Chng 3.

Cc nhin liu t du m, kh thin nhin Hoa Hu Thu

Nhin liu du kh NXB i hc quc gia H Ni 2007. Tr 35 63. T kho: Cc nhin liu t du m, kh thin nhin. Ti liu trong Th vin in t H Khoa hc T nhin c th c s dng cho mc ch hc tp v nghin cu c nhn. Nghim cm mi hnh thc sao chp, in n phc v cc mc ch khc nu khng c s chp thun ca nh xut bn v tc gi.

Mc lc

Chng 3 CC NHIN LIU T DU M, KH THIN NHIN.........................2 3.1 Nhin liu lng nng (FO) (du madt) ............................................................2 3.1.1 B tr cung cp du cho l t ..................................................................2 3.1.2 Phun du v l t bng du .....................................................................3 3.1.3 Yu cu k thut i vi du madt (FO) ..................................................4 3.2 Xng ng c ...................................................................................................4 3.2.1 Xng t nhin (natural gasoline - casing - head spirit) ..............................5 3.2.2 Xng thu c bng cch ct trc tip t du th......................................6 3.2.3 Xng crackinh v xng refominh ..............................................................7 3.3 Nhin liu iezen (DO) ..................................................................................18 3.4 Nhin liu kh ................................................................................................23

Chng 3 CC NHIN LIU T DU M, KH THIN NHIN

3.1 Nhin liu lng nng (FO) (du madt)
Nh trn trnh by, du madt l phn on nng thu c khi chng ct du th parafin v asphalt p sut kh quyn v trong chn khng. Cc du FO c im si cao. Trong k thut i khi ngi ta cn chia thnh du FO nh v FO nng. V th, cc c trng ho hc ca du madt c nhng thay i ng k nhng khng phi tt c cc c trng ny nh hng ti vic s dng chng lm nhin liu v cc k thut s dng t hiu qu cao. Mt trong nhng tnh cht quan trng nht ca du madt l nht c xc nh nhng nhit quy nh, v d 20C v 50C. Ni chung cc t nng v nh c s dng m t cc nhin liu du madt c nht cao v thp tng ng. Nhng du cn c nht cao (> 7000 giy) thng thng phi tri qua bc crackinh nh ph v nhng phn t nng v do lm gim nht ca du. Qu trnh ny cng gy nn s tht thot du di dng kh v qu trnh c gi l visbreaking. Tnh cht quan trng th hai ca du madt l im chp chy. im chp chy cc tiu ca tt c cc du l 65,5C (~ 150F). Tnh cht quan trng th 3 ca du madt l hm lng nc. Bi v cc du nng c t trng gn bng t trng ca nc nn phi gi du khng tip xc vi nc trong qu trnh s n xut v bo qun v nu ln nc rt kh tch ra kh i du. Tnh cht cui cng l cc du khng c cha cn sa lng bi v cc cn ny s tp trung dn dn y b cha. V th, yu t c bn trong vic s dng cc du madt l khng ch s chy ca chng v chn lc cp du cho mc ch s dng thch hp v mt k thut nh kch thc bung t chy, bn cht ca thit b, kiu cch v kch thc thit b t, phng php phun nhin liu. D nhin, gi c cng l mt yu t bi v vic s dng cc du c nht cao cn cung cp nhit cho cc ng t nng trong cc b cha, do cc trm tiu th s c gi thnh cao.

3.1.1 B tr cung cp du cho l t

Du cp cho l t trong cng nghip cn phi khan ngha l loi b ht cc ht nc phn tn trong du v cc ht rn trong . Nhng hu ht cc thit b cung cp khng th p ng c yu cu ny. Khi du c cp bng cch rt t cc b cha th thng thng phi s dng mt cp b. y, ta phi t nng bng hi nc tng cng vic tch nc v tng cng chy lng ca du. S d ngi ta phi dng k thut t nng v: nhit thng, vic tch cc ht nc trong du rt chm do s khc nhau v kh i lng ring gia chng rt nh v v i nht cao ca du th cc ht l lng ny vn tn ti khng th loi ht c. Khi t nng du c hai thay i r rng xy ra: (1) nht ca du b gim i rt nhanh v (2) du dn n nhiu

hn nc v v th s khc nhau v khi lng ring tr nn ln. Nhng h s dn n tng i ca du nng v ca nc tng ng l 0,00070 / v 0,000476 /, v th cn t nng tch c nc ra kh i du. Du c th c t nng s b n trn im chp chy nhng phi di p sut cao v c bn l phi t c mm du c th chy hay phun qua cc van. Nhit ca du phi ng u v p sut phi gi khng i. Khi phun khng kh hay du th vic cp du c th thc hin t mt b cha nhin liu hay nhiu b cao to thnh dng chy cn thit. V cc du rt nht khng th phun mt cch c hiu qu nn vic t nng l cn thit. Thng thng t nng ngi ta dng mt thit b t nng bng hi nc b tr ngay trn ng cp du. Trong thc t nhit cn thit bm du l: 38 120C (100 250F) cn nhit cn thit phun du vo l t l: 65,5 150C (150 300F). V d, du c kh nng bm c nhit 38C c nht khc nhau th nhit bm thay i nh sau:
nht, 38C (st) Nhit bm, C 200 600 1500 7,5 15,5 27,0

Trong cc thit b phun bng p sut, cc thit b lc c trang b gi ng ht nhau c hai pha ht v y ca my bm du. Li lc trong thit b lc ca pha ht c kch thc mt l ln hn so vi li pha phun. Thng thng c li ph thuc vo lng ca du c s dng. Do k thut pht trin, ngy nay ngi ta dng cc thit b l c khc hiu qu hn vic dng li lc nh thit b lc dng chy (streamline filter) hay thit b lc Autoclean. Trong thit b lc Autoclean, du i t bn ngoi qua nhiu tm thp mng c khoan l vi khong h rt nh gia cc l. Gia cc tm thp c nhiu dao bng thp m ng c gi c nh. Khi du i qua thit b ny cc cn bn b gi li v ri vo bn cha, sau b loi ra ngoi.

3.1.2 Phun du v l t bng du

du chy hon ton th du phi trn tht u vi khng kh. V mt l thuyt, iu ny c th thc hin kh d dng i vi hi du, song rt kh thc hin c i vi cc du nng. V ho hi du, phi tng nhit , m tng nhit s dn n ph v phn t du v to nn cn cc trong thit b ho hi v thit b t chy bng kim loi. Tuy nhin, vn c th p dng c i vi cc du c nhit si thp nh du ho, du trung gian. Ngi ta c th thc hin c s ho hi bng cch cho mt lng khng kh thch hp vo thit b ho hi. Vi cc du nng hn (nh du FO nng, nh) c th dng cc my phun khc nhau chuyn du thnh cc ht nh vi khng kh a vo l t. tng din tch tip xc du/khng kh ngi ta dng thit b phun c cc i t 1 1,5 nghn l trn mt cm2. Ngoi ra l t cn c nhim v: Nng nhin liu t mt mc thp hn ln mc cao hn.

a vo m t phn hay t t c h n hp nhin liu/khng kh c tr n u v i m t t c sao cho ng l ng ca n s ko theo mt l ng khng kh ph c n thit c c di ng n la mong mu n. Gi tuy n la b n v ng v ng n la thch hp v i hnh d ng ca l. Hon chnh s chy ca nhng git du nh trc khi ngn la b lm lnh ti khi khi bc ln.

Nu l cho mt ngn la nghing mt gc hp, tc cao th khng kh chy b ht vo ngn la do tc dng ca thit b phun.

3.1.3 Yu cu k thut i vi du madt (FO)

i vi cc du madt, yu t quan trng hng u l nhit tr cao, im chp chy cao, khng c vt nc v cc ht rn. Ngoi nhng yu t ny ra, cn phi la chn du cho thch hp vi nhng iu kin c bit s dng v lu tr du. Nu vic tng tr phi t nng khng c kh nng thc hin c th nn chn du c nht thp. Nu vic t nng c kh nng thc hin c th cc du nng hn v r hn c th s dng c, thm vo kiu l cng c ngha trong vic chn la. V d, Anh nhng yu cu trn c chia thnh cc cp khc nhau v cc cp cng c th b thay i. Vi cc du madt dng cho ng c i bin ca Anh nh sau:
Cp im chp chy (min), C nht , Redwood I 380C, mm2 / s(max) Hm lng nc (max), % Nhit tr, kcal / kg (min) E 65 250 1 F 65 G 65 H 65

450 2500 7000 1 1,5 1,5

10120 9990 9990 9990

Trong cc yu cu k thut i v i du madt th yu t nht l quan trng nht, b i v nht thay i rt nhiu theo nhit . Nu nhit thp, nht ln th khng th iu khin c s ch y ca du. Hm lng lu hunh v tro khng quan trng lm trong nhiu ng dng, song nu dng lm nhin liu luyn kim th hm lng lu hunh v tro c th nh hng ti vt liu b t nng, tc l cc sn phm luyn kim. Mt yu t quan trng cui cng l phi xem xt xem du madt l du chng ct hay du cn, bi v du cn c cha mt t l cao asphalt m du chng ct khng c. Nhng loi du ny c dng trong cc mc ch khc nhau khng nh hng ti vt liu chu t nng.

