Giao Trinh Cong Nghe Che Bien Khi

Gio trnh cng ngh du kh
PHN II: CNG NGH CH BIN KH
CHNG 1: CC KHI NIM C BN
1.1. Cc khi nim v kh thin nhin 1.1.1. Ngun gc 1.1.1.1 Ngun gc v c Theo gi thuyt ny trong lng Tri t c cha cc cacbua kim loi nh Al 4C3, CaC2. Cc cht ny b phn hy bi nc to ra CH4 v C2H2: Al4C3 + 12H2O 4Al(OH)3 + 3CH4 CaC2 + 2H2O Ca(OH)2 + C2H2 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 cc hydrocacbon c trong du kh. chng minh cho iu , nm 1866, Berthelot tng hp c hydrocacbon thm t axetylen nhit cao trn xc tc. Nm 1901, Sabatier v Sendereus thc hin phn ng hydro ha axetylen trn xc tc Niken v st nhit trong khong 200 - 3000C, thu c mt lot cc hydrocacbon tng ng nh trong thnh phn ca du. Cng vi hng lot cc th nghim nh trn, gi thuyt v ngun gc v c ca du m c chp nhn trong mt thi gian kh di. Sau ny, khi trnh khoa hc v k thut ngy cng pht trin th ngi ta bt u hoi nghi lun im trn v: phn tch c (bng cc phng php hin i) trong du m c cha cc Porphyrin c ngun gc t ng thc vt. Trong v qu t, hm lng cacbua kim loi l 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 ha hc xy ra. Chnh v vy m gi thuyt ngun gc v c ngy cng phai m do c t cn c. 1.1.1.2. Ngun gc hu c l gi thuyt v s hnh thnh du m t cc vt liu hu c ban u. Nhng vt liu chnh l xc ng thc vt bin, hoc trn cn nhng b cc dng sng cun tri ra bin. trong nc bin c rt nhiu cc loi vi khun hiu kh v ym kh, cho 1
nn khi cc ng thc vt b cht, lp tc b chng phn hy. Nhng phn no d b phn hy (nh cc cht Albumin, cc hydrat cacbon) th b vi khun tn cng trc to thnh cc cht d tan trong nc hoc kh bay i, cc cht ny s khng to nn du kh. Ngc li, cc cht kh b phn hy (nh cc protein, cht bo, ru cao phn t, sp, du, nha) s dn lng ng to nn lp trm tch di y bin; y chnh l cc vt liu hu c u tin ca du kh. Cc cht ny qua hng triu nm bin i s to thnh cc hydrcacbon ban u: RCOOR + H2O RCOOH + ROH RCOOH RH + CO2 RCH2OH R-CHbngCH2 + H2O R-CHbngCH2 + H2 R-CH2-CH3 Theo tc gi Petrov, cc axt bo ca thc vt thng l cc axit bo khng no, s bin i to thnh lacton, sau to thnh naphten hoc aromat: Thuyt ngun gc hu c ca du m cho php gii thch c nhiu hin tng trong thc t. Chng hn nh: du m cc ni hu nh u khc nhau, s khc nhau c th l do vt liu hu c ban u. V d, nu vt liu hu c ban u giu cht bo th c th to ra loi du parafinic Du c sinh ra ri rc trong cc lp trm tch, c gi l m. Do p sut y cao nn chng b y ra ngoi v buc phi di c n ni mi qua cc tng cha thng c cu trc rng xp. S di chuyn tip tc xy ra cho n khi chng gp iu kin thun li c th li y v tch t thnh du m. Trong qu trnh di chuyn, du m phi i qua cc tng xp, c th s xy ra s hp ph, cc cht c cc b hp ph v li cc lp , kt qu l du s nh hn v sch hn. Nhng nu qu trnh di chuyn ca du b tip xc vi oxy khng kh, chng c th b oxy ha dn n to cc hp cht cha cc nguyn t d nguyn t, lm du b xu i. Khi du tch t v nm trong cc m du, qu trnh bin i hu nh t xy ra nu m du kn. Trong trng hp c cc khe h, oxy, nc kh quyn c th lt vo, s xy ra bin cht theo chiu hng xu i do phn ng ha hc. Cc hydrocacbon ban u ca du kh thng c phn t lng rt ln (C 30 C40), thm ch cao hn. Cc cht hu c ny nm trong lp trm tch s chu nhiu bin i ha hc di nh hng ca nhit , p sut , xc tc (l khong st). Ngi ta thy rng, c ln chm su xung 30 mt, th nhit trong lp trm tch tng t 0,54 1,200C, cn p sut tng t 3 - 7,5 atm. Nhng vy su cng ln, nhit , p sut cng tng v trong cc lp trm tch to du kh, nhit c th ln ti 100 2000C v p sut t 200 - 1000 at. iu kin ny,cc hydrocacbon c phn t ln, mch di, cu trc phc tp s phn hy nhit, to thnh cc cht c phn t nh hn, cu trc n gin hn, s lng vng thm t hn Thi gian di cng l cc yu t thc y qu trnh crcking xy ra mnh hn. Chnh v vy, tui du cng cao, ln chm cng su, du c to thnh cng cha nhiu 2
hydrocacbon vi trng lng phn t cng nh. Su hn na c kh nng chuyn ha hon ton thnh kh, trong kh metan l bn vng nht nn hm lng ca n rt cao. Cng chnh v vy, khi tng chiu su ca cc ging khoan thm d du kh th xc sut tm thy kh thng cao hn. 1.1.2. c im v thnh phn ca kh thin nhin 1.1.2.1. c im. Kh thin nhin c khai thc t ging kh hay du. Ty thuc vo c tnh ca tng ging m khi khai thc c nhng tp cht v thnh phn khc nhau.
KH KHNG NG HNH Thnh phn (%mole) N2 CO2 H2S CH4 C2H6 C3H8 C4H10 C5H12+ 1.0 3.2 3.2 85.3 5.8 2.0 0.8 1.9 Australia (N.W.Sheif) Algeria (Hassi RMel) 6.1 0.2 0.2 83.5 7.0 2.0 0.8 0.4 1.0 44.9 44.9 46.2 5.2 2.0 0.6 0.1 Newzealand (Kapuni) Northsea (West Sole) 1.2 0.5 0.5 94.3 3.1 0.5 0.2 0.2 KH NG HNH Abu Dhabi (Zakum) 0.7 2.3 0.6 72.0 13.9 6.5 2.6 1.4 North Sea (Forties) 1.2 0.7 0.7 46.5 13.2 19.8 10.6 8.0 North Sea (Brent) 0.9 0.9 0.9 74.0 12.4 7.5 2.9 1.4
Bng 1.1. Thnh phn ca cc loi kh thin nhin Kh thin nhin l kh khng mu, khng mi (c mi l do mecaptan cho vo). Kh thin nhin c tnh chy sch. Thnh phn ch yu ca kh thin nhin l metan (CH4). T trng ca kh thin nhin i vi khng kh dao ng trong khong rng t 0,55 - 1,1. Nhit chy cao.
1.1.2.2. Thnh phn ca kh thin nhin Gm 2 thnh phn chnh: hydrocacbon v khng hydrocacbon. Hydrocacbon: ch yu t C1 - C4, C4 - C7 t hn. Khng hydrocacbon: H2O (hi, lng), N2, CO2, H2S, COS, CS2, RSH, H2, He Phn khng hydrocacbon c mt s l tp cht m trong qu trnh ch bin cn phi tch chng nu khng s nh hng trong qu trnh lm vic. V d: H2O Lm tng qu trnh n mn khi c mt CO2 3
nh hng n h thng lm vic nh to hyrat, ng bng gy tc nghn ng ng lm gim cng sut vn chuyn. V vy, ta phi tch nc. Nit: tr, khng n mn. CO2: c tnh axit gy n mn. H2S: c tnh axit gy n mn. H2: khng l tp cht. He: tr, thu hi v c gi tr. Thng loi CO2, H2O, H2S. 1.1.2. Phn loi kh thin nhin: c nhiu cch phn loi khc nhau 1.1.2.1. Theo ngun gc: c 2 loi Kh khng ng hnh (Unassociaed Natural Gas): l kh c khai thc t ging kh hoc ging kh - condensate hay ging kh - du (trong du chim t l thp). M kh (gas well). M kh thun tu (khng c lin h g vi du). M kh - du: trong kh nhiu hn du, hm lng metan thp hn ging kh thun tu. c im ca gas well l tn ti dng kh iu kin va, trong qu trnh khai thc khng c s to thnh lng (nu P, T gim chuyn kh thnh lng), thng th hm lng CH4 cao c th 98%. M kh condensate M ny dng sn xut c condensate v kh thin nhin. c im ca m ny l nhit cao (80 1000C) v p sut cao (P 3.107Pa). Trong iu kin ny condensate ha tan vo kh nn hn hp nm dng kh. Trong qu trnh khai thc, kh n u ming ging s gim p sut v nhit khin phn du b ngng t gi l condensate, tch ra khi kh thin nhin. Condensate cn gi l kh ngng t l phn on nm gia kh v du thng l C5+. c im ca kh khng ng hnh Thnh phn mtan l ch yu 70 - 95%, C2 C5 chim t l rt thp. Thnh phn kh tng i n nh, t thay i theo iu kin ly mu. T khi so vi khng kh thp: 0,55 0,65. Kh ng hnh (Associated Natural Gas): l kh ha tan trong du, li cun theo du trong qu trnh khai thc v c tch ra khi du sau . Kh ng hnh thng c khai thc t cc m du hoc cc m du kh trong du nhiu hn kh. Ti ging c p sut cao v nhit thp, kh ha tan trong du, khi khai thc p sut gim du th c bt kh. c im ca kh ng hnh: 4
Hm lng metan thp hn kh khng ng hnh, hm lng C3, C4 v condensate chim t l ng k. Thnh phn kh thay i nhiu ty theo iu kin ly mu. T khi so vi khng kh cao: 1
1.1.2.2. Theo thnh phn C3+ Kh kh (dry gas): thnh phn kh ch yu l metan, khng cha hoc cha rt t cc hydrocacbon C3+. Kh kh cn c gi l kh ngho hay kh gy (lean gas). Kh thin nhin c khai thc t cc m kh thuc loi kh kh. Kh t (wet gas): ngoi thnh phn ch yu l mtan cn c cha mt lng ng k C3+. Kh t cn c gi l kh bo hay kh giu. Kh khai thc t cc m kh - condensate v kh ng hnh c cha mt lng ng k C3+ nn thuc loi kh bo. Hm lng C3+ 50 g/m3: kh kh, kh gy. 50 g/m3 < hm lng C3+ < 400 g/m3: kh trung bnh. Hm lng C3+ 400g/m3: kh bo, kh t.
1.1.2.3. Theo hm lng kh axit. Kh ngt (sweet gas): hm lng H2S 1/4 grains/100sft3 hay hm lng H2S 6mg H2S/m3. Kh chua (Sour gas): hm lng H2S > 1/4 grains/100sft3 hay hm lng H2S > 6mg H2S/m3. Trong kh chua c cha cc kh axit H2S v CO2 ngoi ra cn c cha cc hp cht khc COS, CS2, RSH. 1.2. S tng qut qu trnh khai thc v ch bin kh 1.2.1. Module x l kh Nhim v dng tch cc tp cht trong kh nh: H 2O, cc hp cht cha lu hunh (H2S, COS, RSH, CS2), CO2, N2, O2 v tp cht c hc, hydrate, asphaltenes, bi c x l bng cc qu trnh: Hp th (absorption). Hp ph (adsorption). Qu trnh ngng t (condensation) 1.2.2. Module x l du th (Crude oil Treating Module) Module ny c nhim v x l t tiu chun sau: tp cht c hc v nc (basic sediment and water), p sut hi, mui (Salt), hm lng lu hunh (Sulfur Content). BS & W l mt tiu chun quan trng nhm gii hn hm lng nc t do trong du th (BS & W = 0,3 3% th tch). 5
Cc qu trnh dng ha cht, in, c v nhit lm gim hm lng nc c gi l qu trnh tch nc du th Crude oil dehydrat Ch tiu v p sut hi gii hn bay hi ca du th. Nu s vn chuyn v tn tr du th p sut kh quyn ch tiu ny quy nh p sut hi ca du th 101,3 kPa ti nhit mi trng. Ch tiu ny c trng bi TVP (True Varpor Pressute) hay RVP (Red Vapor Pressure). Ch tiu v hm lng mui v hm lng lu hunh p dng trong nh my lc du cc qu trnh ch bin (lin quan n thit b).
1.2.3. Module x l nc Nc thi s c x l t cc tiu chun v mi trng. Hm lng hydrocacbon, cht rn t do, cht rn ha tan (CaCO3, NaCl, BaSO4) Ch tiu v hm lng hydrocacbon (HC) l rt quan trng nu nh nc thi sau ra bin. v d quy nh v hm lng hydrocacbon North Sea trong nc thi cc gin khoan nh hn 40ppm. S tch hydrocacbon nc thc hin bng lng trng lc, ly tm, kt hp. Cht rn t do ch cn tch nu em s dng li (tch bng phng php lng, lc, ly tm). Cht rn ha tan phi c x l n mc ca chng c trong mi trng. 1.2.4. Module tch NGL Mc ch ca module ny l iu chnh im sng hydrocacbon, tng cng cht lng sn phm kh v sn phm lng. Thnh phn ca NGL: C2, C3, iC4, nC4, C5+. c x l bng cc qu trnh: Hp th: dng dung mi du nh (karozen) Ngng t: thit b lm lnh, turbo, van tit lu. 1.2.5. Module n nh (Stabilization Module) Nhim v: n nh NGL trong nh my ch bin kh, d dng trong tn tr v vn chuyn, ta tin hnh cc qu trnh sau: Demetan ha v deetan ha 1.2.5. Module x l sn phm (Product Treating Module) Tch CO2 ln trong C2, C2+: khng dng chng ct (v to thnh im ng kh), dng phng php hp th bng dung dch amin (DEA). Tch cc hp cht lu hunh trong LPG: H2S, COS, CS2 v mercaptan, nu hm lng nh hn 100 ppm x l bng phng php hp th phn t.
1.3. ng dng ca kh thin nhin - mt s tiu chun i vi cc sn phm t kh.
1.3.1. ng dng ca kh thin nhin Ni chung kh thin nhin c ng dng rt rng ri, phm vi ng dng ca n ph thuc vo nhiu yu t nh thnh phn kh nhu cu s dng cng nh cc qu trnh ch bin kh. Mt trong nhng ng dng ca kh thin nhin l lm cht t do cc u im nh chy sch, khng to cn, nhit lng chy cao. Kh thin nhin c th lm kh t dn dng (nu n, l si) hay cht t cng nghip (in, gch, ngi, xi mng, snh s, thy tinh, luyn gan thp). T kh thin nhin bng qu trnh ch bin kh ta s thu c nhiu sn phm khc nhau dng lm nhin liu hoc lm nguyn liu cho ha du. Metan: l thnh phn ch yu trong kh thin nhin v kh t nh my ch bin kh c dng lm nguyn liu iu ch H2, sn xut NH3 ( sn xut phn ur, axit nitric, mui amon) hoc dng tng hp mtanol. Etan: l nguyn liu sn xut etylen, l nguyn liu qu ng dng trong sn xut nha (PE, PVC), oxit etylen, cht hot ng b mt v nhiu sn phm khc. M, khong 40% etylen c sn xut t etan. Propan v Butan: chim lng ng k trong kh ng hnh, thng c dng sn xut LPG (propan thng phm, butan thng phm hoc hn hp propan v butan) dng lm nhin liu dn dng, nhin liu ng c hoc dng lm ngun nguyn liu tng hp cc olfin nh propylen, butylen, butadien phc v cho ngnh ha du. Condensate C5+: l thnh phn chnh ca xng thin nhin, dng lm nhin liu hoc dng sn xut cc phn on BTX
Hnh I.1 : Cc sn phm chnh i t kh thin nhin 7
1.3.2. Mt s sn phm i t kh thin nhin Kh kh (Dry gas): thnh phn ch yu l C 1, C2. Kh ny trc khi a vo ng dn cn c nng n p sut cn thit cho qu trnh vn chuyn (trong etan l sn phm nh nht ca NGL c Ts bng -880C). NGL (Natural Gas Liquids): l cht lng ly t kh thin nhin. Thnh phn ca NGL c th C2+ hoc C3+ ty theo iu kin ch bin kh. T NGL bng chng ct phn on c th thu c nhiu sn phm: etan, LPG (propan, butan, hn hp Bu pro), xng thin nhin. LNG (Liquefied Natural Gas): nu dng kh t nh my chng tch NGL c ha lng hon ton th c gi l kh thin nhin ha lng. Thng th kh thin nhin c nn v lm lnh 2690F (-1670C) thnh lng v gim th tch d bo qun v vn chuyn. LPG (Liquefied Petroleum Gas): kh du m ha lng, thnh phn ch yu l C3, C4. iu kin thng, LPG trng thi hi nhng nhit v p sut xc nh n dng lng. Khi th tch ca n gim i v ch cn t 1/235 n 1/275 ln so vi th tch dng hi. Condensate C5+: l thnh phn chnh ca xng thin nhin, dng lm nhin liu hoc dng sn xut cc phn on BTX
1.3.3. Mt s tiu chun i vi kh cho th trng Nhit tr (Heating value): c nh ngha l tng lng nhit c gii phng khi t chy kh mt n v th tch hay mt n v khi lng ktc. C 2 loi nhit tr: Nhit tr tng (Gross Heating Value): l tng lng nhit sinh ra trong qu trnh t chy kh vi lng khng kh l thuyt, trong nc sinh ra c lm lnh v ngng t thnh lng iu kin chun (150C v 1106 mbar). Nhit tr thc (Net Heating Value): l tng lng nhit sinh ra trong qu trnh t chy kh trong nc sinh ra vn tn ti trng thi hi. n v s dng cho nhit tr thng l MJ/m3 hoc Btu/ft3. 1000 Btu/ft3 bng 32,7 MJ/m3. Nhit tr tng ca kh thng trong khong 35 - 45 MJ/m3 Hm lng lu hunh (Sulfur content): hm lng lu hunh cn phi gii hn trnh n mn, tnh c hi v mi khi kh c t chy. Hm lng H 2S cho php khong 4 ppm (khong 0,25g/100ft3). Hm lng lu hunh tng trong kh thng cao hn, do khch hng qui nh v thng qui i sang hm lng H2S. Nhit cc i: nhit phn phi cc i ti im vn chuyn thng qui nh vo khong 1200F (490C). Hm lng nc: tiu chun ny c th nu nh l khi lng nc c trong mt th tch kh hoc nhit im sng i vi m cc i p sut qui nh. M, hm lng nc thng c qui nh l 110mg/m 3, Chu u v Canada l 50 60 mg/m3. 8
im sng theo hydrocacbon: Tiu chun c xc nh nh l nhit im sng i vi hydrocacbon cc i cho php p sut cho trc. Tiu chun ny thay i ty theo kh hu v yu cu ca khch hng. Bc M v Chu u, gi tr ny thng l -100 00C. Cc kh tr: gm c N2, He, Ar trong N2 l kh tr quan trng nht. Hm lng N2 trong kh thng c gii hn khng qu 1 2% th tch. Hm lng N2 nh hng n nhit tr. CO2: Cacbondioxide cng l mt kh tr nhng c qui nh ring v khc vi cc kh tr khc, CO2 c kh nng n mn khi c mt ca nc. Hm lng CO2 ti a thng c qui nh l 2% th tch. 1.3.4. Mt s tiu chun cho cc sn phm lng t kh Xng thin nhin (Natural gasoline): C5+ p sut hi (RVP): 70 235 kPa (10 34 psia). % th tch bay hi 600C (1400F): 25 85% % th tch bay hi 1350C (2750F): min 90% im si cui: max 1900C (3750F). n mn: khng n mn trong php th. Mu: khng nh hn 25 (theo phng php Saybolt). Etan thng phm: y l ngun nguyn liu ha hc dng trong sn xut nha v cc sn phm khc. Cc tiu chun i vi etan thng phm thay i khc nhau nhng thng rt khc khe i vi cc tp cht c th nh hng n qu trnh s dng. S hn ch hm lng CO2 v CH4 trong etan thng phm c bit quan trng. Propan thng phm v Butan thng phm Propan thng phm l hn hp c thnh phn ch yu l propan v hoc propylen. Propan thng phm cn p ng cc tiu chun cht lng nh p sut hi, nhit tr hm lng S tng, hm lng cn, m, hm lng cc hp cht n mn, mi Butan thng phm l hn hp c thnh phn ch yu l butan v hoc butylen. Hn hp Propan - Butan (LPG): hn hp ny phi c p sut khng cao hn so vi propan thng phm 380C v c nhit bay hi 95% th tch tng ng vi butan. LPG cng cn p ng cc tiu chun v sch nh i vi butan. i vi PLG dng lm cht t, thnh phn ca hn hp ny c thay i khc nhau m bo tnh cht bay hi ca cc hn hp trong cc ma khc nhau. Tuy nhin p sut hi ca hn hp bu - pro thng phm t khi vt qu 860 kPa (d) tng ng 125 psia 380C (1000F). 1.3.5. Quy cch cht lng propan thng phm Tng hm lng ca hydrocacbon C2 khng qu 5% mole, c xc nh bng phng php sc k kh, phng php khi ph hoc ph hng ngoi. 9
Tng hm lng ca etylen khng qu 1% mole, c xc nh bng phng php sc k kh, phng php khi ph hoc ph hng ngoi. Tng hm lng ca C4+ khng qu 10% mole, c xc nh bng phng php sc k kh, phng php khi ph hoc ph hng ngoi. Tng hm lng C5+ khng qu 20% mole, c xc nh bng phng php sc k kh, phng php khi ph. p sut hi 450C (1130F) khng ln hn 17,6 bar (255 lbf/ in2 d), c xc nh theo phng php c m t trong tiu chun BS 3324. Hm lng lu hunh tng khng qu 0,002% khi lng, c xc nh theo tiu chun IP243. Hm lng mercapan khng qu 0,005% khi lng, khi c xc nh theo phng php A c m t trong tiu chun BS 4386. Hm lng H2S khng qu 0,75 mg/m3 kh, xc nh bng phng php A m t trong tiu chun BS 4250. Hm lng axtylen khng vt qu 2% mole, c xc nh bng phng php sc k kh, phng php khi ph. Mi ca kh c trng, kh chu khng bn, c th pht hin s c mt ca kh trong khng kh 1/5 gii hn chy di. i vi propan thng phm, gii hn chy di khong 2,4% th tch trong khng kh.
1.3.6. Quy cch cht lng butan thng phm 95% th tch ca sn phm s ha hi nhit 2,2 0C (360F) hoc thp hn, c hiu chnh n p sut 760 mmHg. p sut hi 450C (1130F) khng ln hn 5,86 bar (801 bf/ in2 d). Hn th na i vi cc loi bnh xch tay, p sut hi 45 0C khng nh hn 4,85 bar (701 bf/ in2 d). Tng hm lng cc dien khng qu 10% mole, c xc nh bng phng php sc k kh, phng php khi ph. Hm lng S tng khng qu 0,02% khi lng, c xc nh bng tiu chun IP243. Hm lng sulfua mercaptan khng qu 0,004% khi lng, kh c xc nh theo phng php A c m t trong tiu chun BS 4386. Hm lng H2S khng qu 0,75 g/m3 kh khi c xc nh theo phng php A c m t trong tiu chun BS 4250 Tng hm lng axetylen khng qu 2% mole, c xc nh bng phng php sc k kh, phng php khi ph. Mi ca kh c trng, kh chu, khng bn, c th pht hin s c mt ca kh trong khng kh 1/5 gii hn chy di. i vi butan thng phm, gii hn chy di khong 1,9% th tch trong khng kh. 1.4. Tng quan du kh th gii 10
