Phng php lm sch kh

2011

PHNG PHP LM (NGT) SCH KH T NHIN.

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Phng php lm sch kh

2011

PHNG PHP LM (NGT) SCH KH T NHIN.

I. GII THIU V KH T NHIN. Gm 2 thnh phn chnh: hydrocacbon v khng hydrocacbon. - Hydrocacbon: ch yu t C1- C4, C4 - C7 t hn. - Hdrocacbon khng no: H2O (hi, lng), N2, CO2, H2S, COS, CS2, RSH, H2, He 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. 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; [S] <=22-228 mg/m3, 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. Thc t cho c nhng lng tp cht nh i khi li gy nhng nh hng rt ln n vic la chn dung mi hoc cng ngh lm sch kh. V d nh 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... Kh thin nhin khng k t ngun no khi tch ra khi du th (nu c) thng tn ti trong cc hn hp vi cc hydrocacbon khc, ch yu l C 2H6,
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Phng php lm sch kh

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C3H8, C4H10, v C5H11. Ngoi ra, kh thin nhin th cn cha hi nc, H2S, CO2, He, N2 v cc hp cht khc. Trong thnh phn ca kh t nhin v kh ng hnh, ngoi cc cu t chnh l cc hydrocacbon no cn c mt lng ng k cc tp cht c tnh axit nh CO2, H2S v cc hp cht cha lu hunh khc nh COS, CS2 , mercaptan RSH, thiophen... gy c hi cho ngi s dng, nhim mi trng, ng c xc tc,v gy nhiu kh khn cho qu trnh vn chuyn v s dng. II. CC PHNG PHP LM SCH KH H2S V CO2 (lm ngt kh) C 4 phng php lm sch kh: - Phng php hp th: Hp th Ha Hc v hp th Vt L - Phng php hp ph - Phng php thm thu - Phng php chng ct 1. Phng php hp th: Cc qu trnh hat ng da trn s hp th ha hc hoc vt l gia dung mi v tp cht, sau gii hp han nguyn dung mi v Mt s qu trnh lm sch kh Hp th ha hc Qu trnh Lm bng sch alkanamine: - MEA - DEA - DPA - DGA Econamin Lm sch bng carbonat kali: -Thng thng -Hat ha, nng
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Hp th vt l Dung mi Qu trnh Dung mi

- Vetrocok - Dd mui arsenat kim - Monoethanolamin, e nng (K2AsO3) - Diethanolamine, - Dd mui natri(2,6-2,7 - Diizopropanolamin - Stretford acid antrikhinolsunfon) - Propylene carbonate e, - Diglycolamine - Dd DMEPEG - N-methylpyrolidon - Fluor (NMP) - Selexol - Hn hp dd - Purizon diisopropanolamine v - Sunfinol sunfolan - Dd K2CO3 nng - Methanol - Dd K2CO3 nng + - Rektizon 1,8% DEG

Phng php lm sch kh

2011

chuyn kh chua cha H2S sang thit b sn xut S theo quy trnh Clause. Ring 2 qu trnh Vetrocoke-H2S v Stretford hat ng da trn vic hp th H2S bng dung mi ha hc v oxy ha chng trong thit b han nguyn thnh S. Qu trnh Vetrocoke-H2S v Stretford c ng dng lm sch kh c hm lng H2S thp (p sut ring phn u vo ca H2S l 0,07 MPa v u ra l 0,002 MPa). Tiu chun la chn qu trnh v dung mi hp th: Hm lng trc v sau khi lm sch ca tp cht trong kh; hoc p sut ring phn trc v sau khi lm sch ca tp cht trong kh. - p sut ring phn ban u quyt nh s vng tun han cht hp th. - p sut ring phn sau khi lm sch ph thuc mc tun han cht hp th, p sut cn bng v nhit ca kh khi ra khi dung dch. Yu cu i vi dung mi hp th: R. Khng c. D phn hy khi thi ra mi trng. Bn nhit v bn ha hc, d han nguyn. Kh nng hp th cao, t ph thuc vo thnh phn nguyn liu. C kh nng kt hp vi qu trnh lm kh C kh nng hp th chn lc. Khng gy n mn. mt mt thp. C th thay th bng mt dung mi khc. Kh nng to bt thp. Kh nng ha tan hydrocarbon thp. Nhit ng c thp. A. Phng php hp th ha hc: - Dung mi hp th: dung dch monoethanolamine (MEA), diethanolamine (DEA), diglycolamine (DGA). - u im: o Cho php lm sch n mc tinh H2S v CO2. o ha tan hydrocarbon trong cht hp th khng cao. o Cng ngh v thit b n gin. - Khuyt im: o Khng lm sch han tan H2S, CO2, RSH, COS v CS2. o Mc lai mercaptan v cc hp cht lu hynh thp. o Mercaptan, COS, CS2 c th tng tc vi dung mi v khng th han nguyn trong iu kin phn ng.
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Phng php lm sch kh

