LI GII THIU

Du mo c bit n t rt sm, nhng n th ky XVIII (nm 1859) cng ngh ch bin du mo mi c bt u My .Nh nhng c tnh quy ring cua nguyn liu du mo (gia thanh thp, thun tin cho qua trnh t ng hoa, d khng ch cac iu kin cng ngh , co cng sut ch bin ln, san phm thu c co cht lng cao, t tap cht , d tinh ch, tao ra nhiu chung loai san phm) nganh cng nghip du tng trng rt nhanh a tr thanh nganh cng nghip mui nhon cua nhiu quc gia , ap ng hai muc tiu chnh la : Cung cp cac san phm nng lng cho nhu cu v nhin liu ng c, nhin liu cng nghip va cac san phm v du m bi trn. Ngay nay, san phm nng lng du mo a chim ti 70% tng s nng lng tiu thu trn th gii Cung cp cac hoa cht c ban cho nganh tng hp hoa du va hoa hoc, tao ra s thay i ln v c cu phat trin cac chung loai san phm cua nganh hoa cht vt liu. (San phm phi nng lng). Trong cng ngh lin hp ch bin du, chia ra hai khi qua trnh ch bin chnh : Cac qua trnh ch bin vt ly : phn chia n thun thanh cac nhom co tnh cht gn ging nhau bng cac phng phap phn chia vt ly nh chng ct, hp phu, trch ly, kt tinh . Cac qua trnh ch bin hoa hoc :lam thay i cu truc cua cac hp cht co trong du thanh cac cu t mong mun nh ap dung cac iu kin bin i hoa hoc khac nhau (t 0, P, tac nhn phan ng,cht xuc tac). Cac qua trnh ch bin thun tuy bi nhit a c ap dung t rt lu nhm ch bin cac phn oan du khac nhau thanh cac san phm long (xng , FO) ,kh va coke.Da vao nguyn liu ,san phm chnh thu c va iu kin qua trnh ,ngi ta chia thanh cac qua trnh cracking nhit, giam nht,coke hoa va pyroly (cracking hi). tai nay gii thiu v cng ngh cua qua trnh cracking nhit nhm thu thm xng va cac hp cht tng hp hoa du.

QUA TRNH CRACKING NHIT

I. Gii thiu chung 1. t vn Du mo ,trc khi mun ch bin thanh cac san phm thng mai u phai tin hanh chia nho thanh tng phn oan hep vi cac khoang chia nhit si nht nh bng thap chng ct s khi .Cac phn oan nay co thanh phn t phc tap hn va cac tnh cht vt ly gn nhau hn so vi du th nguyn khai.Cac san phm trng la nhng cht co gia tr cao nht rut c t du mo. Vn t ra : Lng cn Residu cua cac qua trnh o se i v u ? Trc y , khoa hoc cng ngh cha phat trin ngi ta thng x ly lng cn nay lam dung dch t lo trong cng nghip hay dung chay tau thuy , hoc lam nha ng... iu nay rt lang ph , gy n mon thit b do lng kh axit tao ra trong qua trnh t hay do s pha huy thuy nhit cua cac kim loai co mt trong cn , vy nn chi ph bao dng va vn hanh cao . Ngoai ra con c hai i vi sc khoe cua con ngiva nghim trong nht la nhim mi trng . Ngay nay , khoa hoc phat trin a phat minh ra nhng cng ngh khc phuc c nhng han ch k trn x ly cn (Residu) bng cac qua trnh hoa hoc be gy cac phn t ln thanh cac phn t nho hn di tac dung cua nhit , xuc tac, hydro ... Cac phn t nho hn thu c chnh la ngun b sung san phm trng . u im cua phng phap dung nhit - Cu tao thit b n gian nn u t t - X ly c nhng nguyn liu co nhiu tap cht . Gii han vung nguyn liu rng (t phn oan gasoil cho n cn mazut hay san phm cn nng cua qua trinh FCC, RC... . ) - San xut c olephin cung cp cho qua trnh tng hp hu c va hoa du nn chi ph thp

- San phm cua qua trnh la nguyn liu hay la phu gia cua nhiu qua trnh khac nh RC, FCC, san xut du nhn . . . Tuy nhin qua trinh s dung nhit cung co mt s nhc im : + Tiu hao nhiu nhin liu , kho khng ch qua trnh do o d tao ra san phm khng mong mun tn kem trong qua trnh tach cac san phm . + Tao ra xng co ch s octan IO khng cao lm (IO = 30_60) va n nh cua xng kem (do co cha nhiu olefin). 2. Gii thiu phng phap