3.2 Xng ng c
Trc khi nn cng nghip t pht trin, nhin liu thu c ch bng cch chng ct du th. Phn on naphtha c chng ct li cho xng c khong nhit si trong mt vng nht nh. l sn phm cu i a vo s dng. Vic tinh luyn bng cch ra vi axit v ki m

nhm mc ch loi b nhng lng nh cc olefin v ci thin mu ca xng. Vic chng ct trc tip du th l bc x l u tin du th v phn xng ng c c gi l xng trc tip (Straight run spirit). Xng ny l phn on tng i khng b bin i ca du th nguyn thu. V nhu cu ca xng t, my bay ngy cng tng nn hiu sut xng, cht lng xng cn phi ngy cng c ci thin. V th, cng nghip lc du a vo cc qu trnh crackinh cc phn on du nng, refominh phn on naphtha nng, polime ho cc olefin nh, ankyl ha isobutan bng cc olefin... Bng cc phng php ny sn lng xng ng c thu c t du m tng ln, v cht lng xng cng tng. V nhng bin i ho hc k trn nn tn gi cc xng thu c t cng nghip lc ho du kh phc tp.

3.2.1 Xng t nhin (natural gasoline - casing - head spirit)

Xng t nhin hay xng thu c t kh ging du. Kh ging du cha ch yu 5 hirocacbon parafin (t C1 n C5). Ngoi ra, cn c thm mt lng nh hirocacbon phn nhnh v vng c im si rt gn vi cc hirocacbon parafin trn (bng 14).
Bng 14. Nhng tnh cht ca cc hirocabon trong kh ging du Nhit si (C) Metan Etan Propan n-Butan iso-Butan n-Pentan iso-Pentan n-hexan 164 84 44 + 0,3 17 36 30 69 Nhit ti hn (C) 95,5 34 97 197 194 250 p sut ti hn (at) 50 50 44 33 33 30

V ngha thc t v kinh t: hai hirocacbon u tin khng th ngng t cn cc hirocacbon khc cao hn u c th thu h i c. Thng thng ch nhng hirocacbon cao hn propan to nn xng t nhin. C ba phng php c s dng thu h i hirocacbon ngng t : 1 - Nn theo cc giai on v lm lnh. 2 - Hp th vo trong du sau gii hp th ly hirocacbon. 3 - Hp ph trn than hot ng. Cc qu trnh (1) v (2) l ph bin nht. Qu trnh thu h i c iu khin m bo thu h i hon ton cc pentan v tt c cc hirocacbon cao hn. Trong qu trnh , mt t l ng k butan ho tan vo trong v nh vy sn phm c mt p sut hi c th l qu cao i v i

xng t. Mt xng t nhin khng cha butan c p sut hi Reid l 1,4 kg/cm2 38C; nhng nu xng cha 25% butan th p sut hi Reid s tng ln ti 2,3 kg/cm2. Trong xng khng c butan th t l cc hirocacbon c to nn nh sau: cc pentan ln gp hai ln hexan, hexan l n hn hai ln so vi heptan v octan bng heptan. Cng dng chnh ca xng t nhin l dng sn xut cc xng theo yu cu ca th trng bng cch trn xng t nhin vi cc xng khc. V mc ch ny p sut hi ca xng hn hp cng cao cng tt, v ngi ta thy rng p sut h i cng cao th ch s octan cng cao.

3.2.2 Xng thu c bng cch ct trc tip t du th

Thnh phn ho hc ca xng ct trc tip tinh luyn c nghin cu cn thn hn nhiu so vi bt k phn on no ca du m. Cc xng ny g m cc hirocacbon parafin, naphten v aromat. Chng khng cha cc olefin hay cc dn xut vng ca propan, butan hay heptan. Cc dn xut vng c th l xiclopentan v xiclohexan, thm ch c c benzen v toluen. T l cc lo i hirocacbon thay i rt rng tu theo ngun du (xem bng 15). Nh vy, cc naphten v parafin l cc cu t chnh. Xng ct trc tip t du parafin rt giu parafin (~70%); du trung gian c hm lng parafin ti 50%, cn du th asphalt c hm lng parafin khong 3% trong xng ct trc tip. Cc xng giu naphten v aromat khng ph bin. Du th Borneo cho xng ct trc tip giu hirocacbon aromat.
Bng 15. Thnh phn ca cc xng ct trc tip ph thuc vo ngun du Khi lng ring 15C (g/cm3) Pensylvania Oklahoma Texas Mehico Romania 0,732 0,739 0,750 0,727 0,736 im kt thc (C) 207 177 150 200 150 Thnh phn (%) Aromat 7 10 33 10 12 Naphten Parafin 18 29 21 35 30 75 61 57 55 54

Xng ct trc tip thng ly trong gii hn t 40C 200C. Trong khong nhit ny nhng hirocacbon cao cng bay hi to nn thnh phn ca xng (bng 16). Bng 16. Cc hirocabon trong xng ct trc tip + Cc n-parafin
Cng thc Nhit si (C) Khi lng ring 20C (g/cm3) Nhit dung ring (cal/g.C) Nhit ho hi (cal/g)

Pentan Hexan Heptan Octan Nonan

C5H12 C6H14 C7H16 C8H18 C9H20

37 69 98 125 150

0,63 0,66 0,68 0,78 0,72

0,527 0,507 0,505 0,503

85,5 70,4 76,5 71,0 -

+ Cc naphten
Cng thc Xiclo-pentan C5H10 Xiclo-hetan C6H12 Xiclo-heptan C7H14 Xiclo-octan C8H16 Xiclo-nonan C9H18 Nhit si (C) 49,5 81,4 118,0 150,6 172,0 Khi lng ring 20C (g/cm3) 0,754 0,779 0,811 0,839 0,770 Nhit dung ring (cal/g.C) 0,506 Nhit ho hi (cal/g) 87 -

Chng ta thy rng i vi mt xng, t l ca phn ct cng cao mt nhit thp th mc bay hi ca xng cng cao. Nhng xng ct trc tip theo kiu ny bn thn n cha th l xng thch hp cho ng c t v cc c trng s dng ca xng cha tha mn.

3.2.3 Xng crackinh v xng refominh

3.2.3.1 Gii thiu chung Nhng c trng c bn ca mt xng t l g ? Nhng c trng ny g m hai loi: 1 - Nhng c trng gn lin vi ng cong chng ct (xem ph lc 2); 2 - Nhng c trng gn thnh phn ho hc ca cc hirocacbon c mt trong xng. hiu r vn ny, chng ta theo di qu trnh ca xng t bnh cha ti khi ra kh i ng c t trong. Xng i ti b ch ho kh qua ng dn. Nu xng qu d bay hi, n s ho hi mt phn di tc dng ca nhit to ra t ng c v hnh thnh trong ng dn nhng bt kh. Bt kh ny lm gin on dng xng chy vo b ch ho kh. Bi vy, cn thit phi iu chnh ngay ti nh my lc du p sut hi ca xng di mt gii hn thch hp m p sut ny trong ma ng s cao hn ma h.