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o Yu cu h s hi lu cao, chi ph nhit nng ln. o C kh nng to cht gy n mn cao. 1) Qu trnh lm ngt kh bng monoetanol amin (MEA): Trong qu trnh hp th ho hc : Ngi ta s dng dung dch nc cacc alkanol amin nh: Qu trnh lm ngt kh bng dietanol amin (DEA), dizopropanol amin (ADIP), diglycolamin (DGA) v monoetanolamin (MEA) Trong ng ch nht l monoetanolamin (MEA).Phng php ny c s dng t nm 1930, hin nay c ng dng rtrng ri. lm sch kh t nhin ngi ta dng dung dch MEA nng 15... 20% trong nc. Dung mi hp th: dung dch monoethanolamine (MEA), diethanolamine (DEA), diglycolamine (DGA). u im: bin thin p sut ring phn ca kh chua ban u rng. MEA d phn ng, c bn ha hc cao, d han nguyn. Cng ngh v thit k n gin. ha tan hydrocarbon trong MEA thp. Khuyt im: Mc bo ha ca dung dch thp. Chi ph ring cht hp th v chi ph sn xut cao. Dung mi hp th CO2, COS, CS2, HCN, SO2, SO3 kh han nguyn nu trong kh c cha COS v CS2 th khng s dng qu trnh ny. Kh nng thu hi mercaptan v cc hp cht lu hynh hu c km. Nu trong h c hydrocarbon bo, sulfua st, thiosunfit, kh nng to bt ca cht hp th tng cn a thm vo h cht chng to bt. Qu trnh tng tc ha hc gia CO2 v H2S vi MEA: 2RNH2 + H2S (RNH3)2S (RNH3)2S + H2S 2RNH3HS CO2 + 2RNH2 + H2O (RNH3)2CO3 CO2 + (RNH3)2CO3 + H2O 2RNH3HCO3 R = -CH2-CH2-OH nhit thp, phn ng xy ra theo chiu thun; nhit cao, phn ng xy ra theo chiu ngc li. Qu trnh lm sch kh bng dung mi MEA
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Phng php lm sch kh

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Nng dung dch MEA thng <= 15-20%tt. Mc bo ha kh chua trong dung dch ~ 0,3-0,4 mol/molMEA. c ng dng lm sch dng kh c p sut ring phn ca kh chua <= 0,60,7 MPa. Qu trnh hp th H2S v CO2 bng MEA xy ra p sut cao v nhit 25 ... 40oC, cn ti sinh cht hp th MEA thc hin p sut gn p sut kh quyn v nhit trn 150oC. S nguyn l cng ngh hp th lm sch kh khi H2S v CO2 bng MEA xem hnh 1

Hnh 1. 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 ha; IV. Kh phn ly; V. Dung mi nh hp th mt phn; VI. Kh axit; VII. Dung mi ti sinh tun hon tr li thp hp th.
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Phng php lm sch kh

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Thuyt minh quy trnh: Kh nguyn liu c cho vo phn di ca thp hp th 1, cn dung dch lm sch monoetanolamin (MEA) c ti ngc chiu t trn xung. Kh v 1 t dung dich MEA c ln 1 t H2S v CO2 bay ra khi nh thp v i vo thit b phn li 2. Kh ra khi nh thit b phn li l kh sch, cn dung dch MEA c ln 1 t H2S v CO2 s hon lu li vo thp hp th 1. Dung dch MEA hp th H2S v CO2 ( c ln kh ca hirocacbon nh etan, propan..) c tho ra y thp i vo thit b phn li 3, mt phn nh kh ca Hirocacbon nng c thu hi thit b phn ly 3. Cn dung dch MEA s cho qua thit b trao i nhit 9 ( lm nng ), ri qua thp nh hp th 10, H2S v CO2 c ln 1 t duch dich MEA s thot ra ra khi nh thp, ri lm lnh v cho qua thit b phn ly 4, H2S v CO2 s bay ra khi nh, cn dung dich MEA hon lu tr thp nh hp th 10. Dung dich MEA s c ti sinh v ly ra pha di thp 10. Mt phn dung dch thu hi y thp s c cho qua b phn un nng 11 quay li thp nh hp th 10 truyn nhit. Phn cn li cho qua thit b TN v lm lnh ri hon lu quay li thp hp th 1.