Cracking la mt qua trnh chuyn hoa hoa hoc, be gay mach C-C cua hydrocacbon hoc la lam t mach cac lin kt hoa hoc khac co mt trong nguyn liu du.Trong cac lin kt cua phan ng be gay mach th lin kt C-H la bn nht , v vy nng lng be gay mach cung ln nht . - Lin kt C-C cn nng lng la 58.6 Kcal/mol. - Lin kt C-S cn nng lng la 54.5 Kcal/mol. - Lin kt C-H cn nng lng la 87.3 Kcal/mol. Nhng phan ng xay ra co th chu anh hng cua nhit hoc la khng. Tuy nhin cac phan ng cracking cua mt phn oan du th khng co gii han v s t gay lin kt .Chnh v th ma ngi ta thu c kt qua la cac phn t co mach rt ngn hoc rt dai so vi phn t ban u co trong nguyn liu. Trong cng ngh du mo, qua trnh cracking c ng dung bin i cac phn oan nng thanh cac san phm nhe tng ng vi khoang si cua cac san phm trng nh xng kerozen ,diezen Phan ng co th thc hin di tac dung cua nhit hoc xuc tac. Trong o Cracking nhit la qua trnh be gay mach C_C di tac dung cua nhit ,qua trnh nay xut hin t lu i ,khng co mt xuc tac khi tin hanh. 3. Qua trnh cracking nhit 1) Muc ch:

+ Nng cao hiu sut thu hi xng t phn nng + Thu hi mt s olephin dung trong cng nghip tng hp hoa du.

2) .iu kin vn hanh: P = 20 70 at

3)

Nguyn liu :

t 0 C = 470 540 0 C

+ Ph bin nht la phn oan mazut cua chng ct trc tip + Phn oan gasoil nng cua qua trnh Cracking xuc tac hay cn nng cua qua trnh lam sach . 4) San phm

San phm cua qua trnh craquage nhit thng la : - Kh hyrcacbon - Xng cua qua trnh - Phn oan lampa + gasoil - Gasoil nhit - Cn cua qua trnh cracking Chung ta co hiu sut san phm cua qua trnh craquage nhit (trong o hn hp nguyn liu la gouron va gasoil nng cua qua trnh cracking xuc tac) nh sau: Kh HC Sp nh n nh 3.4 Xng cua qua trnh 14.2 Lampant Gasoil 3.9 Gasoil nhit Cn cua qua tnh 74.4 mt mat 1.6

2.5

c trng cua san phm: Xng cua qua trnh co n nh hoa hoc thp va ch s octan khng cao lm (RON = 66-68). Xng cracking nhit co thanh phn khac vi xng chng ct trc tip .V c ban trong xng cracking nhit co nhiu olephin nn tr s octan cao hn tuy nhin cha am bao cht lng cua xng thng dung (RON khoang 70).Mt khac xng cracking nhit co bn kem,di tac dung cua anh sang,nhit ,cac phn t olephin d b ngng tu,polyme

hoa,trung hp hoa tao nha dn n chay khng hoan toan trong xylanh,lai rt d bin i mau sm. Ham lng S trong xng chim t 0,5 - 1,2%,cao gp 5 ln cho phep i vi xng t. V vy nhn chung xng cracking nhit cha am bao cht lng s dung cho ng c xng,thng phai x ly lam sach bng hydro hoa & qua reforming xuc tac nhn xng co tr s octan cao ,co n nh tt.. 0 Phn oan lampant + gasoil (200-350 C) la thanh phn c bit cua diesel.Sau qua trnh hyroraffinage no co th dung nh la thanh phn cua du diesel. Gasoil nhit la san phm mt phn cua phn oan cacbon ky thut, dung lam nguyn liu ch tao mui cacbon hay ch tao cac loai nhin liu FO khac nhau.

Cn cua qua trnh craquage (phn oan co nhit si trn 3500C) c s dung nh la nguyn liu t cho ni hi.S d dung no v nhit t chay cua no rt cao , cung nh la im ng c va nht kem nh la fuel-oil cua qua trnh chng ct trc tip. (Cn cracking nhit c dung ch tao FO hay lam nguyn liu cho qua trnh coke hoa.) San phm kh cua qua trnh , giau nhng HC khng bao hoa , no c s dung nh hp cht dung trong hoa du.