Xng tip tc i qua b ch ho kh to nn mt hn hp vi khng kh. Ngi ta d dng nhn thy rng dng ca ng cong chng ct xng c mt nh hng ng k trc ht ln s ch ho kh, sau ln cch m hn hp xng/khng kh (kk) s hot ng trong ng c. Khi khi ng ng c, hn hp nhin liu v khng kh cn phi tng i giu c th bc chy mc d xng b ngng t kh nhiu khi b tip xc vi cc ng lm lnh. Ni chung, ngi ta chp nhn nhit si ca im 10% c trng cho khi ng my. Nhit si ny thng nm trong khong gia 50C v 60C i vi cc t v my bay. S lm vic bnh thng ca ng c v c bit khi tng tc ph thuc vo s ho hi hon ton ca ton b nhin liu, ngi ta chp nhn rng nhit si ca im trung bnh, im 50%, m bo hot ng ny. i vi cc xng thng thng, nhit ny thng nm gia 90 v 110C. im si cu i cng, cn thit l xng khng cha cc phn t nng kh bay hi hon ton trong cc iu kin bnh thng, nu khng c th gy nn s ho long nhanh du ca cacte. Mt khc, s c mt ca cc phn t nng c th gy nn nhng bt tin khc i vi ng c khi ng c quay nhanh b i v s chy ca cc phn t nng khng nhanh bng cc phn t nh. Vi cc ng c 4000 vng quay hay l n hn, ng c s th i ra mu i do xng chy khng hon ton. Nhng php o chnh xc chng minh rng s phn b ca hn hp xng/khng kh cng bt thng trong xilanh khi nhit ca im 90% cng cao. V tt c cc nguyn nhn ny, im cu i cng ca ng cong chng ct ni chung c gi di 190C i vi cc xng cho t. Cn cc xng cho my bay, im cu i cng ca ng cong chng ct l trc 170C. Chng ta thy rng vic phn on cn thn ca xng l rt quan trng v cc nh my lc ho du quan tm n vn ny sut trong qu trnh sn xut. Ngc li, ngi ta thy rng 2 xng c cng ng cong chng ct, cng mt nhit tr nhng c th c s khc nhau rt ln v hiu sut trong mt ng c. S d nh vy v c trng cho xng cn c kh nng chng kch n. Nm 1927, Graham Edgar a ra thang octan. u cao l iso-octan (2,2,4-trimetylpentan) mt cht chm n nht trong s 18 ng phn ca octan. u thp l n-heptan mt cht d n nht trong 9 ng phn ca heptan v quy nh tng ng cho nhng hirocacbon trn cc gi tr 100 v 0. l thang ch s octan. xc nh ch s octan ca mt xng ngi ta s dng ng c CFR (Cooperative of Fuel Research). l ng c c 1 xilanh v t l nn c th thay i c. T l nn c th thay i bng cch iu chnh sao cho thu c s n ca xng cn xc nh ch s octan. Nh vy, s n ca xng tu thuc vo ng c. cc php o c tnh lp li th cn phi gi cc iu kin o tht chnh xc, c bit l ch quay ca ng c, ch ny s quyt nh s ma st cng nh thi gian tip xc gia khng kh v hirocacbon. Ty theo cch lm vic ca ng c ngi ta c th thu c: Ch s octan nghin cu F1 (RON) hay phng php F1 vi ng c quay 600 vng/pht.

Ch s octan mt F2 (MON) hay phng php F2 vi ng c quay 900 vng/pht.

Ch s octan mt (MON) ca mt nhin liu ni chung thp hn ch s octan nghin cu (RON). S khc nhau gia hai gi tr RON v MON cho ta bit nhy ca nhin liu c nghin cu. Thc t ngi ta thy nhng kt qu o theo phng php mt (MON) l rt tha ng ngay c i vi xng c bn cht parafin. Cc gi tr MON c trng cho tnh cht ca nhin liu khi xe i trn ng vn chuyn di tc cao. Cn ch s RON li c trng cho tnh cht ca nhin liu khi xe i trong thnh ph tc va phi v thng xuyn phi tng tc. Vi xng my bay ngi ta dng phng php F3 vi ng c c s vng quay l 1200 v/ph. Cn phng php F4 c trng cho tnh cht nhin liu dng khi my bay ct cnh hay my bay chin u c xc nh vi ng c c s vng quay 1800 v/ph. Nh vy, ch s octan quyt nh cht lng chy ca nhin liu v cc iu kin ti u c s dng, ch s octan gn lin vi khi nim v hiu sut s dng nhin liu. Hiu sut nhit ng hc ca mt vng hot ng ca ng c t trong t hay my bay tng khi tng t l nn. Ngha l t s ca th tch xilanh ( im cht thp) vi th tch ca xilanh im cht cao cng ln. Nhng c mt gii hn trn cho s tng t s nn ny. trn gii hn ny, hiu sut s gim i v xut hin ting g lch cch ca kim loi. Khi ng c hot ng bnh thng (khng c ting g) s chy ca hn hp khng kh nhin liu (kk - nl) (c bt u bng tia la t bugi) c truyn theo cc sng ng tm v i tc truyn la khong vi mt/giy. Tuyn la trong khi truyn, nn phn cn li ca kk - nl cha b chy lm tng nhit ca hn hp. Nhng iu kin nhit v p sut qu cao ny thun l i cho s hnh thnh cc hp cht peoxit km bn vng. Khi n ng ca chng trong h n hp t n mt gi tr thch hp th chng t phn hy mt cch t ngt gy nn s n. S n ny c c trng bng mt tc rt ln s truyn sng. Sng ny p vo np xilanh v u ca pittong gy nn ting n mnh. Vy ting g lch cch l kt qu ca sng c h c v nhit gy ra. Sng c hc tc ng n ng c, song ngi ta c th ch to c cc ng c khng b nh hng bi sng ny. Nhng hiu ng nhit li rt nguy him, cn thit phi lm lnh lo i bt nhit to ra khi nhin liu chy. Nu khng ng c b t nng thun li cho qu trnh to peoxit, to mu i cacbon bm trn u pittong. Mui ny b nng gy nn s t chy ca nhin liu m khng cn bugi nh la v ng c vn tip tc quay khi ta ngt tip xc. Nh vy, i vi mt nhin liu cho s n gn lin vi vic ch to ng c, h s nn, ri ca dng kk - nl, dng ca np xilanh,... cht lng ca bugi. i vi mt ng c cho, s n ph thuc vo thnh phn nhin liu. Cc yu t trn dn ti vic phi s dng phng php phn loi cc nhin liu tu theo cht lng khng n ca chng trong ng c. Nguyn tc ca vic phn loi cc nhin liu l so snh chng trn cng mt ng c chun tnh cht ca mu nghin cu v i tnh cht ca mt hn hp hirocacbon tinh khit ly lm chun.

Bng 17. Cc c trng ca xng thng v xng cao cp Php Quy nh Xng thng Xng cao cp

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Hn hp cc hirocacbon c ngun gc t nhin hay tng hp Mu Khi lng ring (kg/l) c trng chng ct: % Th tch 70C % Th tch 140C % Th tch 195C Khong cch im 5% v im 90% im cui cng Cn (% th tch) p sut hi 37,8C: T 15/10 n 30/4 (ma ng) T 1/5 n 14/10 (ma h) 0,8 at 0,65 at < 0,20 1b cc i 10 mg/cm 3 89 92 0,40 g/l 97 99 < 0,15 10% 50% 45% > 60C 205C < 2,5 <3 0,765 Vng sng 0,770

Hm lng lu hunh (% khi lng) n mn tm ng Hm lng gm hin hnh RON Hm lng ch

ng c chun l ng c CFR ni trn Hirocacbon chun l: n-C7H16 c OC = 0 v iso-C8H18 (2,2,4-trimetylpentan) c OC = 100.

Nh vy, mt nhin liu c ch s octan l X, nu trong ng c CFR n gy nn mt ting g tng ng vi ting g quan st thy ca mt hn hp g m X phn trm th tch iso-octan v (100 x) phn trm th tch n-heptan. Ngoi nhng cht lng v bay hi v ch s octan ni trn, mt nhin liu t khng c cha cc hp cht ca lu hunh c mi hi, cc hp cht c tnh axit n mn thit b cha xng cng nh ng c. Xng phi khng c cha gm, v gm c th gy nn hiu qu bt nhanh cc l phun v supap. Bng 17 trnh by cc c trng ca xng thng v xng cao cp c s dng Php. Trong thi gian gn y, quy nh ca xng cao cp b thay i v chp nhn s c mt ca nhng hp cht hu c cha oxi nh CH3OH, C2H5OH, C4H9OH hay cc ete nh MTBE. Ni chung, cc hp cht ny c ch s octan cao (>100) nhng chng c th gy n mn thit b hoc gy tr ngi cho s phi trn nhin liu nu chng c ln hi nc. lm tng cht lng ca xng ngi ta c th dng xng crackinh v xng refominh.

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3.2.3.2

Xng crackinh

Xng crackinh l xng thu c sau qu trnh crackinh mt phn on nht nh ca du th. Nhng tnh cht ca xng crackinh: Cc xng crackinh nhit c ch s octan c bit cao hn cc xng chng ct trc tip. Thng thng ch s octan RON ca xng crackinh nhit l 70 80. Xng crackinh nhit khng bn vng, chng c khuynh hng cho gm pht trin tng i mnh trong qu trnh bo qun ti kho vi s c mt ca khng kh. Tuy nhin ngi ta tm ra cc phng php lm sch xng hay dng cht km hm to gm cho php c th dng xng m khng c bt k mt bt tin no i vi t. Nhng ngi ta khng th, ngay c bng cch tng cng cc bin php x l ho hc bng cc cht km hm, lm cho xng crackinh nhit c mt bn vng s dng chng lm xng my bay. Ngc li, crackinh xc tc cho cc kt qu tho mn hn nhiu, v thc t cc xng crackinh xc tc khng cha nhng hirocacbon ietilenic m chng l nhng hirocacbon km bn vng nht. Ch s octan RON > 90 ca cc xng crackinh xc tc l do: Cc hirocacbon nh ca xng cha mt t l ln cc iso-parafin v iso-olefin. Cc hirocacbon nng ca xng c bit giu cc hirocacbon thm. Chng ta bit rng ch s octan ca ba loi hirocacbon ny ln hn nhiu so vi ch s octan ca cc parafin mch thng.
Bng 18. Thnh phn ca phn on hexan (C6) thu c t xng ca cng du th nhng c sn xut theo cc cch khc nhau Cc parafin trong phn on C6 (%) 2-metylpentan 3-metylpentan 2,3-imetylbutan 2,2-imetylbutan Tng s iso-parafin n-hexan Tng Xng thu c t chng ct 32 16 1 49 51 100 Xng crackinh nhit 18 16 3 37 63 100 Xng crackinh xc tc 48 27 13 3 91 9 100

Bng 18 cho thy nhng hirocacbon parafin ca phn on hexan c tch ra t ba xng c cng mt ngun gc du th nhng thu c theo ba phng php khc nhau. Chng ta thy rng cc parafin ca xng crackinh xc tc b phn nhnh hn rt nhiu so v i cc xng khc. Cn cc phn n ng, chng ta s th y thnh phn ca chng trn cc th trong hnh 6 v 7 di y khi x l cng m t nguyn liu u.