1.4.1. Cc nc OPEC Trong lch s u tranh i li quyn li du m ca cc nc sau chin tranh th gii th 2 phi k n s ra i ca t chc cc nc xut khu du m vo thng 9 1960 ti Baghdad (Iraq), gi tt l OPEC (Organisation of Petroleum Exporting Countries). T chc ny ra i nhm chng li s lng on th trng du m ca cc cng ty t bn c quyn. Ban u, n ch quyt nh gi du xut khu ca nm nc thnh vin l: Arab Saudi, Iran, Iraq, Kuwait v Venezuela. T khi OPEC ra i du m tr thnh mt v kh quan trng trong tay cc nc xut khu du m. Dn dn cc nc sn xut du m cng gia nhp vo khi nh Quata (1961), Libya (1962), Indonexia (1962), cc tiu vng quc Arab (1967), Algeria (1969), Nigeria (1971). Ngoi vic u tranh tng gi du th, tng thu nh vo du m, cc nc OPEC u tranh i kim sot ton b ti nguyn thin nhin ca mnh v k hip c New York ngy 5 -12 -1972, theo cc cng ty ngoi quc tha thun bn giao 51% quyn khai thc du cho cc nc vnh Ba T k t nm 1983. Trong th trng du kh th gii, c nhiu iu khng chc chn v gi du trong tng lai. Mc sn xut du cc nc OPEC l cha kha v l nhn t nh hng n s hnh thnh gi du trn th gii. OPEC cung cp hn 2/3 sn lng du ca ton th gii.
Hnh 1.2. Biu sn lng ca cc nc OPEC 1.4.1.1. Arabia Saudi Arabia Saudi, phn ln l xut khu du m v cc sn phm ca du m. Thu nhp t du m khong 24 t USD (90% thu nhp). Mc d s cnh tranh t Mexico, Venezuela v Canada, Arabia Saudi vn l nc xut khu du m cho M v Nht Bn. Ngun d tr du ca Arabia Saudi l khong 264,2 t thng (chim 1/4 tr lng trn th gii). Khai thc du m Arabia Saudi vo khong hn 8 triu thng/ ngy v c khong 77 m du v nhiu m kh, nng sut ch bin vo khong 2 triu thng/ ngy. 11
Tuy nhin m du chnh ca t nc th tp trung 8 khu vc. Mt trong nhng khu vc l Gavar, l m du ln nht trong t lin vi tr lng l 70 t thng, tip theo l Safaniya vi mc d tr l 19 t thng. Cng ty AOC Nht Bn hot ng 2 ging du Hafgy v Hut, khai thc khong 300 ngn thng/ngy. Texaco pht trin vi 3 ging du: Vafra, Nam Favaris v Nam Um Gudafr v khai thc hn 200 ngn thng mi ngy. Dn c, ngi Din tch t, km2 Mt dn c, ngi/km2 GDP, USD/ ngi S tin xut khu du, triu USD Ngun du th d tr, triu thng Ngun kh thin nhin d tr, t m3 Khai thc du th, thng/ ngy Lng sn phm ch bin, thng/ ngy Lng sn phm c tiu th, thng/ ngy Xut khu du th, thng/ ngy Xut khu cc sn phm qua ch bin, thng/ ngy Nng sut ch bin, thng/ ngy Xut khu kh thin nhin, t m3 Bng 1.2. Cc thng s v Arabia Saudi nm 2005 1.4.1.2. Iran. Ngun d tr du m Iran l 136,27 t thng. Nhu cu tiu th hng ngy l 1,512 triu thng. Nng sut ch bin du l 1,474 triu thng/ ngy. Nhng nc nhp khu du t Iran gm c Nht, Nam Triu Tin, Anh, Trung Quc, Th Nh K, Thi Lan, n , Brazil. Cng nghip du kh ca Iran chu hon ton s iu khin t chnh quyn. Nhng m du chnh ti Iran gm: Gararan, Marun, Avaz, Bangistan, Aga Gari, Ragaisafid. Cc nh my ch bin du gm: Abadan (477.000 thng/ ngy), Isfagan (251.000 thng/ngy), Bandar Adas (220.400 thng/ ngy), Teherran (213.750 thng/ ngy), Arak (142.500 thng/ ngy), Tebriz (106.400 thng/ ngy), Shiraz (38.000 thng/ ngy), Kermanshah (28.500 thng/ ngy) v Lanvan (20.000 thng/ ngy). 12 23.956.000 2.150.000 11 12.931 164.710 264.211 6.900 9.353.000 1.974.000 1.227.000 7.209.000 1.385.000 2.091.000 -
Dn c, ngi Din tch t, km2 Mt dn c, ngi/ km2 GDP, USD/ ngi S tin xut khu du, triu USD Ngun du th d tr, triu thng Ngun kh thin nhin d tr, t m3 Khai thc du th, thng/ ngy Lng sn phm ch bin, thng/ ngy Lng sn phm c tiu th, thng/ ngy Xut khu du th, thng/ngy Xut khu cc sn phm qua ch bin, thng/ ngy Nng sut ch bin, thng/ ngy Xut khu kh thin nhin, triu m3 Bng 1.3. Cc thng s v Iran nm 2005 1.4.1.3. Iraq.
68.600.000 1.648.000 42 2.863 48.286 136.270 27.580 4.092.000 1.440.000 1.512.000 2.395.000 402.000 1.474.000 4.735
Iraq gi v tr th hai (sau Arabia Saudi) trn th gii v d tr du v kh (115 t thng). Nu s dng tt c cc ng dn du c nng sut cao, Iraq c th xut khu 1,4 - 2 triu thng/ ngy. Trc chin tranh Iran - Iraq, Petronas v Elfaquitaine cng hot ng Iraq, di s kim sot ca cng ty du m Iraq. Cc m du ln Iraq hin ang c khai thc nh Kircooc (1927), Rumeyla (1953), Buzurgan (1969), Abujirab (1971), Megun (1976) v Narh Umar (1977). Dn c, ngi Din tch t, km2 Mt dn c, ngi/ km2 GDP, USD/ ngi S tin xut khu du, triu USD 28.832.000 438.000 66 1.063 23.710 13
Ngun du th d tr, triu thng Ngun kh thin nhin d tr, t m3 Khai thc du th, thng/ ngy Lng sn phm ch bin, thng/ ngy Lng sn phm c tiu th, thng/ ngy Xut khu du th, thng/ ngy Xut khu cc sn phm qua ch bin, thng/ ngy Nng sut ch bin, thng/ ngy Xut khu kh thin nhin, t m3 Bng 1.4. Cc thng s v Iraq nm 2005 1.4.1.4. Qatar
115.211 3.170 1.913.000 477.000 514.000 1.472.000 14.000 603.000 -
Khch hng ch yu ca Qatar l Nht Bn, M, Anh, Php, c, v Italia. Xut khu du chim 80% tng sn phm xut khu c nc. Qatar xut khu khong 70% lng du n Nht v 10% n cc nc ng Nam . Sn lng du ca Qatar tp trung 7 vng chnh l: Duhan, Bui Hanan, Meydan, Mahzam, Id Al-Shargi, Al-Shahin, Al-Rayan v Al-Halig Dn c, ngi Din tch t, km2 Mt dn c, ngi/ km2 GDP, USD/ ngi S tin xut khu du, triu USD Ngun du th d tr, triu thng Ngun kh thin nhin d tr, t m3 Khai thc du th, thng/ ngy Lng sn phm ch bin, thng/ ngy Lng sn phm c tiu th, thng/ ngy Xut khu du th, thng/ ngy Xut khu cc sn phm qua ch bin, thng/ ngy 824.000 11.000 75 45.937 18.634 15.207 25.783 766 119.000 60.000 677.000 77.000 14
Nng sut ch bin, thng/ ngy Xut khu kh thin nhin, triu m3 Bng 1.5. Cc thng s v Qatar nm 2005 1.4.1.5. Kuwait
80.000 27.600
Vo thi gian, Kuwait v Iraq xy ra chin tranh 8 - 1990, sn phm du kh xp x 100 triu tn, trong 10 triu tn c khai thc cc ging du thuc vng lnh th chung ca Arabia Saudi v Kuwait. Sut thi k chin tranh Kuwait v Iraq, 800 hay hn mt na s ging du Kuwait v vng lnh th chung b ph hy. Khong 1/3 sn lng du khai thc trc chin tranh b t chy trong thi k ny, c tnh thit hi v du xp x 40 t USD Sau khi phc hi li cc ging du, c s bin i ng k v p sut trong cc ging du. Nm 1998, Kuwait khai thc 101 triu thng du t cc ging. Gn 2/3 du khai thc c xut khu, trong xut khu qua M 20%, ng Nam v Nht Bn 10%. Dn c, ngi Din tch t, km2 Mt dn c, ngi/ km2 GDP, USD/ ngi S tin xut khu du, triu USD Ngun du th d tr, triu thng Ngun kh thin nhin d tr, t m3 Khai thc du th, thng/ ngy Lng sn phm ch bin, thng/ ngy Lng sn phm c tiu th, thng/ ngy Xut khu du th, thng/ ngy Xut khu cc sn phm qua ch bin, thng/ ngy Nng sut ch bin, thng/ ngy Xut khu kh thin nhin, triu m3 Bng 1.6. Cc thng s v Kuwait nm 2005 2.760.000 18.000 153 27.028 42.583 101.500 1.557 2.573 911.000 249.000 1.650.000 614.000 936.000 -
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1.4.1.6. Cc tiu vng quc Arab Khch hng xut khu ch yu ca cc tiu vng quc Arab l Nht Bn (vi hn 60% lng xut khu) v cc nc ng Nam (khng di 20%) Dn c, ngi Din tch t, km2 Mt dn c, ngi/ km2 GDP, USD/ ngi S tin xut khu du, triu USD Ngun du th d tr, triu thng Ngun kh thin nhin d tr, t m3 Khai thc du th, thng/ ngy Lng sn phm ch bin, thng/ ngy Lng sn phm c tiu th, thng/ ngy Xut khu du th, thng/ ngy Xut khu cc sn phm qua ch bin, thng/ ngy Nng sut ch bin, thng/ ngy Xut khu kh thin nhin, triu m3 Bng 1.7. Cc thng s v Kuwait nm 2005 1.4.1.7. Indonexia Dn c, ngi Din tch t, km2 Mt dn c, ngi/ km2 GDP, USD/ ngi S tin xut khu du, triu USD Ngun du th d tr, triu thng Ngun kh thin nhin d tr, t m3 Khai thc du th, thng/ ngy 217.990.000 1.904.000 114 1.290 9.248 4.301 2.769 1.059.000 16 4.500.000 84.000 54 29.367 49.700 97.800 6.060 2.378 442.000 204.000 2.195.000 509.000 466.000 7.499
Lng sn phm ch bin, thng/ ngy Lng sn phm c tiu th, thng/ ngy Xut khu du th, thng/ ngy Xut khu cc sn phm qua ch bin, thng/ ngy Nng sut ch bin, thng/ ngy Xut khu kh thin nhin, triu m3 Bng 1.8. Cc thng s v Indonexia nm 2005 1.4.1.8. Algeria Dn c, ngi Din tch t, km2 Mt dn c, ngi/ km2 GDP, USD/ngi S tin xut khu du, triu USD Ngun du th d tr, triu thng Ngun kh thin nhin d tr, t m3 Khai thc du th, thng/ngy Lng sn phm ch bin, thng/ ngy Lng sn phm c tiu th, thng/ ngy Xut khu du th, thng/ ngy Xut khu cc sn phm qua ch bin, thng/ ngy Nng sut ch bin, thng/ ngy Xut khu kh thin nhin, triu m3 Bng 1.9. Cc thng s v Algeri nm 2005 1.4.1.9. Nigeria. Dn c, ngi Din tch t, km2 Mt dn c, ngi/ km2
1.054.000 1.140.000 374.000 142.000 1.057.000 36.600
32.906.000 2.382.000 14 3.113 32.882 12.270 4.580 1.352.000 452.000 246.000 970.000 464.000 462.000 64.266
131.759.000 924.000 143 17
GDP, USD/ngi S tin xut khu du, triu USD Ngun du th d tr, triu thng Ngun kh thin nhin d tr, t m3 Khai thc du th, thng/ ngy Lng sn phm ch bin, thng/ ngy Lng sn phm c tiu th, thng/ ngy Xut khu du th, thng/ ngy Xut khu cc sn phm qua ch bin, thng/ ngy Nng sut ch bin, thng/ ngy Xut khu kh thin nhin, triu m3 Bng 1.10. Cc thng s v Nigeria nm 2005 1.4.1.10. Venezuela Dn c, ngi Din tch t, km2 Mt dn c, ngi/ km2 GDP, USD/ ngi S tin xut khu du, triu USD Ngun du th d tr, triu thng Ngun kh thin nhin d tr, t m3 Khai thc du th, thng/ ngy Lng sn phm ch bin, thng/ ngy Lng sn phm c tiu th, thng/ ngy Xut khu du th, thng/ ngy Xut khu cc sn phm qua ch bin, thng/ ngy Nng sut ch bin, thng/ ngy Xut khu kh thin nhin, triu m3
752 46.770 36.220 5.152 2.366.000 388.000 253.000 2.326.000 464.000 49.000 12.000
26.756.000 916.000 29 5.240 48.059 80.012 4.315 3.128.000 1.198.000 506.000 2.198.000 609.000 1.054.000 18
Bng 1.11. Cc thng s v Venezuela nm 2005 1.4.1.12. Lybia Dn c, ngi Din tch t, km2 Mt dn c, ngi/ km2 GDP, USD/ ngi S tin xut khu du, triu USD Ngun du th d tr, triu thng Ngun kh thin nhin d tr, t m3 Khai thc du th, thng/ ngy Lng sn phm ch bin, thng/ ngy Lng sn phm c tiu th, thng/ ngy Xut khu du th, thng/ ngy Xut khu cc sn phm qua ch bin, thng/ ngy Nng sut ch bin, thng/ ngy Xut khu kh thin nhin, triu m3 Bng 1.13. Cc thng s v Lybia nm 2005 1.4.2. Cc nc khng thuc OPEC 1.4.2.1. Nga. Bt u th k XX, Nga gi v tr u tin trong vic sn xut du m. Khu vc khai thc du chnh trong nm u tin ca ch Soviet l Bakee v Bc Caucasus. Tuy nhin, nhng ging du thuc khu vc ny thiu an ton trong cng vic sn xut. S xy dng bt u Bashkiria v kt qu to thnh mt khu vc du m Volgo Ural ln. Sn phm du Nga chim 10% sn phm du m th gii. Do , c th ni mt cch t tin rng Nga chin v tr mnh nht trn th trung du m quc t. 1.4.2.2. Tim nng du kh ca Tuc-m-ni-xtan Tuc-m-ni-xtan l nc c ngun du m di do, c tnh 45,44 t tn. Tr lng du m v kh t ca t nc nm khu vc Trung ny t lu thu ht s quan tm ca nhiu nc v cc t chc ti chnh quc t. Theo s liu ca Chng trnh pht trin du kh quc gia, n nm 2020 Tuc-m-ni-xtan s t mc khai thc 19 5.853.000 1.760.000 3 6.618 28.324 41.464 1.491 1.693.000 460.000 243.000 1.306.000 609.000 380.000 5.400
100 triu tn du v 240 t m3 kh t. K hoch tng khai thc v ch bin du kh phc v xut khu ca chnh ph s m bo ngun thu ht vn u t trc tip nc ngoi nhm pht trin ngnh du kh ca Tuc-m-ni-xtan. Theo tp on khai thc du kh quc gia Tuc-m-ni-xtan, nc ny s t cng sut lc 32 triu tn du/ nm vo nm 2020. Thng 1/ 2004, Tuc-m-ni-xtan tng sn lng khai thc kh t 6,4% so vi cng k nm trc, t 6,6 t m3, lng kh t t nhin xut khu tng 8%, t 4,69 t m3, sn lng du khai thc 777 nghn tn, tng 3,4% v lng du lc l 486,3 nghn tn, tng 5,4%. Nm 2003, nc ny tng cng sut khai thc kh t ln 11% so vi nm 2002, t gn 60 t m3, xut khu kh t t 3 t m3, tng 10% so vi nm 2002, sn lng du l 10,4 triu tn, tng 11%. Tuc-m-ni-xtan c k hoch khai thc 15 triu tn du th v 74 t m3 kh t t nhin trong nm 2004, trong 58 t m3 phc v xut khu. Khch hng ln nht mua kh t ca nc ny l Ukcraina vi k hoch nhp khu 36 t m3 trong nm 2004. 1.4.3. Mc sn xut v tiu th cc sn phm du kh trn th trng M v Canada Ti M tiu th trung bnh 20 triu thng du mi ngy, trong 45% c dng cho xng t. Phn cn li c dng lm du nhin liu, nhin liu phn lc, cn du v cc loi du khc. Mi thng du cha 42 gallons (159 lt) trong cung cp 19 n 20 gallons (75 lt) l xng. Do , mi ngy United States tiu th khong 178 triu gallons.
Sn xut Tiu th Hnh 1.3. Biu sn xut v tiu th sn phm du kh ca M Canada c cho l nc c ngun d tr c bn ln nht th gii. Canada l nc sn xut kh thin nhin v cc sn phm du th ln th ba trn th gii. Canada sn xut du m v kh thin nhin nhiu hn s tiu th trn th trng. V th, xut khu du m v kh thin nhin l rt quan trng cho nn kinh t ca Canada. 20
1.5. Tng quan du kh Vit Nam Vit Nam cng tc thm d du kh c tin hnh ti ng bng Sng Hng t cui nm 1950 v thm lc a pha nam t nm 1960. Ngy 19/6/1980 x nghip lin doanh du kh Vit - X Petro thnh lp gp phn y nhanh tc thm d ti thm lc a pha nam. Du kh c pht hin vo ngy 26/6/1986, tn du u tin c khai thc t m du Bch H. Cc va du chnh l b Sng Hng vnh Bc B, b Ph Khnh vng duyn hi min Trung v b Nam Cn Sn, b Cu Long v b Malay - Th Chu min Nam. Mi ngy Vit Nam sn xut 350.000 n 400.000 thng. Nm 2002 va qua cung ng kp thi cho sn xut cng nghip v tiu dng ca x hi 147.000 tn condensate v 349.000 tn kh ha lng LPG.
Hnh 1.4. Bn du kh Vit Nam Kh thin nhin l ngun nhin liu sch cho ngnh cng nghip in nc nh em li sn lng in chim trn 40% tng sn lng in ca c nc vi gi thnh r th 2 sau thy in. Ring trung tm in lc Ph M c tng cng sut 3.859 MW vi cng ngh tin tin, hin i vo bc nht ca th gii c hon thnh ng b vo nm 2005. Sau trung tm in lc Ph M, cc nh my in chy kh C Mau, Cn Th, Tr Vinh, ng Nai... ang c trin khai xy dng v s a vo hot ng t nm 2005 n nm 2010, tng bc tng thm ng k ngun in cho t nc. ng Nam , Vit Nam ng hng th ba sau Indonesia v Malaysia. Nm 2004, Vit Nam sn xut 130 triu thng du trong 80% l sn xut m Bch H thuc Vietxopetro. y l mt lin doanh gia PetroVietnam v Zarubezhneft ca Nga. 21
Cng nm 2004, s lng kh t sn xut l 5,6 t m3. Theo PetroViet Nam, tr lng du Vit Nam l 6,5 8,5 t thng v kh t l 2,1 2,86 ngn t m 3. Mi ngy s du s dng l 185 ngn thng. Nh vy, lng bnh qun mi nm mi ngi Vit Nam dng hn 0,8 thng. Con s ny kh thp, ch ngang vi n v bng mt na Trung Quc. Bn thng u nm 2005, xut khu du kh mang li 1,7 t USD. Nh vy. Mi nm ngnh du kh ng gp hn 6 t USD cho quc gia. Hin nay, ngnh Du kh nc ta ang khai thc du kh ch yu ti 6 khu m bao gm: Bch H, Rng, i Hng, Hng Ngc, Rng ng, Bunga Kekwa - Ci Nc v chun b chnh thc a vo khai thc m kh Lan Ty - l 06.l. Cng tc pht trin cc m Rng ng, Ruby v Emeral, Lan Ty - Lan , S T en, S T Vng, Hi Thch, Rng i, Kim Long, c Qu, C Voi...ang c trin khai tch cc theo chng trnh ra, m bo duy tr v tng sn lng khai thc du kh cho nhng nm ti. D kin, m S T en (l 15 - 1) s c a vo khai thc trong qu 4 nm nay. Nhng pht hin v du kh mi y thm lc a min nam nc ta rt ng phn khi, tng thm nim tin v thu ht s quan tm ca cc nh u t l: l 09 - 2, ging C Ng Vng - IX, kt qu th va thu c 330 tn du v 170.000 m3 kh/ ngy. L 16 - l, ging Voi Trng - IX cho kt qu 420 tn du v 22.000 m 3 kh/ ngy. L 15.1, ging S T Vng - 2X cho kt qu 820 tn du v ging S T en - 4X cho kt qu 980 tn du/ ngy. Trin khai tm kim thm d m rng cc khu m Bch H, Rng, i Hng vi cc ging R - 10, 05 - H - 10 cho kt qu 650.000 m 3 kh/ ngy m v dng du 180 tn/ ngy m. Ging R - 10 khoan tng mng cho kt qu 500.000 m3 kh/ ngy m v 160 tn Condensate/ ngy m. Tnh chung, 2 nm u th k mi, ngnh du kh nc ta thm d pht hin gia tng thm tr lng trn 70 triu tn du th v hng chc t m 3 kh tng sn lng khai thc trong nhng nm tip theo. Nm 2006, Tng cng ty Du kh Vit Nam b tr k hoch khai thc 20,86 triu tn du th quy i (tng 1,5 triu tn so vi mc thc hin trong nm 2005). y l nm u tin nc ta khai thc trn 20 triu tn du th quy i. Trong c 17,6 triu tn du th v 3,7 t m3 kh thin nhin. D kin n nm 2010, ngnh du kh nc ta s khai thc t trn 30 n 32 triu tn du th quy i, nhm p ng cc ngnh nng lng v sn xut cng nghip ca c nc. Nhn chung vic khai thc du kh vit nam hin nay hnh thnh nn 4 cm nh sau: Cm m th nht nm vng ng bng Bc B, gm nhiu m kh nh, trong c Tin Hi C, tr lng khong 250 t m3 kh, bt u khai thc t thng 12 nm 1981 vi trn 450 triu m3 khi kh phc v cng nghip a phng. Vi cc pht hin mi trong khu vc ny, y l c s nguyn liu cho cng nghip kh cc tnh pha bc.
22
Hnh 1.5. Bn khai thc du kh Vit Nam Cm m th hai thuc vng bin Cu Long, gm chui 4 m du: Bch H, Rng, Rng ng, Rubi, Hi S Trng l cm quan trng nht hin nay, cung cp trn 96% sn lng ton quc. Trong , m Bch H bt u khai thc 6/1986, tng sn lng t c trn 30 triu tn. Sn lng khong 7 n 9 triu tn/ nm. M Rng bt u khai thc 12/1994, sn lng cha nhiu, t 1200 n 1800 thng/ ngy. Hin nay m Bch H v m Rng c 21 gin khoan khai thc ln nh ang hot ng vi hn 100 ging khoan khai thc v bm p. Kh ng hnh t c thu gom v a vo b bng ng ng dn di 110 km. Thng 4/1995 cung cp trn 1 triu m3 kh/ ngy cho nh my in B Ra. Nm 1997 tng ln 2 triu, ri 3 triu m 3 kh/ ngy cung cp cho nh my in Ph M. Thng 10/1998 nh my x l kh Dinh C t mc thit k 4,2 triu m3 kh/ ngy. Thng 12/1998 bt u sn xut LPG. Hin nay mi ngy nh my Dinh C gom, nn, x l kh t mc 4,6 n 4,7 triu m3/ ngy (khong 1,5 t m3/ nm) sn xut 800 tn LPG, 350 tn condensate. ng thi khu vc ny cng v ang nghin cu tng cng sut chung ca h thng ln trn 2 t m3/ nm. Cm m th ba vng bin Nam Cn Sn gm m du i Hng, bt u khai thc t 10/1994 sn lng 3200 thng/ngy. V cc m kh pht hin khu vc
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xung quanh l Lan Ty (11/2002), Lan (2003), Hi Thch, Mc Tnh v m du kh Rng i Ty ang chun b a vo khai thc. Ring m kh Lan Ty - Lan vi tr lng xc minh l 58 t m 3 s cung cp n nh lu di mc 2,7 t m3 kh/ nm. Trong vi nm ti y khu vc ny s l cm khai thc v cung cp kh ln nht Vit Nam, m bo cung cp 5 n 6 t m3/ nm. Theo d kin ca PetroVietnam, trong khong thi gian t 2003 n 2010, cm m du kh vng bin Cu Long v Nam Cn Sn c th cung cp 6 n 8 t m3 kh/ nm s l c s nguyn liu cho cm cng nghip du kh B Ra - Ph M v Dung Qut. Cm m th t ti thm lc a Ty Nam bao gm m Bunga Kekwa, Ci Nc ang khai thc du, m Bunga Orkid, Bunga Parkma, Bunga Raya ti khu vc tha thun thng mi Vit Nam - Malaysia s l khu khai thc v cung cp kh ln th hai v s l c s m bo s pht trin khu cng nghip du kh C Mau - Cn Th.
Thnh phn i Hng (05 1a) Metan C1 Etan C2 Propan C3 Butan C4 Condensate C5+ N2 CO2 H2S 77,25 9,49 3,38 1,34 0,48 4,50 Lan Ty (06 - 1) 88,5 4,3 2,4 0,6 1,4 0,3 1,9 10,0 Lan (06 - 1) 93,9 2,3 0,5 0,1 0,2 1,6 1,2 Cha o Rng i (11 - 2) 81,41 5,25 3,06 1,47 0,55 0,08 5,64 0,00 Hi Thch (05 - 2) 81,00 5,20 2,8 1,50 4,70 0,11 4,40 Mc Tinh (05 - 3) 89,44 3,80 1,48 0,71 0,54 0,15 3,88 -
Bng 1.14. Thnh phn kh b Nam Cn Sn ( % theo th tch)