Ta co bang thanh phn san phm kh cua qua trnh craking nhit. Thanh phn H2 CH4 C2H6 C3H8 i-C4H10 C4H10 C2H4 C3H8 C4H8 Craquage nhit 0.4 16-20 19-20 25-28 5-7 9-10 2-3 9-10 9-10

C4H6

1-5

II. S cng ngh Thuyt minh s cng ngh S cng ngh cua qua trnh cracking nhit phu thuc vao muc ch cua qua trnh , phu thuc vao nguyn liu c s dung va cac yu cu v cht lng san phm . Ph bin rng rai nht la s cng ngh vi hai lo t. S nh hnh ve bn. S c dung linh hoat cracking cn du hoc ch mm ( vibreking) hoc ch cng (cracking) , hoc nu cracking phn ct cung vi muc ch va nhn xng va nhn phn oan gasoil cha nhiu hyrocacbon thm lam nghuyn liu cho qua trnh san xut cacbon mui ( black cacbon). Hoat ng cua s cng ngh nh sau : Nguyn liu la du nng c bm 14 cho qua thit b trao i nhit 12 , vao phn bn di thap tinh ct 8 , ng thi cho vao phn nh thap bay hi ap sut thp 9.T thit b 9 , nguyn liu c trn vi phn oan gasoil nng va c a vao ay thap 8. Dong nguyn liu va phn tun hoan c trn vi nhau ri nh bm 18 cho qua lo t nguyn liu nng 1 , sau o vao bung phan ng 3. Phn oan gasoil thu c a ic cua thap 8 nh bm 19 cho qua lo t 2 cracking su va tip tuc vao phan ng 3. T thit b 3 nay , san phm i vao thit b bay hi ap sut cao 4 y phn nng cracking c tach ra va c cho vao ay thap bay hi ap sut thp 9 , t thit b nay se tach c phn oan gasoil . Phn nng c ngng tu va cho quay lai tun hoan cung vi nguyn liu , con phn nhe c tach ra nh thap 9 c cho qua thit b trao i nhit sau o i ra khoi dy chuyn. Dong hi t nh thit b 4 c cho vao thap 8 . T nh thap 8 , tach ra phn kh va xng , sau o c lam lanh tai cac thit b 5 , va tip theo c tach trong thit b tach kh 7. Kh tach ra c dn n dy chuyn phn tach kh , con xng c cho vao ct n nh xng , cui cung vao b cha xng. Ch cng ngh cua dy chuyn cracking nhit loai hai lo t nh sau : Nhit 0C Lo t 1 Vao 400- 410 4.0 - 5.5 Ap sut MPa

Ra Lo t 2 Vao Ra Lo phan ng 3
Thit b bay hi ap sut cao

450 - 490 380 - 390 540 - 550 470 - 500 415 - 430 410 - 420

2.2 - 2.7 4.0 - 4.5 2.2 - 2.8 1.5 - 2.5

nh thap ay thap Thap tinh ct 8 nh thap Gia thap ay thap

Thap bay hi sut thp 9 ap

0.8 - 1.2 190 - 210 275 - 320 380 - 410 0.15 - 0.35 190 - 195 290 - 310 380 -410

nh thap Gia thap ay thap

III. Cac yu t anh hng qua trnh. Qua trnh ch bin nhit kh cu truc, co 2 vn quan trong cn giai quyt + Ngn nga s tao thanh coke trong ng phan ng hay trong cac thit b trao i nhit . + am bao hiu qua s dung cao cac trang thit b trong dy chuyn. Thanh phn v s lng cung nh cht lng san phm cui c quyt nh bi cac thng s cng ngh cua qua trnh nh nguyn liu,nhit , ap sut, thi gian phan ng . 1. Nguyn liu Qua trnh bin i nguyn liu la mt qua trnh rt phc tap , trong o xay ra hang loat cac phan ng va ni tip va song song . Cht lng nguyn liu la mt thng s quan trong xac nh cht lng san phm. Khi iu kin Cracking khng i nu s dung nguyn liu co thanh phn khac nhau se cho kt

qua khac nhau. Khi tng gii han t0 si cua nguyn liu, tc phan ng cung tng ln . Nguyn liu cang nng (gii han si cao) th bn nhit cua nguyn liu cang kem, qua trnh be gay mach xay ra d hn, dn n tc be gay mach nhanh, cho hiu sut xng cao. Do vy vi nguyn liu nng , t0 phan ng thp hn so vi nguyn liu nhe . ng thi thanh phn hoa hoc cua cac hp cht hydrrocarbon co trong nguyn liu cung anh hng n cht lng san phm . Naphten co bn nhit cao hn so vi parafin co cung s nguyn t cacbon trong mach , khi tham gia phan ng co xu hng tao thanh cac phn t co trong lng trung bnh tc nhiu san phm long hn so vi nguyn liu parafin. 2. Nhit Khi tng nhit , tc cracking nhit tng theo quy lut ham s mu. 1 0t / 10