12

Hnh 6. Thnh phn ca cc loi hirocacbon thu c trong crackinh nhit

Hnh 7. Thnh phn ca cc loi hirocacbon thu c trong crackinh xc tc

3.2.3.3 -

Xng refominh

nng cao cht lng xng, ngi ta c th dng xng refominh. Xng refominh nhit c ch s octan cao hn nhiu so vi xng ct trc tip t du th. Bng 19 di y trnh by cc c trng ca xng refominh nhit ca 2 phn on tng i khc nhau ca cng du th Irc.
Bng 19. c trng xng refominh nhit ca 2 phn on t cng ngun du th Irc c trng Phn on 1 Phn on 2

13

im u (C) im cui (C) RON ca nguyn liu u RON ca phn refominh nh RON ca phn refominh nng

90 205 40 78 71

125 240 32 72 65

Chng ta thy rng refomat nhit c ch s octan cao hn nhiu so vi ch s octan ca nguyn liu u. Xng refominh xc tc. Qu trnh refominh xc tc cc hirocacbon l mt qu trnh rt phc tp bao gm:

+ ehiro ho cc naphten thnh cc hirocacbon thm; + ehiro vng ho cc parafin thnh cc naphten; + ng phn ho cc parafin v naphten thnh isoparafin... Cc qu trnh ny u dn ti cc loi hirocacbon c ch s octan cao. Chnh v th, cc c trng ca xng refominh xc tc l rt tt cho cc ng c t v my bay. V d, ch s octan RON l 92,5, im chng ct 50% 111C. 3.2.3.4 Xng tng hp t kh Trong cc nh my lc ho du c cc kh d: Loi parafin: CH4, C2H6, C3H8, C4H10 v iso-C4H10 Loi etilenic: C3H4, C3H6, 1-buten, 2-buten v iso-buten.

y l ngun nguyn liu qu tng hp cc xng c ch s octan cao. Chng ta bit rng cc hirocacbon c tnh khng n cao l cc ng phn phn nhnh, ngha l trong cc phn t ny cha nguyn t cacbon bc ba. S phn nhnh cng nhiu th ch s octan ca phn t cng cao. Hn na ngi ta cng nhn thy rng bn ca phn t vi s va chm tng ln khi phn t t tp trung li hay di tc dng ca hiu ng phn nhnh. V d i vi hirocacbon parafin C7: - n-heptan: CH3-(CH2)5-CH3 c ch s octan 0 (theo quy c). - 2-metylhexan : CH3-CH(CH3)-CH2-CH2-CH2-CH3 c ch s octan 45. - 3-metylhexan: CH3-CH2-CH(CH3)-CH2-CH2-CH3 c ch s octan 65. Ch s octan tng ln khi cc nhnh tp trung v trung tm ca phn t: - 3,3-imetylpentan: CH3 -CH2-C(CH3 )2 -CH2-CH3 c ch s octan 94. - 2,2,3-trimetylbutan (triptan): CH3-C(CH3)2-CH(CH3)-CH3 c ch s octan 105. Triptan c th c s dng trong mt m t m t l nn l khong 15/1. Lut tng ch s octan ca cc hirocacbon parafin vi s tp trung ca phn t vo pha tm ca n l rt tng qut v ta c th thy s thay i hon ton tng t i vi cc hirocacbon

14

C6, C8... v nn nh rng nhy hay hiu s gia RON v MON tng ln vi s tp trung ca phn t vo pha tm ca n. Ni chung, ngi ta nhn thy rng nhng hirocacbon etilenic ring bit c ch s octan cao hn mt cht so vi cc parafin tng ng, trc ht l nhng hirocacbon C8. Mt khc, nhy v ch s octan ca hn hp cc hirocacbon etilenic l cao hn nhiu so vi nhy v ch s octan ca hn hp cc parafin c cng s nguyn t cacbon. Ch s octan ca cc naphten cao hn m t cht so v i ch s octan ca cc parafin t ng ng nhng nh y ca chng khng cao hn. Nhng hirocacbon aromat c ch s octan rt cao. nhy ca chng trong hn hp cng rt ln nh ch s octan khi nng ca chng trong hn hp nh. T nhng nhn xt trn y ta s thc hin chuyn ho cc kh thnh cc nhin liu c ch s octan cng cao cng tt. Cc phng php tng hp nh sau: * Polime ho xc tc (oligome ho) Nguyn liu u l cc olefin ni trn. Xc tc: axit H3PO4, pyrophotphat ng, quartz tm H3PO4 lng. L phn ng c cha cht xc tc c th l mt thng ln hay l nhng ng phn ng c ng knh tng i nh m ngi ta c th lm lnh chng bng nc. Nhit phn ng thng thng l 150 220C v chuyn ho ca olefin c th t ti 85 95% ch qua 1 vng phn ng. Tc cung cp olefin c th dng t 0,1 0,5 m3/h tu theo hot ng ca xc tc v p sut c th i t 35 bar 70 bar.

trnh s phn hu ca xc tc, gi hot ng lu di ca chng, ngi ta thng a khong 5% nc vo nguyn liu u v lm lnh phn ng, gi nhit phn ng sao cho khng vt qu 220C. Vic polime ho chn lc nh ime ho isobuten hoc ng ime ho isobuten v buten, tip theo l hiro ho cho ta nhng iso-octan c ch s octan F3 ~ 100. Cc phn ng ime ho chn lc ny dn dn c thay th bng ankyl ho c tnh u vit hn. * Ankyl ho hirocacbon phn nhnh bng olefin nh Nhng hirocacbon bo ho c cha nguyn t cacbon bc 3 nh isobutan, isopentan... kt hp d dng vi cc hirocacbon etilenic khi c mt ca cc xc tc nh H2SO4, HF. C2H4 + iso-C4H10 C2H4 + iso-C4H10 C2H4 + iso-C4H10 2,2-imetylbutan, 2,3-imetylbutan, RON = 92 RON = 101

2,2,4-trimetylpentan, RON = 100

Hai hirocacbon u tin, 2,2-imetylbutan v 2,3-imetylbutan c ch s octan RON tng ng l 92 v 101, cn 2,2,4-trimetylpentan c RON = 100 theo nh ngha. Nu chng ta dng cc iso-olefin, ta s c cc sn phm sau y:

15

iso-C4H8 + iso-C4H10 C3H6 + iso-C4H10

iso-octan iso-nonan iso-heptan

RON = 92 94 RON = 90 92 RON = 89 91

iso-C5H10 + iso-C4H10

Trong cng nghip, nu dng H2SO4 lm xc tc cho cc phn ng trn, thng ngi ta phi quay vng phn ng nhiu ln i vi iso-butan sao cho gi c trong l phn ng t l isoC4H10/olefin = (6 8)/1. S d phi gi t l ny v olefin b hp th bi axit H2SO4 rt d dng. Nu t l ny cng ln th hiu sut s cng cao v vic tiu tn axit H2SO4/1 lt ankylat cng thp. Xc tc H2SO4 nng lc ban u l 98% sau c th kt hp dng H2SO4 s dng c nng 90%. Thng thng ngi ta dng axit H2SO4 vi nng ban u 98% v vic tiu tn tng cng axit l t 1,5 kg 6,5 kg /1m3 alkylat. Nu H2SO4 khng th ti sinh c th ngi ta c th dng chng vo mc ch khc nh tinh ch du bi trn. Ankyl ho vi s c mt ca axit H2SO4 l mt phng php t tin do phi tiu tn nhiu axit. Vi vic dng axit HF lm xc tc th ngi ta c th thu h i HF cu i m i mt vng phn ng nn s tiu tn axit HF gim xung (t 0,8 2,3 kg/m3 ankylat). 3.2.3.5 Xng khng ch Nh chng ta bit, lm tng ch s octan ca xng, ngi ta dng cc ph gia nh Pb(C2H5)4, Pb(CH3)4 hay hn hp Pb(C2H5)4 v Pb(CH3)4. Do s pht trin qu nhanh ca nn cng nghip t nn vic tiu th xng cng tng rt nhanh. Mt dy c t trn cc ng ph thi vo khng kh mt lng ch khng nh v gy nn nhim mi trng, gy hi cho sc kho con ngi. V th, vic dng xng khng ch ngy cng ph bin. Cc nc cng nghip pht trin a ra nhiu lut t hn ch dng xng c ch tin ti dng xng khng ch.
Bng 20. Th trng th gii v chu u v vic dng xng khng ch (tnh n thng 6 - 1990) Cc loi nhin liu khng ch (%) Nhin liu khng ch Thng thng Eurosuper Supermium (%) 100 92 90 53 30 50 10,5 4 86 65 60 30 4 6 23 28 50 2 4 14 23 24 2 8,5 -