2) Qu trnh lm sch kh bng dung mi DEA Nng dung dch DEA ph thuc hm lng kh chua trong kh v mc bo ha kh chua trong dung dch, ~ 20-30%kl: - Nng kh chua 0,05-0,08 m3/l DEA 20-25%. - Nng kh chua 0,14-0,15 m3/l DEA 25-27%. - Nng kh chua 0,15-0,17 m3/l DEA 27-30%. c ng dng lm sch dng kh c p sut ring phn ca kh chua >= 0,2 MPa (DEA 25-27%) hoc >=0,4 MPa (DEA 27-30%). Mc bo ha dung dch: 1-1,3 mol/mol DEA. u im: o Cho php lm sch n mc tinh H2S v CO2 vi s hin din COS v CS2. o Dung dch DEA bn ha hc, d han nguyn, o p sut hi bo ha thp nn mt mt thp o Cng ngh v thit k n gin. o Tin hnh nhit cao hn qu trnh dng MEA 10-200C. o Kh nng to bt thp i vi dng kh c cha thnh phn hydrocarbon nng cao.
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Khuyt im: o Kh nng hp th ca dung mi thp. o Chi ph ring cht hp th v chi ph sn xut cao. o C s tng tc gia CO2 (mt phn) v HCN (han tan) vi cht hp th to thnh hn hp khng han nguyn c. o Kh nng lm sch mercaptan v hp cht lu hynh hu c thp.

3) Qu trnh lm sch kh ADIP Dung mi hp th: dung dch nc diisopropanolamine (DIPA), nng c th ln n 40%. Cho php lm sch tinh H2S n 1,5 mg/m3; ng thi lm sch CO2, COS, RSR (c th lai b 40-50% COS v RSR). Hat dung dch DIPA i vi CO2 thp hn so vi MEA. Kh nng to hp cht gy n mn thp. S phn hy DIPA do tng tc vi cc hp cht cha S v O thp hn so vi qu trnh dng MEA.

4) Qu trnh lm sch kh Econamin c p dng khi nng kh chua trong kh nguyn liu ~ 1,5-8%. Dung mi hp th: dung dch nc diglycolamine (DGA), vi nng ~ 60-65%kl. C th lm sch tinh H2S n 5,7 mg/m3. Hat ca DGA vi CO2 cao hn si MEA. Kh nng lai CO2, COS, CS2, mercaptan cao; d han nguyn. Mc bo ha kh chua cao: 40-50 l kh chua/ l dung dch. Chi ph ring cht hp th v ch ph sn xut thp hn 25 -40% so vi qu trnh dng MEA. Kh nng mt mt dung mi thp hn so vi MEA. Kh nng gy n mn v ha tan hydrocarbon tng t MEA v DEA.

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Phng php lm sch kh

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5) Qu trnh lm sch kh Stretford Dung mi hp th: dung dch lang Na2CO3, NaVO3, v ADA (anthraquinone disulfonic acid). Nguyn tc: lai b H2S v thc hin cc phn ng oxy ha kh thu S v ti to cht oxy ha. u im: dung dch khng n mn. Nhc im: kh thu hi lu hynh, d gy nght ng ng trong h thng. Phng trnh phn ng: H2S + Na2CO3 = NaHS + NaHCO3 4 NaVO3 + 2 NaHS + H2O = Na2V4O9 + 4 NaOH + 2 S Na2V4O9 + H2O + 2 ADA = 4 NaVO3 + 2 ADA

6) Qu trnh lm sch kh bng dung dch K2CO3 nng Dung mi hp th: dung dch lang K2CO3 25-35%. Hp th chn lc i vi H2S v CO2, ha tan cc lai kh khc khng ng k. C kh nng to bt nu trong h cha cc hydrocarbon lng. Qu trnh thc hin nhit cao 220-4000F. K2CO3 + CO2 + H2O = 2 KHCO3 + Q K2CO3 + H2S = KHCO3 + KHS + Q

