng hi nc cao) s nhng nhit cho dng kh chua ti thit b trao i nhit. Trong qu trnh lm lnh dng kh ngt c mt phn nc b ngng t, v vy n phi c a vo thit b tch tch nc. Dung dch Kalicacbonat giu ra khi y thp hp th (vi hm lng hi nc cao) s c a vo mm trn cng ca thp Stripping (2) vn hnh p sut khong 2 10 Psia. Do s gim p sut t ngt trong thp Stripping nn mt lng ln kh Acid c loi ra ngay mm trn cng ca thp. Sau dung mi c Stripping i xung (trong thp Stripping ) ti sinh su hn na bi dng hi Stripping c cung cp bng thit b gia nhit (5) phn y thp Stripping. Kh Acid cng vi hi nc i ra nh thp Stripping, s i qua thit b ngng t (4) ngng t hi nc c trong
kh Acid dng hi nc c ngng t v kh Acid s c a vo bnh hi lu (3) nh thp Stripping, ti y nc v kh acid s c tch ra, nc s c quay li thp Stripping nh mt dng hi lu cn kh acid s c em t hoc ch bin su hn. Dung mi ti sinh t y thp Stripping c bm n nh thp hp th ti s dng, tip tc mt chu trnh mi. Nhit ca y thp Stripping thng dao ng trong khong 240 2500F. 2.5. hp. Dung mi t hp c ng dng c nhit ho tan thp, kh nng hp th cao kh acid v cc cu t khng mong mun khc. Kh nng ny ph thuc r rt vo p st ring phn ca n trong iu kin hp th. Khi p st ring phn thp, cc dung mi c kh nng hp th thp nht. p sut ring phn c 5Mpa v ln hn (ca H2S hoc CO2) th tnh u vit ca dung mi vt l cng cao hn dung mi hp th ho hc. Tt c cc dung mi vt l u ho tan c H2S v CO2, tuy nhin hiu qu ca mi cht i vi H2S v CO2 l khng ging nhau. V vy mt cht hp th c th s dng thun li hp th CO2, cn cht khc hp th H2S, cht th bao thu hi chn lc vi s c mt ca cc cu tu khc. Gii thiu mt s quy trnh dng dung mi t
48
Ni chung quy trnh lm ngt kh dng dung mi t hp l kt hp trit c tnh u vit ca dung mi hp th ho hc v vt l. 2.5.1. Quy trnh Selecson. Dung mi c s dng trong qu trnh l: Di Metyl etepolyetylen glycol (DMEPEG). DMEPEG l cht khng c, bn ho hc trong iu kin ca quy trnh, khng c hot tnh n mn, khng si bt, d phn hu khi lm sch nc thi bng phng php vi sinh, c tnh chn lc cao v bo m hp th chn lc H2S trong s c mt ca CO2 ( 200C v 0,1 Mpa ho tan ca H2S trong DMEPEG gp 10 ln CO2). Kh nng ho tan ca DMEPEG i vi cc cht khc nhau nh sau: C2H6 < CO2 < C3H8 < C4H10 < CO S < C5H12 < H2S < CH3SH < CS2 < H2O Nh vy DMEPEG c th ho tan cht acid v cc Hydrocacbon. iu ny lm hn ch phm vi ng dng ca quy trnh. Nu mun s dng quy trnh Selecson th kh nguyn liu phi c hp th s b cc Hydrocacbon nng trc khi a vo lm ngt. Trong quy trnh Selecson do dung mi DMEPEG c tnh chn lc cao v bo m hp th chn lc H2S vi s hin din ca CO2. c tnh ca qu trnh Selecson c ngha trong thc t v trong trng hp ny chng ta c th tin hnh lm ngt hai bc, c th thu c bt th nht kh acid c hm lng kh H2S cao dng sn xut Lu
