Bi vit c hon thnh di s hng dn ca PGS. TS. Nguyn Th Minh Hin B mn CN Hu c- Ha du. HBK.

HN
(bi vit ch c tnh cht tham kho; khng l ti liu hay gio trnh chnh thc no)

M u................................................................................................................... 1 Tng quan v cc cng ngh lm ngt kh t nhin v kh ng hnh ................ 2

I. Gii thiu chung .......................................................................................................2 II. Qu trnh hp ph....................................................................................................3
II.1 C s ha l.................................................................................................................. 3 II.2. Mt s cht hp ph c th dng lm ngt kh ...................................................... 4

III. Qu trnh hp th ...................................................................................................4

III.1. C s ha l ............................................................................................................... 4 III.2. Qu trnh hp th ha hc.......................................................................................... 5 III.3. Qu trnh hp th vt l ............................................................................................. 9 III.4. Qu trnh t hp....................................................................................................... 12

V. Qu trnh lm ngt kh bng phng php hp th ha hc s dng dung mi monoetanol amin (MEA) ...........................................................................................13

H tr tnh ton, thit k thp hp th lm ngt kh bng phng php hp th ha hc s dng dung mi MEA ............................. 17
I. Cn bng vt cht ca thp hp th ........................................................................17 III. Cn bng nhit lng ca thp hp th ................................................................20 IV. Thit k thp hp th ...........................................................................................22

Ti liu tham kho ............................................................................................... 26

Lm sch kh khi H2S,CO2 v cc hp cht hu c cha lu hunh

m u

Kh t nhin v kh ng hnh l nhin liu, nguyn liu quan trng, c hiu qu kinh t cao cho i sng v cng nghip ha hc. Trong nhng nm gn y, Vit Nam cng nh nhiu nc trn th gii c xu hng tng cng sut cc nh my ch bin kh. Ti cc nh my ch bin kh mi xy dng, ngi ta lp t cc thit b mi thc hin ng thi mt vi qu trnh cng ngh ch bin kh. Ti Vit Nam theo d on ti nm 2010 tiu th LPG t 10 t m3/nm. Vi nhu cu ln nh vy vic tnh ton thit k xy dng cc nh my ch bin kh c cng sut ln, sn phm phong ph, hiu qu kinh t cao l mt yu cu cp thit. Tng cng sut cc nh my ch bin kh l tng nhp pht trin ca cng nghip ch bin kh. iu ph thuc rt nhiu yu t nh: cng ngh ch to thit b, vn khai thc, vn chuyn kh, s dng nguyn liu v sn phm. c bit l ngun ti nguyn kh t nhin v kh ng hnh ca tng nc. Kh t nhin v kh ng hnh bn cnh thnh phn ch yu l cc hydrocacbon no cn c mt lng nh cc kh khc nh He, N2, CO2, H2S ... Trong cc kh CO2, H2S gi l cc kh axit c c bit quan tm v khi c mt mt hm lng ln s gy nhng nguy hi cho cc qu trnh ch bin, vn chuyn, s dng v bo qun kh. Do vy vn lm sch kh khi cc cu t axit l mt vn khng th thiu khi thit k nh my ch bin kh.

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Lm sch kh khi H2S,CO2 v cc hp cht hu c cha lu hunh

Tng quan v cc cng ngh lm ngt kh t nhin v kh ng hnh

I. Gii thiu chung

Trong thnh phn ca kh t nhin v kh ng hnh bn cnh thnh phn chnh l cc hydrocacbon no cn c cha mt lng ng k cc tp cht c tnh axit nh cacbonic (CO2), hydrosunfua (H2S) v cc hp cht cha lu hunh khc nh oxyt lu hunh cacbon (COS), disunfua cacbon (CS2), mecaptan (RSH)... Cc tp cht k trn l cc tp cht khng mong mun trong qu trnh khai thc, ch bin, vn chuyn, s dng v bo qun kh cho mc ch lm nguyn liu t, tng hp hu c-ha du... S tn ti ca cc kh axit gy nn s n mn kim loi, gim hiu qu ca cc qu trnh xc tc, lm ng c xc tc, gy nhim mi trng, c hi cho ngi s dng... Bn cnh s c mt hm lng cao CO2 trong kh cng lm gim nhit chy ca kh, gim hiu qu ca qu trnh vn chuyn kh. Vi cc nguy hi trnh by, th s c mt ca cc cu t mang tnh axit trong kh cn phi c khng ch mt hm lng nh nhm gim thiu nhng tc hi m cc kh axit ny gy ra cho thit b, my mc, mi trng v sinh vt. Cng ha lin bang Nga quy nh hm lng H2S khng c vt qu 22mg/m3 cn M quy nh kht khe hn: hm lng H2S khng c vt qu 5,7mg/m3; nng CO2 trong khong 1~2% th tch... Do vy qu trnh lm ngt kh l mt qu trnh quan trng v khng th thiu trong bt k nh my ch bin kh no. Trn th gii c rt nhiu nghin cu nhm lm sch kh t nhin v kh ng hnh khi cc cu t axit bng cc phng php hp ph v phng php hp th. Vic la chn cc phng php lm ngt kh cn ch nh gi thnh phn ca nguyn liu bao gm c tp cht m trong kh thnh phm yu cu phi loi b. Mt s tp cht khi tc dng vi cc dung mi c th hnh thnh cc hp cht ha hc m trong giai on ti sinh s khng b phn hy (phn ng khng thun nghch trong iu kin qu trnh). iu ny dn n gim hot tnh dung mi v kt qu l dung mi mt hon ton hot tnh.
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Lm sch kh khi H2S,CO2 v cc hp cht hu c cha lu hunh

Thc t cho thy, nhng lng tp cht nh i khi li gy nhng nh hng rt ln n vic la chon dung mi hoc cng ngh lm sch kh. T l H2S/CO2 trong kh nguyn liu cn phi c cc nh cng ngh xem xt thn trng do nng H2S trong cc kh axit l yu t quyt nh la chn cng ngh, phng php lm sch kh, phng php x l v thu hi cht thi ca cng ngh... Di y xin trnh by cc phng php v cng ngh lm ngt kh v ang c p dng trn th gii c mt ci nhn tng quan v quy trnh quan trng ny.
II. Qu trnh hp ph