Nc

Nht Canada M o B Phn Lan Php Italia

16

Luxembourg H Lan an Mch B o Nha Ty Ban Nha Anh Thy in

21 40 45 0,2 0,5 25 42

19 33 45 0,2 0,5 21 41,5

2 7 4 0,5

Xng khng ch dng chu u chia lm 3 loi: 1 - Mc bnh thng (Regular-grade) c dng ch yu c, c RON t 92 93 v MON t 82 83. 2 - Nhin liu ng c chun dng cho tt c cc nc trong khi cng ng chu u c RON cc tiu l 95, MON cc tiu l 85 (nhng nc khng thuc cng ng chu u cng dng l o, Phn Lan, an Mch, Thu in v Thy S, tnh n nm 1990). 3 - Nhin liu c ch s octan cao RON 98 v MON 88. Cc nc dng xng ny l Php, H Lan. Bng 20 gii thiu vic dng nhin liu ng c xng khng ch trn th gii. Ton b chu u dng xng khng pha ch khong 118 triu tn/nm chim khong 26% th trng nhin liu. Nh trn trnh by, tu thuc vo gi tr RON v MON ngi ta chia xng t thnh cc cp khc nhau v nh th thnh phn ha hc ca chng cng khc nhau v ngay xng cng cp (Eurosuper vi RON 95, MON 85) cng c hm lng olefin v aromat khc nhau tu thuc vo tng quc gia chu u (bng 21). Bng 22 cho bit hm lng olefin v aromat trong cc xng c cp khc nhau chu u.
Bng 21. Hm lng olefin v aromat ca cc nhin liu khng ch chu u (cp Eurosuper vi RON 95, MON 85) Hm lng olefin (%V) RON 95 Ty c Italia B Anh 7,7 5,9 7,4 6,4 MON 85 22,4 13,8 14,4 9,0 Hm lng aromat (%V) RON 95 38,9 35,3 36,0 35,8 MON 85 45,5 43,4 45,0 43,6

Quc gia

17

an Mch, Thy in

9,1

18,2

42,1

45,6

Ph gia quan trng v ph bin nht thay th cho cc hp cht c ch l MTBE (metyl-tecbutylete). Vic s dng MTBE trong xng khng ch chu u c trnh by trong bng 23.

Bng 22. S khc nhau ca cc loi xng khng ch chu u Kiu xng Regular (c) Eurosuper (EEC) Superpremium (Php) Hm lng olefin trung bnh Hm lng aromat trung bnh (%V) (%V) 12,1 7.3 5,4 31,8 37,6 50,1

Ta thy rng MTBE c dng trong tt c cc loi xng. Ngoi MTBE ngi ta cn dng cc tc nhn lm tng ch s octan khc l: ch.
Bng 23. Vic s dng MTBE trong xng khng ch chu u Hm lng MTBE quan st c (% liu trng lng) Cc tiu B Eurosuper Superpremium c Eurosuper Regular Anh Italia Eurosuper Eurosuper 100 64 42 42 25 50 0,8 1,0 0,7 0,1 2,2 Trung bnh 2,1 6,8 1,1 0,5 4,4 4,0 Cc i 4,0 11,4 1,6 1,1 6,2

TAME, (Tec-amylmetyl ete). Metanol vi hm lng trung bnh ~ 1,2 %. Tec-butanol hm lng trung bnh ~ 1,4 %.

Ngi ta cng c th kt hp cc ancol ny vi MTBE thm vo thnh phn ca xng khng

Nc

Kiu xng

Phn nhin cha MTBE

S c mt ca cc hp cht cha oxi dng nh khng c bt k nh hng g n hp xc tc x l kh thi. Tuy nhin, cc nh sn xut t khng mun c mt khong qu rng v nng ca cc cu t cha oxi. Bi v h phi nghin cu nhng thnh phn phn cc c th cho

18

nhin liu t thu c s chy tho mn trong tt c cc trng hp. V d, s khc nhau v t l ng lng cc cu t ca xng do s thay i hm lng MTBE c th lm thay i s pht thi cc sn phm cha chy ht (CO v CH) trong giai on u khi hp xc tc cha hot ng. Ni tm li, xng khng ch l mt t hp phc tp ca cc hirocacbon v cc ph gia. Ph gia tng ch s octan l cc hp cht cha oxi nh MTBE, CH3OH, C2H5OH, (CH3)3C-OH, tecamylmetylete... Thnh phn xng ny c th c thay i nh tu thuc vo kh hu v a hnh c th ca tng nc s dng xng. Cc nh nghin cu cho rng ph gia C2H5OH cho xng c trin vng sng sa nht v C2H5OH khng c hi, v ngi ta c th sn xut c nhng lng rt ln t ngun nguyn liu nng nghip v du m.

3.3 Nhin liu iezen (DO)

Khi chng ct s cp du th ta thu c phn on si gia 200C v 320C. Phn on ny c g i l gazoin hay du iezen. Du gazoin thu c t cc sn phm crackinh nhit v crackinh xc tc rt khc vi gazoin thu c t chng ct trc tip du th do thnh phn ca chng b bin i. Hm lng parafin b gim i do s hnh thnh cc hirocacbon khng bo ho v hirocacbon thm, cht lng n v ch s xetan ca du b gim i. Tn gi du gazoin c ngun gc t vic dng du ny sn xut kh thp sng bng crackinh v mc du ngy nay ngi ta khng cn dng na nhng tn phn on ny vn c gi nguyn v nhng lng ln du vn c dng sn xut kh t. V mc ch ny, du gazoin phi c c trng parafin khi crackinh nhit ngi ta thu c hiu sut cao kh c nhit tr ln. Bi vy, du gazoin phi l distillat ct trc tip t du m parafin. Nhin liu iezen (Diezel fuel) c cng mt khong nhit chng ct (200 320C) nh du gazoin v d nhin chng l cng mt nhin liu nhng c s dng cho ng c nn - n (c g i l ng c iezen) v th chng c gi l nhin liu iezen. Cc ng c iezen c rt nhiu dng v tc , s dng mt khong rt rng cc nhin liu t cc distillat ca du th n cc phn on chng ct du than v cc du thc vt. 3.3.1. Du gazoin V l m t s n ph m thu c t ch ng ct nn du gazoin thay i v thnh ph n tu theo b n cht c a d u th nh ng m t s tnh ch t c trng ph i c tho mn l i m ch p chy, kho ng nhit ch ng ct (t 200 320 C). B ng d i y minh ho m t s tnh cht ca du gazoin khc nhau ty theo kh i l ng ring ca chng. Bng 24. Thnh phn v tnh cht ca cc du gazoin T trng (15,5 / 15,5C) im chp chy, C nht Redwood 37,7C Nhit khong si thp nht, C 0,84 200 35 220 0,88 186 33 200 0,86 186 37 210

19

% chng ct ti 300C Ch s xetan Cn cacbon Conradson (% trng lng) im rt, C

65 62 0,02 4

34 34 0,07 9

47 47 0,02 12

Cng dng chnh ca du gazoin l dng sn xut kh t v tch benzen t kh than (coal gas), nhng du gazoin c th c dng lm nhin liu cho ng c iezen tu thuc vo ch s xetan ca n. Nu ch s xetan cao th n rt thch hp cho cc ng c iezen c nh v tc cao. Nu nht ca du gazoin cao th khng thch hp cho cc ng c iezen chy ng bin, trong cng nghip c tc thp v vic bm nhin liu kh khn. 3.3.2. Nhin liu iezen v ng c iezen Nhng tnh cht ca nhin liu iezen c gii thch tt nht sau khi nghin cu cc c trng ca ng c nn-n - ng c iezen. S ng c nn-n iezen c cho trn hnh 7.