hunh sn phm, v bt th hai ta thu c kh acid cha phn ln l CO2 sn xut CO2 sn phm. Do vy quy trnh Selecson c hiu qu cao khi sn xut ng thi c 2 sn phm, hiu qu ca quy trnh tng cng vi s tng ca p sut lm vic v nng H2S, CO2 trong kh nguyn liu. Quy trnh Selecson l mt quy trnh rt hon ho, nng cc cu t kh acid cha trong kh ban u c th thay i trong khon rng m khng lm gim hiu qu ca quy trnh. Trong quy trnh Selecson thng ch thu hi c CS2 khng qu 50%. Ch cng ngh trong qu trnh hp th trong h thng Selecson: nhit dao ng trong khon 10 150C, p sut gia trong khon 6,8 7 Mpa. Vic ti sinh cht hp th khng cn cp nhit m thc hin bng cch gim p sut nhiu bc trong h thng. Thc hin lm ngt kh bng quy trnh Selecson cn chi ph u t v vn hnh thp hn ng k so vi quy trnh MEA: chi ph vn hnh gim 30%, chi ph u t gim 70%. 2.5.2. Quy trnh Sulfinol. Quy trnh ny c cng ty Shell (ca M) nghin cu, c ng dng lm sch ton b kh kh khi H2S, CO2, COS, Mecaptan, CS2 dung mi hp th s dng trong quy trnh Sulfinol l hn hp dung dch nc Diizo propanol amin (DIPA) v Tetra Hydrocacbon. 1 1 Diocid, c gi l Sulfolan: hn hp dung dch thng gm 30% Diizopropanol amin, 64% sul folan v 6% l nc. Thnh phn ca dung mi
hp th c thay i ph thuc vo cht lng kh nguyn liu. Dung mi Sulfolan ho tan tt H2S, CO2, Mecaptan CO2, CS2 v cc Hydrocacbon, rt bn ho hc, c nhit dung ring v p sut hi bo ho thp, O xy khng mong mun. Kh nng hp th ca dung mi Sulfolan gp hai ln dung dch Mono Etanol amin v c kh nng hp th cao ngay c khi p sut ring phn ca H2S v CO2 thp cng nh cao. bo ho ca dung mi Sulfinol c th t 85% ln hn bo ho ca dung mi MEA vi ln. V vy thc hin quy trnh Sulfinol cn tun hon mt lng dung mi hp th t hn v chi ph vn hnh thp hn. Quy trnh Sulfinol din ra thun li khi c t l cc cu t Acid trong kh: H2S/CO2 1 v p sut ring phn ca chng nm trong khon t 7 8 Mpa. Thc t cho thy cc thit b v h thng dung cho qui trnh lm ngt kh bng dung mi MEA c th dng tin hnh cho quy trnh Sulfinol, khi nng sut h thng tng ng k. S cng ngh ca quy trnh Sulfinol v MEA khng khc nhau nhng trong quy trnh Sulfinol th p sut trong thp hp th c xc nh bi kh u vo: p sut cng ln th quy trnh lm ngt cng hiu qu.
51
phn III. Tnh ton cc tham s c bn ca thp lm ngt kh bng dung dch MoNOL Etanol AMIN (MEA).
3.1. Gii thiu v ti: Tnh ton thp lm ngt kh B Nam Cn Sn. Kh ti Vit Nam ni chung v b Nam Cn Sn ni ring, hm lng kh chua nh, khng nh hng nhiu n qu trnh vn chuyn v ch bin nhng mun c c kh t tiu chun cn nghin cu, tnh ton qu trnh lm ngt ph hp, t hiu qu kinh t cao. Cc yu t cn quan tm khi la chn quy trnh cng ngh: 1. Nhng tp cht acid cn loi ra khi dng kh. 2. Hm lng ca cc tp cht acid v mc lm sch mong mun. 3. Tnh chn lc ca qa trnh l kh acid. 4. Th tch kh cn s l v iu kin nhit - p sut ca dng kh cn s l. 5. Tnh kh thi v kh nng thu hi lu hunh khi hm lng lu hunh trong kh l ng k. 6. Chi ph u t cho qu trnh. 7. T l CO2: H2S. Cc yu t cn quan tm khi la chn cht hp th cho quy trnh lm ngt
52
1. C tnh cht hp th chn lc, y l tnh cht quan trng nht

2. nht ca cht hp th nh.