Thnh phn Metan C1 Etan C2 Propan C3 Butan C4 Condensate C5+ N2 CO2 H2S PM3 77,91 6,86 4,09 1,98 0,42 0,80 7,86 UNOCAL 89,65 2,74 0,40 0,17 0,05 2,14 4,38 L Ty Nam 89,42 4,26 2,38 1,12 0,32 0,34 1,88 -
Bng 1.15. Thnh phn kh b Malay - Th Chu (% theo theo th tch)
24
CHNG 2: LM KH KH
2.1. Khi nim chung Kh ng hnh v kh thin nhin sau khi khai thc thng bo ha hi nc v hm lng nc ph thuc vo p sut nhit thnh phn ha hc ca kh. Hm lng m ( m): l khi lng hi nc c trong mt n v th tch hoc mt n v khi lng (g/m3 hoc g/kg khng kh). Nu p sut khng i, khi nhit tng th hm lng m cn bng tng, khi nhit khng kh gim c cha hm lng m bo ha cc i th mt phn hi nc s ngng t. Hm lng m cn bng l hm lng nc cc i m kh c th cha nhit v p sut xc nh. Cch xc nh hm lng m cn bng i vi kh ngt c t trng g = 0,6 xc nh hm lng m cn bng ca kh t nhin thng thng ta s dng th hnh IV.1 i vi kh c g 0,6 ta cn xc nh h s hiu chnh t trng CRD (Relative Density). Xc nh CRD phi c: M gas hoc gas T ( 0F) Hm lng m cn bng c 0,6: W = CRD.W0.6 W0.6 : Hm lng cn bng vi = 0,6 i vi kh c cha mui ha tan: ta cn xc nh h s iu chnh theo hm lng mui CS W = CS.CRD.W0.6 i vi kh chua (c mt CO2 v H2S): lm tng hm lng m cn bng khi xc nh theo hnh IV.1 l khng chnh xc. W = y.WHC + y1.W1 + y2.W2 Trong : W : hm lng m ca hn hp khng kh W1: hm lng m ca CO2 tra hnh IV.2 W2: hm lng m cn bng ca H2S tra hnh IV.3 WHC: hm lng m cn bng ca hydrocacbon tra hnh IV.1 ph thuc vo mui v t trng y1: % mol CO2 25
y2: % mol H2S y = 1 - y1 - y2 : % mol hydrocacbon 2.2. nh hng ca nc hydrat 2.2.1. nh hng ca nc To hydrat (cc tinh th rn) d ng cc, chim cc khong trng trong ng ng ph v iu kin lm vic bnh thng. L tin thc y n mn kim loi khi c mt H 2S, CO2 lm gim tui th v thi gian s dng thit b. 2.2.2. nh hng ca hydrat Hydrat l nhng tp hp cht c th tn ti mt cch bn di dng tinh th, thc cht chng l nhng dung dch rn ging nc kh. Cu to: gm khung l cc phn t nc lin kt bng lin kt vi nhau bng lin kt hydr, cc phn t kh chim cc khong trng trong cc khoang ca khung ny, cc phn t kh c kh nng to hidrat nh CH4, C2H6, C3H8, H2S, CO2, N2,.s chim ch. iu kin hnh thnh hydrat ph thuc vo p sut, nhit , thnh phn v nhiu yu t khc. Xc nh iu kin hnh thnh hydrat hnh IV.4. T khi kh g v P (hoc T) ta tm c T (hoc P) hn ch s hnh thnh hydrat. Tch nc t do (sy kh kh) Nu khng tch nc phi dng cht c ch (Metanol) h nhit to thnh hydrat 2.3. Phng php s dng cht c ch, ngn nga s to thnh hydrat. 2.3.1. Mc ch S dng cht c ch lm gim p sut hi nc v lm gim nhit to thnh hydrat. Cht c ch thng s dng Metanol v Glycol Phng php s dng cht c ch c s dng trc khi vn chuyn kh. 2.3.2. Xc nh nhit to thnh hydrat
t = 0,556
K M 100
Trong : t = T1 T2 : h nhit to thnh hydrat p sut cho (0C) : % khi lng ca cht c ch M: Khi lng phn t cht c ch K: Hng s 26
i vi metanol K = 2335 i vi glycol K = 4000 V d: Tnh t s dng Metanol 5%
t = 0,556
2335 5 = 2,14 0 C 32 100 5 4000 5 = 1,88 0 C 62 100 5
Tnh t s dng etylen glycol 5%
t = 0,556
Metanol c p sut hi bo ha cao do kh thu hi t dng kh, kh hon nguyn v dn n mt mt nhiu. V vy metanol ng dng ch yu trong h dng ng khoan, ng nhnh v h thng ng dn kh chnh, nhm ph hy cc nt hydrat. Ngi ta s dng zeolit NaA thu hi metanol. Cht c ch c s dng rng ri l glycol (etylen glycol, dietylen glycol...), mc d gi thnh ca n cao hn metanol. Chng c p sut hi bo ha thp hn v v vy c th hon nguyn hon ton bng cch loi nc nh cc qu trnh vt l n thun nh un si chng ra khi dung dch nc - glycol. 2.3.3. S cng ngh ca qu trnh lm kh kh s dng cht c ch metanol
(8) (9) (10) (11)
II
III (12)
(14)
IV
(13)
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(15) I
Hnh 2.6. S cng ngh lm kh kh bng metanol 1, 2, 3: thit b phn ly; 4, 5, 6, 7: thit b hp ph; 8, 9, 10, 11: l nung kh ti sinh; 12, 13: thit b lc bi; 14: thit b trao i nhit; 15: thit b phn ly kh ti sinh. I: kh m; II: kh sy kh; III: kh kh tun hon; IV: kh kh; V: dung dch mtanol trong nc. Trn hnh 4.6 trnh by s cng ngh cm lm kh kh trong dng metanol lm cht c ch. Kh cng metanol i vo thit b phn ring 1, 2, 3, dung dch nc - metanol tch ra v i vo b cha thu hi metanol t dung dch nc. T thit b phn ring 1, 2, 3 kh c chia vo hai thit b hp ph lm vic song song 4 v 5 (hoc 6 v 7) v i qua lp hp ph t trn xung di, trong qu trnh hi 27
nc v metanol c tch ra. ng thi mt phn kh nguyn liu ra khi thit b phn ring 1, 2, 3 i vo l nung 8 v 9 (hoc 8, 9, 10 v 11), c nung nng ti nhit 3000C i vo phn di ca hai thp hp ph khc 6 v 7 ang trong giai on hon nguyn zeolit. Kh c lm kh v sch hi metanol t di thp hp ph, i qua thit b tch bi v trao i nhit 14 v i vo ng dn chnh. Kh hon nguyn nng vi hm lng m cao v metanol i ra t nh thp hp ph v sau thit b lc bi 13 c lm lnh trong trao i nhit 14, ti hi nc v metanol ngng t. Hn hp hai pha to thnh ti y i vo thit b tch 15, trong metanol tch ra khi kh. T thit b tch 15 metanol ngm nc c a vo b cha (cng vi sn phm tng t i t thit b tch 1, 2, 3) sau a i hon nguyn metanol, cn kh sau thp hon nguyn trn vi kh nguyn liu v i vo thp hp ph tng ng (4 v 5) lm sch. Sau khi hon nguyn zeolit thp hp ph chuyn sang giai on lm lnh bng dng kh kh (sau kh kh i vo ng dn kh chnh). Cc thng s: Nhit dng kh m I: 150C Nhit dng kh ti sinh: 300C Thi gian ti sinh:7 - 12h Thi gian hp ph: 7 - 12h Sau khi hp ph hm lng nc trong kh gim t 0,2 - 0,7 g/m3 xung cn 0,003 - 0,004 g/m3. Nhit dng kh kh l 45 - 620C. 2.3.4. S cng ngh s dng cht c ch glycol Trn hnh 2.7 trnh by s cng ngh tch nc v hydrocarbon nng t kh, s dng cht c ch l glycol. Nguyn liu i vo thp tch 1, cc git nc tch ra khi kh, sau kh c trn vi glycol v lm lnh trong trao i nhit 2 n nhit thp hn nhit hidrat ha. T trao i nhit 2 hn hp kh, glycol ngm nc v condensat c dn vo thp tch 3, t nh thp tch kh kh i ra, t pha di c 2 dng - glycol ngm nc v condensate. Phn di thp 3 c trao i nhit dng ng rut g cho hi nc i qua. Thit b ny gi nhit sn phm y ca thp tch cao hn nhit to thnh nh tng bn vng "glycol - hydrocarbon". Do vy to iu kin tch glycol ngm nc ra khi condensat. Condensate hydrocarbon ra khi thp tch 3 dng lm nguyn liu sn xut cc sn phm tng ng, cn glycol ngm nc c a vo thp hon nguyn 4, ti nc c bay hi, sau glycol c lm khan n m xc nh v li c phun vo dng kh nguyn liu trc khi vo trao i nhit 2. Nhit to nh tng: etylenglycol (EG) vi nc l 00C, dietylen glycol (DEG) vi nc l 15 - 200C. Do vy i hi cht ti nhit VII y thp tch ba pha (3) phi ln hn 15 - 200C. 28
Ch : Vic la chn glycol (EG, DEG hoc TEG) ph thuc vo nhit ng c, nht, h nhit to thnh hydrat v kh nng ha tan ca glycol trong hydrocacbon ngng t nhit phn ly v thnh phn kh. p sut trong thp 3 phi thch hp sao cho C3, C4 ngng t c m nc v Glycol khng b ng c. Nng glycol c s dng thng th 60 - 80% khi lng. Lin Bang Nga thng s dng etylenglycol (EG) v n t tan trong kh ngng t (0,25 - 0,27 lit EG/ 1000 lit khi ngng t).
II
(2) I (1)
(3) III
VIII VI (5) (4)
V IV
VII
Hnh 2.7: S cng ngh qu trnh lm kh kh bng cht c ch glycol 1,3: thp tch; 2: thit b trao i nhit; 4: thp hon nguyn; 5: my bm I: kh nguyn liu; II: kh kh; III: hydrocacbon ngng t; IV: glycol bo ha; V: hi nc; VI: glycol hon nguyn; VII: cht ti nhit.
Thit b Nng sut dy chuyn (kg/h) Khi lng glycol s dng (kg/h) Lng glycol tiu hao (g/kg) Nng glycol (%) Trc khi ti sinh Sau khi ti sinh 68 76 -20 68 77 -17 68 76 -16 70 76 -18 67 71 -20 66 70 -20 1 123300 5000 40 2 102600 3600 35 3 145000 4700 32 4 155000 6200 40 5 126000 4000 32 6 127000 4300 34
Tglycol (0C) khi i vo thit b ti sinh Cc thng s ca thp ti sinh Nhit (0C)
102
29
Gio trnh cng ngh du kh Thit b nh y 1 102 120 0,03 2 103 123 0,018 3 102 122 0,01 4 102 122 0,01 5 102 120 0,02 6 122 0,02
p sut (MPa)
Bng 4.1: Mt s thng s cng ngh ca cc thit b sy kh 2.4. Cc phng php sy kh kh 2.4.1. Phng php hp th Phm vi s dng: dng trong qu trnh vn chuyn kh trong nh my ch bin kh. Yu cu im sng t: -25 -300C Cht hp th glycol: MEG, DEG, TEG 2.4.1.1. DEG (Dietylenglycol) u im: Kh nng ht m (nc) cao. Kh bn khi c mt ca CO2, hp cht S v O2. im ng c thp. Nhc im: p sut hi cao dn n hao ht nhiu v vy nng DEG thu c < 95%. Gi thnh cao hn TEG.
2.4.1.2. TEG (Trietylenglycol) u im: Kh nng ht m cao. Kh bn khi c mt CO2, hp cht S, v O2. im ng c thp. p sut hi thp, hao ht thp v nng thu hi cao >99% Nhc im: Kh nng ha tan trong cc hydrocacbon lng cao hn DEG Chi ph u t cao Cc tiu ch khi chn cht hp th: Yu cu im sng Kh nng ht m Kh nng ti sinh Tnh kinh t
2.4.1.3.S cng ngh lm kh kh bng phng php hp th glycol
30