Trong khoang nhit chon trc , s thay i v nhit va thi gian phan ng co tac dung tng h ln nhau . gi cho su bin i la nh nhau khi tng nhit cn thit phai giam thi gian phan ng . Khi tng nhit , tc phn huy tng ln va ngc lai khi giam nhit tc phan ng trung hp lai tng ln . Giam nhit Cracking se giam tc phan ng a tu . Nh vy tng hiu sut thu cac san phm la kh, long & giam hiu sut cac san phm a tu (cn, nha, coke) cn thit phai gi nhit phan ng cao ng vi thi gian phan ng thch hp . o chnh la nhim vu cua qua trnh Cracking nhit . Lu y : nu qua trnh tin hanh t 0 va phai th s phn huy xay ra vi s bin i cu truc rt t . Vd : + Nu nguyn liu cha nhiu paraphin th san phm thu c cha nhiu paraphin nhe hn. + Nu nguyn liu gasoil cha 1 lng ln hydrocarbon vong th san phm thu c se co nhiu Naphten & Aromat.

3. Ap sut Ap sut xac nh trang thai pha cua h cung nh chiu hng va tc cua phan ng . Ap sut khi cracking phn oan gasoil nhe cn am bao trang thai long cua tac nhn phan ng bi v trang thai long tao iu kin tt cho qua trnh trao i nhit , khng xay ra s qua nhit cuc b, khng tao coke . S tao coke luc nay la cc tiu, con hiu sut xng la cc ai. Nu cracking cn nng cn phai gi cho h thng trang thai pha hn hp long_hi .Nhit cang cao ap sut cang thp th pha kh se cang nhiu, tc dong trong lo ng cang ln cho phep giam s ong coke trong cac ng xon cua lo . Ap sut cao thng lam tng nng cua cac tac nhn phan ng trong pha hi, iu nay se tao iu kin cho cac phan ng kt hp nh phan ng polyme hoa, akylhoa, hydrohoa . Khi cracking xay ra trong pha long vi nguyn liu nng nh mazut, gudron th ap sut khng anh hng nhiu . Khi ap sut va nhit cung cao , v tr t mach nghing v cui mach iu nay lam tng hiu sut san phm kh, giam san phm long . Nu ap sut cao, nhit thch hp th v tr t mach C-C xay ra v tr gia mach dn ti hiu sut san phm long tng . 4. Thi gian lu Thi gian lu cua nguyn liu trong vung phan ng cang lu th san phm tao thanh d b ngng tu dn n tao nha , coke lam giam hiu sut xng , kh. Nh vy tng hiu sut san phm kh ,xng va giam hiu sut phan ng trung hp (cn,coke) th vung phan ng , nhit duy tr cao va thi gian lu cua nguyn liu trong vung phan ng phai ngn. V du: T0 phan ng (0C) chuyn hoa (%) Hiu sut phan ng Sp phn Sp trung huy hp Ty l phn huy/trung hp

375 400 425 Nhn xet:

52.2 53.5 50.8

55 62.2 72.4

44.2 37.2 27.6

1.26 1.65 2.26

Khi nhit tng th chuyn hoa hu nh xp x.San phm phn huy tng ,san phm trung hp giam.V vy i vi mi nguyn liu khac nhau ,cn nghin cu chon nhit ti u. Trong thc t ,cac qua trnh cracking nhit cng nghip : san phm coke tao thanh chu yu vung t0 va phai ch khng phai vung t0 cao (do coke sinh ra b chay) IV. C ch cua qua trnh A. Gii thiu chung Cracking nhit la mt qua trnh chuyn hoa hoa hoc ht sc phc tap do phn oan nguyn liu la mt hn hp rt nhiu cac cu t thanh phn.Trong qua trnh, din ra nhiu phan ng, chung ta rt kho kim soat. i vi cracking nhit xay ra theo c ch gc t do. Cac hydrocacbon tham gia phan ng cracking di tac dung cua nhit

1. Phan ng cracking u tin do co s khac nhau gia cac phn t cua hn hp. Trong mt s trng hp t ho hydrocarbua:parafin,naphten, aromatic , chung ta thu cung qua trnh chuyn hoa sau: Parafin Olfin + parafin nhe hn Naphten Olfin (do qua trnh cracking cua vong) Armatic Olfin (do qua trnh craking tai v tr nhanh) +Armatic Nhn thy khi thiu vng hyrgen dn n vic hnh thanh cac san phm olefin khng bao hoa.