7) Phng php hp th bng hn hp etanol amin vi etylen glycol lm sch kh ng thi khi H2S, CO2 v nc, ngi ta ng dng hn hp etanol amin vi etylen glycol.Vic lm sch kt hp nh vy ng thi lm khan ho nguyn liu v gim lng hi nc cn thit ti sinh dung mi. Trn hnh 2, ra s cng ngh lm sch kh t nhin bng hn hp etanol amin vi etylen glycol. Qu trnh lm sch c thc hin trong thp hp th v cc thit b ph tr.Thp hp th v nh hp th cng c cu to nh thp sy kh bng glycol. Khi c dn vo t phn di ca thp,dng kh chuyn ng t di ln, cn dung dch lm sch gm c etylen glycol v etanol amin c ti ngc chiu t trn xung. Kh c lm sch c dn ra t nh thp, cn dung dch c hp th H2S v CO2 c tho ra y thp. Dung dch ny c dn qua b phn trao i nhit t nng bng hi nc v a vo
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Phng php lm sch kh

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gia thp nh hp th, H2S v CO2 gii phng ra pha nh thp, cn dung dch hp th ti sinh c ly ra pha di.Mt phn dung dch c un nng bng hi nc v quay li thp nh hp th truyn nhit, phn cn li c lm ngui v ti t nh thp hp th. S quy trnh cng ngh

Hnh 2. S lm sch kh bng dung dch etanolamin v etylen glycol 1. Thp hp th; 2. Thp nh hp th; 3,4. Thit b un si y thp; I. Kh vo; II. Kh sch; III. Dung dch MEA; IV. Dung dch DEG; V.Nc; VI. Kh axit (H2S, CO2)

Khi nng cc tp cht H2S v CO2 cao hn 2 ... 2,5% mol th trc khi dng etanolamin hp th, ngi ta dng cc cht hp th r tin nh nc hoc dung dch nc ca Na2CO3, K2CO3 lm sch kh s b, gim nng tp cht ti 2

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Phng php lm sch kh

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... 2,5% mol, sau mi dng etanolamin lm sch tip ti sch yu cu nh hn 0,5%.

B. Phng php hp th vt l (quy trnh trnh Flour, Selecsol, Purizol ) Ngoi cc phng php lm ngt bng phng php hp th ha hc s dng dung mi ankanolamin cng hay thy s dng phng php hp th vt l nh qu trnh Flour, Selecsol, Purizol... Kh nng hp th ph thuc p sut ring phn ca kh chua trong iu kin lm vic: p sut ring phn thp th kh nng hp th thp. qu trnh hp th vt l din ra hiu qu, cn thc hin qu trnh nhit thp. p sut ring phn >= 5MPa: dung mi vt l c u th hn hn dung mi ha hc, p sut cng cao, hiu qu qu trnh cng tng. Kh nng hp th CO2 v H2S ca mi cht hp th khc nhau c th dng hp th chn lc. Dung mi hp th: propylene carbonate, dimethyl-tert-polyethyleneglycol (DMEPEG), N-N-methylpyrolidone, u im: o C th lm sch hon ton H2S, CO2, RSH, COS, CS2. o Khng to bt, khng n mn thit b. o Nhit ng bng thp. o u t v chi ph sn xut thp. Khuyt im: o ha tan tan hydrocarbon trong dung mi hp th cao. 1) Qu trnh FLOUR Cht hp th: propylene carbonate
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Phng php lm sch kh

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Tnh cht ha l ca propylene carbonate Nhit si, 0C Phn t lng Nhit nng chy, 0C nht 180C, m2/s T trng 200C, kg/m3 p sut hi bo ha 270C, Pa 242 102 -49 6,64.10-6 1200 0,666

Kh nng ha tan tt H2S, CO2, COS, CS2, RSH v hydrocarbon. C tc dng n mn yu i vi thp carbon thng. Bn ha hc, p st hi bo ha thp. c p dng thun li nht khi kh c p sut ring phn tng ca kh chua > 0,4 MPa. Hp th nhit thp: 0-60C. Qu trnh han nguyn cht hp th c thc hin bng gim tng bc p st. mt mt cht hp th: 16 g/1000 m3 kh nguyn liu.