3. nhit dung ring b, tiu tn nng lng cho qu trnh ti sinh nh. 4. nhit si khc xa vi nhit si ca cu t b hp th, nh vy d dng ti sinh dung mi bng trng ct 5. nhit ng rn thp, khng b ng rn ti nhit lm vic 6. khng to thnh kt ta kh hp th. 7. t bay hi, mt mt t trong qu trnh tun hon cht hp th.
8. khng c khng gy nhim mi trng, khng
gy n mn thit b Vi hm lng v thnh phn kh t nhin B Nam Cn Sn m bo cc yu cu trn. Ti chn quy trnh hp th bng MEA vi thp hp th l thp a lm ngot kh Quy trnh m bo c yu cu sau :
1. Ch cn s l kh CO2 vi hm lng nh
2. Lu lng dng kh ln
3. Nng lng cung cp cho qu trnh nh 4. Lm sch trit lng CO2
S dng MEA c c nhng u im sau

1. Lm sch CO2 trong khong p sut ring phn rng 2. C tnh n nh ho hc cao Phm Vn Thinh Lp: Lc ho du k46 53
n tt nghip B mn : Lc ho du 3. D ti sinh, c kh nng phn ng cao 4. Kh hp th cc Hydrocacbon 5. c s dng nhiu trong thc t, gi thnh r, d
kim. Thnh phn % th tch kh thin nhin ca mt m c trng

Cu t CO2 N2 CH4 C2H6 C3H8 iC4H10 nC4H10 iC5H12 nC5H12 C6H14
%V
2,6
0,1 0
89,1 4,0 2 4
1,71 0,37
0,48
0,20
0,16
0,12
3.2 Tnh ton cc thng s ca thp hp th
kh ngt
1 2
MEA ngho
j1 j j+1
n1 n Phm Vn Thinh Lp: Lc ho du k46 54
kh chua
S nguyn tc mt thp hp th cc kh acid bng MEA
3.2.1. S cng ngh ca phn xng lm ngt kh bng MEA

II VI 2
6
8 4
1
1 IV 0
III 3 7
5
V 11
9 VII
55
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. u tin kh chua cha H2S v CO2 phi c a qua thit b tch u vo tch cc cht pha lng hoc cc ht rn c trong dng kh. Sau kh chua c a vo y thp hp th v chuyn ng dng ln trng thp hp th tip xc trc tip, ngc chiu vi dng MEA ngho c ti vo a trn cng ca thp hp th. Dng kh ngt i ra nh thp hp th c a sang phn xng tch m trc khi tiu th. Dng MEA ngho ra khi y thp gii hp c nhit cao c bm qua thit b trao i nhit gia hai dng MEA (ngho v giu) nhng nhit cho dng MEA giu v sau c a sang thit b lm lnh bng khng kh trc khi c a vo nh thp hp th. Dng MEA ngho chuyn ng i xung trong thp hp th tip xc trc tip vi dng kh chua i ln v hp th cc kh acid (H2S v CO2) c trong dng kh chua. Dng MEA giu i ra khi y thp hp th c a vo bnh tch Hydrocacbon p sut thng, y c s
gim p nn c kh Hydrocacbon b hp th vt l vo dng MEA giu s c gii hp ra khi dng MEA giu. Dng MEA giu sau khi c tch Hydrocacbon c a sang thit b lc bng than hot tnh lc cc cn bt v sau c l nng bi dng MEA ti sinh (ngho) i ra t y thp gii hp ti thit b trao i nhit gia hai dng MEA trc khi i vo nh thp gii hp. Cc kh acid i ra nh thp hp th s c a qua thit b ngng t bng nc ri sau c a vo bnh tch kh, tch kh acid ra khi nhng gt MEA b cun theo dng kh acid ra khi nh thp. MEA ra khi bnh tch c bm hi lu v gii hp cn kh acid ra khi bnh tch c a sang cc phn xng k tip ch bin su hn. 3.2.2. Nhng cng thc tnh ton
57