Hnh 7 S ng c nn-n iezen

Nguyn l c bn ca ng c ny l da trn nhit nn lm bc chy nhin liu. Nhin liu c tim vo bung nn m khng kh c nn ti 1 p lc t 41,5 - 45,5 kg/cm2 v t ti nhit t nht l 500C. Nhit ny lm bc chy nhin liu v kh dn n lm tng p lc ln ti trn 70 kg/cm2. p lc ny tc ng ln pittong v lm ng c chuyn ng. Trong ng c nn-n 4 k bnh thng, 1 vng c th chia thnh 4 k: 1. Ht khng kh vo xilanh, sau van vo ng li.

20

2. 3. 4.

Nn khng kh trong xilanh ti mt th tch xc nh (trong k nn ny p sut v nhit tng ln), khi nhin liu iezen c phun vo bung nn. Nhin liu chy. Kh chy dn n trong khi tt c cc van ng, p lc tc ng ln u pittong lm my chuyn ng. Van x m v kh chy c thi ra ngoi bung nn. K ny hon thnh 1 vng ca ng c v vng tip theo c bt u vi vic ng van x. Nh vy c 1 k sinh cng v 3 k khng ti cho hai chuyn ng ca tay quay.

Trong ng c 2 k khng kh b nn nh trn, nhng ngay gn u k sinh cng, van x m ra v xilanh c qut bng khng kh sch t 1 my bm sao cho k tr li nn khng kh sch. Nn khng kh sch l cn thit t hiu qu ca tay quay v ng c lm vic mnh hn v m hn so vi ng c bn k c cng c v tc . Nhng thun li ch yu ca ng c iezen l s gn gng ca ng c, sch s v hiu qu nhit cao, c th k ra nh sau: 1. 2. 3. 4. 5. 6. Vi mc ch hng hi, ng c iezen chim ch t hn so vi ng c hi nc c cng cng sut nng lng. N khng tiu tn nc v nc lm lnh c th quay vng. Vi mc ch chy ng b, h thng tim nhin liu ca ng c iezen hiu qu hn ng c xng v tiu tn nhin liu ch vo khong mt na cho cng mt cung ng. ng c c th xut pht trong iu kin lnh v c th t c cng sut hu nh ngay thc thi, mt thun li rt ln so vi bt k ng c hi nc no. c kt hp vi vic sn xut in th ng c iezen hiu qu hn bt k ng c no khc cung cp nng lng cho vic s dng trung gian. ng c iezen lm vic vi hiu sut nhit cao khong 30 35%.

Nh trn trnh by, trong chu trnh lm vic ca ng c iezen, nhin liu t bc chy trong iu kin nhit v p sut ti hn, khng cn m i la t bugi. V th tnh cht quan trng ca nhin liu iezen l cht lng chy ca n. u tin, nhin liu phi c kh nng d dng chy nhit nn thp m bo s chy, thm ch khi xut pht iu kin nhit thp. Th hai, thi gian gia khi tim nhin liu vo xilanh v chy phi khng c qu di hay qu nhiu du trong xilanh khi s chy xy ra v nh th p sut cao khng cn bng s sinh ra v ng c hot ng khng tt. Bi vy, cht lng chy ca nhin liu iezen phi c o bng nhit chy tc thi v bng cc php th ng c c ch to c bit thu c cc gi tr s i vi s tr chy. Nhit chy tc thi (SIT - Spontaneous Ignition Temperature) lin quan rt nhiu n hm lng hiro ca du v ng thi n c xem nh php o s tin li ca vic dng nhin liu iezen. Mt phng php chun l im chp chy trong kh quyn oxi c xc nh bng cch nh tng git du vo mt ci cc kim loi c t nng lin tc. Mt gi tr nhit thp ca s t bc chy trong oxi c xem l thun tin cho vic dng du . Php th ny ch l mt ch dn rt chung cho s tin li ca vic dng nhin liu iezen.

21

Gi tr SIT ca xng t (OC 75) l khong 500C, ca du iezen (ch s xetan 50) l 260C v ca octan l 235C. Phng php tt nht nh gi cht lng nhin liu iezen l th trong ng c, nhng mt phng php th gn ng c th thu c l xc nh t l parafin trong nhin liu iezen. Trong trng hp cc nhin liu i t du m th hm lng parafin cng cao th cht lng chy cng tt. iu ny khng phi lun ng vi cc nhin liu thu c t du v cc phn on thu c t than . Mt php th khc l im anilin. Ngi ta da trn thc t l cc hirocacbon thm trn ln d dng vi anilin nhit phng, nhng vi cc parafin cn t nng ti mt nhit tng i cao chng mi trn ln hon ton vi anilin. V d, hirocacbon thm, hexylbenzen c i m anilin < 12C, trong khi mt parafin (octan) c gi tr l 15,1C. Nh vy im anilin cao l mt ch dn v hm lng parafin cao v nh th tnh tin li s dng cao. im anilin c chuyn thnh ch s iezen theo biu thc: im anilin (F) Trng lng (API) Ch s iezen = 100 Ch s iezen khng tht tin tng nh ch s xetan nhng n l mt ch dn hu ch khi khng c iu kin th ng c. V gi tr s, ch s iezen thng cao hn 3 n v so vi ch s xetan v n c th chuyn thnh ch s xetan theo cng thc sau: Ch s xtan (tnh ton) = Ch s iezen + 0,068 T si trung bnh (F) 22 Khi cht lng chy c th trong mt ng c iezen chun th kt qu c biu th bng ch s xetan. Xetan l mt parafin, C16H34 c cht lng chy cao v ngi ta gn cho n c ch s xetan bng 100. -Metylnaphtalen l mt hirocacbon thm m ngi ta quy c n c ch s xetan bng 0. Chng to nn thang o ch s xetan. Vy ch s xetan ca mt nhin liu iezen l phn trm theo th tch ca xetan trong hn hp hai hirocacbon xetan v -metylnaphtalen m n c cng cht lng n nh nhin liu . C hai phng php xc nh ch s xetan bng ng c. Trong mt ng c iezen, c mt khong thi gian tr chy xc nh t 0,5 10 mili giy gia thi i m tim nhin liu v thi i m chy. Kho ng thi gian tr chy ny l khng i i v i mt nhin liu cho khi o theo gc quay ca tay quay ca ng c. Kho ng thi gian tr chy c dng lm php o cht lng chy v c g i l ch s xetan. Phng php 1 o trc tip thi gian tr chy cc iu kin bnh thng qua s gc m tay quay quay. lm iu ny cn phi dng mt thit b ghi c s thay i p sut v im chnh xc khi van m. Thng thng ngi ta s dng mt ch th tia catot gm mt thit b van ion nhit kt hp vi p sut v thi gian quay v nh vy cho php o c gc tr hay gc quay ca maniven. Phng php 2 n gin hn. Mt hp iu tc c gn vo van tit lu v chng c gn vo u ht ca ng c. Khi van ny ng li th p sut ca hp iu tc b gi m i, p sut nn l nh hn, th i gian tr tng ln cho n khi khng xy ra s n v pht

22

ra khi trng. p sut khng kh trong hp iu tc i m ny c coi nh mt hm ca th i gian tr v c so snh v i p sut tng t t hn hp ca nhin liu so snh v kt qu c biu th bng ch s xetan. M, ngi ta dng mt ng c CFR c tiu chun ho tin hnh php th di nhng iu kin chun v nhit khng kh, tc , tc nhin liu v nhit lm lnh. T l nn c th thay i c v c o so vi mt thi gian tr chun. Bi vy ngha chung ca cht lng chy l nhin liu c thi gian tr chy thch hp trong ng c. Mt ch s xetan cao, vt qu 48 l cn thit cho ng c tc cao nhng mt ng c tc thp khng i h i nh vy bi v n i h i nhiu thi gian cho s chy. nhit khng kh cao hn hay s trn khng kh vo nhin liu k cng hn s cn nhin liu vi ch s xetan thp hn cng mt tc . Tht vy, m i quan h gia tc ng c v ch s xetan l gn ng nh sau: Tc ng c (v/ph) > 1500 1500 800 800 400 400 100 < 100 Ch s xetan thch hp 60 50 55 45 50 35 40 30 30 15