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Phng php lm sch kh

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S quy trnh cng ngh

III
(1)

VI IV
4

II
3

THP HP TH
(2) (2) (2)

THP
PHN

THP
PHN LY

THP
PHN LY

LY

V 5 6

Hnh s quy trnh cng ngh Fluor 1. Thp hp th 4. My nn I. Kh m 2. Thit b phn li 3. Tuc bin 6. B phn truyn ng

5. Tuc bin thy lc

II. Kh acid III. Kh sch IV. Dung mi ti sinh VI. Dung mi tun hon

V. Dung mi bo ha

Thuyt minh s quy trnh cng ngh Kh nguyn liu ( I )c cho vo thp hp th gn y thp ng thi dung mi ( IV ) c bm t nh thp xung, qu trnh hp th s tin hnh trong khong nhit t 060C. Kh i ra t nh thp l kh sch (ngt) III. Dung mi bo ha (V) c bm vo thit b phn li th nht (2) , thit b phn li th nht mt kh nguyn liu c my nn y dng kh hon nguyn v dng nguyn liu ban u,phn tp cht cn li c a qua thit b phn li th hai (2). thit b ny kh acid i ra t nh thp v c Tuc - Bin bm thi ra
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Phng php lm sch kh

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cng vi dng kh acid ca thit b phn li th ba (2) i ra ngoi. Phn dung mi bo ha tip tc c ua vo thit b phn li th 3 , ti y th kh acid c phn li hon ton v thi ra ngoi cn phn dung mi sch (dung mi ti sinh) c bm tr li thp hp th tin hnh qu trnh hp th. 2) Qu trnh SELEXOL Cht hp th: dimethylether polyethyleneglycol (DMEPEG). Tnh cht ha l ca DMEPEG Nhit si, 0C Phn t lng Nhit nng chy, 0C nht 250C, Pa.s T trng 250C, kg/m3 p sut hi bo ha 250C, Pa Nhit dung 250C, kJ/kg.K 151 280 22-29 5,8.10-3 1000 1,33 2,43

Khng c, bn ha hc. Khng gy n mn. D phn hy khi lm sch sinh hc nc thi. C chn lc cao i vi H2S: 200C v 0,1 MPa, ha tan H2S cao gp 10 ln CO2. c p dng lm sch kh c nng H2S v CO2 trung bnh v cao. C th lm sch n 97% H2S v 85% CO2. c ng dng lm sch v sn xut ng thi S v CO2 thng phm.
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Phng php lm sch kh

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Kh nng ha tan hydrocarbon cao nn ch ng dng lm sch kh kh. Kh nng ha tan ca DMEPEG tng dn: C2H6 < CO2 < C3H8 < C4H10 < COS < C5H12< < H2S < CH3SH < CS2 < C7H16 < H2O Hiu qu qu trnh tng khi tng p sut v hm lng H2S, CO2 trong nguyn liu. Hm lng kh chua trong nguyn liu c th thay i rng. Lai c <50% CS2. Chi ph cht hp th ~ 1 m3/1000 m3 kh. iu kin qu trnh hp th: 10 -150C; 6,8-7 MPa. Han nguyn cht hp th bng gim p tng bc. Chi ph sn xut gim 30%, chi ph u t gim 70% so vi qu trnh dng MEA. S quy trnh cng ngh

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3) Qu trnh PURIZOL Cht hp th: N-methylpyrolidon (NMP). Tnh cht ha l ca NMP Nhit si, 0C Phn t lng Nhit nng chy, 0C nht 200C, Pa.s T trng 250C, kg/m3 p sut hi bo ha 400C, Pa Nhit dung 200C, kJ/kg.K 275 99 24 1,87 1000 133,3 1,67

Khng c, bn ha hc. Ha tan tt H2S, CO2, RSH v hydrocarbon. Khng gy n mn. D phn hy khi lm sch sinh hc nc thi. C chn lc cao i vi H2S: 200C v 0,1 MPa, ha tan H2S cao gp 10 ln CO2. C th to bt nu trong h c hydrocarbon lng. Kh nng mt mt cao do c p sut hi bo ha cao. c s dng lm sch su v tinh H2S v CO2, t l H2S:CO2 cao. iu kin hp th: 0-150C, 5-7,5 MPa. Han nguyn cht hp th bng gim p tng bc.

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S quy trnh cng ngh

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