2. Cac phan ng tip theo bin i cua nhiu san phm do qua trnh cracking u tin. Chung ta co th thu c: Phan ng cracking tip theo cua nhiu parafin nh gii thiu trn. Hnh thanh nhiu olefin mi - La cac olefin rt nho bi qua trnh cracking su Olefin hai olefin nho hn - La diolefin bi s thiu vng hydrogen. Phan ng dehydro hoa la qua trnh be gay mach C-H. Olefin Diolefin + hydrogen - S chuyn hoa nhiu olefin cho ra parafin va diolefin hoc aromatic Olefin1 + Olefin2 Diolefin + parafin Olefin1 + Olefin2 +.. Aromatic + parafin - Nhiu phan ng cng hp nhng san phm ma ta thu c nh diolefin, aromatic cho ra san phm nng vong chnh la du nng va san phm cc.(Nu khng nhm san xut coke th iu nay rt bt li). B. Nng lng lin kt: Nng lng lin kt C_H la 412 kj/mol. Nng lng lin kt C_C la 360 kj/mol Trong trng hp alcane mach thng dai th nng lng be gay lin kt C_C va C_H la giam s t n im gia cua nhanh , ri lai tng n cui mach : VD : CH3 - CH2- CH2- CH2- CH2- CH2- CH2- CH3 Nng lng lin kt C_C: 335 , 322 , 314 , 310 , 314 , 322 , 335. Nng lng lin kt C_H: 394 , 373 , 364 , 360 , 360 , 364 , 373, 394. Khi nhit tng , chnh lch bn cua lin kt la giam dn. gia tr nhit t = 400-5000C , s be gay nhanh cua HC u n gia ,trn nhng lin kt la rt nho. Khi nhit tng cao th s t gay cua nhng lin kt khac la co th. Nhiu lin kt cua C_C cua cycloalcan la kem bn so vi vi nhiu parafin bnh thng: 8 kj/molvi cyclohexan, 25 kj/mol vi cyclopentan.

Lin kt cua C_C,C_H cua alcen la xp x vi bn trn cacbon mang lin kt i va rt la yu, do lin quan vi alcan , v tr . 375 321 R - CH2- CH2 - C - C - CH2 - CH = CH3 33 259 Nng lng pha v lin kt thanh lin kt , la 239 kj/mol. CH2 = CH2 CH 2 CH 2 239 kj / mol Nu co hai lin kt i c lin kt , nng lng pha v lin kt giam khoang 50 kj/mol.
CH 2 = CH CH = CH 2 CH 2 = CH CH CH 2 188kj / mol

Nhiu lin kt c lin kt vi nhn Aromatic la rt yu , xem gn nh trong cung gii han lam nhng lin kt c lin kt n lin kt i. C. C ch cua phan ng craking nhit. C ch cua phan ng craking nhit theo hng c ch gc, la c ch gc mach nhanh hoc khng nhanh. Nhng phan ng ion khng th thc hin trong iu kin nhit cua qua trnh , v s be gay mach hoa hoc cua lin kt C-C khi o oi hoi nng lng1206 kj/mol, nng lng qua ln so vi nng lng be gay mach ng nht :360 kj/mol. Ngay nay c ch gc nhanh thng dung nhiu trong phan ng cracking. L thuyt v phan ng mach cua Semenov la thanh vin cua Vin han lm X vit la rt quan trong trong vic xy dng nhng nguyn l cua nhiu phan ng ng th trong pha kh. C ch gc Bao gm 3 giai oan + Tao gc t do + Phat trin chui + Dng phan ng 1. Xet cu th cho ho Parafin a) Giai oan tao gc t do:

Do lin kt C_C kem bn , nhit cao no b tach trc va tao ra gc t do.

R _ R1 R + R1

V tr t mach C_C phu thuc nhiu vao iu kin tin hanh qua trnh. + v tr nhit cang cao va ap sut cang thp,v tr t mach co xac sut ln la hai u mach .San phm chu yu la kh cha olefin . + v tr nhit va phai (450_540 0C) va ap sut cao th v tr t mach lai co xac sut ln gia mach .San phm long,giam bt hiu sut kh. Tai iu kin ap sut thng va nhit >600 0C,ch co cac gc H*,*CH3,*C2H5 la co kha nng tn tai trong khoang thi gian ngn trc khi chung va cham vao nhau va gy nn phan ng hoa hoc . Con cac gc ln hn, rt khng bn, chung lp tc tao ra cac gc nho va ng thi tao nn olefin.
C 5 H 11 C 4 H 8 + CH 3

Trong khoang thi gian nht nh (phn nghn giy) nng cac gc t do tng ln rt nhanh . b) Giai oan phat trin chui Gc t do phan ng vi nguyn liu ban u va tao thanh gc mi :
RH + H H 2 + R R1 H + R RH + R1*

Do bn cua gc t do bc 3>bc 2>bc 1 ma s tach nguyn liu se u tin trc tin la cac iso parafin, sau o mi n n-parafin Co nhiu gc nhng la nhng gc v mt hoa hoc khng bao hoa , chi phi n kha nng phan ng cao va tin hanh vi tc nhanh trong phan ng khac. Ta co th a ra v tr giam dn cua cac gc sau
C 2 H 3 > CH 3 = C 3 H 7 = sec C 4 H 9 > C 6 H 5 > C 2 H 5 > ter C 4 H 9 > C 6 H 5 CH 2 > CH 2 = CH CH 2 > (C 6 H 5 ) 2 CH

Cac gc ln rt d b phn huy thanh cac gc nho va do vy tao ra hng phan ng mi. Chnh v th ma ngi ta goi la phan ng dy chuyn phn nhanh.