VI III V (3) I (1) (2) (8) (9) (10 ) IX IV II VIII (6) (5) (4) V (7) VII
Hnh 2.8. S cng ngh lm kh kh bng phng php hp th glycol (DEG) 1: thit b tch nc; 2: thp hp th; 3, 8: thit b trao i nhit; 4: thit b lm lnh; 5: bm; 6: bn cha DEG; 7: thit b thi kh (thp phong ha); 9: thp gii hp th; 10: thit b ti sinh hi. I: kh m; II: nc; III: kh sy kh; IV: DEG bo ha hi nc; V: DEG ti sinh (hon nguyn); VI: hydrocacbon; VII: hi nc; VIII: DEG b sung; IX: cht ti nhit. Trn hnh 4.8 trnh by s nguyn l cng ngh sy kh kh bng phng php hp th. Dng kh m a vo thit b 1, mt phn nc c tch ra khi y thp 1. Dng kh i ra khi nh thit b 1 c a vo y thp hp th 2, cn dng glycol ti sinh (DEG) s c a vo mm trn ca thit b ny. Trong thp 2 c cc mm chp (hoc mm van) v c g chy trn, kh i ln qua cc chp cn DEG lng i xung chy qua g chy trn, hi nc trong dng kh s c DEG hp th, do nh thp 2 ta thu c dng kh kh. y thp 2 l dng glycol bo ha hi nc c a vo thit b trao i nhit 3 v sau a vo thp thi kh 7, ti y s tch phn hydrocacbon b hp th. Tip theo glycol c un nng trong thit b trao i nhit 8 v thit b gii hp 9. T pha trn ca thit b 9 s ly ra hi nc, phn cn li pha di chnh l glycol ti sinh c lm ngui trong thit b trao i nhit 8, 3 v sinh hn 4 i vo bn cha 6 t dy bng bm 5 s i vo thit b hp th 2. Yu t nh hng ln nht n lng gim im sng ca kh l nng glycol a vo thp hp th. Hm lng glycol trong thp hp th do nhit hon nguyn xc nh. nhit cao hn 164,40C DEG b phn hy mt phn, cn TEG phn hy mt phn 206,70C. Khi hon nguyn glycol p sut kh quyn thc t khng th nhn c dung dch vi hm lng ln hn 97 98% khi lng. V vy glycol thng hon nguyn trong chn khng. nhn c glycol nng trn 99% khi lng bn cnh hon nguyn chn khng cn s dng rng ri phng php hon nguyn glycol bng kh thi, nh thu 31
c glycol hm lng 99,5 99,9%. Kh thi thng s dng l kh thin nhin loi xng. ng dng hon nguyn ng ph c th nhn c glycol nng cao (trong trng hp ny i hi nhit thp hn). Nhit si ca cht ng ph cn phi thp hn nhit phn hy cht lm kh. Cht ng ph cho DEG v TEG l benzen, toluen hoc xylen (chng c a vo pha di thp gii hp).
VI III V (7)
(11)
(5) (2) VII (4)
(6)
(8)
(10)
(13) VIII (12) (14) IX
(15)
(3) IV (1) I (16)
(9) V
II
Hnh 2. S cng ngh lm kh kh dng phng php hp th bng glycol vi h thng ti sinh chn khng 1: thit b tch nc; 2: thit b hp th; 3, 9, 12: bm; 4: thng cha glycol; 5: thit b lm lnh; 6, 8: thit b trao i nhit; 7: thit b thi kh; 10: thp gii hp th; 11: thit b ngng t; 13: Bn cha cht lng ngng t; 14: thit b ti sinh hi; 15: bm chn khng. I: kh m; II: nc; III: kh sy kh; IV: glycol bo ha; V: glycol ti sinh; VI: hydrocacbon; VII: glycol b sung; VIII: kh thi ra kh quyn; IX: cht ti nhit. Trn hnh 4.9. trnh by s nguyn tc cng ngh sy hp th kh vi s ti sinh chn khng glycol. Dng kh m c a vo pha di ca thp hp th 2, cn glycol m c c bm vo mm trn cng ca thp ny. Kh sy kh i ra t pha trn, cn pha di i ra l glycol bo ha hi nc. ti sinh, dung dch glycol c un nng trong thit b trao i nhit 6, sau c a vo thp thi kh 7 tch hydrocacbon. Tip theo s i qua thit b trao i nhit 8 v i vo phn gia ca thp ti sinh 10 c p sut t 10 - 13 KPa. Nh hi nc trong thit b ti sinh hi 14, nhit ca phn y thit b ti sinh c duy tr trong khong 190 - 204 0C. Di nhng iu kin ny t TEG nc s bc hi v nng ca n s t 99,5% khi lng. Glycol ti sinh c ly ra t pha di ca thit b ti sinh bng bm 9, sau qua 32
cc thit b trao i nhit 8, 6 v thit b sinh hn 5, ri i vo thng cha 4. T y bng bm 3 c a vo pha trn ca thp hp th 2. Nhit ca thp hp th l 300C. Nng TEG bng 99 - 99,5% khi lng. im sng ca khng kh gim t -18 -250C. thu c glycol c nng > 99% khi lng, ngoi phng php ti sinh chn khng, cn s dng rng ri phng php thi kh (stripping gas). Kh thi ny l kh sch (kh khng cha xng v cc cht hu c). Tc dng ca kh thi lm gim p sut hi trn b mt cht lng do s thc y s bc hi nc t dung dch.
III
IV
V (4)
IX (7) VI
(2)
VII (5) VIII (6)
(8)
(1) I II XI
XII
VII (3)
Hnh 2.10. S quy trnh lm kh kh s dng phng php hp th bng TEG 2 giai on. 1: thit b tch nc; 2: thp hp th; 3: thit b thi kh; 4: bn cha pentan; 5, 6: thit b sinh hn; 7: thp gii hp th 1; 8: thp gii hp th 2. I: kh m; II: nc; III: kh sy kh; IV: pentan sch; V: hn hp pentan v TEG; VI: TEG thu hi; VII: TEG ti sinh hon ton; VIII: TEG ti sinh mt phn; IX: hi nc; X: kh thi vi nhit 2040C; XI: TEG bo ha hi nc; XII: hydrocacbon. c im ca thp hp th ny l hai ngn, v cu to cc ngn ny ging nhau, nhng mm trn ca ngn trn (thng l mm th 2) s a glycol m c hn so vi mm trn ca ngn di. Nng ca glycol a vo ngn trn l 99,95% khi lng, cn ngn di l 99%. Kh i vo pha di ca thp hp th 2, c sy kh mt phn ngn u v sau t im sng tng i thp ngn th hai (c th t n -84 0C khi kh i ra khi thit b hp th). S ti sinh glycol trong trng hp ny c nhng c im sau: nc c chng tch trong hai thit b, u tin trong ct gii hp th 7 (ti y nng glycol t n 99%) v trong ct 8 (nng glycol nng ln 99,95%) nh h 33
thng thi kh nng. p dng cng ngh ti sinh hai giai on cho php tit kim nhin liu, gim tiu hao nng lng kh nng, c bit khi sy kh c hm lng m cao. Trong cng ngh ny, hng Pritchard s dng pentan ra cht hp th, ng thi trnh s tht thot TEG cng vi kh thi ra ngoi. 2.4.2. Cc phng php hp ph Cc phng php hp ph cho php t im sng n -85 -1000C. Hp ph l qu trnh tp trung cc cht trn b mt hoc trong khng gian ca cc vi l xp ca cht rn. Cc cht hp ph thng l oxit nhm (Al2O3), zeolit (natri hoc kali silicat). Cc cht hp ph c b mt ring rt ln (500 800 m2/g) v b mt ny c to thnh t cc mao qun hay mng tinh th. Cc qu trnh hp ph c th thc hin gin on trong cc thit b c tng hp ph c nh, v nguyn tc h thng thit b hp ph phi cha ti thiu 2 thit b hp ph tr ln: trong mt thit b ng vai tr hp ph, thit b th hai ng vai tr gii hp v khi cn thit thit b th ba ng vai tr lm ngui cht hp ph. Trong cc thit b cng nghip th cht hp ph c ti sinh bng cch thi kh ng hnh hay kh thin nhin qua n (i khi ngi ta cn s dng c kh tr). ti sinh cht hp ph, ngoi tr zeolit, kh c t nng n 176 2040C. Zeolit c ti sinh nhit 316 3700C. Th tch kh ti sinh vo khong 5 15% so vi tng cng sut ca thit b sy. Thi gian ca mt chu trnh sy thng l 8, 12, 16 hoc 24 gi. Thi gian lm vic ca cht hp ph t 2 5 nm. 2.4.2.1. Gii thiu v thp hp ph (hnh 2.11) 2.4.2.2. S nguyn tc qu trnh lm kh kh bng cht hp ph 1, 6: thit b tch lng; 2, 5: thit b trao i nhit; 3: thp hp ph; 4: thp gii hp. I: kh m; II, VI: nc; III: kh sy kh; IV, V: kh trc v sau khi ti sinh.
(1)
II I
(2)
(3)
(4) (6) VI (5)
IV
III
Hnh 2.12. S nguyn tc qu trnh lm kh kh bng cht hp ph 34

IV
(2) I (1) (5) (6) (7) (8)
II
(3) (4) V III
Hnh 2.13: S nguyn tc qu trnh lm kh kh bng cht hp ph rn vi chu trnh ti sinh h - phng n 1 1, 3: thit b tch nc; 2: thit b iu chnh lu lng; 4: thit b sinh hn; 5: thit b hp ph; 6: thit b ti sinh; 7: thit b lm ngui; 8: thit b gia nhit. I: kh m; II, V: nc; III: kh sy kh; IV: kh m lm ngui. c im: gii hp v lm lnh thc hin bng kh m. u im: nhit ca kh ti sinh i ra t thit b hp ph (thit b lm ngui) c s dng t nng kh ti sinh i vo thit b hp ph giai on ti sinh. Nhc im: s dng kh m s dn n bo ha mt phn cht hp ph bng hi m.
(2) (1) I (5) (6) (7) (8)
II IV
(9) (3) (4) III V
Hnh 2.14: S nguyn tc qu trnh lm kh kh bng cht hp ph rn vi chu trnh ti sinh h - phng n 2 1, 3: thit b tch nc; 2: thit b iu chnh lu lng; 4: thit b sinh hn; 5: thit b hp ph; 6: thit b ti sinh; 7: thit b lm ngui; 8: thit b gia nhit; 9: thit b trao i nhit. I: kh m; II, V: nc; III: kh sy kh; IV: kh m ti sinh. 35
c im: gii hp v lm lnh thc hin bng kh m.