II.1 C s ha l Hp ph l qu trnh ht cc cht ln b mt xp ca cht rn nh cc i lc trn b mt. Cc vt liu ny c gi l cht hp ph, cht b ht gi l cht b hp ph. Lc hp ph ha hc do lc ht phn t Vanderwall tc dng trong khong khng gian gn st b mt gi l hp ph vt l. Mi phn t b hp ph (pha kh hay lng) u gim t do, nn hp ph lun km theo s ta nhit. Khi tin hnh la chn cht hp ph trong cng nghip cn ch ti cc yu cu sau: - Cht hp ph c b mt ring ln. - C hp ph chn lc. - C tr lc nh i vi dng kh. - C th ti sinh d dng. - Thi gian lm vic lu. - bn c chu s rung ng v cc tc ng trong nhiu cng on ca qu trnh. Trong cng ngh lm ngt kh nu dng phng php hp ph s p ng tt vi kh c hm lng H2S , RSH trung bnh v thp. Phng php c chn

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Lm sch kh khi H2S,CO2 v cc hp cht hu c cha lu hunh

lc cao, H2S thu c c tinh khit cao, t chu nh hng ca p sut. Chi ph cho cht hp th l tng i thp. Nhng nhc im ln ca qu trnh hp ph trong lm ngt kh l qu trnh xy ra chm, cht hp ph kh ti sinh, hiu qu ca qu trnh thp nn phng php s dng cht hp ph l t ph bin. II.2. Mt s cht hp ph c th dng lm ngt kh Silicagel, Al2O3, than hot tnh, zeolit. Cc oxit kim loi: Fe2O3, ZnO,...
III. Qu trnh hp th

III.1. C s ha l Hp th l qu trnh pha lng ht pha kh. Kh c ht gi l cht b hp th, cht lng dng ht gi l cht hp th. i km vi qu trnh hp th l qu trnh nh hp th. Hp th v nh hp th l hai qu trnh chuyn khi c bn c s dng tch cc cu t khng mong mun ra khi kh t nhin v kh ng hnh. Bn cht ha l ca qu trnh l s hnh thnh cn bng pha gia hai pha kh-lng do s khuch tn ca cc cht t pha n sang pha kia. ng lc ca qu trnh khuch tn l s chnh lch p sut ring phn gia cc cu t trong pha lng v pha kh. Nu p sut ring phn ca cc cu t trong pha kh ln hn trong pha lng th s xy ra qu trnh hp th (cht lng hp th cht kh), cn ngc li th xy ra qu trnh nh hp thu (cht kh c tch ra khi pha lng) Thc t, tnh ton ng lc ca qu trnh khuch tn c tnh qua nng cc cu t, v p sut ring phn t l thun vi nng . Cht hp th cn tha mn cc yu cu sau: - C kh nng hp th chn lc - C p sut hi bo ha b mt mt dung mi trong qu trnh l b nht. - Nhit dung ring b, tiu tn nng lng cho qu trnh ti sinh nh. - Nhit si khc xa vi nhit i si ca cht b hp th, nh th d dng ti sinh dung mi bng chng ct.
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Lm sch kh khi H2S,CO2 v cc hp cht hu c cha lu hunh

- Nhit ng rn thp, khng b ng rn ti nhit lm vic. - nht ca cht hp th nh. - Khng to thnh kt ta khi hp th. - t n mn, t bay hi, mt mt t trong qu trnh. - C bn nhit v bn oxy ha - Khng c hi cho con ngi v mi trng. - Gi thnh r, d kim. Trong nh my ch bin kh ni ring v trong cng ngh lc-ha du ni chung qu trnh hp th c s dng kh ph bin. Qu trnh hp th v nh hp th c tin hnh theo mt chu trnh kn v lin tc. tch cc cu t c tnh axt trong kh t nhin v kh ng hnh ngi ta s dng ch yu l cc qu trnh hp th [2] bi tnh hiu qu v kinh t ca n. Di y l cc qu trnh hp th c phn loi theo c im tng tc ca kh axit vi dung mi (cht hp th): hp th ha hc v hp th vt l. III.2. Qu trnh hp th ha hc Cc qu trnh hp th ha hc lm sch kh bng dung mi l nhng dung dch nc alkanolamin (monoetanol amin, dietanol amin, diglycol amin...) chng da trn phn ng ha hc ca cc hp cht khng mong mun vi alkanolamin. Cc qu trnh amin m bo lm sch trit kh khi H2S, CO2 vi p sut v nng lm vic ca chng trong kh ban u khc nhau, ha tan cc hydrocacbon trong nhng cht hp th ny khng cao. Thit b v cng ngh ca qu trnh n gin v bn. Nhc im c bn ca qu trnh l khng tch c ton b H2S, CO2, RSH, COS v CS2. Mc tch mercaptan v cc hp cht cha lu hunh khc thp, tng tc ca mercaptan, COS v CS2 vi mt s dung mi k trn to thnh hp cht khng th ti sinh c trong iu kin ca qu trnh. Mun ti sinh dung mi khi c mt mercaptan, COS v CS2 trong kh t nhin v kh ng hnh cn phi c bc tun hon ca cht hp th cao, tiu hao nhit lng ln. Mt iu cn lu rng cht hp th v sn phm tng tc ca chng vi cc

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Lm sch kh khi H2S,CO2 v cc hp cht hu c cha lu hunh

tp cht cha trong kh c th lm tng tnh n mn thit b, i hi vt liu v cng ngh ch to thit b tn km. S gia tng nng cht hot ng v mc bo ha dung mi bi H2S v cc hp cht khng mong mun khc s lm tng tnh n mn ha hc.V vy kh nng hp th ca cc dung mi ny thng b hn ch bi mc bo ha gii hn cho php ca cc cht hp th bng cc kh axit. Bng 1 di y a ra mt vi tnh cht ho l cn bn ca alkanolamin.
Bng 1: Tnh cht ha l c bn ca MEA, DEA, DIPA, DGA MEA DEA DIPA DGA