nh hng ca vic s dng mt nhin liu c ch s xetan qu thp l tp trung qu nhiu nhin liu trong xilanh trc khi s chy xy ra, nh th mt p lc cao s c hnh thnh v tr nn nghe thy ting g iezen. Nhng php th ho hc v vt l cho nhin liu iezen Mt s php th cn thit cho nhin liu iezen nh: php th tinh khit ( sch), hm lng tro, cht sa lng, hm lng nc v hm lng asphalt. Hm lng tro thp l rt quan trng trong vic lm gim s hao mn ng c. Trong mt du chng ct hm lng tro khng c qu 0,01%. Hm lng cht sa lng v nc phi khng c trong du, nhng thc t hm lng nc ch cn khng vt qu 0,25%. Cc asphalt hay cc asphalaten l nhng cht c thnh phn rt phc tp. Chng c trng lng phn t ln v c khuynh hng b chy khng hon ton, gy nn cn cacbon bm vo ng c. C hai kiu asphalt chnh. Mt kiu c g i l asphalt cng, n khng tan trong ete du ho. Mt kiu khc c gi l asphalt mm, n c kt ta t mt dung dch trong ete ca du khi thm ancol vo dung dch . Asphalt mm gn nh khng gy nn s kh chu nh asphalt rn. Cc ng c iezen c th chy rt tt khi trong du c cha hm lng cao asphalt mm. Cc ng c iezen tc rt thp c th dng du c cha t 4 8% asphalt rn, nhng cc ng c tc cao th hm lng asphalt rn phi nh hn. Vi th tch bu ng t gii hn, thi gian cn thit cho s chy l ngn th du c cha hm lng asphalt rn > 0,1% l khng m bo. Ni chung, cc du chng ct cn ph i khng cha cc vt asphalt m i dng tt cho cc ng c iezen. loi cc ht sa lng hay cc ht asphalt, thng ngi ta dng phng php lc. Cn lm tng ch s xetan ca du hay lm gim thi gian tr chy ngi ta thng dng ph gia etyl nitrat, C2H5ONO2, iso-amyl nitrat hay axetoperoxit.

23

Khi thm cc lng nh t 1 1,5% cc cht trn s lm tng ch s xetan ln 23 29%. Mt iu bt tin l khi thm cc cht lm tng ch s xetan s lm cho ng c kh khi ng iu kin lnh, v th vic s dng cc ph gia loi ny khng c ph bin.

3.4 Nhin liu kh

Nhin liu kh l cc nhin liu c t chy trng thi kh trong khng kh hay oxi to ra nhit s dng cho mc ch dn dng hay cng nghip. c trng chnh ca cc nhin liu kh l khng cha cc cht bn v c, hm lng nhin liu cao, thun tin v hiu qu trong s dng, nhng h thng dn kh, bo qun v tng tr li t nht trong tt c cc nhin liu. Cc nhin liu kh quan trng t du m v kh thin nhin l: Kh thin nhin (natural gas); Kh ha lng - LPG (Liquified Petroleum Gas); Kh t nh my lc du (refinery gas); Kh c sn xut t du (Oil gas from oil gasification Processes).

Hai kh quan trng nht l hiro v axetilen c s dng rt rng ri hn, ct kim lo i, ... Cc nhin liu kh cn l i c g i tn l: Kh giu, nu nhit tr ca n ln hn 4000 kcal/Nm3; Kh ngho, nu nhit tr ca n nh hn 1500 kcal/Nm3.

Cc kh hirocacbon l nhng kh giu, cn kh l hay kh sn xut l nhng kh ngho. Nhit tr khng phi l thng s tha ng trong phn loi cng ngh nhin liu kh. Nhit thot ra t mt l t dng nhin liu kh ph thuc vo ch s Wobbe. Ch s ny c xc nh nh sau: C.V Wobbe Index = kcal/Nm3

T trng kh

trong C.V l nhit tr ca kh hay hn hp kh. Bng 25. Phn loi nhin liu kh theo ch s Wobbe
Loi nhm nhin liu kh 1 2 3 4 5 6 Ch s Wobbe, kcal/Nm3 7650 380 6790 285 6400 285 5870 240

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5350 285

Ch s Wobbe c th nguyn cng vi th nguyn ca nhit tr. bt chy nhanh ca kh ph thuc vo tc truyn la ca n. Cc kh giu c ch s Wobbe > 8500 (v d, kh thin nhin t 9000 n 13000, LPG t 18000 n 22000 kcal/Nm3). Ngi ta c th phn loi nhin liu kh da vo ch s Wobbe (bng 25). Thng thng cc kh giu thuc v nhm 1, 2; cn cc kh ngho thuc v nhm 5, 6, 7. 3.4.1.1 Kh thin nhin Kh thin nhin thng l hn hp ca cc hirocacbon parafin m trong metan (CH4) l thnh phn ch yu. Kh thin nhin tn ti trong cc m kh trong lng t, ng thi cng tn ti trong cc m du, g i l kh ng hnh. Kh ng hnh sau khi ly t ging du ln, c x l loi b hi nc v bn ct phn tn, sau c x l thu h i phn xng v kh thin nhin ha lng (LNG). Khi kh thin nhin cha rt t phn condensat (< 5 mg/m3) c th thu h i c th ngi ta gi l kh thin nhin kh, cn khi kh thin nhin cha phn condensat nhiu hn (> 50 mg/m3), ngi ta gi l kh thin nhin t. Phn condensat c thu h i ny chnh l xng t nhin v xng ny c s dng trn vi cc nhin liu khc. Vic thu h i condensat t kh thin nhin c thc hin bng cch nn v lm lnh, hay hp ph trn cc vt liu rn xp. Thnh phn in hnh v tnh cht ca kh thin nhin c trnh by trong bng 26. Kh thin nhin mt s m cha nhiu N2, CO2 v mt lng heli c kh nng thu h i. i khi H2S cng c trong thnh phn kh thin nhin, ngi ta c th thu hi lu hunh di dng nguyn t. Kh thin nhin khng c H2S c gi l kh ngt. Kh thin nhin c dng lm nhin liu nu nng, si m v t nng cng nghip. Kh thin nhin cn c dng lm nguyn liu u sn xut phn bn, v l ngun cung cp cacbon v hiro cho cng nghip ha hc. Bng 26. Thnh phn v tnh cht ca kh thin nhin
Thnh phn (% th tch) CH4 C2H6 C3H8 C4H10 C5H12 CO2 N2 Nhit tr th, kcal/Nm3 (kh) T trng (khng kh = 1) Kh kh v ngt 96,91 1,33 0,19 0,05 0,02 0,82 0,68 9000 0,574 Kh t v ngt 77,22 11,18 5,83 2,34 1,18 0,80 1,39 11200 0,741

25

Sau khi c x l ti m, kh thin nhin c a n cc cn h qua mng li ng dn (ng knh 0,5 0,6 m) vi p sut t 15 30 kg/cm2. vng kh hu lnh, kh thin nhin phi c loi nc (ehirat ha) trnh s to thnh cc tinh th nc ln metan, etan, propan v iso-butan, cc tinh th ny bn vng nhit di 19C. 3.4.1.2 Kh ha lng (LPG) LPG ch yu l h n hp ca propan v butan. LPG ch yu c s dng lm kh t nu n, t nng cng nghip trong cc l t. Cc hirocacbon C3 v C4 d dng b ha l ng nhit thng v i p sut nn khng ln l m. Do propan v butan c ha l ng, lu kho v vn chuyn trong cc thit b hnh tr bng kim lo i nh. Ni chung, LPG cng nghip l h n hp g m khong 80% butan v 20% propan. LPG c sn xut t kh thin nhin t v t kh nh my l c du. Tnh cht cc cu t chnh ca LPG c cho trong bng 27. Bng 27. Tnh cht ca cc cu t chnh ca LPG Kh tinh khit im si (C) p sut ha lng nhit thng (at) Nhit tr th (kcal/Nm3) Kh (khng kh = 1) T trng Lng Gii hn n trong khng kh (%) Lng khng kh chy l thuyt (Nm3/Nm3) %S Nhit bc chy (C) butan 0,5 3 30608 2 0,5844 1,9 8,5 30,94 0,02 500 propan 42 10 23670 1,52 0,5079 2,2 9,5 23,80 0,02 480

1925 1995 Nhit ngn la trong khng kh (C) LPG c nhit tr cao, t trng cao, t l chy vi khng kh cao v tc truyn la thp. V LPG khng mi nn ngi ta thng thm vo LPG cc cht c mi nh mecaptan hay H2S pht hin s r r ca vt cha hay cc ng ng dn. LPG l nhin liu dn dng rt ph bin v s dng tin li v cho nhiu nhit, ng thi LPG cng l mt nhin liu rt ph bin cho t nng cng nghip m nhng nhin liu khc kh c th thay th. Propan v butan cng cn c s dng lm giu cc kh ngho nh kh thnh ph. Butan c pha long bng khng kh to ra nhng nhin liu thch hp cho tc t nng c th iu khin c. V d hn hp g m 20% butan v 80% khng kh c nhit tr 6136 kcal/Nm3, v nm ngoi gii hn n ca butan trong khng kh. Trong thc t, LPG c dng rng ri lm nhin liu dn dng c pha long bng kh tr nh nit hay khng kh gim nhit tr ca n, v m bo khng ch c tc t nng nhm trnh cc nguy him c th xy ra khi nhit chy qu cao.