Qu trnh hp th ha hc lm ngt kh dng dung dch Alkanol amin ni chung cng nh MEA ni ring thng chu nh hng ca rt nhiu yu t khc nh: p sut lm vic ca thp hp th, nhit dng amin giu i ra y thp hp th, lu lng ca dung dch amin vo v ra khi thp hp th, s a ca thp v ng knh ca thp nhng yu t c tc ng qua li vi nhau, tng quan ln nhau, nh hng trc tip n hiu a ca qu trnh hp thu, hiu sut ca thp hp th, chi ph vn hnh v chi ph sn xut ca qu trnh lm ngt dung dch lm ngt kh. Thng thng thp hp th c khong 10 20 a, lm vic p sut tng i cao, nhit tng i thp, lu lng ca dung dch amin vo ra khi thp hp th tu thuc vo: lu lng kh nguyn liu vo thp, hm lng kh acid c trong kh nguyn vt liu v mc lm ngt. Do tm quan trng ca cc thng s trn trong qu trnh thit k tng th mt cm lm ngt kh. Sau y s trnh by c th ln lt v c s l thuyt v p dng tnh ton mt s thng s quan trng ca thp lm ngt kh bng Alkanol amin ni chung v MEA ni ring. 3.2.2.1. Cng thc tnh p sut lm vic ca thp hp th
58
p sut c nh hng rt ln n trng thi cn bng v ng lc hc trong qu trnh hp th. Khi p sut tng, qu trnh cng din ra thun li hn v ng lc trung bnh ca qu trnh cng ln hn, nhng s tng p sut lun km theo s tng nhit s lm cho qu trnh hp th km hiu qu (do qu trnh hp th xy ra thun li nhit thp). Mt khc, s tng p sut s tng kh khn cho vic ch to thit b. Do vy, cn thit phi tnh thng s p sut ca thp hp th sao cho gi tr p sut va m bo hiu sut hp th tt va hp l trong u t ch to thp v vn hnh qu trnh. * Tnh p sut ca thp hp th theo cng thc : b PCO2/P, hay: P PCO2/b Trong : b: Nng phn mol CO2 cn li trong kh ngt ra nh thp hp th p: p sut lm vic ca thp hp th PCO2: p sut ring phn ca CO2 / dung dch amin ngho i vo nh thp hp th. PCO2 c tnh da vo phng trnh Claplayron Clausius: (3.1)
59
LnPCO2 = -A/T + B Vi; T: nhit ca dng amin ngho A,B: l nhng hng s m ta c th tnh c da vo biu ph lc 1 (khi ta bit hm lng CO2 trong amin ngho). 3.2.2.2. hp th Lu lng dng amin ngho i nh thp hp th c lin quan trc tip n hiu qu dung dch ca qu trnh lm sch kh khi CO2, lu lng v nng dung dch amin ngho vo nh thp hp th ph thuc vo mc chua ca kh nguyn liu. Kh cng giu CO2, lu lng kh cng ln khi vo thp th lu lng amin ngho vo thp, phi cng ln. Nu dung dch amin c dng cng long th lu lng ca n cng phi ln. Nh vy nu dung dch amin cng ln, nng amin cng cao trong dung dch th qu trnh hp th CO2 trong kh chua cng tt, nhng li tng chi ph sn xut v li i hi nhiu thit b ph tr nh: Bm duy tr lu lng dng amin tun hon, nhit qu trnh ti sinh, ngun nhit lnh lm lnh dung dch amin ngho trc khi i vo nh thp hp th. Do , cn phi tnh lu lng dng amin ngho
Cng thc lu lng dng MEA ngho vo thp
vo thp hp th sao cho va nhm m bo hp th trit H2S v CO2 ra khi kh va tit kim chi ph sn xut. Trong qu trnh hp th bng amin (MEA, DEA) t l amin/ kh acid (H2S v CO2) thng c chn t l 3/1 (mol/mol). S d c s la chn nh vy l v trong qu trnh hp th ha hc H2S v CO2 bng Alknol amin (MEA, DEA) xy ra theo cc phn ng sau: 2RNH2 2R2NH 2R2NH 2RNH2 + H2S + H2S + H2O + CO2 (RNH3)2S (R2NH2)2S (R2NH2)2CO3 (RNH3)2CO3