Khi lng phn t Khi lng ring (kg/m3) Nhit si (0C) p sut 110 Pa 660 Pa 1320 Pa p sut hi bo ha (Pa) 200C Nhit ng c (0C) nht tuyt i (Pa.s)

61 1018 171 100 69 48 10,5 0,241 ( 200C)

105,1 1090 --187 150 1,33 28 0,38 ( 300C) 96,4 1205,9

133,2 989 248,7 167 133 1,33 42 0,198 ( 450C) 87 722,5

105,1 1055 221 ----1,33 9,5 0,026 ( 240C) hon ton 917,4

ha tan trong nc(%KL) hon ton 200C Nhit ha hi (J/kg) 1.105Pa 1486,4

Di y l mt s cng ngh lm ngt kh s dng qu trnh hp th ha hc c ng dng ph bin trn th gii. III.2.1. Qu trnh lm ngt kh bng dietanol amin (DEA) [2] Qu trnh lm ngt kh bng phng php hp th ha hc s dng dung mi l dietanol amin (DEA). Nng DEA trong dung dch ph thuc vo nng kh axit trong nguyn liu ban u, bo ha kh axit ca dung dch thay i t 20% ti 30% khi lng. Nu nng trong dung dch ca kh axit l
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Lm sch kh khi H2S,CO2 v cc hp cht hu c cha lu hunh

0,05 -0,08m3/l th s dng dung dch DEA 20%-25%, nu 0,14 0,15%m3/l th s dng dung dch DEA 25%-27%, nu 0,15 0,17%m3/l th s dng dung dch DEA 25%-30% [2]. Qu trnh lm ngt kh s dng DEA vi nng 25%-27% c ng dng khi p sut ring phn kh axit l 0,2MPa v ln hn. Qu trnh s dng DEA vi nng 25%-30% c s dng khi p sut ring phn kh axit l 0,4MPa v cao hn. iu ny cho php m bo s bo ha dung dch cn thit v nh vy s dng c cc u im ca qu trnh hp th ha hc s dng dung mi ankanolamin. u im ca qu trnh l m bo lm sch trit kh khi H2S v CO2 vi s c mt ca COS v CS2 (sn phm ca phn ng gia DEA vi COS v CS2 b thy phn trong ti sinh dung mi ti H2S v CO2). Dung mi DEA bn v mt ha hc; d dng ti sinh; c p sut hi bo ha thp; cng ngh v thit b n gin, bn; s hp th nhit 10-200C nn loi tr c s to bt mnh lit ca dung dch khi lm sch kh c nng hydrocacbon nng cao. Nhc im ca qu trnh l kh nng hp th ca dung mi thp, lu lng ring ca cht hp th cao v chi ph vn hnh ln. Mt s tp cht c trong kh nguyn liu khi tng tc vi dung mi to thnh hp cht khng ti sinh c, kh nng hp th cc mercaptan v cc hp cht hu c cha lu hnh khc thp. III.2.2. Qu trnh lm ngt kh ADIP [2] Dung mi c s dng l dung dch nc diizopropanol amin (ADIP); hm lng cht hot ng trong c th t ti 40%. Nh dung mi ny vic lm sch trit kh t nhin v kh ng hnh khi H2S (n 1,5mg/m3) c bo m, diizopropanol amin c th lm sch ng thi c CO2, COS, v RSR. Diizopropanol amin tng tc vi CO2, COS, v RSR to thnh cc hp cht d ti sinh. ha tan cc hydrocacbon trong qu trinh ADIP l khng ln. S cng ngh dn gin, d chuyn i.

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Lm sch kh khi H2S,CO2 v cc hp cht hu c cha lu hunh

III.2.3 Qu trnh lm ngt kh bng iglycolamin (DGA) [2] Qu trnh s dng dung mi l dung dch nc diglycolamin (DGA) vi nng cht hot ng 60%-65% khi lng. Vi nng cao nh vy dung mi c th lm sch trit kh t nhin v kh ng hnh khi H2S (n 5,7mg/m3). Tng tc ca DGA vi CO2, COS, CS2 v mercaptan to thnh cc hp cht d ti sinh. Trong qu trnh ti sinh kh nng thu hi CO2, COS, CS2 v mercaptan l tng i cao. bo ha ca dung dch DGA c th t ti 40-50 lt kh axit trn 1 lt dung dch. Qu trnh rt thun li khi lm ngt kh nguyn liu c hm lng kh axit t 1,5% ti 8%. ha tan cc hydrocacbon trong kh nguyn liu v hot tnh n mn ca dung mi l khng cao. Tht thot dung mi trong qu trnh l b. III.2.4. Qu trnh lm ngt kh bng monoetanol amin (MEA) [1, 2] Qu trnh s dung mi l dung dch nc monoetanol amin (MEA). Nng MEA khng c vt qu 15-20% th tch. Khi bo ha dung dch MEA c nng cao hn bng cc kh axit th vn tc n mn kim loi tng. Trong thit k h thng lm sch kh t nhin v kh ng hnh bng MEA cc nh k thut nhn thy rng nng kh axit i ra t dy thp hp th phi khng ln hn 65-75% nng cn bng (theo t l vi kh nguyn liu ban u). Khi mc bo ha dung dch phi khng ln hn 0,3-0,4 mol/mol MEA. u im ca qu trnh l lm sch trit kh khi H2S v CO2 trong mt khong p sut ring phn rng. MEA c tnh n nh ha hc cao, ti sinh d dng, kh nng phn ng cao, cng ngh v thit b n gin c bn cao khi vn hnh ng. Dung mi MEA rt t hp th hydrocacbon nn trong qu trnh ti sinh c th thu hi cho qu trnh sn xut lu hunh. Nhc im ca qu trnh l mc bo ha dung dch thp, lu lng ring ln v chi ph vn hnh cao (cao hn 25-40% so vi DGA). Cc tp cht nh CO2, COS, CS2, HCN, SO2, SO3 khi tng tc vi dung mi to thnh hp cht cao phn t khng ti sinh c hoc kh ti sinh, lm mt hot tnh ca cht hp th, tng tnh to bt v tnh n mn ca dung mi. V vy khi c COS v CS2 qu trnh khng c ng dng. Mc thu hi mercaptan v cc hp cht hu c cha lu hunh khc thp. Tng khuynh hng to bt khi c cc hydrocacbon lng, sunfua st, thiosufit v cc sn phm phn hy MEA.
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Lm sch kh khi H2S,CO2 v cc hp cht hu c cha lu hunh