IV V (2) (5) I (1) (6) (8) 10 II (3) (7)
(4)
(9) III
VI
Hnh 2.15: S nguyn tc qu trnh lm kh kh bng cht hp ph rn vi chu trnh ti sinh h - phng n 3 1, 3: thit b tch nc; 2, 10: thit b iu chnh lu lng; 4: thit b sinh hn; 5: thit b hp ph; 6: thit b ti sinh; 7: thit b lm ngui; 8: thit b gia nhit; 9: thit b trao i nhit. I: kh m; II, VI: nc; III: kh sy kh; IV: kh m ti sinh; V: kh kh lm ngui. c im: gii hp bng kh m, lm ngui bng kh kh. Phng n ny cho php thu c kh c hm lng m thp hn, tuy nhin chi ph kh ti sinh ln hn.
IV V (9)
(1)
(5)
(7)
(6)
II (2) III (8) (4)
(3)
VI
(10)
Hnh 2.16: S nguyn tc qu trnh lm kh kh bng cht hp ph rn vi chu trnh ti sinh kn 36
1, 3: thit b tch nc; 2: thit b iu chnh lu lng; 4: thit b sinh hn; 5: thit b hp ph; 6: thit b ti sinh; 7: thit b lm ngui; 8: thit b trao i nhit; 9: thit b gia nhit; 10: thit b thi kh. I: kh m; II, VI: nc; III: kh sy kh; IV: kh ti sinh; V: kh kh lm ngui. S gii hp hi m t lp hp ph c thc hin bng kh kh tun hon trong h thng (nh h thng thi kh), cht hp ph c lm ngui bng kh sy kh. Chi ph u t v vn hnh ca phng n ny so vi chu trnh ti sinh h. Tuy vy n thng c chn s dng do tnh n nh ca qu trnh v mc sy kh t hiu qu cao. 2.4.2.3. u nhc im ca phng php hp ph u im: Phng php hp ph cho php h im sng thp hn so vi phng php hp th (c ngha l gim im sng cao hn t). Qu trnh ca phng php hp ph n gin hn. Kh nng ti sinh ca qu trnh hp ph t hiu qu cao hn trong 1 khong thay i cc thng s k thut rng. Nhc im ca phng php hp ph: Chi ph u t cho cc thit b c nng sut ln cao. Chi ph vn hnh ln. Cc qu trnh l gin on (khng c qu trnh lin tc). Sau thi gian s dng cht hp ph mt hot tnh.
37
CHNG 3: LM SCH KH
3.1. Khi nim chung Kh du m v kh thin nhin bn cnh thnh phn chnh l hydrocarbon cn cha cc kh chua - kh cacbonic, dihydrosunfua v cc hp cht lu hunh hu c: COS, CS2, mercaptan (RSH), tiophen v cc hn hp khc, lm phc tp qu trnh vn chuyn v s dng kh trong iu kin xc nh. S hin din ca CO2, H2S, RSH to iu kin xut hin n mn kim loi, chng lm gim hiu qu ca cc qu trnh xc tc v u c xc tc. CO2, H2S, RSH l cc cht c. Tng hm lng CO2 cn lm gim nhit lng chy ca nhin liu kh, gim hiu qu s dng h thng dn kh chnh do tng t trng v ch. Thc t cho thy vi hm lng khng ng k mt s hp cht c th lm thay i c bn cch la chn dung mi hoc qu trnh lm sch kh. T l H 2S: CO2 trong kh nguyn liu (hm lng dihydrosunfua trong kh chua) c ngha quan trng trong vic chn qu trnh v cng ngh lm sch nguyn liu v kh nng tn dng cc nguyn t ph liu. Cc chuyn gia hng Fluor Cooperation cho rng theo phng php Clause c th x l kh chua vi hm lng hydrosunfua ln hn 15% th tch. Trong mt s s Clause hm lng H2S trong kh chua t ti 50% th tch. v cao hn (ngha H2S : CO2 1). Vi hm lng H2S v CO2 thp trong kh nguyn liu nhn c kh chua c hm lng hydrosunfua cao s dng thit b lm sch chn lc kh, trong giai on u thu hi ch yu l hydrosunfua v nhn c nguyn liu tt iu ch lu hunh, cn trong giai on hai thu hi CO2 v lng hydrosunfua cn li. Tiu chun v cht lng i vi kh thin nhin v kh du mt s nc nh sau: Nga hm lng hydrosunfua khng c cao hn 22 mg/m 3, mercaptan - 36 mg/m3 kh; M hm lng hydrosunfua khong 5,7 mg/m 3, hm lng CO2, tng hm lng lu hunh v mercaptan do cc cng ty vn chuyn kh qui nh v ph thuc vo yu cu ca khch hng (hm lng CO2 l 1 2% th tch, mercaptan: 1,5 5 mg/m3, tng lu hunh: 22 228 mg/m3) lm sch H2S, CO2 v cc hp cht ph cha lu hunh, oxy trong kh thin nhin v kh ng hnh ng dng phng php hp th l chnh. Ph thuc vo kh nng tng tc ca cc hp cht ny vi dung mi - cht hp th c chia thnh cc nhm sau:
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Qu trnh hp th ha hc lm sch kh bng cc dung mi l dung dch nc alkanolamin: monoetanolamin (MEA), dietanolamin (DEA), diglycolamin (DGA)..., t c s trn phn ng ha hc ca cc hp cht khng mong mun vi alkanolamin. Qu trnh amin cho php lm sch n mc tinh hydrosunfua v kh cacbonic cc p sut v hm lng ca chng trong nguyn liu khc nhau; ha tan ca hydrocarbon trong trong cht hp th khng cao. Cng ngh v thit b ca cc qu trnh n gin v ng tin cy. Khuyt im chnh ca qu trnh: khng lm sch hon ton H2S, CO2, RSH, COS v CS2 trong kh; mc loi mercaptan v cc hp cht lu hunh thp; mercaptan, COS v CS2 tng tc vi mt s dung mi to thnh cc hp cht ha hc khng th hon nguyn trong iu kin phn ng; qu trnh thc hin c cn c bi s hi lu cht hp th cao v chi ph nhit nng ln; cht hp th v sn phm tng tc vi cc hn hp cha trong nguyn liu trong khng t trng hp to thnh cc cht c hot tnh n mn cao. Khi tng hm lng hot cht v mc bo ha ca hydrosunfua v cc hp cht khng mong mun khc trong dung mi hot n mn ca cht hp th alkanolamin tng. V vy, kh nng hp thu ca chng thng khng cao do iu kin cn bng nhit ng hn ch m do gii hn mc bo ha kh chua cho php ca cht hp th. Qu trnh lm sch kh bng phng php hp th vt l cc hn hp khng mong mun bng cc dung mi hu c: propylencarbonat, dimetyl ter polyetylenglycol (DMEPEG), N - metyl pyrolidon... Chng da vo s hp th vt l, ch khng phi phn ng ha hc. Cc dung mi hu c v c bn c th c s dng lm sch hon ton H2S, CO2, RSH, COS v CS2 trong kh vi nng cao; cc cht hp th ny khng to bt v khng n mn thit b, nhiu cht hp th c nhit ng bng thp. Khi hm lng tp cht cao thc hin qu trnh lm sch bng dung mi hu c i hi u t v chi ph sn xut thp hn so vi qu trnh hp ph ha hc amin, v kh nng hp thu ca dung mi hu c t l thun vi p sut ring phn ca kh chua v cc hn hp khng mong mun khc. Hon nguyn cc cht hp th vt l trong nhiu trng hp khng cn phi gia nhit m nh h p sut trong h. Khuyt im c bn ca cc qu trnh ny l: dung mi hp ph tt hydrocarbon. Qu trnh lm sch kh bng dung mi l hn hp dung dch nc ca alkanolamin vi dung mi ha c - sunfolan, metanol... Chng t c s trn vic hp th vt l cc hp cht khng mong mun bng cc dung mi hu c v tng tc ha hc vi alkanolamin. Cc qu trnh ny c nhiu u im v hp th ha hc v vt l. Chng c th c ng dng lm sch n mc tinh H2S, CO2, RSH, COS v CS2. Khuyt im c bn ca cc qu trnh ny l: dung mi hp th tt hydrocarbon (c bit l hydrocarbon thm), iu ny lm hn ch lnh vc ng dng ca qu trnh nhm hai v ba.
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Tm li, ta dng phng php hp th ha hc: c phn ng ha hc xy ra gia dung mi v cc cht b hp th nh CO2, H2S, mercaptan. Dung dch hp th l cc alkanolamin. MEA (Mono etanolamin) DEA (Di - etanolamin) TEA (Tri - etanolamin) DIPA (Di - iso - propanolamin) DGA (Di - glycolamin) Dng phng php hp th vt l: khng xy ra phn ng ha hc gia dung mi v cht hp th. Cc dung mi thng s dng l: Propylencacbonat N - metyl pirolidon. Hp th kt hp: thng dng dung mi ha hc v dung mi vt l: Alkanolamin + sulfolan Alkanolamin + metanol. 3.2. Phng php hp th bng alkanolamin Dung dch MEA (HO-CH2-CH2-NH2). C tnh baz mnh nht trong cc amin, tc dng vi CO2, H2S vi tc nhanh so vi cc cht khc. Kh nng hp th H2S cao hn CO2. L cht hp th khng c tnh chn lc (mc d hp th H 2S cao hn CO2 nhng khng r rng). Khi lng phn t thp nht nn mang kh acid l tt nht. C p sut hi cao nht trong cc loi amin, kh nng thu hi km nht. MEA c kh nng lm sch CO2 v H2S nhng nng khc nhau. Mt vi tp cht COS, CS2, SO2 khi tng tc vi MEA th to thnh cc hp cht cao phn t khng ti sinh c hoc kh ti sinh nn kh nng mt mt MEA cao. MEA khng n mn pH = 8 - 10, nhng khi MEA bo ha kh acid CO 2, H2S, pH ca dung dch gim s gy n mn. Dung dch DEA (HO-CH2-CH2-NH-CH2-CH2-OH) thng s dng nhiu nht. C hot tnh km hn so vi MEA. Kh nng n mn cng thp hn (khi c mt kh acid). Kh nng phn ng ca DEA so vi COS v CS2 thp hn MEA. Kh nng mt mt thp hn MEA. Dung dch TEA [(HO- CH2- CH2)3N] 40
Phn t lng ln. Kh nng phn ng km. Dung dch c hot tnh km, khng c kinh t nn t dng. Dung dch DGA (HO-CH2-CH2-O-CH2-CH2-NH2)
p sut hi bo ha thp nn d thu hi. Kh nng tng tc vi kh acid tng ng vi DEA. Dung dch MDEA (Metyl di etanolamin) [(HO-CH2-CH2)2N-CH3] C kh nng hp th chn lc gia H2S v CO2. C th thu hi H2S sn xut S v H2SO4. Dung dch DIPA (Di-iso-propanolamin): (HOC3H6)2NH
Kh nng hp th CO2 km hn MEA khi tng tc vi CS2, COS, RSH to thnh nhng cht d ti sinh, gim mt mt so vi MEA.
MEA T0s (0F) T0 (0F) M (g) (g/cm3) 338,9 50,9 61,08 1,018 DEA 516,2 82,4 105,14 1,095 TEA 680 72,3 148,19 1,124 DGA 430 9,5 105,14 1,058 DIPA 479,7 107,6 133,19 0,999 MDEA 477 -5,8 119,17 1,0426
Bng 3.1. Tnh cht vt l ca mt vi dung mi alkanolamin c im ca phng php hp th ha hc bng alkanolamin Cc phn ng ha hc l ta nhit v thun nghch H < 0 2R- NH2 + H2S (RNH3)2S H < 0 (R-NH3)2S + H2S 2RNH3 HS H < 0 2R- NH2 + CO2 + H2O (RNH3)CO3 H < 0 (RNH3)CO3 + CO2 + H2O 2RNH3HCO3 nhit thp phn ng xy ra t tri sang phi hp th. nhit cao phn ng xy ra t phi sang tri gii hp. C kh nng lm sch H2S v CO2 trit c nng thay i trong 1 khong rng. Quy trnh cng ngh n gin, d vn hnh. Kh nng hp th cc hydrocacbon thp. Nhc im ca phng php hp th ha hc bng alkanolamin Mt s amin khi tc dng vi COS, CS2, RSH s to ra nhng cht kh ti sinh, gy mt mt dung mi .
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C hin tng to bt nn kh nng hp th km, nn phi dng cht chng to bt. Khi bo ha kh acid s gy n mn, v vy khi vn hnh s dng nng cao phi s dng cht chng n mn.
3.3. S quy trnh cng ngh lm sch kh bng dung dch ankanolamin 3.3.1. Qu trnh lm sch kh bng dung dch MEA
Hnh 3.1. S cng ngh lm sch bng dung dch MEA 1, 2: thit b tch lng; 3: thit b hp th; 4, 5, 13: bm; 6: thit b lm lnh bng khng kh; 7: thit b tch nhanh (flash tank); 8: thit b lc; 9: thit b trao i nhit; 10: thp ti sinh; 11: thit b ngng t; 12: bnh cha hi lu (thit b tch ba pha); 14: ni si li; 15: bn cha alkanolamin. I: kh chua; II: kh ngt; III: etanolamin bo ha kh axit; IV: etanolamin ti sinh; V: kh phn ly (hydrocacbon); VII: kh axit; VIII: cht ti nhit. Dung mi c ng dng l dung dch nc monoetanolamin. Hm lng MEA trong dung dch khng cao hn 15 20% th tch, do khi bo ha kh chua dung dch c hm lng cao hn s lm tng tc n mn kim loi. Kt hp s dng vi cht c ch n mn c th tng nng MEA n 30% v lm tng hiu qu ca qu trnh lm sch MEA. u im ca qu trnh: lm sch n mc tinh H2S v CO2 trong khong bin thin ca p sut ring phn kh chua thay i rng. Monoetanolamin c bn ha hc cao, d hon nguyn, c kh nng phn ng cao. Cng ngh v thit k n gin
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v c tin tng cao. Dung dch MEA ha tan hydrocarbon km do tng hiu qu sn xut lu hunh t kh chua. Nhc im ca qu trnh: mc bo ha ca dung dch cht hp th thp, chi ph cht hp th v chi ph sn xut cao. Mt s hp cht (CO 2, COS, CS2, HCN, SO2 v SO3) cha trong kh tng tc vi dung mi to thnh hn hp khng hon nguyn c hoc cc hn hp phn t lng cao kh hon nguyn, dn ti u c cht hp th, tng to bt v hot tnh n mn. Nu trong kh c cha COS v CS2 qu trnh ny khng c ng dng, kh nng thu hi mercaptan v cc hp cht lu hunh hu c km. Nu trong h c hydrocarbon bo, sunfua st, tiosunfit v cc sn phm khc ca qu trnh phn hy MEA, cng nh cc hp cht c hc v cht c ch kh nng to bt ca cht hp th tng. Hnh 3.1 l s cng ngh lm sch bng dung dch nc alkanolamin. Kh nguyn liu vi nhit 10 400C c a vo mm di ca thp hp th 3, ti n c ti bng dung dch MEA hoc alkanolamin khc. Kh sch thot ra t nh thp, cht hp th bo ha kh chua thot ra t y thp (nhit cht hp th bo ha l 55 600C, p sut trong thp thay i trong khong 0,2 5,5 MPa). Kh sch sau thp tch 3 c a i s dng. Cht hp th bo ha i vo thp tch 7, ti nh tit lu dung dch nn kh hydrocarbon tch ra khi cht hp th. Sau thp tch 7 cht hp th bo ha c gia nhit trong trao i nhit 9 n nhit 95 1000C v c dn vo phn gia ca thp gii hp 10, ti kh chua, nc v cc hydrocacbon cn li bay hi v tch ra khi cht hp th. Nhit trong phn ni chng di thp gii hp 10 gi khong 115 1300C nh nung nng dung mi ly ra t mm di ca thp gii hp trong ni si li 14 (p sut trong thp gii hp l 0,15 MPa). Hn hp kh chua, hi nc v hydrocarbon tch ra t nh thp gii hp 10 c lm lnh trong thit b lm lnh bng khng kh (11), sau hn hp hai pha c a vo b tch 12, nc tch ra khi kh chua v hydrocarbon, nc t b 12 c a i ti mm trn ca thp gii hp nhm hn ch MEA b cun ra cng vi sn phm nh, cn kh chua a i sn xut lu hunh. Dung dch hon nguyn alkanolamin sau khi lm lnh trong trao i nhit 9, qua thit b lm lnh bng khng kh (6), c a vo thp hp th 3 vi nhit 35 450C. Hnh 3.2 l s cng ngh lm sch bng dung dch nc alkanolamin kiu tch dng. 1: thp hp th; 2: thp gii hp th; 3, 4, 9: thit b lm lnh bng nc; 5, 7: thit b trao i nhit; 8: bm; 10: bnh cha hi lu (thit b tch ba pha); 11: ni si li. I: kh chua; II: kh sy kh; III: dng MEA bo ha kh axit; IV: MEA ti sinh hon ton; V: MEA ti sinh mt phn; VI: kh axt; VII: cht ti nhit.
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Hnh 3.2. S cng ngh lm sch bng dung dch alkanolamin kiu tch dng
Hnh 3.3. S cng ngh lm sch bng dung dch MEA vi cc thng s nhit 1: thp hp th; 2: bnh cha MEA; 3: thit b tch nhanh (flash tank); 4, 11: thit b lm lnh; 5, 6: thit b trao i nhit; 7: thit b lc; 8: bm; 9: thp gii hp th; 10: thit b lm lnh bng khng kh; 12: bnh cha hi lu (thit b tch ba pha); 13: ni si li. I: kh chua; II: kh sy kh; III: dng MEA bo ha kh axit; IV: MEA ti sinh; V: kh phn ly (hydrocacbon); VI: kh axt, nc v hydrocacbon; VII: kh axit; VIII: nc; IX: cht ti nhit.
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Hnh 3.3 l s cng ngh lm sch bng dung dch nc alkanolamin. Kh nguyn liu vi nhit 10 400C c a vo mm di ca thp hp th 1, ti n c ti bng dung dch MEA (nng 20% khi lng). Kh sch thot ra t nh thp, cht hp th bo ha kh chua thot ra t y thp (nhit cht hp th bo ha l 1360F). Kh sch sau thp tch 1 c a i s dng. Cht hp th bo ha i vo thit b tch nhanh 3, ti nh tit lu dung dch nn kh hydrocarbon tch ra khi cht hp th. Sau thp tch 3 cht hp th bo ha c gia nhit trong trao i nhit 5 n nhit 1600F v tip tc c gia nhit trong thit b trao i nhit 6 n 200 0F, sau c dn vo nh ca thp gii hp th 9, ti kh chua, nc v cc hydrocacbon cn li bay hi v tch ra khi cht hp th. Nhit trong phn ni chng di thp gii hp 9 gi khong 2400F nh nung nng dung mi ly ra t mm di ca thp gii hp trong ni si li 13. Hn hp kh chua, hi nc v hydrocarbon tch ra t nh thp gii hp 9 (nhit khong 2200F) c lm lnh trong thit b lm lnh bng khng kh 10 n nhit 1400F v thit b lm lnh bng nc 11 n 1000F, sau hn hp hai pha c a vo b tch 12, nc tch ra khi kh chua v hydrocarbon, nc t b 12 c a i ti mm trn ca thp gii hp nhm hn ch MEA b cun ra cng vi sn phm nh, cn kh chua a i sn xut lu hunh. Dung dch hon nguyn alkanolamin sau khi lm lnh trong trao i nhit 6 v 5, qua thit b lm lnh bng nc (4), c a vo thp hp th 1 vi nhit 900F. 3.3.2. Qu trnh lm sch kh bng dung dch DEA Qu trnh lm sch bng dung mi dietanolamin (DEA). Nng DEA trong dung dch ph thuc vo hm lng kh chua trong nguyn liu v mc bo ha dung dch thay i t 20 30% khi lng, vi nng kh chua 0,05 0,08 m3/m3 s dng dung dch 20 25% DEA, vi hm lng kh chua 0,14 0,15 m3/m3 s dng dung dch DEA t 25 27%, vi nng kh chua 0,15 0,17 m3/m3 nng dung dch DEA l 25 30% (qu trnh SNPA). Vic s dng nng dung dch DEA cao cho php tng bo ha kh chua ca dung dch v do u im ca qu trnh l: mc bo ha dung dch trong qu trnh SNPA t ti 1 1,3 mol/mol DEA (so vi 0,3 0,4 i vi qu trnh MEA). u im ca qu trnh SNPA cho php lm sch n mc tinh H 2S v CO2 vi s hin din ca COS v CS2, dung dch DEA bn ha hc trong iu kin phn ng v d hon nguyn v c p sut hi bo ha thp. Cng ngh v thit k n gin v tin cy cao, hp th tin hnh nhit cao hn qu trnh lm sch MEA 10 200C, cho php ngn nga s to bt mnh ca dung dch khi lm sch kh c cha hydrocarbon nng vi hm lng cao. Nhc im ca qu trnh l kh nng hp th ca dung mi thp, chi ph ring ca cht hp th v sn xut cao, mt s hp cht cha trong kh tc dng vi dung
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mi (tc dng mt phn vi CO2 v han ton vi HCN) to thnh hn hp khng th hon nguyn v kh nng lm sch mercaptan v cc hp cht lu hunh hu c thp. S cng ngh cc qu trnh lm sch DEA tng t MEA (hnh 5.1). 3.3.3. Qu trnh AIDP Dung dch nc diisopropanolamin (DIPA) c s dng lm dung mi. Hm lng DIPA trong dung dch c th t ti 40%. DIPA cho php lm sch tinh kh khi dihydrosunfua (n 1,5 mg/m3), diisopropanolamin ng thi cng lm sch CO2, COS v RSR. Hot ca dung dch DIPA i vi CO2 thp hn so vi MEA. Trong qu trnh lm sch c th loi 40 50% COS v RSR. Khi tng tc diisopropanolamin vi CO2, COS v RSR to thnh hp cht d hon nguyn. Trong trng hp s dng DIPA thit b c th c lm t thp cacbon. S cng ngh qu trnh lm sch MEA v ADIP thc t khng khc nhau, v vy s lm sch MEA c th d dng chuyn sang lm vic vi ADIP. 3.3.4. Qu trnh Econamin Dung mi l dung dch nc diglycolamin (DGA) vi hm lng 60 65% khi lng. Vi dung mi ny c th thc hin lm sch n mc tinh H 2S (ti 5,7 mg/m3). Khi diglycolamin tng tc vi CO2, COS, CS2 v mercaptan to thnh cc hp cht d hon nguyn (hot DGA i vi CO2 cao hn so vi MEA). Mc loi CO2, COS, CS2 v mercaptan trong kh cao. Mc bo ha dung dch DGA c th t ti 40 50 lt kh chua trong 1 lt dung dch (thay v 30 35 lt/lt trong qu trnh MEA). S cng ngh v ch lm vic ca qu trnh lm sch MEA v DGA tng t nhau. Thay th MEA bng DGA lm gim 25 40% chi ph ring cht hp th v chi ph nhit, in. 3.4. Quy trnh cng ngh lm sch kh bng dung mi vt l v tng hp Cc cht hp th c ng dng c nhit ha tan thp v kh nng hp th kh chua v cc tp cht khc cao. Kh nng hp th ph thuc nhiu vo p sut ring phn ca cc cht trong iu kin lm vic. Vi p sut ring ca dung mi thp kh nng hp thu rt thp. Vi p sut ring phn 5MPa v cao hn, dung mi vt l c u th hn hn so vi dung mi ha hc, tng p sut u th ca n tng. Tt c cc cht hp th vt l ha tan hydrosunfua v CO2, tuy nhin hiu qu ca mi cht hp th i vi H2S v CO2 khng ging nhau, v vy mt s cht c dng loi CO2 c li hn, mt s khc loi H2S, loi th ba lm sch la chn nguyn t ny vi s hin din ca nguyn t kia. 3.4.1. S quy trnh cng ngh ca qu trnh Fluor Cht hp th c ng dng rng ri l propylencacbonat. Propylencacbonat ha tan tt H2S, CO2, COS, CS2, RCH v hydrocacbon, n c tc dng n mn yu i vi
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thp cacbon thng thng, bn ha hc trong iu kin phn ng, c p sut hi bo ha thp. Hm lng kh chua trong kh sau x l l: CO2 - 2% th tch, H2S - 5,7 mg/m3. Qu trnh Fluor c th p dng lm sch kh thin nhin, kh ng hnh c hm lng CO2 cao v t l H2S : CO2 thp. iu kin thun li nht l khi p sut ring phn tng cng ca cc cu t axit trong nguyn liu ln hn 0,4 MPa. Hp th tin hnh trong khong nhit t 0 n -60C (lm lnh nh chu trnh lm lnh amoniac). Cng thc phn t
H3 C H C O C O CH2 O
Khi lng phn t
: 102
Khi lng ring 200C (kg/m3) : 1200 Nhit si (0C) Nhit nng chy (0C) : 242 : -49
Bng 5.2. Tnh cht vt l ca propylencacbonat
Hnh 3.4. S quy trnh cng ngh Fluor nm 1960 1: thp hp th; 2, 3: thit b phn ly; 4: thit b stripping; 5: my nn; 6: tuc bin; 7: tuc bin thy lc v b phn truyn ng. I: kh chua; II: kh lm sch; III: dung mi ti sinh; IV: dung mi bo ha kh axit; V: kh tun hon; VI: kh axit; VII: kh thi (stripping air).
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Hnh 5.4 l s cng ngh Fluor. Kh nguyn liu nn ti p sut 1000 2200 psi c a vo mm di ca thp hp th 1, ti n c ti bng dung dch propylencacbonat. Kh sch thot ra t nh thp, cht hp th bo ha kh chua thot ra t y thp. Kh sch sau thp tch 1 c a i s dng. Cht hp th bo ha i vo thit b gin n tuc bin 7, n thit b phn ly p sut cao (300 1000 psi) ti nh qu trnh gim p nn kh hydrocarbon v mt t CO2 tch ra khi dung dch v c tun hon tr li thp hp th. Dng lng i ra t y thit b phn ly 2 c tit lu trc khi vo thit b phn ly p sut trung bnh 3. Kh CO 2 c ly ra t nh thit b phn ly 3 qua tuc bin gin n 6 n p sut kh quyn v nhp cng dng t nh thp stripping 4. Dng propylencacbonat ti sinh t y thit b phn ly 4 c bm tun hon tr li thp hp th. 3.4.1.1. Cng ngh Fluor s dng nm 1974 Qu trnh s dng dung mi Propylen Cacbonat loi b kh CO2 v H2S. Hn hp kh c nn p sut cao 1000 2000 psi, sau n qua thit b trao i nhit vi kh nh thp hp th. Sau i vo y thit b hp th tip xc vi dng dung mi hp th i t trn xung, dng kh x l CO2 v H2S t thp hp th qua thit b trao i nhit vi dng nguyn liu vo v sau ri khi qui trnh.
Hnh 3.5. S quy trnh cng ngh Fluor nm 1974 Dung mi Propylen Cacbonat hp th CO2 v H2S t y ca thp hp th i qua tuc bin gin n thu hi mt lng cng do qu trnh gim p gy nn, sau a vo thit b flash drum p sut cao tch mt phn hydrocacbon cn ln trong dng b hp th cng CO2 v H2S. Thit b flash drum p sut cao ny hot ng 300 n 100 psi.
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Kh b hp th trng hp ny l mt s ng k hydrocacbon, CO 2, H2S. V vy ta phi c mt dng hon lu quay li thp hp th cng vi nguyn liu ban u trnh tht thot hydrocacbon. Dng dung mi cha gii hp kh acid i qua thit b trao i nhit, n van tit lu ri c bm vo thit b flash drum p sut thp. Ti thit b flash drum p sut thp mt phn kh acid c gii hp y v c bm ra ngoi i qua qu trnh x l khc. Cht lng t thit b flash ny n thit b stripper ni y n c tip xc vi kh thi gii hp kh acid nhm hon lu dung mi tr li qui trnh. Phn lng ca y stripper i qua bm dung mi tr li nh ca thp hp th thc hin mt chu trnh mi. 3.4.1.2. Cng ngh Fluor s dng hin nay (2004) Tch H2S v CO2 khi hm lng CO2 tng i thp v trung bnh Qu trnh ny c thit k s dng x l cho kh khi c p sut ring phn ca CO2 t 60 - 120 psi, trong khi p sut ca dng nhp liu l 1000 psi ti nhit thng. Nguyn liu c a vo qui trnh, c sy kh ti cm sy TEG loi b hon ton nc ngn nga nc ln trong kh. Sau khi tch nc, nc c thu hi, cn dng kh tip tc c a vo thit b hp th thc hin qu trnh hp th kh acid bng dung mi propylen cacbonat, kh axt b hp th gi li trong dung mi, dng i ra t nh thp l phn kh hydrocacbon c x l, n c a ra ngoi sau khi c lm lnh. Phn ny s c em i lm nguyn liu cho cc qu trnh sn xut tip theo. Yu cu thp hp th ny l nhit khng c qu cao do qu trnh hp th ch xy ra tt khi nhit thp. Sn phm hp th s c chuyn ra phn di y ca thp thng qua bm dng tuabin hi thu hi nng lng, sau c a vo pha di thp gii hp th. Thp gii hp th c thit k chia lm ba phn ring bit trong thp, phn di cng l phn p sut cao nhng cng nh hn so vi p sut ca thp hp th, phn gia thp l phn p sut trung bnh, phn trn cng ca thp l phn p sut thp. S d ngi ta thit k nh vy bi v qu trnh gii hp tng khi p sut gim. Tuy nhin, iu kin p sut y ch cho php gii hp phn hydrocacbon b hp th trong dung mi, trong qu trnh hp th kh axt th mt lng hydrocacbon cng b hp th theo. Phn hp th (bao gm dung mi, CO2, H2S ln mt s hydrocacbon b hp th) s c ly ra y thp gii hp th, kh hydrocacbon gii hp s c a n my nn tun hon, sau qua thit b lm lnh v c ly ra ngoi l sn phm condensate (kh hydrocacbon ngng t).
