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Phng php lm sch kh 2011

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PHNG PHP LM (NGT) SCHKH TNHIN.


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PHNG PHP LM (NGT) SCHKH TNHIN.

I. GII THIU VKH TNHIN.Gm 2 thnh phn chnh: hydrocacbon v khng hydrocacbon.

- Hydrocacbon: chyu tC1- C4, C4 - C7 t hn.- Hdrocacbon khng no: H2O (hi, lng), N2, CO2, H2S, COS, CS2, RSH, H2,Hecn c cha mt lng ng kcc tp cht c tnh axit nh cacbonic(CO2), hydrosunfua (H2S) v cc hp cht cha lu hunh khc nh oxyt luhunh cacbon (COS), disunfua cacbon (CS2), mecaptan (RSH)... Cc tp chtktrn l cc tp cht khng mong mun trong qu trnh khai thc, chbin,vn chuyn, sdng v bo qun kh cho mc ch lm nguyn liu t, tnghp hu c-ha du... Stn ti ca cc kh axit gy nn sn mn kim loi,gim hiu quca cc qu trnh xc tc, lm ngc xc tc, gy nhim mitrng, c hi cho ngi sdng... Bn cnh sc mt hm lng caoCO2trong kh cng lm gim nhit chy ca kh, gim hiu quca qu trnhvn chuyn kh. Sc mt ca cc cu tmang tnh axit trong kh cn phic khng chmt hm lng nhnhm gim thiu nhng tc hi mcc 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 qu22mg/m3 cn Mquy nh kht khe hn: hm lng H2S khng c vt qu5,7mg/m3; nng CO2trong khong 1~2% thtch; [S]


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C3H8, C4H10, v C5H11. Ngoi ra, kh thin nhin th cn cha hi nc, H2S,CO2, He, N2v 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 axitnhCO2, H2S v cc hp cht cha luhunh khc nh COS, CS2, mercaptanRSH, thiophen... gy c hi cho ngis dng, nhim mitrng, 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 thHa Hc v hp thVt 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 giadung mi v tp cht, sau gii hp han nguyn dung mi v

Mt squ trnh lm sch kh

Hp thha hc Hp thvt l

Qu trnh Dung mi Qutrnh

Dung mi

Lm bng schalkanamine:

-MEA-DEA-DPA-DGA

Econamin

Lm sch bng carbonatkali:

-Thng thng

-Hat ha, nng

-Monoethanolamin,-Diethanolamine,-Diizopropanolamin

e,-Diglycolamine

-Dd K2CO3nng-Dd K2CO3nng +1,8% DEG

-Vetrocoke

-Stretford

-Fluor-Selexol-Purizon-Sunfinol

-Rektizon

Dd mui arsenat kimnng (K2AsO3)Dd mui natri(2,6-2,7acid antrikhinolsunfon)

Propylene carbonateDd DMEPEGN-methylpyrolidon(NMP)Hn hp dddiisopropanolamine vsunfolanMethanol


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chuyn kh chua cha H2S sang thit bsn xut S theo quy trnh Clause. Ring 2 qu trnh Vetrocoke-H2S v Stretford hat ng da trn vic

hp thH2S bng dung mi ha hc v oxy ha chng trong thit bhannguyn thnh S.

Qu trnh Vetrocoke-H2S v Stretford c ng dng lm sch kh chm lng H2S thp (p sut ring phn u vo ca H2S l 0,07 MPa vu 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. Dphn hy khi thi ra mi trng. Bn nhit v bn ha hc, dhan nguyn. Khnng hp thcao, t phthuc vo thnh phn nguyn liu. C khnng kt hp vi qu trnh lm kh

C khnng hp thchn lc. Khng gy n mn. mt mt thp. C ththay thbng mt dung mi khc. Khnng to bt thp. Khnng ha tan hydrocarbon thp. Nhit ng c thp.

A.Phng php hp thha hc:

-

Dung mi hp th: dung dch monoethanolamine (MEA), diethanolamine(DEA), diglycolamine (DGA).- u im:oCho php lm sch n mc tinh H2S v CO2.o ha tan hydrocarbon trong cht hp th khng cao.oCng ngh v thit b n gin.

- Khuyt im:oKhng lm sch han tan H2S, CO2, RSH, COS v CS2.oMc lai mercaptan v cc hp cht lu hynh thp.oMercaptan, COS, CS2c th tng tc vi dung mi v khng th han

nguyn trong iu kin phn ng.


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oYu cu h s hi lu cao, chi ph nhit nng ln.oC 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 nccacc alkanol aminnh: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 sdng t nm 1930, hin nay c ng dng rtrng ri. lm sch kh tnhin ngita dng dung dch MEA nng 15... 20% trong nc .Dung mihp 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 MEAthp.