III.3. Qu trnh hp th vt l Cc qu trnh lm sch kh bng phng php hp th vt l cc cu t axit trong kh t nhin v kh ng hnh bng dung mi hu c (propylen cacbonat, imetyl ete polyetylenglycol, N-metyl pirrolidon...). Chng da trn hp th vt l ch khng phi l cc phn ng ha hc nh qu trnh hp th ha hc. Trn nguyn tc cc dung mi hu c c th s dng lm sch ton b kh khi H2S, CO2, RSH, COS v CS2 khi p sut ring phn ca chng ln trong iu kin hp th. Cht hp th thng khng si bt, khng n mn thit b, c nhit ng c thp... Vi cc u im ny th vic s dng dung mi hu c cho qu trnh rt thch hp khi p dng ti nhng vng c iu kin nhit kh hu lnh. Khi p sut ring phn ca cc hp cht khng mong mun cao, qu trnh lm sch kh bng dung mi hu c c yu cu chi ph u t v vn hnh t hn i vi vic thc hin qu trnh hp th ha hc bng amin. Vic ti sinh cht hp th vt l din ra trong nhiu trng hp khng cn cp nhit m nh gim p sut h thng. Nhc im c bn ca qu trnh l dung mi hu c c s dng li hp th thng i tt cc hydrocabon. Nhiu trng hp vic lm sch kh l cha trit . Bng 2 di y trnh by mt vi tnh cht vt l ca mt s dung mi hp th vt l thng gp
Bng 2: Tnh cht vt l ca mt s dung mi hp th vt l Propylencacbonat DMEPEG NMP

Nhit si (0C) Nhit nng chy (0C) Khi lng ring 250C (kg/m3) Khi lng phn t nht 250C (Pa.s) p sut hi bo ha 250C (Pa) Nhit dung ring (KJ/(kg.))

242 -49 1200 102 6,64.10-6 0.666 ---

151 22-29 1000 280 5,8.10-3 1,33 2,43 ( 250C)

275 24 1000 99 1,87 133,3 1,67 ( 200C)

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Lm sch kh khi H2S,CO2 v cc hp cht hu c cha lu hunh

Di y l mt s cng ngh lm ngt kh s dng qu trnh hp th vt l c ng dng ph bin trn th gii. III.3.1. Qu trnh Flour [2] Qu trnh c nghin cu bi cng ty Flour. H thng cng nghip u tin c xy dng M nm 1960 lm sch kh thin nhin khi CO2 (45% th tch) v H2S (70mg/m3). Cht hp th c s dng rng ri l propylencacbonat. Propylencacbonat ha tan tt H2S, CO2, RSH, COS, CS2 v cc hydrocacbon; c tc dng n mn yu i vi thp cacbon thng thng, bn v mt ha hc trong iu kin qu trnh, c p sut hi bo ha thp. Qu trnh Flour c th s dng lm sch kh thin nhin, du m vi nng CO2 cao v t l H2S/CO2 thp. iu kin thun li nht l m bo c p sut ring phn tng cng ca cc cu t axit trong kh nguyn liu ln hn 0,4MPa. Nhit hp th trong khong t 0 n 60C. Ti sinh cht hp th khng cn cp nhit m bng cch gim p sut qua tng bc ca h thng (c thit b phn ly). Qu trnh hp th mt lng ng k cc hydrocabon nn khng th s dng lm nguyn liu cho h thng sn xut lu hunh. III.3.2. Qu trnh Selecsol [2] Qu trnh Selecsol c nghin cu bi cng ty Ellaid Chemical Corporation vo cui nhng nm 60. Cht hp th c s dng l eteimetyl polyetylenglycol (DMEPEG); dung mi ny khng c, bn v mt ha hc trong iu kin qu trnh, khng si bt, khng c tnh n mn, d b phn hy khi lm sch nc thi bng vi sinh vt, c tnh chn lc cao. Bng nhng ci tin cng ngh qu trnh c th lm sch trit kh thin nhin c nng H2S v CO2 cao v trung bnh (qu trnh hp th c 97% H2S v 85% CO2). Kh nng ha tan ca DMEPEG i vi cc hp cht khc nhau tng nh sau: C2H6<CO2<C3H8<C4H10<COS<C5H12<H2S<CH3Sh<CS2<C7H16<H2O. Nh vy r rng rng DMEPEG ha tan cc cu t axit v hydrocacbon. iu ny lm hn ch kh nng ng dng ca qu trnh.