49
Hnh 3.6. Quy trnh cng ngh Fluor x l CO2 nng thp Phn lng ca thp gii hp p sut cao s c a ln thp gii hp p sut trung bnh, tip tc gii hp phn hydrocacbon cha gii hp, phn kh thu hi phn p sut trung bnh cng vi phn kh phn gii hp p sut cao c a vo my nn tun hon. Phn lng ca thp p sut trung bnh tip tc a ln phn gii hp p sut thp tch trit phn kh hydrocacbon cn li thu hi condensate, phn dung mi cha kh axt c a qua thp gii hp th vi p sut kh quyn v p sut chn khng, vn y l phn tht thot hydrocacbon trong phn dung mi ny bao nhiu l ph hp, theo nh thit k ca qui trnh ny th phn hydrocacbon mt mt khong 0,5 % l ph hp. Sau khi c a vo thp gii hp th hai ny th qu trnh gii hp th CO 2 v H2S xy ra v loi kh axt, ti sinh dung mi, nh hnh v th phn y ca phn gii hp vi p sut kh quyn s a ln phn gii hp vi p sut chn khng, phn y ca thit b gii hp chn khng l dung mi propylen cacbonat ti sinh c bm tun hon bm tr li nh thp hp th, phn kh c gii hp s em x l. u im ca qu trnh l d thc hin, nhng nhc im ca n l hp ph c hydrocacbon v vy cn phi thm mt thit b tch hydrocacbon, v qu trnh nu trn ch dng cho kh c p sut ring phn ca kh axt tng i nh 60 - 120 psi. Tch H2S v CO2 khi hm lng CO2 cao Khi hm lng CO2 cao th phi c mt qu trnh cng ngh ring bi v qu trnh hp th xy ra hon ton khng ging nh khi hm lng CO 2 thp. Lc ny i hi phi c thm cc thit b lm lnh lm lnh ti mc cc kh CO 2 c th hp th hon ton, ngoi ra cn phi c thm cc thit b tch nhanh (flash drum) lm cho cc dung mi hp th kh axt c th tch nhanh hn trong thp gii hp th. 50
V vy qu trnh c thit k s b nh sau (hnh 3.7), s cng ngh c cung cp bi cng ty Flour hin ang c p dng ti cng ty ny. Qu trnh thc hin khi p sut ring phn ca CO2 t 400 n 1200 psi. Hot ng ca qui trnh ny cng tng t nh s trn nhng m s lng cc flash drum nhiu hn tch trit hn v kh c lm lnh su hn qu trnh lm lnh trc khi a vo trong thp hp th. Bi v khi chng ta gim nhit xung th sc cng b mt v nht ca dung mi tng, cho nn thun li hn cho qu trnh hp th kh axt, ng thi qu trnh lnh lnh su dung mi s cho chng ta lng nhit lnh lm lnh ngng t condensate hay ngng t CO2.
Hnh 3.7. Quy trnh cng ngh Fluor x l CO2 nng cao Nguyn liu cho vo qu trnh u tin qua cm tch nc TEG vi dung mi trietylenglycol bng qu trnh hp th v loi b nc. Sau qua thit b trao i nhit lm lnh s b trc khi c lm lnh n nhit cho php thc hin c qu trnh hp th hon ton kh axt, dng kh sau khi qua thit b lm lnh t nhit khong -390C. Dng kh sau khi lm lnh kt hp vi dng hydrocacbon hon lu cho vo thp hp th cng dng cht hp th hon lu chy t trn xung s tin hnh hp th cc kh axt theo c ch hp th vt l, sn phm nh l kh x l, sn phm y l dung mi bo ha kh axt qua bm v cho vo thp gii hp th nht, y tin hnh gii hp cc hydrocacbon b hp th trong qu trnh hp th v y s dng dung mi propylen cacbonat n hp th c hydrocacbon, iu kin y s c khng ch cho qu trnh ch gii hp hydrocacbon mc ti a m khng gii hp kh axt. 51
y thit b gii hp hydrocacbon, s c thit k theo kiu gim dn p sut khi cho gii hp tng t nh cng ngh nu trn, nhng c s khc bit so vi cng ngh trn l dng hon lu t y thp p sut cao ln thp gii hp p sut trung bnh c gia nhit. Sn phm nh ca 3 phn trong thp gii hp c a n my nn ly ra ngoi sau khi c lm lnh v ngng t (condensate), sn phm y ca thp gii hp th 1 cha nhiu kh axt s c a qua thp gii hp kh axt v hon lu dung mi, tuy nhin y khc vi qu trnh trc ch nhiu thit b flash drum hn. Ra khi qui trnh l kh x l, condensate v phn kh axt c lm lnh trc khi i ra ngoi. Tch H2S v CO2 khi hm lng H2S cao Khi hm lng H2S tng th i hi phi c mt qui trnh mi loi b n nhm p ng yu cu ca sn phm. Kh x l theo tiu chun phi t hm lng H2S t 4 - 50 ppmv (phn triu th tch).
Hnh 3.8. Quy trnh cng ngh Fluor x l H2S nng cao s cng ngh ny c mt thit b stripper hot ng di p sut chn khng, n dng ti sinh dung mi v c nhim v loi b kh axt mt cch trit . Thit b ny nhn dng trc tip t thp gii hp hydrocacbon p sut trung bnh, phn ny nhiu CO2, mt s hydrocacbon nh v cng nhiu H2S t do, n c stripping a kh axt ra bn ngoi v ti sinh dung mi, mt phn na m n nhn vo l t thp stripper kh quyn. Phn stripper kh quyn s khng th tch ht kh axt ly t phn gii hp hydrocacbon p sut thp thp gii hp, kh H 2S c loi b v sau c cho qua cc xng x l lu hunh trc khi tng p n p sut kh quyn.
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Lng H2S mt mt s tng nu hm lng H2S trong kh nguyn liu tng, v vy trong qu trnh ny s mt mt mt lng hydrocacbon ln hn. u nhc im ca qu trnh Fluor Qu trnh Fluor c ng dng rng ri tch kh axt trong kh thin nhin v kh ng hnh n tng i n gin v cu to s cng ngh, hp th hu nh hon ton cc hp cht axt. Qu trnh Fluor khng tiu hao mt lng nhit ti sinh dung mi v mt s thng s na hn hn so vi cc qu trnh khc, sau y l so snh s b ca qu trnh Fluor vi hp th bng MDEA ( biu din qua biu ).
Hnh 5.9. Biu so snh qu trnh Fluor v MDEA Nhng qu trnh Fluor c mt s nhc im nh dung mi cho qu trnh tng i t tin v mt iu quan trng l lng hydrocacbon b mt mt do dung mi hp th kh ln. V vy m cn mt qui trnh gii hp c tnh ton k lng khng b tht thot hydrocacbon.
Hnh 3.10. Biu so snh v chi ph u t v vn hnh 53
3.4.2. S quy trnh cng ngh qu trnh Selexol Dung mi hp th c s dng l dimetyl eter polyetylenglycol (DMEPEG). Dung mi ny khng c, bn ha hc trong iu kin lm vic, khng c hot tnh n mn, d phn hy, c la chn cao v lm sch la chn H2S trong mi trng c CO2 ( 200C v 0,1 MPa ha tan ca H2S cao gp 10 ln so vi CO2). Qu trnh Selexol do Hng Elline Chemical Cooparation xut vo cui nhng nm 1960. Trong nhng nm 1970 qu trnh c p dng lm sch tinh kh thin nhin c nng hydrosunfua v CO2 trung bnh v cao (nh vo qu trnh ny c th lm sch n 97% H2S v 85% CO2). Ngoi kh chua DMEPEG cn ha tan tt hydrocarbon. iu ny hn ch lnh vc ng dng ca qu trnh - khng c giai on loi trc hydrocarbon nng - chng ch c ng dng lm sch kh kh. Kh H2 N2 CO C1 C2 CO2 C3 iC4 Selexol (DMEPEG) 0,047 0,10 0,24 1,52 3,63 3,70 6,79 Kh nC4 COS iC5 NH3 nC5 H2S nC6 CH3SH Selexol (DMEPEG) 8,46 8,46 16,2 17,7 20,1 32,4 39,9 82,4
Bng 3.3. hp th ca dung mi Selexol vi cc hydrocabon Dung mi DMEPEG c la chn cao v lm sch la chn H2S trong mi trng c CO2. c tnh ny c ngha thc t cao, c th ng dng qu trnh lm sch hai bc thu c nguyn liu tt cho qu trnh sn xut lu hunh trong bc 1 (kh chua c nng H2S cao) v trong bc 2 nhn c nguyn liu tt sn xut CO2 thng phm. V vy qu trnh Selexol l qu trnh c hiu qu cao nu c ng dng sn xut ng thi c hai sn phm. Qu trnh Selexol c tnh mm do cao - hm lng nguyn t chua trong kh nguyn liu c th thay i trong khong rng khng nh hng n cht lng qu trnh lm sch. Chi ph cht hp th khong 1m3/1000m3 kh nguyn liu. Cng thc phn t CH3(CH2CH2O)nCH3 Khi lng phn t : 280
Khi lng ring 200C (kg/m3) : 1000 Nhit si (0C) Nhit nng chy (0C) : 151 : 22 29
Bng 3.4. Tnh cht vt l ca DMEPEG 54
Ch cng ngh ca qu trnh hp th trong thit b Selexol nh sau: nhit i vi tng i tng dao ng trong khong t -150C n 100C, p sut gi trong khong 6,8 7 MPa. Hon nguyn cht hp th khi lm sch thc hin khng cn gia nhit m nh gim tng bc p sut trong h. Chi ph sn xut v u t ban u ca qu trnh Selexol thp hn so vi qu trnh MEA: chi ph sn xut gim 30%, u t gim 70%. H thng cng ngh qu trnh Selexol trnh by trong hnh 5.11.
210F
(IV)
750F
(VI)
(11) (II) 750F (2)
(12)
(8) 850F (I) (1) (3) 1000 psi (III) (4) 345 psi (5) 130 psi (6) 16 psi 400F
(10)
(11)
(V) (7)
(9)
Hnh 3.11. S quy trnh cng ngh Selexol (1): thit b trao nhit; (2): thp hp th; (3): bn cha p sut cao; (4): bnh tch p sut cao; (5): bnh tch p sut trung bnh; (6): bnh tch p sut thp; (7), (8): thit b gia nhit; (9): bm; (10), (12): turbin thy lc; (11): my nn. (I): Kh chua; (II): kh lm sch; (III): dng DMEPEG bo ha kh axit; (IV): dng DMEPEG ti sinh; (V): kh tun hon; (VI): kh axit. Qu trnh selexol vi t l CO2 v H2S cao Thc s qu trnh ny c thit k vi nng sut 275 triu ft 3/ ngy. Kh cha 43% CO2 v mt lng nh H2S (1grain/ 100 ft3 nguyn liu), (1grain = 0,0648 gram).
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Kh chua c tch nc a vo thit b hp th 1000 psi, t di ln tip xc vi dung mi sch t trn nh thp xung. Dung mi vo thit b hp th c lm lnh thit b trao i nhit sau khi tch ra khi thit b tch nhanh. Bi v hm lng CO2 cha trong kh nguyn liu ln nn, nn dung mi i vo thp c hai dng hon lu. Dung mi sch nht i vo nh thp v mt phn dung mi t thit b stripping c a vo gia ca thp. Dung mi bo ha t y thp hp th c tch p sut trung bnh 400 psi, kh i ra c nn p sut cao v tun hon tr li thp hp th. Dung mi i ra tip tc tch thit b tch nhanh cn li bng cch gim p sut n 200 psi, phn ln CO2 s c tch ra. Ti qu trnh ny nng lng sinh ra c s dng lm quay tuabin tn dng nng lng, kh CO 2 thot ra c s dng lm lnh kh nguyn liu ban u. Giai on tch th ba p sut kh quyn, tch phn kh axt ha tan vo dung mi. Dung mi i ra t thit b ny c bm mt phn vo gia thp hp th. Phn dung dch cn li cha mt lng H2S cn phi gia nhit tch chng. Dung mi sch c bm tun hon tr li thp hp th.
Hnh 3.12. S quy trnh Selexol vi t l CO2 v H2S cao Qu trnh Selexol tch H2S vi hm lng CO2 nh S (hnh 3.13) biu din qu trnh hot ng ca h thng lm sch kh vi hm lng CO2 thp, nhng hm lng H2S cao. Cacbondioxit trong kh nguyn liu 3,5% cn H2S khong 8grain/ 100ft3 kh, kh ngt ra khi thp c hm lng H2S ch cn 0,25 grain/ 100ft3, nu s dng dung mi thch hp th hm lng CO2 ch gim 3%. 56
Kh chua c loi H2O c a vo y thp hp th, dng kh i t di ln tip xc vi dung mi selexol sch 1000psi, nhit xp x vi nhit mi trng xung quanh. Dung mi bo ha kh axt i ra t y thp i qua ba thit b tch nhanh. Kh c gim p trong thit b tch nhanh p sut cao t 1000psi gim p sut n 300psi, kh thot ra hu ht l metan, c tun hon tr li dng kh nguyn liu ban u. Kh thot ra t thit b tch p sut trung bnh 175psi, c s dng lm nhin liu. Kh tch thit b tch p sut kh quyn l CO2, dng dung mi c a vo ct stripper. Ti y, ngi ta dng khng kh li cun loi trit H2S.
Hnh 3.13. Quy trnh Selexol tch H2S vi hm lng CO2 nh Tch kh axit vi nng H2S v CO2 tng ng nhau Hnh 3.14 m t qu trnh selexol lm ngt kh trong trng hp hm lng kh H2S v CO2 l tng ng nhau. Kh nguyn liu cha 18%CO2 v 8grain H2S/100ft3. Kh ngt ra khi thit b hp th vi hm lng 1,5% CO2 v 0,25 grain/ 100ft3.
Hnh 3.14. Quy trnh Selexol tch kh axit vi nng H2S v CO2 tng ng nhau
57
Kh ngt sau khi tch nc i vo thit b hp th, dng kh i t di ln tip xc theo nguyn tc ging nh nguyn tc hot ng ca s cng ngh loi kh axt vi t l H2S : CO2 cao trn. Giai on 1 dung mi c tch bng cch h p sut t 1000 250psi. Kh tch ra t thit b tch vi p sut cao ch yu l cc hydrocacbon v c tun hon tr li thp hp th. Kh thot ra t thit b tch p sut trung bnh 190psi c dng lm nguyn liu, cn kh thot ra t thit b tch p sut kh quyn l CO2 v H2S. Dung mi t qu trnh tch ny c gia nhit a qua ct stripping, dng khng kh tch hon ton H2S. Qu trnh selexol x l kh chua giu H2S S hnh 3.15 trnh by quy trnh selexol cho qu trnh x l kh chua giu H 2S (25% H2S). Quy trnh hot ng theo nguyn tc ging trn.
Hnh 3.15. Qu trnh selexol x l kh chua giu H2S S cng ngh selexol x l chn lc H2S Trong trng hp hp th chn lc H2S v sau hp th hon ton CO2 th cng ngh c hai h thng hp th v ti sinh hot ng c lp nhng lin tc trong mt qui trnh. S c biu din hnh 5.16. Quy trnh cng ngh ny c a ra bi Van Deraerschot, Valentine (1976) v c b sung nm 1980 bi Sweny. Cc tc gi cho rng: thit b khi c thit k chun nht th vic loi b thnh phn lu hunh n nng rt thp khong vi phn triu, v cng c th hiu sut ny i vi CO2.
58
Hinh 5.16. S cng ngh selexol x l chn lc H2S S ca UOP y l mt trong nhng s Selexol tiu biu ca UOP. Qu trnh x l kh tun hon trong cc thit b nh hnh 5.17. Kh axt c a vo thit b hp th, dung mi s dng hp th l DMEPEG. Dung mi c ti sinh i t trn xung v kh chua i t di ln, trong qu trnh ny xy ra s trao i nng cc cht, kh sch i ra t trn nh thp hp th. Kh axt ha tan vo dung mi i ra t y thp hp th qua thit b tch nhanh. Hn hp c b gim p sut t ngt, mt phn kh b tch khi hn hp v quay tr li thp hp th.
Hnh 3.17. S cng ngh ca UOP
59
Hn hp cn li qua thit b ti sinh dung mi sau khi gia nhit thit b trao i nhit. Nh hi nc ti sinh li cun kh axt ra khi dung mi, kh axit c lm lnh qua thit b trao i nhit. Dung mi b li cun c bm tun hon v thp ti sinh. Kh axt c tch ra, dung mi ngng t c hon lu tr li thp. Dung mi ti sinh i ra t y thp tun hon tr li thp hp th sau khi c lm lnh. Trong trng hp kh nguyn liu c ln bi hoc cc cht khng bay hi, sau khi lm lnh dung mi phi a qua thit b lc dung mi c sch hn. Trong thc t, tn dng nng lng sinh ra do qu trnh gim p sut t ngt ngi ta t vo cc my pht in bc mt v bc hai vi mc ch cung cp nng lng in ti ch cho nh my. Qu trnh lm vic theo c ch ging trn, nhng c im khc nhau c bn l: h thng ny c hai thp ti sinh dung mi, trong mi thp c t h thng my pht in. nng cao hiu sut, ngi ta cn t thm mt my nn thp ti sinh ln mt. Hiu sut cng cao khi thp hp th c hai dng hi lu dung mi. H thng ny va thu c kh ngt, kh axit, kh ti sinh lm nguyn liu, bn cnh cn p ng nhu cu v in nng cho nh my. y l h thng hon ho nht c p dng rng ri nht hin nay.
Hnh 3.18. S cng ngh qu trnh Selexol 3.4.3. S qu trnh cng ngh ca qu trnh Purizol Cht hp th c s dng l N - metyl - 2 pyrollidon (NMP). NMP khng c, ha tan tt H2S, CO2, RSH v hydrocacbon, hp th hi nc v 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 chn lc cao v bo m hp th chn lc H 2S trong s hin din CO2 ( 200C v 0,1 MPa ha tan ca H2S ln hn CO2 10 ln). p sut hi bo ha ca NMP tng i cao, gim tht thot NMP ngi ta ra kh lm sch trn h thng purisol bng nc. 60
Qu trnh ny c nghin cu bi cng ty Lurgi. H thng cng nghip c xy dng c vo nm 1963 lm sch kh thin nhin khi CO2 v H2S (nng sut theo kh l 50.000 m3/h, theo lu hunh 4,2 tn/h). Cng thc phn t Khi lng phn t : 99
Khi lng ring 200C (kg/m3) : 1000 Nhit si (0C) Nhit nng chy (0C) Bng 3.5. Tnh cht vt l ca NMP Qu trnh Purizol c s dng lm sch th v trit kh khi H2S v CO2 vi nng ca chng khc nhau trong kh ban u. : 275 : 24
VII III X IV V XII 2 3 4 5 6 VIII IX
XIII 8
1 VI II 10 7
XI
Hnh 3.19. S cng ngh quy trnh Purizol nm 1978 Nhit ca kh nguyn liu: 0 150C p sut thp hp th: 50 - 75 at p sut thp gii hp: 0,5 Mpa. Nhit thp gii hp: 130 - 1800C S mm trong thp hp th khong 30 mm. Trong , nh thp cn c 5 mm hp th dung mi NMP.
61
Hnh 3.20. S cng ngh quy trnh Purizol nm 2000
62
CHNG 4: NGNG T NHIT THP
Sau khi c lm kh, tch bi v lm ngt, kh c a i ch bin tip trong nh my ch bin kh. Trong giai on ny hn hp kh c tch thnh cc phn on hp hn nh C2+ (etan v hydrocarbon cao hn), C3+ (propan v hydrocarbon cao hn), condensate...hoc cc n cht nh etan, propan, butan... thng phm. thc hin mc ch ny trong ch bin kh ng dng ba nhm phng php chnh: ngng t nhit thp, hp th nhit thp v chng ct nhit thp. Qu trnh ngng t kh coi l qu trnh lm lnh ng p n nhit xut hin pha lng. Trong phn ny xem xt qu trnh ngng t kh ng hnh v kh thin nhin ngoi vng ti hn v cn ti hn. Ngng t nhit thp v hp th nhit thp l hai qu trnh c bn trong ch bin kh v c s dng rng ri, cho n nay vn cha c s phn chia mt cch r rng lnh vc ng dng gia chng. Trong chng ny gii thiu cc s cng ngh ngng t c bn ch bin kh, ngng t lm lnh ngoi v lm lnh ni. 4.1. S nguyn tc qu trnh ch bin kh bng phng php NNT
Hnh 4.1. S nguyn tc qu trnh ch bin kh bng phng php NNT I: kh nguyn liu, II: nc + hydrocacbon, III: kh kh 1: thit b tch lng, 2: my nn kh, 3: cm sy kh, 4: thit b lm lnh, 5: thp tch, 6: thp deetan ha (hoc demetan ha) S nguyn tc ch bin kh bng phng php ngng t nhit thp (hnh 6.1) bao gm cc b phn sau: nn kh n p sut cn thit, lm kh, lm lnh kh n nhit to thnh hn hp hai pha, tch hn hp hai pha, kh kh t nh thp tch a i s dng, pha lng (phn on hydrocarbon) a i loi etan hoc metan trong cc thp deetan ha hoc demetan ha ph thuc vo sn phm mong mun l C 3+ (propan v cc hydrocarbon cao hn) hay C2+ (etan v cc hydrocarbon cao hn). 63
Nu sn phm l C2+ th sau thp demetan ha thm thp deetan nhn c etan sn phm. Qu trnh ngng t nhit thp din ra trong cm cng ngh lun bao gm ngun lnh v thit b tch, ngoi ra trong s thng t h thng trao i nhit thu hi vi mc ch tn dng nhit lnh ca dng kh v dng lng ngng t gim nhu cu v ngun nhit lnh. Nh vy, trong cc h thc ngng t mt giai on bao gm c h thng trao i nhit thu hi, ngun lnh v thit b tch. Nhng giai on tch ch gm ngun lnh v thit b tch, hoc trao i nhit thu hi v thit b tch (trong trng hp ny trao i nhit thu hi ng vai tr ngun lnh). S cng ngh ch bin kh theo phng php ngng t nhit thp c phn loi theo: S giai on tch Theo dng cht lm lnh Theo sn phm chnh Trong tng qut nht l phn loi s theo dng ngun lm lnh. Theo dng ngun lnh s ngng t nhit thp c th chia thnh cc loi: chu trnh lm lnh ngoi, chu trnh lm lnh ni v chu trnh lm lnh hn hp, trong ngun lnh l c chu trnh ngoi v ni. Cc cht lm lnh n cht thng s dng l etan, etylen, propan...C th ng dng cc thit b lnh vi cht lm lnh l cc hn hp hydrocarbon nh hn hp metan, etan, propan, butan...gi l cht lm lnh hn hp. S dng cht lm lnh hn hp cho php nhn c nhit thp hn nhiu so vi lm lnh bng propan v do c th thu hi c cc cht chnh cao hn. Khi tham s chu trnh lm lnh c chn sao cho sau khi nn trong my lnh v lm lnh bng dng kh kh hn hp cht lm lnh ngng t hon ton. Tt c cc s vi chu trnh lnh l cc cht lm lnh hn hp c th chia thnh 2 nhm: nhm 1 cht lm lnh c thnh phn c nh c chun b sn ngoi, nhm 2 cht lm lnh nhn trc tip trong s - thnh phn ca n thay i i cht ph thuc vo thnh phn nguyn liu. Khc vi s chu trnh lm lnh ni, trong s vi cht lm lnh ngoi hn hp cht lm lnh tun hon trong h thng kn gm, my nn kh - my lnh khng kh (nc) - bay hi - my nn kh, v lng tht thot c b li mt cch h thng. Nh vy, chu trnh lnh vi cht lm lnh hn hp l chu trnh lnh ngoi. S ng dng cht lm lnh nhn c trc tip trong thit b s phc tp hn. S s dng cht lm lnh hn hp iu ch bn ngoi thc t khng c g khc vi s ngng t nhit thp mt giai on thng vi chu trnh lnh propan ngoi. 4.2. Ngng t lm lnh ngoi 4.2.1. S ngng t mt giai on vi chu trnh lnh propan thu C3+
64
Trong hnh 6.2 trnh by s cng ngh ngng t nhit thp. y l s c in c s dng u tin ch bin kh v c ng dng rng ri. Trn c s s ny pht trin nhng s hin i. S c mt ngun lnh ngoi - chu trnh lnh propan v mt b phn phn ring hn hp hai pha.
Hnh 6.2. S ngng t mt giai on vi chu trnh lnh propan 1, 7: thp tch; 2: my nn; 3: thit b lm lnh bng khng kh; 4, 5: thit b trao i nhit; 6,10: thit b bay hi propan; 8: thp deetan; 9: b cha hon lu; 11: ni si li. I: kh nguyn liu; II: hydrocacbon + nc; III: kh kh Kh nguyn liu t ng dn c a vo thit b tch 1, ti n c loi sch cc bi rn v cht lng git (du, condensate, nc...). Sau khi lm sch trong thit b tch 1 kh nguyn liu c nn trong my nn kh 2 ti p sut 3 4 MPa hoc cao hn. Sau khi lm lnh trong my lnh khng kh 2, trao i nhit 4 (vi kh kh) v 5 nh ngun lnh ca condensate t thit b phn ly 7, kh c nhit t -20 n -35 0C. Tip theo, trong thit b lm lnh bng propan 6 kh ngng t mt phn v i vo thit b phn ly 7, hydrocarbon ngng t c tch ra. T nh thp phn ly 7 kh kh thot ra sau khi i qua trao i nhit 4 c dn vo ng dn kh chnh. T y thp 7 condensate c dn ra v sau khi trao i nhit vi kh nguyn liu trong trao i nhit 5 nhit ca n tng n 20 300C v kh tip tc c np vo gia thp deetan ha 8. Sn phm trn ca thp deetan ha l hn hp metan (20 70% th tch), etan (30 75% th tch) v propan (khng qu 5% th tch) trn vi kh kh ca thp phn ly 7 v i vo ng dn kh. Sn phm y ca thp deetan ha - phn on hydrocarbon l hn hp propan v cc hydrocacbon cao hn (C 3+) s dng sn xut propan, butan, pentan v kh xng (C5+) hoc kh dn dng. Cc thng s vn hnh ca quy trnh: p sut my nn l 4MPa (40 atm) p sut thp kh etan3 MPa 65
Nhit nh thp kh etan bng -300C Nhit y thp kh etan bng 900C
Cm deetan ha l mt trong nhng cm c bn ca s ngng t nhit thp, cht lng sn phm v hiu qu kinh t ca thit b ph thuc vo hiu qu lm vic ca n. Tng hm lng propan trong sn phm nh ca thp deetan ha dn n tng mt mt sn phm chnh, cn nu hm lng etan trong sn phm y ca thp deetan ha cao hn 2 3% khi lng th propan hoc phn on propan - butan sn xut ra khng hp qui cch trong phn xng phn on kh. Deetan ha l thp chng ct c 10 12 mm l thuyt. Thi gian sau ny thit b tip xc trong thp deetan ha c ng dng l mm supap, thng l 30 mm, p sut trong thp gi 3 3,5 MPa. Vic la chn p sut trn xut pht t: Trong iu kin ch bin kh bng phng php ngng t nhit thp vi p sut t 4 MPa tr ln th vic duy tr p sut trong thp deetan ha khng i hi chi ph thm nng lng. Mt khc, vi p sut nh vy vic s dng propan lm cht lm lnh p ng ch nhit cho vng nh thp deetan ha. p sut cao hn khng c li v s lm xu iu kin phn tch pha.
4.2.2. S ngng t mt giai on vi chu trnh lnh ngoi propan - tch s b tan thu sn phm C3+
Hnh 4.3. Chu trnh lm lnh propan - tch s b etan thu C3+ 1: my nn; 2: thit b trao i nhit bng khng kh; 3, 4, 5: thit b trao i nhit; 6, 10: thit b bay hi propan; 7, 8: thp tch; 9: thp kh etan; 11: bnh cha hon lu; 12: ni si li I: kh nguyn liu; II: kh kh Nguyn tc hot ng ging s hnh 6.2 4.2.3. S quy trnh mt giai on - chu trnh lm lnh ngoi bng tc nhn lnh hn hp thu sn phm C3+ 66