Cac gc t do co kha nng phan ng ln hn nhiu ln kha nng phan ng trc tip cua Hydrocarbon nguyn liu.Nng lng hoat hoa cua cac phan ng gia cac gc t do nho hn rt nhiu ln nng lng hoat hoa cua phan ng phn huy trc tip . V du
C 2 H 6 2CH 3

E = 84kcal / mol
* 5

CH + C 2 H 6 CH 4 + C 2 H C2 H C2 H 4 + H
* 5 * H + C2 H 5 * H + C2 H 6 C2 H 5 + H 2

E = 8kcal / mol E = 40kcal / mol E = 7 kcal / mol E = 0kcal / mol

C2 H 6

c) Giai oan dng phan ng Khi tc tao thanh bng tc mt i cua cac gc t do,phan ng chui coi nh kt thuc. S mt cac gc t do co th do cac gc va cham vi nhau, phan ng vi nhau tao thanh phn t trung hoa :
R + H RH
R1 + R2 R1 _ R2

2H

H2

V du minh hoa: + Phn ln nhng phan ng gc t do c miu ta nh sau : 1) S phn tach 1 va 2 phn t thanh hai gc t do :
C 2 H 6 CH 3 + CH 3

C 2 H 6 + C 2 H 4 2C 2 H 5

2)

S thay th :
CH 3 + C 2 H 6 CH 4 + C 2 H 5

3) S phn tach thanh mt gc di dang phn t khng bao hoa va mt gc mi t do. S t gay mach thng tai v tr (quy tc ) .

CH 3 CH 2 CH CH 3 CH 2 = CHCH 3 + CH 3

4) 5)

Cng gc t do trn lin kt bi .

CH 3 + C 2 H 4 C 3 H 7

ng phn hoa gc t do .

CH2CH2CH2CH2CH2CH2CH3

H2C H2C

H2 C C H2

H CH2

CH3CH2CH2CH2CH2CHCH3

S hnh thanh dang vong cua hexan la rt d dang. Dang vong cua hexan la kem bn so vi vong pentaee va heptan. Mach vong vi 3 va 4 mc xch la rt cng dung, va qua trnh ng phn hoa nhiu alcoyle 1, 2 va alcoyle 1, 3 la rt co th thc hin. +S be gay mach cua phan ng c thc hin sau y : 6) 7) S kt hp nhiu gc.
CH 3 + CH 3 C 2 H 6

S khng cn i.
CH 3 + C 2 H 5 CH 4 + C 2 H 4

V du vi ETHALNE :
C 2 H 6 2CH 3

CH 3 + C 2 H 6 CH 4 + C 2 H 5 C2 H 5 C2 H 4 + H H + C2 H 6 H 2 + C2 H 5

2C 2 H 5 C 4 H 10 (C 2 H 6 + C 2 H 4 ) C 2 H 5 + H C 2 H 6 (C 2 H 4 + H 2 )

Nhn xet : Phan ng 5, 6 la phan ng be gay mach bc hai ( tc be gay bc hai cua nhanh t l vi bnh phng nng cua gc). S be gay mach thng la co th . Tc cua s be gay mach t l vi nng cua gc cao co th tin n bng 1 ng hoc cua nhng phan ng craking nhit thng anh hng n san phm cua phan ng . 2. Cac ho hydrocarbon khac

Trong du th,hu ht cac ho cua hydrocarbon u co mt nh parafin naphtenic,aromatic tr olefin co ham lng rt t.Tuy nhin di tac dung nhit cao,cac hp cht olefin se c tao thanh. Cac Olefin co kha nng phan ng cao hn so vi parafin, no bin i a

dang hn va cung phu thuc rt nhiu vao iu kin tin hanh phan ng . + iu kin nhit thp , ap sut cao , cac hydrocacbon olefin co trong lng phn t thp d b trung hp. + Nu tng nhit , tc phan ng trung hp giam xung, phan ng phn huy tng nhanh. Thi gian lu trong vung phan ng cang lu , th s phn huy xay ra cang manh lit, thun li t mach lin kt C_C v tr so vi ni i. Ngoai ra cac olefin con tham gia cac phan ng ngng tu,alkyl hoa vi cac hydrocarbon naphten hay aromatic tao ra cac hp cht cao phn t va cui cung la tao thanh nha va coke Cac hydrrocarbon naphten