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Lm sch kh khi H2S,CO2 v cc hp cht hu c cha lu hunh

c tnh ca dung mi DMEPEG l m bo hp th chon lc H2S vi s hin din ca CO2. iu ny l rt c ngha khi tin hnh lm sch hai bc, bc th 1 c th thu c nguyn liu tt sn xut lu hunh cn bc th 2 ta c nguyn liu sn xut CO2 thng phm. V vy qu trnh Selecsol c th c hiu qu khi cn sn xut ng thi c hai sn phm. Hiu qu ca qu trnh tng cng vi s tng p sut lm vic v nng CO2, H2S trong kh nguyn liu. Qu trnh Selecsol c tnh uyn chuyn cao, nng cc cu t axit trong kh ban u c th thay i trong mt khong rng m khng lm gim cht lng ca qu trnh lm ngt kh. Ch nhit ty theo i tng dao ng t 10 ti 150C, p sut c gi trong khong 6,8-7 MPa. Ti sinh cht hp th bng cch gim p theo tng bc ca h thng m khng cn cp nhit. III.3.3. Qu trnh Purizol [2] Qu trnh ny c nghin cu bi cng ty Lurgi, h thng cng nghip u tin c xy dng c vo nm 1963 lm sch kh thin nhin khi H2S v CO2. Cht hp th c s dng l N-metylpirrolydon (NMP). NMP khng c, ha tan tt H2S, CO2, RSH v hydrocacbon, hp th hi nc, khng c tc dng n mn, bn v mt ha hc, d phn hy khi lm sch nc thi bng phng php vi sinh, c trng bi tnh chon lc cao v m bo hp th chn lc H2S khi c mt CO2 ( 200C v 0,1MPa ha tan H2S ln gp 10 ln CO2). Quy trnh cng ngh Purizol khi c mt hydrocacbon lng d to bt. Do p sut hi bo ha ca NMP ln nn mt mt dung mi cao nu khng p dng cc bin php thch hp. Ch cng ngh ca qu trnh hp th: nhit cht hp th 20-280C, nhit kh nguyn liu trong cc i tng khc nhau dao ng trong khong t 0 ti 150C, p sut c gi trong khong 5-7,5 MPa. Ti sinh cht hp th c th bng cch gim p sut qua tng bc h thng m khng cn cp nhit, nu lm sch trit ta p dng bin php tit lu p sut v cp nhit.

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Lm sch kh khi H2S,CO2 v cc hp cht hu c cha lu hunh

III.4. Qu trnh t hp Qu trnh t hp lm sch kh t nhin v kh ng hnh khi cc cu t axit bng hn hp dung dch nc alkanolamin vi dung mi hu c nh sulfolan, metanol... Chng da trn hp th vt l cc hp cht khng mong mun bng dung mi hu c v tng tc ha hc vi alkanolamin, l phn phn ng tch cc ca cht hp th. Qu trnh kt hp c nhiu u im ca hp th vt l v hp th ha hc, ni bt l vic lm sch trit H2S, CO2, RSH, COS v CS2 khi kh t nhin v kh ng hnh. Nhc im c bn ca qu trnh l s hp th tng i tt cc hydrocacbon. iu ny lm hn ch vic thu hi sn xut lu hunh sau khi tin hnh ti sinh cht hp th. c trng cho qu trnh t hp l qu trnh sulfinol. Qu trnh c nghin cu bi cng ty Sell (M), h thng cng nghip u tin c a vo s dng nm 1964. Cht hp th c s dng l hn hp dung dch nc diizopropanolamin vi sulfinol (xiclotetrametilensulfon). Hn hp gm 30% diizopropanolamin, 64% sulfolan v 6% nc c gi l Sulfinol. Thnh phn cht hp th c th thay i ph thuc vo cht lng kh ban u.
Bng 3: Tnh cht ha l ca diizopropanolamin v sulfolan Diizopropanolamin Sulfolan

Nhit si ( C) Nhit nng chy (0C) Khi lng ring 250C (kg/m3) Khi lng phn t nht (Pa.s) p sut hi bo ha 250C (Pa)

248 42 --133,2 0,192 ( 480C) 1,33

288 8-10 1,27 ---2 0,99.10 ( 250C) ---

Sulfinol ha tan tt H2S, CO2, RSH, COS , CS2 v hydrocacbon. N bn nhit v bn ha. C nhit dung ring v p sut hi bo ha thp. c th c s dng lm sch ton b kh kh khi cc hp cht cha lu hunh v oxy khng mong mun; cho php tin hnh lm sch ton b kh khi mercaptan, CS2 ng thi; mt mt do tng tc ha hc ca dung mi vi CO2 l khng ng k (s phn hy trong cng nghip t hn MEA 4-8 ln). Kh nng hp th ca sulfinol cao hn MEA khong 2 ln.
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Qu trnh hot ng hiu qu nht khi m bo t l cc cu t axit trong kh H2S/CO21 v p sut ring phn ca chng 7-8MPa. bo ha ca sulfinol c th t 85% (cao hn ca MEA vi ln). V vy thc hin qu trnh sulfinol cn tun hon dung dch t hn, chi ph vn hnh thp hn. Nhng thc t cng cho thy khi p sut ring phn nh th s dng dung mi MEA v Sulfinol hiu qu l nh nhau.
V. Qu trnh lm ngt kh bng phng php hp th ha hc s dng dung mi monoetanol amin (MEA)

Phng php ny c s dng t nm 1930, hin nay c ng dng rt rng ri. Qu trnh tng tc ca H2S v CO2 vi MEA c m t bng cc phn ng sau: 2HO-C2H4 NH2 + H2S (HO-C2H4-NH3)2S + H2S Hay HO-C2H4-NH2 + H2S 2HO-C2H4-NH2 + CO2 + H2O (HO-C2H4-NH3)2CO3+ CO2 + H2O Hay HO-C2H4-NH2 + CO2 + H2O (HO-C2H4-NH3)2S 2HO-C2H4-NH3HS HO-C2H4-NH3HS (HO-C2H4-NH3)2CO3 2HO-C2H4NH3HCO3 HO-C2H4- NH3HCO3 HO-C2H4-NHCOO-NH3-C2H4- HO

Hoc 2HO-C2H4-NH2 + CO2

Hiu ng nhit ca phn ng l: khi tng tc H2S v CO2 vi dung dch MEA tng ng l 1905 v 1917,6 KJ/kg. nhit thp cc phn ng xy ra t tri sang phi, nhit cao phn ng xy ra t phi sang tri. Trong trng hp u H2S v CO2 lin kt vi cht hp th, trong trng hp th hai din ra s phc hi cht hp th v tch cc kh axit c MEA hp th (H2S v CO2). Qu trnh hp th H2S v CO2 bng MEA xy ra p sut cao v nhit t 25 ti 400C, cn ti sinh cht hp th MEA thc hin p sut gn p sut kh quyn v nhit trn 1500C. S nguyn l cng ngh lm sch kh khi H2S v CO2 bng MEA c m t hnh 1:
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Lm sch kh khi H2S,CO2 v cc hp cht hu c cha lu hunh