+ H2O+ CO2
Theo cc phn ng trn ta thy, hp th mt mol CO2 cn 2 mol amin (MEA, DEA). Tuy nhin trong thc t iu kin lm vic ca thp hp th, cc phn ng xy ra khng hon ton. Theo gi thuyt ca Zapff th phn ng ch t hiu sut l 65% y thp hp th, cn theo gi thuyt ca Koh1 v Rie senfeld th phn ng t hiu sut 75%. T hai gii thuyt ny ta chn ra hiu sut phn ng l 70% tin hnh tnh ton. Vy hp th ht mt mol CO2 th cn dng. 2 x 100/70 3mol amin (DEA, MEA)
- Chn nng dung dch amin (DEA, MEA) thng l t 15 25 khi lng vi MEA, 20 45% khi lng i vi DEA. - Tnh lu lng ca CO2 trong kh chua (kh nguyn liu), NCO2(kc) (mol/gi). NCO2(kc) = (3.2) - Tnh lu lng CO2 trong kh ngt : NCO2(kc) (mol/gi), c tnh theo cng thc: NCO2(kc) = %V(CO2) trong kh ngt x (lu lng kh chua%V(CO2). (lu lng kh nguyn liu)
lu lng kh b hp th) (3.3) - Tnh lng CO2 b hp th : NCO2(ht) (mol/gi) c tnh: NCO2(ht) = NCO2(kc) NCO2(kn) (3.4)
Tnh lng amin nguyn cht cn dng: Namin(nc)
(mol/gi) Namin(nc) = 3 NCO2(ht) (3.5)
Vy lu lng amin vo thp: mamin (vo) (kg/gi) mamin (vo) = [Namin(nc) . Mamin/% khi lng (amin)] + mCO2 (amin
ngho)
(3.6) Vi mCO2 (amin ngho) khi lng CO2 c trong amin ngho
62
* Lu lng kh ngt ra khi thp hp th: (mol/gi) Nkh ngt = { lu lng kh nguyn liu ( lulng kh CO2 b hp th + khi lng kh HC b hp th vo amin} (3.7)
3.2.2.3. Cng thc tnh lng dng MEA (kg/gi) giu ra khi y thp mMEA (3.8) 3.2.2.4. Cng thc tnh nhit dng MEA giu ra khi y thp hp th. Nhit l mt trong nhng thng s rt quan trng cho qu trnh hp th. Phn ng hp th ha hc dng MEA loi b CO2 l phn ng to nhit nn xy ra thun li nhit thp, nu nhit cao th phn ng xy ra theo chiu ngc li. Mt khc nhit cao th nht ca dung mi hp th gim, vn tc lu chuyn ca pha lng tng cng chuyn khi tng, n kch thch qu trnh chuyn pha lng thnh hi; lm nghch vi qu trnh hp th kh acid v amin. Do vy qa trnh hp th thng c tin hnh nhit thp gn vi nhit thng. Trong thp hp th ha hc bng MEA th nhit y thp lun lun cao hn nhit nh thp (do v phn ng hp th ha hc l cc phn ng to nhit), nu nhit y thp hp th
giu
= mMEAngho
mCO2ht
+mHC(ht)
qu cao s lm gim hiu qu ca qa trnh hp th v cc phn ng hp th xy ra theo chiu ngc li nhit cao. Do ta cn thit phi tnh ton nhit dng MEA ra khi y thp, nu nhit thp hp th qu cao ta phi tin hnh lm lnh y thp hp th gi nhit y thp ph hp vi iu kin ca qu trnh hp th. Sc xut ta coi nhit ca dng MEA ra ti y thp l nhit y thp hp th. xc nh nhit dng MEA giu ra khi y thp hp th. Ta cn phi tnh nhit lng ta ra v nhit lng thu vo trong thp l nhit y thp hp th v p dng nh lut bo ton nhit lng: Qta = Qthu (3.9)
Gi T l nhit dng MEA ra khi y thp * Nhit lng thu vo bao gm: Nhit nng vt liu thnh thp v phn nhit
tht thot Q(tt) = 2%Qto (3.10)
Coi nhit tht thot c lng l2% - Nhit lng lm nng dung dch MEA vo thp khng k CO2
64
QMEA(vo) (3.11)
mamin(ngho).