RH naphten co bn nhit cao hn so vi parafin co cung s nguyn t C trong mach.Cac bin i c trng cua hydrocarbon naphten nhit cao thng xay ra theo s u tin sau: + Kh nhanh alkyl + Kh hydro tao olefin vong ,tip tuc tao thanh hydrocarbon thm. + Phn huy vong i vi cac Naphten a vong thanh n vong. + Kh naphten n vong thanh parafin va olefin hay diolefin. Nh vy ,cac naphten khi tham gia phan ng phn huy nhit,san phm tao thanh co c trng nohn so vi parafin ,co xu hng tao nhiu san phm long (M trung bnh)
Cac

hydrocarbon thm (Aromatic)

nhit cao ,s bin i cua hydrocarbon thm xay ra theo quy lut sau : + Kh nhanh alkyl + Cac gc thm ngng tu vi nhau,kh hydro tao thanh gc mi co phn t lng ln hn,nhiu vong thm hn,cui cung phat trin thanh hp cht cao phn t goi la coke.
V.

S chuyn hoa nhit cua nhng HC trong pha kh:

1.

Chuyn hoa cua nhng parafin:

Vi nhiu phan ng cua parafin co th nhit ng c m ta nh sau . 0 Phan ng deshydro hoa C2-C10 .. t K > = 1000 0 Phan ng khep vong C6 cho cyclo C6 + H2 .. t K > = 1100 C10 cho cyclo C10 + H2 .. t 0 K > = 800 Phan ng thm hoa C6 - C10 .. t 0 K > = 630 Phan ng craquage C3 - C10 .. t 0 K > = 600-700 Vic a ra nhng phan ng trn u co th thc hin c, lin quan n thanh phn san phm cua qua trnh tach nhit cua nhiu alcane , la hoan toan c giai thch theo c ch gc nhanh . Qua trnh craquage cua butan co th c m ta theo biu di y . u tin , nhiu gc t do xut hin nh qua trnh be gay lin kt C_C la nhng lin kt kem bn .
CH 3 CH 2 CH 2 CH 3 2CH 3 CH 2

CH 3 CH 2 CH 2 CH 3 CH 3 + CH 3 CH 2 CH 2

Tip theo , qua trnh mn trc tip hai gc co th. Nhiu gc co s nguyn t cacbon t 3 tr ln th kem n nh, vic tach t phat theo quy tc , a ra nhiu gc methyl va ethyl co n nh cao, la mt phn t alcen va hyrgen :
CH 3 CH 2 CH 2 CH 3CH = CH 2 + H CH 3 CH 2 CH 2 CH 2 = CH 2 + CH 3

Nhiu gc ethyl, methyl, bn vi s tach , nhng la mt cht phan ng cc im , cung nh nhng phn t hyrgen , phan ng tac ng ln trn cac phn t ban u li keo cac phn t hyrgen :
H + C 4 H 10 H 2 + C 4 H 9

CH 3 + C 4 H 10 CH 4 + C 4 H 9

CH 3 CH 2 + C 4 H 10 CH 3 CH 3 + C 4 H 9

Ta co th nhn thy s hnh thanh hyrgen , metan , etan , va nhiu gc butyl bc hai. Vic hnh thanh nhng gc butyl u tin la kem. Lin kt C_H la rt bn trn cacbon u tin ri n cacbon tip theo . Tai nhit 6000 C , xac sut li keo cua cac gc cua hyrogen vi cac cacbon bc 1:bc2: 3 cua cac phn t t l 1 : 2

: 10. T l nay dn n xac sut hnh thanh gc butyl bc 1 va bc 2 la (6*1) : (4*2) = 3 : 4 . Vic tach i vi phn t butyl theo quy tc , va nhiu gc co s nguyn t cacbon nho la kt qua cua vic tn cng cac phn t mi u tin. Qua trnh trong nhanh t phat trin. Nhanh gay t bi s kt hp nhiu gc va khng ng u .
2.

Chuyn hoa nhiu cycloalcan .