Hnh 4.4. Chu trnh lm lnh ngoi bng tc nhn lnh hn hp thu sn phm C3+ 1, 4: my nn; 2, 5: thit b trao i nhit bng khng kh; 3, 6, 9: thit b trao i nhit; 7: thit b bc hi tc nhn hn hp; 8,10: thit bj phn ly; 11: thp tch etan; 12: bnh cha hi lu; 13, 14: van tit lu I: kh nguyn liu; II: kh kh Trong cc s ngng t nhit thp bn cnh cc chu trnh lm lnh bng cc n cht (etan, etylen, propan...), c th ng dng cc thit b lnh vi cht lm lnh l cc hn hp hydrocarbon. S s dng cht lm lnh hn hp iu ch bn ngoi, thc t khng c g khc vi s ngng t nhit thp mt giai on thng thng vi chu trnh lnh propan ngoi. S ng dng cht lm lnh nhn c trc tip trong thit b s phc tp hn. V vy di y s xem xt phng n phc tp hn. Trong hnh 6.4 trnh by s h thng qu trnh ngng t nhit thp ch bin kh ng hnh vi chu trnh lnh bng cht lm lnh hn hp. Cng sut kh 1 t m3/nm, h s thu hi propan bng 84%. Kh c nn ti 3,7 MPa, qua lm lnh khng kh 2, trao i nhit 3, thit b lm lnh bng hn hp kh 7 v trong cc thit b ny kh lm lnh n -600C. Hn hp hai pha to thnh c tch ra trong thp tch 10 - kh kh sau khi hon tr lnh trong trao i nhit 6 c a i s dng, cn condensate chia thnh hai dng, mt dng a vo mm trn thp deetan, dng cn li c gia nhit trong trao i nhit 6 bng cht lm lnh v vo phn gia ca thp deetan ha. Kh t thp deetan sau khi hon tr lnh trong trao i nhit 3 a i s dng, phn on hydrocarbon tch ra t di thp deetan v sau trao i nhit hon nguyn 9 a vo b cha thng phm. Mt phn condensate t thp tch 10 c th c a i nhn c cht lm lnh hn hp. Phn condensate ny c gia nhit trong trao i nhit 9 bng sn phm di ca thp deetan n nhit 20 450C, bay hi mt phn v tch kh trong thp phn ring 8, tit lu trong thit b tit lu 67
13 n p sut 0,118 0,125 MPa, bay hi hon ton v hi nhn c a vo bung tip nhn ca my nn kh 4 ca chu trnh lnh, v c dng lm cht lm lnh. S chu trnh lnh gm my nn hi cht lm lnh trong my nn kh 4 n 1,1 1,5 MPa, lm lnh, ngng t v lm lnh li cht lm lnh lng n 40 500C trong my lnh khng kh 5, trao i nhit hon nguyn 6 v bay hi 7, tit lu cht lm lnh trong thit b tit lu 14 n 0,1 0,125 MPa. Sau khi qua thit b tit lu 14 cht lm lnh vi nhit -650C c a vo khng gian gia cc ng ca thit b bay hi 7. Trong thit b ny cht lm lnh bay hi hon ton, nng nhit t -65 0C ln n 15 200C, cn kh nguyn liu c bm vo ng dn ca thit b bay hi 7 b lnh i. Hi cht lm lnh t thit b bay hi 7 i n bung tip nhn ca my nn kh 4.
Di y l s liu so snh cc ch tiu c bn ca h thng ngng t nhit thp mt giai on vi thit b lm lnh c cc cht lm lnh khc nhau (c hai trng hp cng sut kh l 1 t m3/nm):
Chu trnh lnh tc nhn hn hp p sut kh nguyn liu Nhit 0C Gia nhit cht lng ngng t Ca tc nhn lnh trc tit lu Nng sut lnh ca tc nhn lnh (kJ/ kmol) Lng tc nhn (kmol/ h) Lng tc nhn (tn/ h) Thnh phn tc nhn, % mol C1 C2 C3 n-C4 n-C5 C6 v cc phn on cao Khi lng phn t Chi ph nng lng nn tc nhn lnh kw.h 14,915 12,793 36,888 25,699 8,432 1,237 44,5 6240 9,54 11,30 37,02 28,70 11,47 1,97 47,8 4201 4296 20 -44 7512 2435,9 108,4 3,7 MPa 3,43 MPa Chu trnh lnh c tc nhn etan - propan
45 -52 11154 1652,8 79,0
8727 2517,0 98,45
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T s liu trn ta thy, tng phn t lng cht lm lnh cng sut lm lnh ca n tng. Do khi lng cht lm lnh trong chu trnh lnh gim xung v nng lng chi ph cho vic nn n gim. Thnh phn cht lm lnh c th la chn sao cho vic ng dng n c kinh t hn so vi s dng chu trnh propan. R rng, ng dng chu trnh lnh vi cc cht lm lnh hn hp trong h thng ch bin kh hu hiu v n cho php gim chi ph nng lng v n gim ha thit b qu trnh. 4.2.4. S quy trnh mt giai on - chu trnh lm lnh ngoi bng tc nhn propan v etan thu sn phm C2+
Hnh 4.5. Chu trnh lnh ngoi bng tc nhn propan v etan thu C2+ 1, 4, 10: thit b phn ly; 2: my nn; 3: thit b ngng t bng khng kh; 5: cm lm kh; 6, 8: thit b trao i nhit; 7, 12, 15: thit b bc hi bng propan; 9: thit b bc hi bng etan; 11: thp kh metan; 13, 16: bnh cha hi lu; 14: thp kh etan I: kh nguyn liu; II, III: hydrocacbon; IV: kh kh c im ca s (hnh 6.5) l c hai ngun lnh ring r trn mt giai on: cc chu k lm lnh propan v etan. Theo s , kh c lm lnh trc tip v ngng t mt phn trong my lnh khng kh 3, trao i nhit 6, thit b lm lnh propan 7, trao i nhit 8 v thit b lm lnh etan 9 m khng tch pha lng. iu ny cho php ci thin ng k iu kin tng thu hi etan do n c ha tan nhiu hn trong hydrocarbon lng. c im th hai ca s l c b phn loi metan v thp etan, do s c ng dng sn xut sn phm C2+. Thp demetan loi ton b metan ra khi phn on hydrocarbon nng v trnh mt mt etan. Thp demetan ha lm vic p sut 3,5 4,0 MPa, nhit trong b cha dng chy ngc t -60 n -900C. Nhit ny xc nh mc loi etan: nhit trong b cha cng thp, mc loi etan cng cao. Nhit di ca thp demetan c gi 20 600C v thp c khong 20 25 mm supap. Khi thp demetan lm vic cn tha mn cc iu kin sau y v lm sch sn phm: 69
Nng etan trong sn phm trn khng qu 5% khi lng so vi tng lng etan trong nguyn liu ca thp. Nng metan trong sn phm di khng qu 2% khi lng so vi etan trong
sn phm di ca thp. Thp etan thng lm vic vi p sut v nhit di thp nh trong thp demetan, nhng nhit trn ca thp cao hn nhiu, trong khong 0 100C. iu ny c th gii thch l do hm lng metan trong nguyn liu cng nh trong sn phm trn ca thp etan thp (khng qu 2% khi lng). Sn phm nh ca thp etan thng c ly ra trong pha hi, nhng trong mt s trng hp n c ha lng. Thp etan cn p ng sch ca cc sn phm nh sau: nng propan trong sn phm nh khng qu 2% khi lng so vi etan trong sn phm nh; nng etan trong sn phm y khng qu 2% khi lng so vi hm lng propan trong sn phm y. 4.2.5. S quy trnh hai giai on - chu trnh lm lnh bng tc nhn propan v etan thu sn phm C2+ S ngng t nhit thp n gin nht vi chu trnh lm lnh ni tip l s ng dng chu trnh lm lnh propan - etan hoc propan - etylen. Trong cc s hai giai on nh vy, trong giai on I kh c lm lnh nh nhit lnh ca chu trnh lm lnh propan, cn trong giai on II - nh chu trnh lm lnh etylen hoc etan. Cc s ny c c ng dng thu hi su propan (cao hn 80%), hoc tch etan v cc hydrocarbon nng. Trong hnh 6.6 trnh by s cng ngh mt nh my ch bin kh Gastn (M). Cng sut nh my theo nguyn liu l 4,25 triu m3 kh thin nhin/ ngy (khong 1,5 t m3/nm).
Hnh 4.6. S hai giai on nhn C2+ vi chu trnh lm lnh bng propan v etan 70
1: thp tch lng s b; 2: thit b lm kh kh; 3: thit b lc kh; 4: thit b trao i nhit v bc hi propan; 5, 7: thit b tch nhit thp; 6: thit b trao i nhit v bay hi etylen; 8, 15, 19, 23, 29, 36: bnh cha hi lu; 9: thit b lm lnh etylen; 10: thp tch metan; 11, 16, 21, 25, 31, 39: ni si li; 12: bnh cha trung gian; 13: thp etan; 14: thit b bay hi propan; 17: cm lm lnh CO2; 18, 22, 27, 28, 32, 40: thit b ngng t bng khng kh; 20: thp tch propan; 24: thp tch butan; 26: thit b trao i nhit; 30: thp tch iso - butan; 34: bnh cha etan; 35: cm tch tp cht lu hunh; 37: thit b gia nhit; 38: cm tch xng; 41: thp chng ct cht lng ngng t. I: kh nguyn liu; II: hydrocacbon + nc; III: kh kh Nh my c a vo hot ng nm 1969 v dng sn xut cc phn on t C2 tr ln. Theo thit k nh my s cho cc sn phm chnh nh sau: etan khong 162.000 tn/ nm; propan 238.000 m3/ nm; n - butan 71.200 m3/ nm; iso butan 33.300 m3/ nm v xng 71.900 m3/ nm. Kh thin nhin sau khi loi ht hn hp c hc v nc t do trong thp tch 1 c a vo thp lm kh 2, n c lm kh trn ry phn t n im sng -840C v sau lm sch bi trong b lc 3. Sau trao i nhit 4 kh c lm lnh trong thit b lm lnh bng propan n -370C. Khi c khong mt na hydrocarbon cn tch c ngng t. Phn ngng t ny c tch ra trong thp phn ring 5 v c a vo thp demetan 10. Kh ra khi thp tch 5 c lm lnh n -93 0C trong thit b trao i nhit vi kh kh loi xng, condensate v thit b lm lnh bng etylen 6. Phn on lng to thnh tch ra trong thp phn ring 7 v sau khi thu hi nhit lnh i vo thp demetan 10, cn kh c a i s dng. Trong h ny thu hi tng cng khong 85% etan, 99% propan v hu nh ton b hydrocacbon nng. Vi mc ch gim tht thot etan bay ra cng kh pha trn thp khi s dng cht lm lnh etylen th p sut trong thp demetan gi 3,5 MPa, nhit nh thp nh nhit lnh ca etylen gi -950C. Khi loi metan (trong mt s trng hp c mt phn etan) hydrocacbon lng thot ra t y thp demetan c dn trc tip vo thit b phn on kh nhn c cc hydrocarbon n cht: etan, propan, isobutan, n butan v xng. Cm cng ngh xem xt trn y l dng in hnh s dng trong cc nh my ch bin kh thin nhin, kh ng hnh thu c etan v cc hydrocarbon cao hn. Cm phn on kh c th xy dng cho tng nh my hoc tp trung thnh cm ring dng cho mt s nh my. V nguyn tc khng c s khc nhau gia chu trnh lnh propan - etylen v propan - etan. Chu trnh propan - etylen cho php nhn c nhit thp hn i cht (nhit si ca etan l -88,65 0C, ca etylen l -103,710C), nhng u th c bn ca chu trnh propan - etan l c hai cht lm lnh nhn c trc tip trong nh my ch bin kh, do nh my c tnh ch ng cao. 4.2.6. S quy trnh ba giai on - chu trnh lnh ngoi propan thu sn phm C3+ 71
Hnh 4.7. Chu trnh ba giai on thu C3+ 1, 7, 9, 11: thit b phn ly; 2: my nn; 3: thit b ngng t bng khng kh; 4, 5: thit b trao i nhit; 6, 8, 10, 13: thit b bc hi tc nhn lnh propan; 12: thp tch; 14: bnh hi lu; 15: thit b gia nhit. I: kh nguyn liu; II: hydrocacbon; III: kh kh S mt bc v nhiu bc cng c nhng u im v nhc im. Theo l thuyt ca qu trnh ngng t th trong qu trnh mt bc lng pha lng to ra s nhiu hn so qu trnh nhiu bc ( cng mt ch v thng s cng ngh). Tuy nhin trong trng hp th nht pha lng s cha nhiu cu t nh khng mong mun (metan) hn trng hp th hai v cn phi bit rng thc hin qu trnh ngng t nhiu giai on i hi dung lng u t cao hn. So snh cc qu trnh trn v mt chi ph cho thy, tham s kinh t k thut ca qu trnh ngng t mt v ba giai on nh nhau. Do thu hi C 3+ khng ng dng h thng ngng t nhit thp qu mt giai on. S hai v ba giai on c dng trong qu trnh yu cu mc thu hi C3+ hoc C2+ cao. Trong cc s ny hoc s dng lm lnh ni tip, hoc lm lnh ni hoc hn hp. so snh ta xt hiu qu ca s mt bc (hnh 6.2) vi p sut 2 Mpa, nhit -300C v s ba bc (hnh 6.7) vi p sut 3 Mpa, nhit 5 0C (bc 1), -150C (bc 2) v -300C (bc 3). Nng sut ca c hai s l 500 triu m3 kh ng hnh/ nm.
Mt bc Mc tch hydrocacbon t kh cm ngng t nhit thp % CH4 C2H6 C3H8 T C3 tr ln Mc tch C3 v cao hn trong ton b h thng, % Tng cng 23,3 68,3 90,2 93,25 92,1 15429095 14,1 53,6 87,0 91,8 90,5 13817100 Ba bc
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Gio trnh cng ngh du kh Mt bc Cm ngng t nhit thp Cm kh etan Tng chi ph nhit kJ/ h 7452860 7976235 12139000 Ba bc 8039040 5778060 10884000
Phn tch cc ch s nhn thy kh chuyn t s mt bc ln s ba bc mc li cun metan v etan gim tng ng l 1,7 ln v 1,26 ln; mc li cun cc hydrocacbon chnh t C3 tr ln gim 1,6%; chi ph lnh gim 12%; lng metan v etan i vo thp kh etan cng gim so vi s mt bc. 4.3. Ngng t lm lnh ni ch bin kh vi hm lng C3+ khng qu 70 75 g/m3 s dng s ngng t nhit thp vi ngun lnh duy nht l thit b gin n turbin, cho php thu hi su cc nguyn t cn thit: etan, propan v cc hydrocarbon nng hn. Thng trong cc s vi chu trnh lnh ni bn cnh cht lm lnh l kh loi xng cn s dng s tit lu cc dng lng. S tiu biu ca nh my ch bin kh trang b thit b lm lnh turbin gm cc b phn chnh sau y: Nn kh nguyn liu. Lm kh kh. Trao i nhit ca cc dng. Phn ring p sut cao. Gim p turbin vi cm phn ring tch p sut thp.
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Demetan ha cht lng ngng t nu nh sn phm chnh l etan v hydrocarbon nng hn, v deetan ha condensate nu sn phm chnh l propan v cao hn. Nn kh kh n p sut cn thit a n vo ng dn chnh.
4.3.1. S nguyn tc ca qu trnh ch bin kh s dng thit b lm lnh kiu turbin
Hnh 4.8. S nguyn tc s dng cc m khai thc 73
Sau x l s b trong thp tch 1 kh c h nhit trong trao i nhit 2, i qua thp phn ring giai on I (3), gin n, lm lnh v ngng t mt phn trong thit b gim p turbin 4 v i vo thp phn ring giai on II (5). T thp phn ring kh i vo khng gian gia cc ng ca trao i nhit 2 v sau khi nn trong my nn kh 6 nm cng trc vi thit b gim p turbin (s dng nng lng sinh ra trong qu trnh gin n) sau i vo ng dn chnh. Condensate to thnh trong qu trnh phn ring c a i n nh. Trong hnh 4.9. m t mt dng ca s nguyn tc lm lnh ni bng thit b lm lnh kiu turbin. Kh nguyn liu a vo cm sy 1, sau c a qua cc cm trao i nhit lnh 2, hn hp hai pha c a vo thit b tch p sut cao 5. Trong thit b 5, pha kh c a qua turbin gin n chuyn t p sut cao n p sut thp v a vo thit b phn ly p sut thp 6, dng kh ly ra t nh thp 6 l C 1, C2. Dng lng thit b phn ly 5 v 6 c a vo thp kh metan 7. nh thp 7 l C1 v C2 (kh c gim p), sau khi trao i nhit lnh s c a vo my nn 3, kh kh ly ra c em i s dng. y thp 7 l cht lng sau khi kh metan l C2+.
Hnh 4.9. S nguyn tc s dng thit b lnh kiu turbin 1: cm sy; 2: cm trao i nhit; 3: my nn; 4: turbin gin n; 5: thit bi phn ly p sut cao; 6: thit b phn ly p sut thp; 7: thp kh metan; 8: thit b gia nhit. I: kh nguyn liu; II: kh kh 4.3.2. S quy trnh hai giai on - lm lnh bng cch gim p turbin v tit lu dng thu c sn phm C3+ Nh my ch bin kh u tin vi chu trnh lm lnh turbin c ng dng M nm 1964. N c Hng Fluor thit k v xy dng. Cng sut nh my theo kh nguyn liu l 3,7 triu m3/ngy. Trong nh my ny etan khng c tch ra v khng 74
c h tiu th. Thu hi c 85% propan v hu nh hon ton hydrocarbon nng. Kh kh c a trc tip vo h thng cung cp ca thnh ph San - Antonio di p sut 2,1 MPa. Kh nguyn liu vi p sut 5,2 MPa i qua thp tch 1, cht lng dng git c tch ra. Sau khi tch nc, kh c lm lnh trong trao i nhit 2, 3, 4 vi kh kh v condensate t thp phong ha 8 v nhit h xung n -54 0C v a vo thit b tch ba pha 5. Phun metanol vo kh nguyn liu trc khi vo cc trao i nhit. Trong thit b tch ba pha 5 metanol bo ha nc, hydrocarbon ngng t v kh c tch ra. Dung dch nc metanol a i hon nguyn trong thit b 10. Hydrocarbon ngng t t thp tch 5 c dn vo thp phong ha 8, p sut c gim xung n 1,8 MPa v nhit kh gim xung n -840C. Kh to thnh sau khi tit lu v tch ra trong thp phong ha 8 c a vo ng dn kh kh, cn condensate qua trao i nhit 2 v vo gia thp deetan 11.
Hnh 4.10. S hai giai on vi chu trnh lm lnh ni 1: thit b phn ly; 2, 3, 4: thit b trao i nhit; 5: thit b tch 3 pha; 6: my nn; 7: turbin gin n; 8: thit b phong ha; 9: van tit lu; 10: bnh cha metanol; 11: thp kh etan; 12: thit b gia nhit; 13: thit b phn ly. I: kh nguyn liu; II: hydrocacbon; III: kh kh Kh t thit b tch ba pha 5 i vo thit b gin n turbin 7, trong p sut ca n h xung n 1,8 MPa. Kh lnh i vo thp tch 13 t trn thp 11. Kh t thp tch 13 sau trao i nhit thu hi 3 v 4 c nn n p sut 2,1 MPa bng my nn
75
kh 6 t cng trc vi turbin 7. T di thp deetan phn on hydrocacbon rng thot ra. c im ca s ny l lng nhit lnh cn thit do lm lnh kh loi xng v tit lu condensate cung cp. 4.4. Ngng t lm lnh kt hp 4.4.1. S quy trnh mt giai on - lm lnh kt hp thu sn phm C3+ Trong hnh 4.11 trnh by s ngng t nhit thp mt giai on c tit lu condensate t thp tch 10. Trong s ny kh ng hnh sau khi nn vi p sut 2,0 MPa i thng vo ni si li 13 ca thp bay hi 12 (thp deetan), qua my lnh khng kh 3, sau qua cc trao i nhit 4, 6, 7, 9 v thit b lm lnh bng propan 5, 8, kh ngng t mt phn v vi nhit -100C i vo thp phn ring 10 tch condensate. Kh kh t nh thp phn ring sau trao i nhit vi dng kh nguyn liu ra khi h v a i s dng. Condensate t y thp phn ring ny i qua thit b tit lu 11, p sut condensate gim xung n 1,0 MPa v nhit gim n 180C. Dng lnh ca condensate i qua trao i nhit 9 t ngay trc thp tch 10, sau vo trao i nhit 7 v a vo pha trn thp bay hi 12, di p sut 1,0 MPa din ra qu trnh loi etan. T di thp 12 phn on hydrocarbon c a i ch bin tip. Hydrocarbon nh bay hi t trn thp 12 i qua trao i nhit 4, nn bng my nn kh 2 n p sut ca dng nguyn liu, lm lnh trong my lnh khng kh 1 v trn vi kh nguyn liu.
Hnh 4.11. S quy trnh mt giai on 1, 3: thit b lm lnh bng khng kh; 2: my nn; 4, 6, 7, 9,13: thit b trao i nhit; 5, 8: thit b gia nhit; 10: thit b phn ly; 11: van tit lu; 12: thp kh etan. I: kh nguyn liu; II: kh kh. 76
c im ca h thng ny l lng nhit lnh c c nh tit lu condensate v cho php nhn c nhit thp hn nhit ca dng tit lu. So vi h tng t nhng khng c b phn tit lu th s ny kinh t hn: sn xut 1 kmol phn on hydrocarbon theo s ny cn 5,65 m3 nhin liu thay v 6,23 m3 theo h thng thng. Nh vy, trong s ny chu trnh lnh ni c ng dng ci thin ch s kinh t - k thut ca qu trnh do tit kim nhit lnh propan hiu sut cao. 4.4.2. S quy trnh hai giai on - lm lnh kt hp thu c sn phm C 3+ (propan ngoi v tit lu dng lng) S th hin trong hnh 6.12 c dng thu hi su propan. c im ca s : lm lnh kh trong giai on ngng t I nh chu trnh lm lnh propan ngoi, cn trong giai on II nh tit lu condensate ly t thp tch ca giai on II v mt phn condensate t thp tch giai on I.
Hnh 4.12. S quy trnh hai giai on 1, 13: my nn; 2, 14: thit b lm lnh bng khng kh; 3, 4, 7, 8, 9, 15: thit b trao i nhit; 5, 17: thit b bay hi propan; 6, 10: thit b tch 2 pha; 16: thp kh etan; 11, 12: van tit lu; 18: thit b tch kh; 19: bm hon lu; 20: thit b gia nhit. I: kh nguyn liu; II: kh kh. Kh ng hnh c nn ti 3,7 MPa, lm lnh trc tip trong my lnh khng kh 2, trao i nhit 3 v 4 v bay hi propan 5 n nhit -30 0C v ngng t mt phn. H hai pha to thnh c phn ring trong thp phn ring 6. Condensate t thp tch giai on II (10) cng vi mt phn condensate ca giai on I tit lu trong thit b tit lu 11 v 12 n p sut 0,3 MPa i vo trao i nhit 8 v 9. Kh ca thp tch 77
giai on I c lm lnh tip n -640C trong trao i nhit 7 nh nhit lnh ca kh kh thu c t thp tch giai on II (10) v trong trao i nhit 8, 9 nh nhit lnh ca condensate tit lu. Sau khi cho nhit lnh, dng hi sau tit lu c nn bng my nn kh 12 n p sut 3,5 MPa v cng phn condensate cn li t thp tch giai on I (6) c a vo thp deetan 16. Tnh ton kinh t - k thut cho thy s ny kinh t khi ng dng ch bin kh vi hm lng C3+ xp x 300 g/m3. Khi ch bin kh thnh phn nh vy chi ph nng lng tng tin hnh qu trnh theo s trn xp x vi chi ph nng lng tng cho qu trnh vi chu trnh lnh ni tip. u im ca s ny l ch cn mt cht lm lnh v yu cu thit b t hn nhn c nhit thp. 4.4.3. S quy trnh hai giai on - lm lnh kt hp thu sn phm C3+ (propan ngoi, tit lu dng lng v gim p turbin) Thi gian sau ny M c xu hng ng dng thit b lm lnh trong s ch bin kh du theo phng php ngng t nhit thp vi mc ch ch thu hi C 3+. Di y trnh by s cng ngh ch bin kh ng hnh c hm lng C3+ bng 300 g/m3 v mc thu hi C3+ l 90%.
Hnh 4.13. S quy trnh hai giai on 1, 3, 5: thit b bay hi propan; 2, 4, 11, 14: thit b trao i nhit; 6, 8: thit b lm lnh bng khng kh; 7, 9: my nn; 10: turbin gin n; 12, 17: van tit lu; 13, 15: thit b tch hai pha; 16: thp kh etan; 18: thit b gia nhit. Nguyn liu c nn n 4,0 MPa, sau thit b lm sch CO 2 v lm kh bng cht hp ph rn, i vo b phn ngng t nhit thp. Mt phn kh i qua thit b lm lnh bng propan 1, 3, 5 v trao i nhit 2, 4, n c lm lnh ti -30 0C, kt hp vi phn kh t thp tch 13 c lm lnh bng condensate n nhit tng 78
t. Condensate t thp 13 c tit lu n p sut 1,7 MPa c a vo thp deetan 16 vi nhit 200C sau khi tn dng nhit lnh. T thp tch 13 kh c lm lnh bng kh kh, l sn phm nh ca thp deetan 16, n -510C v i vo thit b tch nhit thp 15, kh tch ra khi condensate vi nhit -510C, p sut 3,7 MPa i vo thit b gim p turbin 10. Condensate t thp tch nhit thp 15 qua tit lu 17, p sut ca n gim xung n 1,8 MPa v c dn vo thp deetan 16. Trong thit b gim p turbin 10 p sut kh gim xung n 1,8 MPa, kh ngng t mt phn v h nhit ti -780C. Kh vi condensate t thit b gim p turbin 10 c a vo phn trn ca thp deetan 16. Phn on hydrocacbon loi etan t di thp deetan 16 vi nhit 690C c a i ch bin tip. Kh kh t thp deetan 16 sau khi hon tr nhit lnh c nn trong my nn kh 9 n 2,0 MPa nh nng lng sinh ra ca ng c turbin 13, sau nn trong my nn 7 n p sut 4,0 MPa. Nh vy, trong s trn y chu trnh gim p c dng thay cho chu trnh lnh etan (etylen). 4.4.4. S quy trnh ba giai on - lm lnh kt hp thu sn phm C3+ (propan ngoi, tit lu dng lng v gim p turbin) Xt s cng ngh sau y ca nh my Bang Texat (M) lm vic vi b phn gim p v c ng dng thu hi t 50 n 70% etan (hnh 6.14). Mc thu hi propan khong 95%. Trong 1 m3 kh nguyn liu cha 140 cm3 etan, 103 cm3 C3+ v khong 0,12% mol CO2 v N2. c im ca nh my l hon ton khng c lm lnh bng nc. Din tch xy dng nh my nh hn 2 ln so vi nh my tng t lm vic theo ch hp th nhit thp.
Hnh 6.14. S quy trnh ba giai on
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1: thit b lc phn ly; 2: thp hp th; 3: thit b bay hi propan; 4, 7, 11: thit b phn ly; 5, 6: thit b trao i nhit; 8: thp phong ha; 9: ni si li; 10: thp kh etan; 12: turbin gin n; 13, 14: my nn; 15: thit b lm lnh bng khng kh. I: kh nguyn liu; II: hydrocacbon ; III: kh kh T trao i nhit 5 v 6 hn hp hi - lng vi p sut 5,84 MPa v nhit -62 0C c a vo thp phn ring p sut cao 7. Cht lng t thp 7 bay hi on nhit trong thp phong ha nhit thp 8 -92,20C v p sut 2,0 MPa (gn vi p sut trong thp demetan 10). Thp phong ha c s dng gim ti trng hi i vi thp demetan. T thp phn ring 7 kh c a vo thit b gim p turbin 13, n gim p on nhit n p sut xp x 2,0 MPa. Trong qu trnh ny nhit ca kh h xung n -980C. Nng lng gin n kh c s dng trong my nn kh 14. T thit b gim p turbin hn hp kh lng i vo thp phn ring p sut thp 12 v t cht lng c a vo phn trn ca thp demetan 11. Thp demetan lm vic p sut 1,9 MPa, nhit nh -97 0C, nhit pha di 16,70C. y thp demetan 11 c nung nng nh nhit lng kh nguyn liu. Ngun nguyn liu cp cho thp 11 ly t thp phn ring 4 v thp phong ha 8. Kh t thp demetan 11, thp phn ring p sut thp 12 v thp phong ha 8 trn ln, to thnh mt dng kh d, dng ny sau khi gia nhit trong trao i nhit 6 v 5 n nhit -17,80C vi p sut 1,8 MPa c nn tip bng hai my nn kh ly tm 14 v kh 15. Trong s ny b phn gim p c ng dng thay cho chu trnh lnh etan (hoc etylen). Nh vy thit b gim p turbin ng dng tt trong h thng ch bin kh trong vng nhit thp t -45 n -750C. Nu nh hm lng C3+ trong kh nguyn liu cao qu 70 75 g/m3, c c mc thu hi C3+ cao lng nhit lnh do gim p sut khng v i hi phi lm lnh thm. c im ca thit b gim p sut turbin nh sau: Mc gim p cho php: 2 3,5 0 Gim nhit ( C): 26 48 ha lng kh (%): 5 20 nn kh kh nh nng lng to ra do gim p sut: 1,3 1,5 p sut ti ca vo thit b gim p sut turbin (MPa): 1,103 9,240
80