Camin.
(T-Tamin
(ngho)
Trong : Camin: nhit dung ring ca dung dch MEA Tamin (ngho): nhit dung ca dng MEA ngho vo thp hp th. - Nhit lng thu vo lm nng lng CO2 b hp th QCO2(ht) = mCO2(ht). CCO2 . (T- Tkh chua ) (3.12)
- Nhit thu vo lm nng lng CO2 sn c dung dch amin ngho Q(CO2/MEA)ngho = mCO2 (MEAngho) . CCO2 . (T-TMEA (ngho)) (3.13) - Nhit thu vo lm nng lng CO2 trong kh ngt Tkh chua ln Tkh ngt (nuTkh chua > Tkh ngt ). QCO2(kn) = NCO2(kngt) . MCO2.CCO2 (Tkn Tkc) (3.14)
- Nhit thu vo lm nng kh Hydrocacbon t Tkh

chua
ln Tkh ngt (nuTkh chua < Tkh ngt ). Qhc(tkc - tkn) = mhc(kh ngt) . Ckh hc . (Tkn - Tkc) (3.15)
Ckh hc : nhit dung ca hn hp kh Hydrocacbon

65
- Nhit thu vo lm nng Hydrocacbon b hp th vo dung dch amin giu. QHC(MEA giu) = mHC(ht) . Ckh hc . (T Tkc) * Nhit lng to ra bao gm: Nhit lng ta ra do qu trnh hp th cc (3.16)
Hydrocacbon vo dung dch amin: QHC(MEA) = mHC(ht) . (nhit hp th) (3.17)
- Nhit ta ra do phn ng hp th CO2 vo dung dch amin: QCO2(MEA) = mCO2(ht) . (nhit phn ng hp th CO2 vo amin) (3.18)
3.2.2.5. Cng thc tnh s a ca thp hp th S a trong thp hp th lin quan n mc sch ca kh ngt ra khi thp. S a cng ln th kh nng tip xc ca dng kh chua vi dng amin lng theo thi gian cng lu, mc hp th ca qu trnh tng, kh c lm sch cng trit hn. Nhng s a ln qu s gy cn tr cho dng kh v dng lng, tc ca dng gim i ng k, dn n nng sut gim v lm gin hiu qu ca qu trnh. Mt khc nu s a tng th chi ph xy dng ca thp cng tng, chi ph vn hnh, bo dng, sa cha cng tng theo. V vy, cn tnh ton v chn a
cho ph hp, qu trnh hp th t c kt qu cao nht v kinh t nht. S a l thuyt ca thp hp th c xc nh theo cng thc: Nlt = [Ln .1/q(a-1)]/LnA + 1 (3.19) Trong : A; yu t hp th, c xc nh theo cng thc A = [a.(1 + Rr)(1- q)]/P1/P Vi q = s mol CO2 trong kh u ra (kh ngt)/s mol CO2 trong kh nguyn liu (kh chua). a: phn mol ca kh CO2 trong kh nguyn liu R: t l s (mol MEA/s mol CO2 , thng chn theo t l 3/1 . r: s mol CO2 cn li trong mt mol MEA ngho i vo nh thp P: p sut lm vic ca thp hp th P1: p sut ring phn ca CO2 trong dung dch MEA giu y thp hp th P1c tnh theo phng trnh Clapayon Clausius:
(3.20)
LnP = - A/T + B Trong ; A,B: l nhng hng s m ta c th tnh c da vo biu ph lc 1 (khi bit c lng CO2 c trong mt mol MEA giu y thp hp th). S a thc ca thp hp th c tnh : Nthc = Nlt/hiu sut a (3.21) (hiu sut a theo kinh nghim vo khon 0,25 0,4) 3.2.2.6. Cng thc ng knh thp hp th ng knh thp hp th c tnh theo cng thc
D = 0,0114 0,1.