Hnh 1: S nguyn l cng ngh hp th bng MEA

1-Thp hp th 5,6-Thit b lm ngui bng khng kh 9-Thit b trao i nhit 11-Reboiler I-Kh nguyn liu III-Dung mi bo ha V-Dung mi nh hp th mt phn

2,3,4-Thit b phn ly 7,8-Thit b lm lnh bng nc 10-Thp nh hp th

II-Kh sch (kh ngt) IV-Kh phn ly VI-Kh axit

VII-Dung mi ti sinh tun hon tr li thp hp th

Nhn trn s hnh 1 ta thy kh nguyn liu c a vo thp hp th 1 pha di y thp c nhit khong t 10 ti 400C, n c ti bng dung mi MEA c cho vo t nh thp hp th 1. T nh thp kh sch (kh ngt) i ra, cn pha di y thp hp th cht hp th bo ha kh axit (nhit cht hp th bo ha khong 55-600C). Kh sch sau thit b phn ly 2 c a ti ni s dng. Cht hp th bo ha i vo thit b phn ly 3, y nh s tit lu dung dch, cc hydrocacbon b hp th s c tch ra v c th c a i s dng lm nhin liu. Sau thit b phn ly 3 cht hp th bo ha kh axit c un nng trong thit b trao i nhit 9 n nhit khong t 950C ti 1000Cri c a vo phn gia ca thp nh hp th 10. Ti thp nh hp th

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10, cc kh axit, nc, hydrocacbon cn st s c bay hi. p sut lm vic ca thp nh hp th l 0,15MPa, nhit ca y thp nh hp th 10 c gi trong khong 115-1300C nh t nng dung mi i ra t y thp bng thit b gia nhit y thp (reboiler) 11. Hn hp kh axit, nc, hydrocacbon i ra t nh thp nh hp th 10 c lm lnh qua thit b trao i nhit bng khng kh 6 v bng nc 8. Sau hn hp hai pha i vo thit b phn ly 4, y nc c tch ra khi kh axit v hydrocacbon. Nc thit b phn ly 4 c hi lu nh thp nh hp th 10 nhm loi tr s li cun MEA ln cng sn phm nh. Kh axit c a ti khu sn xut lu hunh. Dung dch MEA sau khi ti sinh c a qua thit b trao i nhit tn dng nhit, qua thit b lm ngui bng khng kh 5, thit b lm lnh bng nc 7 c tr li thp hp th 1 nhit 35-450C . Qu trnh lm sch kh thin nhin v kh ng hnh khi H2S v CO2 bng MEA yu cu nng MEA khng c vt qu 15-20% th tch. Khi bo ha cc dung dch c nng cao hn bng cc kh axit th vn tc n mn kim loi tng (dung dch MEA tinh khit khng c tnh n mn). Mi lin quan gia nng dung dch v vn tc n mn nh vy lm hn ch kh nng tng hiu qu ca qu trnh lm sch kh bng MEA. Tuy nhin trong nhng nm gn y nh vic nghin cu cc cht c ch n mn xut hin kh nng tng nng cht hp th trong dung dch ti 30% th tch, nn qu trnh MEA tr nn c li hn. Hn na, kh khai thc t m Bch H c p sut ring phn ca cc cu t kh axit l thp nn p dng quy trnh lm ngt kh bng MEA l hp l v hiu qu (qu trnh lm sch bng MEA c ngh dng lm sch kh khi H2S v CO2 khi p sut ring phn ca chng khng ln hn 0,6-0,7 Mpa [2]). u im ca qu trnh l lm sch trit kh khi H2S v CO2 trong mt khong p sut ring phn rng. MEA c tnh n nh ha hc cao, ti sinh d dng, kh nng phn ng cao, gi thnh r v d kim. Cng ngh v thit b n gin c bn cao khi vn hnh ng. Dung mi MEA tng i kh hp th hydrocacbon nn trong qu trnh ti sinh c th thu hi cho qu trnh sn xut lu hunh.
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Nhc im ca qu trnh l mc bo ha dung dch thp, lu lng ring ln v chi ph vn hnh cao (cao hn 25-40% so vi DGA). Cc tp cht nh CO2, COS, CS2, HCN, SO2, SO3 khi tng tc vi dung mi to thnh hp cht cao phn t khng ti sinh c hoc kh ti sinh, lm mt hot tnh ca cht hp th, tng tnh to bt v tnh n mn ca dung mi. V vy khi c COS v CS2 qu trnh khng c ng dng. Mc thu hi mercaptan v cc hp cht hu c cha lu hunh khc thp. Tng khuynh hng to bt khi c cc hydrocacbon lng, sunfua st, thiosufit v cc sn phm phn hy MEA cng nh cc tp cht c hc v mt s dng cht c ch n mn ri vo h thng. Theo s liu ca Kempbel vn tc phn hy MEA do tng tc khng thun nghch ca MEA vi CO2, COS v CS2 c th t 3,35kg/1000m3 CO2; 1kg/1m3 COS; 1kg/1m3 CS2. Cc hp cht hu c cha lu hunh (mercaptan, iunfua, thiophen...) cha trong kh t nhin v kh ng hnh thc t khng tng tc vi MEA. loi cc tp cht c hc v sn phm ca phn ng khng thun nghch ngi ta p dng nhiu bin php khc nhau nh lc, bay hi trong bnh c bit... Nng ca cc sn phm ny trong dung mi khng c vt qu 0,1-0,5%. loi tr s to bt ngi ta cho thm vo dung dch MEA ph gia chng to bt (0,001-0,0015% khi lng) nh cc ch phm KE-10-12, KE-1021 ca Lin X... iu ny cho php gim tht thot dung mi, h thng hot ng n nh hn, tng nng sut.