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 hannguyn nu trong kh c cha COS v CS2 th khng s dng qutrnh 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 CO2v H2S vi MEA:

2RNH2+ H2S (RNH3)2S(RNH3)2S+ H2S 2RNH3HSCO2+ 2RNH2+ H2O (RNH3)2CO3CO2+ (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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Nng dung dch MEA thng


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Thuyt minh quy trnh:

Kh nguyn liu ccho vo phn di ca thp hp th 1, cn dungdch lm sch monoetanolamin (MEA) c ti ngc chiu t trn xung.

Kh v 1 t dung dich MEA c ln 1 t H2S v CO2bay ra khi nh thp v ivo thit b phn li 2. Kh ra khi nh thit b phn li l kh sch, cn dung dchMEA c ln 1 t H2S v CO2s hon lu li vo thp hp th 1. Dung dchMEA hp th H2S v CO2( c ln kh ca hirocacbon nh etan, propan..) ctho ra y thp i vo thit b phn li 3, mt phn nh kh ca Hirocacbonnng c thu hi thit b phn ly 3. Cn dung dch MEA s cho qua thit btrao i nhit 9 ( lm nng ), ri qua thp nh hp th 10, H2S v CO2c ln 1 tduch dich MEA s thot ra ra khi nh thp, ri lm lnh v cho qua thit b

phn ly 4, H2S v CO2s 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 thp10. Mt phn dung dch thu hi y thp s c cho qua b phn un nng11 quay li thp nh hp th 10 truyn nhit. Phn cn li cho qua thit bTN 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/lDEA 20-25%.- Nng kh chua 0,14-0,15 m3/lDEA 25-27%.- Nng kh chua 0,15-0,17 m3/lDEA 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:

oCho php lm sch n mc tinh H2S v CO2vi s hin din COSv CS2.

oDung dch DEA bn ha hc, d han nguyn,

op sut hi bo ha thp nn mt mt thp

oCng ngh v thit k n gin.

oTin hnh nhit cao hn qu trnh dng MEA 10-200C.

oKh nng to bt thp i vi dng kh c cha thnh phnhydrocarbon nng cao.


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Khuyt im:

oKh nng hp th ca dung mi thp.

oChi ph ring cht hp th v chi ph sn xut cao.oC s tng tc gia CO2(mt phn) v HCN (han tan) vi cht

hp th to thnh hn hp khng han nguyn c.

oKh 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 CO2thp 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 hnso vi qu trnh dng MEA.

4) Qu trnh lm sch kh Econaminc 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/m

3.Hat ca DGA vi CO2cao 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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5) Qu trnh lm sch kh StretfordDung 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 K2CO3nngDung mi hp th: dung dch lang K2CO325-35%.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 etanolamin vi etylen glycol

lm sch kh ng thi khi H2S, CO2v nc, ngita ng dnghnhpetanol amin vi etylen glycol.Vic lm sch kt hp nh vy ng thi lmkhan ho nguyn liu v gim lnghi nccn thit ti sinh dung mi.Trn hnh 2, ra s cng ngh lm sch kh t nhinbng hn hp etanolamin vi etylen glycol. Qu trnh lm sch cthc hin trong thp hp th vcc thit b ph tr.Thp hp th v nh hp th cng c cu to nhthp sykh bng glycol. Khi cdn vo t phn dica thp,dng kh chuyn ngt diln, cn dung dch lm sch gm c etylen glycol v etanol amin cti ngc chiu t trn xung. Kh c lm sch c dn ra t nh thp,

cn dung dch c hp th H2S v CO2c tho ra y thp. Dung dchny cdn qua b phn trao i nhit t nng bng hi ncv a vo


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gia thp nh hp th, H2S v CO2gii phng ra pha nh thp, cn dungdch hp th ti sinh cly ra pha di.Mt phn dung dch cun nng bng hi ncv quay li thp nh hp th truynnhit, phn cnli clm ngui v tit nh thp hp th.

S quy trnh cng ngh

Hnh 2. S lm sch kh bng dung dch etanolamin vetylen 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 CO2cao hn 2 ... 2,5% mol th trckhi dngetanolamin hp th, ngita dng cc chthp th r tin nhnchoc dungdch ncca Na2CO3, K2CO3lm sch kh s b, gimnng tp cht ti 2


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... 2,5% mol, sau mi dng etanolamin lm schtip ti sch yu cu nhhn 0,5%.

B.Phng php hp thvt l (quy trnh trnh Flour, Selecsol, Purizol )

Ngoi cc phng php lm ngt bng phng php hp thha hc sdng dung mi ankanolamin cng hay thy sdng phng php hp thvt lnh qu trnh Flour, Selecsol, Purizol...