QT WP
(3.22)
Trong : D - ng knh ca thp hp th Q: lu lng kh cn lm sch (m3/gi) T: nhit kh cn lm sch (K) P: nhit kh cn lm sch (Mpa)
(m)
W: Vn tc kh trong thit din t do ca thp , thng ly bng 0,13 (m/s). 3.2.2.7. Cng thc tnh chiu cao ca thp hp th Chiu cao ca thp hp th c tnh nh sau: H = (Nthc .d) + h Trong ; d: l khon cch gia cc a thng chn trong khong 50-60 cm h: l h s b tr, tng chn trong khong 1,0 1,5m 3.3 p dng tnh ton 3.3.1. yu cu bi ton Gi thit tinh ton thp lm ngt kh vi hm lng cho bng sau
C u t %V CO
2
(3.23)
N2
CH4
C2H6
C3H
8
i-
n-
i-
nC5H12 0,16
C6H1
4
C4H1 C4H1 C5H12

0 0
2,6 0,10
89,12
4,04
1,7 1
0,37 0,48 0,20
0,12
Vi lu lng kh chua KTC)
1,8.106 m3/ngy (
Nhit u vo : 250C *Yu cu + Hm lng CO2 trong kh ngt : 0,2% + Lng Hydrocacbon b hp th vo MEA l 0,3% th tch * Chn s liu
+ S dng dung dch MEA ngho c nng 15% khi lng cha 0,03 mol CO2/1 mol MEA + Nhit dung dch MEA ngho :300C + Nhit kh ngt l 32oC * Cc i lng s dng trong qu trnh tnh ton + Khi lng phn t MEA : 61 + Nhit dung ca dung dch MEA : 3,89 0 (kj/kg C ) + Hiu sut ca a l : 20% + Nhit hp th CO2 Hht : 1919 (kj/kg ) + Nhit dung ca CO2 : 0,84 0 (kj/kg C) + Nhit dung ca hn hp kh : 2,7 0 (kj/kg C) 3.3.2. Gii quyt bi ton thun li cho qu trnh tnh ton v tra bng biu ta tnh ton mt s i lng c lin quan n hn hp kh. T thnh phn ca hn hp kh ta c s liu sau. Cu t CO2 N2 CH4 C2H6 C3H8 i-C4H10 Vi (%) 2,60 0,10 89,12 4,04 1,71 0,37 Mi 44 28 16 30 44 58 Mi.Yi 1,5840 0,028 14,2592 1,2120 0,7524 0,2146
70
n- C4H10 i- C5H12 n- C5H12 C6 Tng Gi
0,48 0,20 0,16 0,12 1,00
58 72 72 86
0,2784 0,1440 0,1152 0,1032 18,5758
M l khi lng phn t trung bnh ca hn hp kh M = M i .Yi = 18,5758
T khi ca hn hp kh so vi khng kh l = M /29 =0,6405 Th tch 1mol kh nguyn liu iu kin (15,60C, 1at ) l
V=
Vo .Po .T15, 6 22,4.1.288,6 = = 23,63(lit / mol ) To .P 273 . 1 15 , 6
Vy s kmol kh chua vo thp trong 1 gi ( ktc) l :
1,8.10 6 N= = 3173,93(kmol / h) 24.23,63

* Tnh ton cc thng s trong thp hp th 1. Tnh p sut lm vic ca thp(cha tnh) 2. Tnh lu lng MEA ngho vo thp _ Lu lng CO2 trong kh chua NCO2(kc) (kmol/h) NCO2(kc) = YCO2(kc) . N = 82,522 (kmol/h) _ Lu lng hydrocacbon b hp th NHC(ht) (kmol/h) NHC(ht) = 0,3 . N/100 = 9,5218 (kmol/h) _ Lu lng CO2 trong kh ngt NCO2(kn) (kmol/h) NCO2(kn) = 0,2 .Nkn/100 Nkn = (N - NHC(ht) - NCO2(ht) ) NCO2(ht) = NCO2(kc) - NCO2(kn)
NCO2(kn) _ _ (kmol/h) mMEA(ngho) mCO2
NCO2(kn) =0,2 . ( N -NHC(ht) - NCO2(kc) + )/100 Vy NCO2(kn) = 6,176 (kmol/h) Lu lng CO2 b hp th NCO2(ht) (kmol/h) NCO2(ht) = NCO2(kc) NCO2(kn) NCO2(ht) = 73,346 (kmol/h) Lu lng MEA nguyn cht cn dng l NMEA(nc)
NMEA(nc) = 3. NCO2(ht) = 229,038 (kmol/h) Vy lu lng dung dch MEA ngho vo thp (kg/h) mMEA(ngho) = NMEA(nc) .MMEA .100/15 + mCO2 /MEAngho = NCO2/MEAngho .MCO2 (NCO2/MEAngho l lu lng CO2 trong MEA ngho) mCO2/MEAngho = 0,03 . NMEA(nc) .