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h tr Tnh ton, thit k thp hp th lm ngt kh bng phng php hp th ha hc s dng dung mi MEA

iu kin lm vic ca thp hp th ty thuc vo yu cu lm sch, nng sut, nng MEA v.v... m thay i trong mt phm vi hp (cc s liu a ra di y c tnh cht tham kho, khi tnh ton vi cc ni dung c th cn tnh lp ti khi cn bng vt liu v cn bng nng lng c tha mn m tm ra ch lm vic thch hp cho thp):
Nhit kh nguyn liu vo thp: Nhit dung dch MEA ti sinh: Tv = 38oC Tts = 44C

p sut lm vic trong thp hp th: P = 3,5 MPa

Dung dch MEA nn chn c nng 15% (theo khi lng) c tun ton lin tc. C th coi qu trnh ti sinh MEA l hon ton khng c mt mt, suy hao. Kh sau khi ra khi thp hp th yu cu hm lng H2S khng qu 0,001 phn th tch; hm lng CO2 khng qu 0,005 phn th tch.
I. Cn bng vt cht ca thp hp th

Gr Ats

Dng kh nguyn liu Gv c a vo phn di ca thp hp th, cn kh sch Gr c a ra t nh thp. Dung dch nc monoetanol amin Ats c a vo t trn ca thp, cn dung dch bo ho cc cu t axit Abh c a ra t y thp. Dung dch nc monoetanol amin hp th cc cu Gv t axit, trong thp hp th xy ra cc phn ng ho hc sau:
2OHCH2CH2NH2 + CO2 + H2 O (OHCH2CH2NH3) 2CO3 + CO2 + H2O 2OHCH2CH2NH2 (OHCH2CH2NH3) 2S + H2S + H2S (OHCH2 CH2NH3) 2CO3 2OHCH 2CH2NH3HCO3 (OHCH 2CH2NH3) 2 S 2OHCH2CH2RNH3HS (1) (2) (3) (4)

Abh

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Cc cu t axit v cc hydrocacbon nh b ho tan mt phn trong dung dch nc MEA Phng trnh cn bng vt cht ca thp hp th: Gv + Ats = Gr + Abh trong : Gv : lu lng khi lng ca kh nguyn liu i vo thp hp th (kg/h) Ats : lu lng khi lng ca dung mi MEA 15% ti sinh tun hon tr li thp hp th (kg/h) Gr : lu lng khi lng ca kh sch ra khi thp hp th (kg/h) Abh : lu lng khi lng ca dung dch MEA bo ha ra khi thp hp th (kg/h) II.1. Tnh lu lng khi lng ca kh nguyn liu vo thp (GV) II.2. Lu lng khi lng ca dung mi MEA 15% ti sinh (Ats) Da vo ton c xy dng bng cc s liu thc nghim [4] c tnh by hnh 2 ta xc nh c khi lng ring ca MEA 15% trong nc ti nhit ti vo thp hp th tts = 440C l ts = 996 (kg/m3). Xc nh lu lng th tch MEA ti vo thp trong mt n v thi gian bng cch ni suy th c m t hnh 3 vi ph thuc vn tc kh nguyn liu vo v tng hm lng kh axit axit trong kh nguyn liu
Hnh 2: Ton xc nh khi lng ring ca dung dch etanolamin nc

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Hnh 3: th tra cu tc tun hon ca dung dch MEA [3]

II.3. Lu lng khi lng kh sch ra khi thp hp th So vi propan, butan, pentan th metan, etan tan ng k trong dung mi. Lng metan, etan ha tan trong mt n v thi gian (m3/h) c tnh theo cng thc sau:

Vht CH 4 = CH 4 .VH2 O .
trong :

273 T + 273

Vht C2 H6 = C2 H6 .VH2 O .

273 T + 273

VH2O : lu lng th tch nc c trong dung dch MEA (m3/h) CH4, C2H6 : ha tan ca CH4, C2H6 trong nc ti nhit t v p sut thng (m3/m3) II.4. Lu lng khi lng dung dch MEA bo ha ra khi thit b

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III. Cn bng nhit lng ca thp hp th

Phng trnh cn bng nhit lng ca thp hp th: Qv + Qts + Qa = Qr + Qbh Trong : Qv : Lng nhit ca dng kh nguyn liu mang vo thp (kW). Qts : Lng nhit dung dch MEA ti sinh mang vo thp (kW). Qa : Lng nhit ta ra do hp th cc cu t (kW). Qr : Lng nhit m kh sch mang ra khi thp (kW). Qv

Qr Qts

Qa

Qbh

Qbh : Lng nhit m dung dch MEA bo ha mang ra khi thp (kW). III.1. Lng nhit ca kh nguyn liu mang vo thp (QV) III.2. Lng nhit do dung dch MEA ti sinh mang vo (Qts) Lng nhit do dung dch MEA ti sinh mang vo thp hp th c xc nh bng cng thc: Qts = Ats . HLts Trong Ats l lu lng khi lng dung mi MEA 15% ti sinh tun hon tr li thp hp th. HLts: entanpy ca dung mi MEA 15% ti nhit t=440C (kJ/kg) Dung mi c ti sinh hon ton nn c th coi entanpi ca dung dch MEA ti sinh bng entanpy ca dung dch MEA 15%. Khi entanpy c tnh theo cng thc: HLts = Cp . t Cp : Nhit dung ring ca dung mi MEA 15% ti t = 440C (KJ/kg.). Cp c xc nh bng cch tra th c a ra hnh 4:

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Hnh 4: th tra nhit dung ring ca MEA ti cc nng khc nhau 1- Nc tinh khit 2- MEA 15% 3- MEA 30% 4- MEA 50%

III.3. Lng nhit ta ra do hp th cc cu t (Qa) III.4. Lng nhit theo dng kh sch mang ra khi thp (Qr) III.5. Lng nhit do dung dch MEA bo ha mang ra khi thp (Qbh) III.6. Lng nhit do mt mt

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IV. Thit k thp hp th

IV.1. Tnh ng knh ca thp hp th ng knh thp hp th c tnh theo cng thc:
1800 L Da =

(K oC + 35)
K oC + 35

3600G K ( L K )

trong : L l lu lng cht hp th bo ho i ra khi thp, kg/s.