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Propan v butan cn c dng sn xut nhiu sn phm ha hc khc nh t butan sn xut axit axetic, butanien, ... V LPG nng hn khng kh nn LPG c xu hng chm xung khi cc vt cha b r r. Di dy l mt s c trng ca LPG cng nghip. LPG gm 80% butan v 20% propan c nhit tr khong 29.275 kcal/Nm3, t trng l 1,9 (so vi khng kh l 1), lng khng kh chy l thuyt tng ng l 29 Nm3/Nm3. LPG g m 70% propan v 30% butan (thng dng cho mc ch dn dng) c nhit tr khong 25.775 kcal/Nm3, t trng 1,65 (so vi khng kh l 1), lng khng kh chy l thuyt l 26 Nm3/Nm3. 3.4.1.3 Kh t nh my lc du Khi chng ct du th v thc hin cc qu trnh ch bin du nh my lc du ngi ta thng thu c cc kh: - Parafin nh metan, etan, propan, butan. - Olefin nh etilen, propen, buten. - Cc kh khc nh hiro sunfua, hiro. Thng thng cc hirocacbon C3 v C4 c tch ra kh i kh nh my lc du bng cch ha lng v bn trn th trng di dng cc kh LPG. T hiro sunfua ngi ta thu h i l y lu hunh nguyn t sn xut axit sunfuric. Hiro v cc hirocacbon cao hn c s dng lm nguyn liu sn xut trong cng nghip ha du, cn cc kh khc khng th thu hi th c t trong khng kh gim nhim. Ty thuc vo bn cht ca du th v phm vi ch bin cc sn phm du, thnh phn cc kh t nh my lc du c th nh sau:
Propen + propan Buten + butan Etilen + etan Metan Hiro Hiro sunfua Nhit tr, kcal/Nm3 (kh) T trng (so vi khng kh = 1) 40 55% > 30% 8 12% 8 10% 6 8% 6 8% 20,500 1,35

Hiu sut kh t nh my lc du di dng LPG ty thuc vo cc qu trnh ch bin nh my. Hiu sut thu hi LPG thng thng t cc qu trnh ch bin c trnh by trong bng 28.

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Bng 28 Hiu sut thu hi LPG t cc qu trnh ch bin trong nh my lc du Qu trnh ch bin Nguyn liu u (NL) Cn, du nng Cc Sn phm ch yu Hiu sut LPG, % trng lung theo NL 5 10

Visbreakinh /cockinh

Refominh xc tc

Naphta nh

Aromat, xng

5 10

Ankyl ha /polime ha Cc kh C4H10 v olefin

Xng Olefin C2, C3 cho ha du

10 15

Crackinh xc tc

Du gazoin

15 20

3.4.1.4 Kh c sn xut t du - Kh du (Oil Gasification Processes - Oil gas) Kh du c sn xut bng cch kh ha cc sn phm du. Kh du c s dng lm nhin liu kh hay c s dng lm kh tng hp dng sn xut amoniac trong cc nh my phn m. Nguyn liu u dng kh ha du l cc phn on nh v trung bnh hay cc du nng. Kh ha du c th l crackinh, crackinh vi hi nc hoc oxi ha khng hon ton du. Khi mi trng kh ha l oxi v hi nc, th qu trnh kh ha du c biu din theo cc phng trnh phn ng sau: CxHy +
x O2 2

xCO

y H2 2 y )H2 2

(phn ng oxi ha khng hon ton, pht nhit) CxHy + xH2O xCO + (x +

(phn ng refominh vi hi nc, thu nhit) CnH2n+2 + nH2O nCO + (2n + 1)H2 (phn ng crackinh vi hi nc, thu nhit) Cc qu trnh kh ha du c phn loi nh sau: - Qu trnh vng khng xc tc - qu trnh Semet-Solvay; - Qu trnh vng xc tc - qu trnh Segas v qu trnh Onia-Gegi; - Qu trnh refominh xc tc vi hi nc lin tc; - Qu trnh t chy khng hon ton - qu trnh Koppers-Totzek, Shell v Texaw; - Qu trnh hiro ha.

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Trong s cc qu trnh trn, cc qu trnh Semet-Solvay, Segas, Onia-Gegi v refominh vi hi nc naphta l quan trng. a) Qu trnh Semet-Solvay y l qu trnh quay vng khng xc tc nhm sn xut nhin liu kh giu t cc phn on du nh, nng, ... Qu trnh kh ha du Semet-Solvay l qu trnh refominh du vi h i nc nhit cao. Qu trnh c thc hin lin tc trong hai l phn ng t song song vi nhau. M i m thc hin trong 4 pht. Thnh phn v tnh cht ca kh du c sn xut theo phng php ny nh sau:
CH4 H2 CO Nhit tr th T trng so vi khng kh (= 1) 40% 18% 35% CnHm N2 CO2 30% 6,5% 2,5%

10.000 kcal/Nm3 (kh) 0,72

b) Qu trnh Segas y l qu trnh quay vng xc tc, v c th ti sinh. Thit b ca qu trnh ny g m 3 b phn chnh: - Bu ng ha h i nguyn liu u (ha h i d u) v s n xu t h i n c. - Bung gia cha xc tc (g m MgO + 1% CaO) - bu ng phn ng. - Bung cui t nng s b khng kh - bung thu hi nhit. Qu trnh c vn hnh nh sau: hi nc c a vo y bung th nht chuyn thnh hi nc qu nhit. Du nguyn liu c phun vo bung ny t pha trn. Hn hp du v hi nc qu nhit i qua bung xc tc (bung th hai), trong bung ny qu trnh kh ha xc tc xy ra. Kh nng c dn vo bung th 3 t nng s b khng kh dng cho cc qu trnh khc. Cui cng kh du i vo b phn ra v ngng t. Nhit bung xc tc c gi 1000C Thi gian mt vng phn ng khong 4 pht. Thnh phn v tnh cht in hnh ca kh du c sn xut theo phng php ny nh sau:
CO2 O2 H2 N2 5,8% 0,4% 50,3% 4,8% CnHm CO CH4 4,2% 8,3% 16,2%

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Nhit tr th T trng so vi khng kh (= 1)

4.700 kcal/Nm 3 (kh) 0,52

c) Qu trnh Onia-Gegi y l qu trnh vng v xc tc nh qu trnh Segas. Xc tc c dng y l Ni/cht mang. Nguyn liu u cho qu trnh ny l cc hirocacbon nh n du nng. Kh du c sinh ra di tc dng ca xc tc, nhit cao (800 900C) v hi nc. CnHm + nH2O nCO + (
1 m + n) H2 2

Qu trnh Onia-Gegi cn sinh ra c c v m t s s n ph m ph khc. Thit b ca qu trnh Onia-Gegi g m cc b phn sau: - B phn cha xc tc Ni; - B phn ti sinh bng khng kh nng; - B phn pht hi nc. Vn hnh qu trnh Onia-Gegi gm hai bc: - Bc u tin t nng vng xc tc ln ti 800 900C; - Bc th hai l kh ha du. Du c phun vo vng xc tc cng vi hi nc. Ti y du c chuyn thnh kh du. Kh du i qua b phn thu h i nhit v i vo b phn ra thu kh em i dng. Sn phm kh ny cng cn c gi l kh thnh ph. Thnh phn v tnh cht in hnh ca kh thnh ph sinh ra t kh ha du nng nh sau:
CO2 CO CnH2n+2 N2 Nhit tr th 10,2% 17,2% 13,5% 9,4% 4.316 kcal/Nm 3 CnHm H2 O2 5% 43,8% 0,9%

d) Qu trnh refominh xc tc vi hi nc naphta Naphta sau khi c loi lu hunh c kh ha bng hi nc vi s c mt ca xc tc niken.

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Qu trnh ny c thc hin trong cc l ng cha xc tc, c gi l l phn ng kh ha. L ny c dng 3 lp ng thp khng g cha y xc tc. Chng c t nng trong mt l t 960C. Kh thi ca l t c dng pht hi nc qu nhit. Hn hp hi naphta sau khi c loi ht lu hunh, hiro v hi nc qu nhit i vo ng phn ng t trn nh ng. Phn ng kh ha xy ra ti y p sut 28 at, nhit 840C. Qu trnh refominh vi hi nc naphta c thc hin hu ht sn xut kh nhin liu v mt phn sn xut kh tng hp trong cc nh my phn m. S qu trnh refominh vi h i nc naphta sn xut kh du - kh thnh ph ca hng ICI c minh ha trong hnh 8.

Hnh 8 Qu trnh ICI sn xut kh thnh ph bng refominh vi hi nc

Thnh phn v tnh cht ca kh du c sn xut theo phng php ny nh sau:

CH4 H2 N2 Nhit tr th T trng so vi khng kh (= 1) 4,8% 51,7% 1,4% 2.870 kcal/Nm 3 (kh) 0,52 CO CH4 41,8% 0,3%