Khnng hp thphthuc p sut ring phn ca kh chua trong iu

kin lm vic: p sut ring phn thp th khnng hp th thp. qu trnh

hp thvt l din ra hiu qu, cn thc hin qu trnh nhit thp.

p sut ring phn >= 5MPa: dung mi vt l c u thhn hndung mi ha hc, p sut cng cao, hiu ququ trnh cng tng.

Khnng hp thCO2v H2S ca mi cht hp thkhc nhau c th

dng hp thchn lc. Dung mi hp th: propylene carbonate, dimethyl-tert-polyethyleneglycol

(DMEPEG), N-N-methylpyrolidone,

u im:

o C thlm 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 thcao.

1)Qu trnh FLOUR

Cht hp th:propylene carbonate


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Tnh cht ha l ca propylene carbonate

Nhit si, 0C 242

Phn tlng 102

Nhit nng chy, 0C -49

nht 18 C, m /s 6,64.10-

Ttrng 200C, kg/m3 1200

p sut hi bo ha 27 C, Pa 0,666

Khnng 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 khchua > 0,4 MPa.

Hp thnhit thp: 0-60C.

Qu trnh han nguyn cht hp thc thc hin bng gim tng bc

p st. mt mt cht hp th: 16 g/1000 m3kh nguyn liu.


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S quy trnh cng ngh

Hnh s quy trnh cng nghFl uor

1. Thp hp th 2. Thit bphn li 3. Tuc bin

4. My nn 5. Tuc bin thy lc 6. Bphn truyn ng

I. Kh m II. Kh acid III. Kh sch IV. Dung mi ti sinh

V. Dung mi bo ha VI. Dung mi tun hon

Thuyt minh s quy trnh cng ngh

Kh nguyn liu ( I)c cho vo thp hp thgn y thp ng thi dungmi (IV) c bm tnh thp xung, qu trnh hp thstin hnh trongkhong nhit t060C. Kh i ra tnh thp l kh sch (ngt) III. Dungmi bo ha (V)c bm vo thit bphn li thnht (2) , thit bphn lithnht mt kh nguyn liu c my nn y dng kh hon nguyn vdng

nguyn liu ban u,phn tp cht cn li c a qua thit bphn li thhai(2). thit bny kh acid i ra tnh thp v c Tuc - Bin bm thi ra

6

5

V

I

II

IV 34

(1)

THP

HP

TH

(2)

THP

PHN

LY

(2)

THP

PHN

LY

(2)

THP

PHN

LY

III VI


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cng vi dng kh acid ca thit bphn li thba (2) i ra ngoi. Phn dungmi bo ha tip tc c ua vo thit bphn li th3 , 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 trli thp hp thtin hnh qu trnh hp th.

2)Qu trnh SELEXOL

Cht hp th: dimethylether polyethyleneglycol (DMEPEG).

Tnh cht ha l ca DMEPEG

Nhit si, 0C 151

Phn tlng 280

Nhit nng chy, 0C 22-29

nht 25 C, Pa.s 5,8.10-



Nhit dung 25 C, kJ/kg.K 2,43

Khng c, bn ha hc.

Khng gy n mn.

Dphn 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 CO2trung bnh v cao.

C thlm sch n 97% H2S v 85% CO2.

c ng dng lm sch v sn xut ng thi S v CO2 thngphm.


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Kh nng ha tan hydrocarbon cao nn ch ng dng lm sch khkh.

Khnng ha tan ca DMEPEG tng dn:

C2H6 < CO2 < C3H8 < C4H10 < COS < C5H12< < H2S < CH3SH < CS2 < C7H16 < H2O

Hiu ququ trnh tng khi tng p sut v hm lng H2S, CO2 trongnguyn liu.

Hm lng kh chua trong nguyn liu c ththay i rng.

Lai c


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3)Qu trnh PURIZOL

Cht hp th: N-methylpyrolidon (NMP).

Tnh cht ha l ca NMP

Nhit si, 0C 275

Phn tlng 99

Nhit nng chy, 0C 24

nht 20 C, Pa.s 1,87



Nhit dung 200C, kJ/kg.K 1,67

Khng c, bn ha hc.

Ha tan tt H2S, CO2, RSH v hydrocarbon.

Khng gy n mn.

Dphn 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 thto bt nu trong hc hydrocarbon lng.

Khnng mt mt cao do c p sut hi bo ha cao.

c sdng lm sch su v tinh H2S v CO2, tlH2S:CO2cao.

iu kin hp th: 0-150C, 5-7,5 MPa.

Han nguyn cht hp thbng gim p tng bc.


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