L l K l

khi lng ring ca cht hp th bo ho, kg/m3. khi lng ring ca kh nguyn liu, kg/m3.

Ko = 0,3 l h s ca a lm vic. C = 480 l h s vi cht hp th khi khong cch gia cc a l 0,6m. IV.2. Tnh chiu cao ca thp hp th Chiu cao ca thp hp th c xc nh bng cng thc Hw = Ht + H0 + Hd trong : Ht : chiu cao nh thp thp (m) H0 : chiu cao phn gn a (m) Hd : chiu cao y thp (m) Ta chn chiu cao ca nh thp v y thp Ht = Hd = 1,5 (m) Chiu cao thp phn c gn a c tnh theo cng thc:
H 0 = ( N w 1).h0

trong : Nw: s a lm vic. h0: khong cch gia cc a ng vi ng knh Da =3 (m) = 3000 (mm). Theo [5, tr.169] nu ta la chn loi thp hp th l loi chp lm bng thp h0 = 600 (mm) = 0,6 (m). S a lm vic thc t ca thp c tnh theo cng thc:
Nw = N LT

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NLT : s a l thuyt : h s s dng hu ch ca a. H s ny thng khng vt qu 25% - 40% [2] nn ta chn =30%=0,3 S a l thuyt cn thit m bo h s tch ca mt cu t trong thp vi h s tch khng i trong tng a. S a l thuyt c xc nh bng cng thc:
N LT = lg(1 a ) lg(1 )

trong : a: h s tch cc cu t trong thp hp th. : h s tch trong cc a. H s tch cc cu t trong thp hp th c tnh da vo hng s cn bng pha kh (ch tnh vi CO2 v H2S, hp th C1, C2 th b qua)
mi = m i ,cb . M T .R.T

Vy hng s cn bng pha kh mCO2, mH2S no ln hn th tnh theo h s tch pha kh . H s tch trung bnh ca cc a c tnh theo cng thc:
K . A.ha WK

= 1 e
trong :

K: h s chuyn khi khi hp th ha hc. A: b mt tip xc pha. ha: chiu cao ca lp kh, chn ha=0,059 (m). WK: Tc quy c ca dng kh trong iu kin lm vic (m/s). Tnh K - h s chuyn khi khi hp th ha hc c tnh thng qua h s chuyn khi khi hp th vt l:
K= 1 1 + m

K; L : h s chuyn khi trong pha kh lng (m/h).

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m: hng s cn bng pha trong thp hp th vi h s hiu chnh vi lc ion ca dung dch do hp th ha hc. K - h s chuyn khi trong pha kh bng: K = Ks.Fw=A.WKm.hn.Fw Ks h s chuyn khi trong pha kh tnh cho mt n v lm vic ca a vi Fw=7m2 A=41700; WK=0,29; m=1; n=0,5; h=0,04 K = 41700 . 0,291 . 0,040,5 . 7 = 16933 (m/h). L - h s chuyn khi trong pha lng bng: L = Ls.Fw=A.WKm.hn.Fw Ls h s chuyn khi trong pha lng tnh cho mt n v lm vic ca a Fw=7m2 A=240; WK=0,29; m=0,35; n=0,58; h=0,04 L = 240 . 0,290,35. 0,040,58 . 7 = 169 (m/h) Qua cc s liu tnh ton c trn ta c h s tch trung bnh ca cc a. Vy tnh c s a l thuyt: v s a thc t: Chiu cao thp phn c gn a: Vy chiu cao ton thp: IV.3. Mt s tnh ton cc chi tit ca chp trn [5] a) ng knh ng hi chn dh = 100 (mm). b) S chp phn b trn a:

vi

D2 n = 0,1. 2 dh D l ng knh trong ca thp (mm)

dh l ng knh trong ca ng hi (mm) c) Chiu cao chp pha trn ng hi:
h2 = 0, 25.d h

d) ng knh chp:

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d ch = d h2 + (d h + 2 ch ) 2
vi ch l chiu dy chp thng ly t 2-3 (mm). e) Khong cch t mt a ti chn chp S = 0 25 (mm) chn = 2 (mm) f) Chiu cao mc cht lng trn khe chp h1 = 1540 (mm) chn = 20 (mm) g) ng knh ng chy chuyn:
dc = 4.Gx 3600. . x .c .z

trong :

Gx: lu lng lng trung bnh i trong thp (kg/h) x: khi lng ring ca lng (kg/m3). z = 2 s ng hy chuyn. c: tc lng chy trong ng chy chuyn ly bng 0,15 (m/s)

h) Khong cch t a ti chn ng chy chuyn:

S1 = 0, 25.d c

i) Khong cch t tm ng chy chuyn ti tm chp gn nht:

t1 = dc d + c + ch + ch + l1 2 2

trong : dc b dy ng chy chuyn, thng ly c = 2 4 (mm); l1 khong cch nh nht gia chp v ng chy chuyn, thng chn l1=75 (mm).

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Ti liu tham kho [1]. Nguyn Th Minh Hin, Cng ngh ch bin kh t nhin v kh ng hnh, NXB Khoa hc v K Thut, H Ni, 2006. [2]. M.A. Berlin, V.G. Gortrencop, H.P. Volcop, Cng ngh ch bin kh t nhin v kh du m (bn ting Vit). [3]. Kunhexov, Tnh ton cc qu trnh cng ngh ch bin kh (bn ting Nga), 1983. [4]. S tay qu trnh v thit b cng ngh ha cht, Tp 1, NXB Khoa hc v K thut, H Ni 2004. [5]. S tay qu trnh v thit b cng ngh ha cht, Tp 2, NXB Khoa hc v K thut, H Ni 2004.

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