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Gio trnh cng ngh du kh

PHN II: CNG NGH CH BIN KH

CHNG 1: CC KHI NIM C BN

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Gio trnh cng ngh du kh

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1.3. ng dng ca kh thin nhin - mt s tiu chun i vi cc sn phm t kh.

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Hnh I.1 : Cc sn phm chnh i t kh thin nhin 7

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Gio trnh cng ngh du kh

Gio trnh cng ngh du kh

Gio trnh cng ngh du kh

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115.211 3.170 1.913.000 477.000 514.000 1.472.000 14.000 603.000 -

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Gio trnh cng ngh du kh

Gio trnh cng ngh du kh

1.054.000 1.140.000 374.000 142.000 1.057.000 36.600

131.759.000 924.000 143 17

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Gio trnh cng ngh du kh

Gio trnh cng ngh du kh

Gio trnh cng ngh du kh

Gio trnh cng ngh du kh

Gio trnh cng ngh du kh

Gio trnh cng ngh du kh

Bng 1.14. Thnh phn kh b Nam Cn Sn ( % theo th tch)

Bng 1.15. Thnh phn kh b Malay - Th Chu (% theo theo th tch)

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Gio trnh cng ngh du kh

i vi metanol K = 2335 i vi glycol K = 4000 V d: Tnh t s dng Metanol 5%

2335 5 = 2,14 0 C 32 100 5 4000 5 = 1,88 0 C 62 100 5

Tnh t s dng etylen glycol 5%

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Gio trnh cng ngh du kh

VIII VI (5) (4)

2.4.1.3.S cng ngh lm kh kh bng phng php hp th glycol

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Gio trnh cng ngh du kh

(5) (2) VII (4)

(13) VIII (12) (14) IX

(3) IV (1) I (16)

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VII (5) VIII (6)

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(4) (6) VI (5)

Hnh 2.12. S nguyn tc qu trnh lm kh kh bng cht hp ph 34

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(2) I (1) (5) (6) (7) (8)

(3) (4) V III

(9) (3) (4) III V

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c im: gii hp v lm lnh thc hin bng kh m.

II (2) III (8) (4)

Hnh 2.16: S nguyn tc qu trnh lm kh kh bng cht hp ph rn vi chu trnh ti sinh kn 36

Gio trnh cng ngh du kh

Gio trnh cng ngh du kh

Gio trnh cng ngh du kh