44 mCO2/MEAngho = 302,33 (kg/h) mMEA(ngho) = 93444,532 (kg/h) 3. Tnh lu lng kh ngt ra khi nh thp (kg/h) _ Tnh khi lng CO2b hp th (kg/h) mCO2(ht) = NCO2(ht) .44 = 3359,228 (kg/h) _ Tnh khi lng hydrocacbon b hp th (kg/h) mHC(ht) = 0,03.N._ M /100 mHC(ht) = 176,874 (kg/h) Vy lu lng kh ngot mkn (kg/h) l : mkn = mkc - mCO2(ht) mHC(ht) mkc = M .N = 58958,289 (kg/h) mkn = 55422,187 (kg/h) 4. Tnh lu lng dng MEA giu ra khi y thp mMEAgiu (kg/h) mMEAgiu = mMEAngho + mCO2(ht) + mHC(ht) mMEAgiu = 96980,634(kg/h) 5. Tnh nhit dngMEA giu ra khi y thp T0 C
_ Nhit thu vo lm nng MEA ngho (khng tnh CO2) Q1 = (mMEAnqgho-m CO2/MEAngheo). CMEA . (T30) Q1 = 363499,23.(T-30) _ Nhit thu vo lm nng lng CO2 b hp th Q2 = mCO2(ht) .CCO2 . (T-25) Q2 = 2821,751 (T-25) _ Nhit thu vo lm nng CO2 trong MEA ngho Q3 = mCO2/MEAngho . CCO2 . (T-30) Q3 = 253,957.(T-30) _ Nhit thu vo lm nng lng hydrocacbon b hp th Q4 = mHC(ht) .CHC . (T-25) Q4 = 477,56 .(T-25) _ Nhit thu vo lm nng lng hydrocacbon trong kh ngt Q5 = ( mkn - mCO2/kn ) .CHC .(Tkn0 25) , (Tkn =32 C) mCO2/kn = NCO2/kn .MCO2 =271,744 (kg/h) Q5 = 148906,196 .(32-25) Q5 = 1042343,373 (kj) _ Nhit thu vo lm nng lng CO2 trong kh ngt Q6 = mCO2/kn .CCO2 .(Tkn-25) Q6 = 1597,855 (kj) Vy tng nhit lng thu vo l Qthu = Q1 + Q2 + Q3 + Q 4 + Q5 + Q6 + Qtt Vi Qtt = 2% Q to (Nhit tht thot) Qthu = 367052,498.T -9949867,372 + Qtt _ Nhit lng to ra trong qu trnh hp th l Qto = mCO2(ht) . Hht Qto = 3359,228 .1919 = 6446358,532 (kj) Qtt = 128927,17 (kj)
M ta c Qthu = Qto y tnh c T = 44,3180 C Vy nhit dng MEA giu ra khi y thp l T = 44,3180 C 6. Tnh s a ca thp hp th 7. Tnh ng knh ca thp hp th: p dng cng thc:
D = 0,0114. 0,1
QT WP
273 = 298 m/h m3/h
D: ng knh ca thp T: Nhit ca kh cn lm ngt T = 25 + K P: p sut kh P = 1at 0,1 Mpa W: Vn tc ca dng kh W =0,13m/s = 468 Q: Lu lng dng kh Q = 1,8.106/24 = 75. 103
75.103.298 D = 0,0114. 0,1 468.0,1

=2,49 (m) 8. Tnh chiu cao ca thp :
74

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