Nhng phan ng chuyn hoa cycloalcan phu hp nhit ng thng thng cua cac phan ng : tach cac nguyn t , deshyro hoa cua cac cyclopentan , cyclopentandien va nhiu cyclohexan cua aren. Thc hin cac phan ng tach nhit cua nhiu cycloalcan tao thanh nhiu alcen thp phn t (C 2 - C3) , methal, ethal, butylen, hyrogen, cyclopentadien va nhiu aren . Vic tach u tin cua nhiu cycloalcan t v tr u tin n v tr cua nhiu lin kt nho C_C va sinh ra hai gc :
*CH CH CH CH CH * CH2 2 2 2 2 2

Hai gc nay t phn li thanh nhng phn t n nh :

CH 2 CH 2 CH2 CH 2 CH 2 CH2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH2

CH 2 CH 2 CH2 CH 2 CH 2 CH2 CH 2 C 2 H 4 + CH2 CH2 CH 2 CH2 3C 2 H 4 CH 2 CH 2 CH2 CH 2 CH 2 CH2 CH 2 C 2 H 4 + CH2 = CHCH2 CH3 CH 2 CH 2 CH2 CH 2 CH 2 CH2 CH 2 2CH3CH = CH 2
S be gay mach lin kt u tin C_H vi vic hnh thanh mt gc t m ra mt cach chm rai, va qua trnh be gay mach khng thc hin v tr u tin , vi tc nho khi u . Th nhng , vic tach cua hai gc dn n s kt tu cua nhiu alcen, va qua trnh nay mn c ch mach n mc cai tin nh sau :
CH 3 CH 2 CH = CH 2 CH 3 + CH 2 CH = CH 2

CH3

CH4

*H

ARENES

* CH2=CHCH2CH2CH2CH2

CH2=CH2

* CH2=CHCH2CH3

CH2=CHCH2CH3

3. Chuyn hoa cac olefin : 450 alcen hanh sut Trong iu kin vn hanh cua qua trnh nhit , t 500 C , nhng phan ng nhit co th hnh thanh nhiu khac nho hn, alcadien, va alcan, vic hnh thanh aren tin nhit cao hn, acetylen . S tach cua nhiu alcen co nguyn l theo c ch gc Ethylen xay ra phan ng nhit cao , di ap thp : Chung ta co th th hin bng cng thc nh sau :
0

CH2=CH2 CH2=CH* H* + CH2=CH2

CH2=CH2

* CH2=CH

H*

C2H2 + H* CH2=CH* + H2
C2H2

H2

Nhn xet : acetylen va hyrogen la nhng san phm chnh . Tai gia tr nhit khng cao lm ( < 6000C) th gc vinyl c u ai c nh trn ethylen u tin vi vic hnh thanh butylen va butadien :

* CH2=CH + CH2=CH2

* CH=CHCH2CH2

CH2=CHCH=CH2 + H*

* CH2=CHCH2CH3 + CH2=CH

Tai gia tr nhit thp va ap sut giam dn , th phan ng (b) vi vic tch tu cua butylen la rt quan trong hn so vi phan ng (a) hnh thanh butadien . Propylen phu hp vi nhit cao va ap sut thp t phn tach thanh hydrogen, methal,ethylen va allen:
CH2=CHCH3 * CH2=CHCH2 H + CH2=CHCH3 * * H + CH2=CHCH2 CH2=CH=CH2 + H* * H2 +CH2=CHCH2 CH2=CH2 + CH3

CH2CH2CH3 * CH3 + CH2 =CHCH3

0

* CH4 + CH2 = CHCH2

Di ap sut kh quyn va tai nhit kha cao ( t = 600 - 700 C) , phan ng cua gc allyle la cng hp vao ni i cua phn t u tin. Co s trung hp cua propylen thanh gc
C 6 H 11

* CH2=CHCH2 + CH2=CHCH3

CH2=CHCH2CH2* CHCH3 * CH2=CHCH2CHCH3CH2

Nhng phan ng cua gc C 6 H 11 a ra trong hn hp cua san phm la : butadien, butylen, propylen , ethylen, methal, hyrgen cung nh cht long . Qua trnh tach nhit cua - butylen va mt s alcen thng nhanh dai be gay mach lin kt kem bn , lin kt i, cho ra ethal, methal, butadien, nhiu alcen va mt s cacbon thp phn t khac . n nh nhit cua alcen (M ln) la ln cn vi alcan (M ln) . Co nhiu cycloalcan co n nh nhit ln hn nhiu so vi alcen .

VD:Vi cyclohexen nhit 6000C, no c tao thanh t phan ng dehyro cua benzen.
4.

S chuyn hoa cua alcadien va alkin.

Nhiu alcadien va alkyl co n nh nhit hn so vi alcen .Vi gia tr nhit khng cao lm ( t = 400 0C) va di ap sut ln cn ap sut kh quyn, nhiu alcadien chuyn hoa nhanh tao hp cht khac. Nhiu phan ng u th la tng hp dene ma theo c ch phn t :
CH2 CH CH CH2 CH2 CH CH CH2 CH CH=CH2 CH=CH2 CH2 CH2

+
CH2

Tai gia tr nhit cao khoang 7000C , chung ta khng cn chu y n t l khng ang k cua tng hp diene . Qua trnh tach nhanh cua acetylen c m ta nh sau :
C2H2 + C2H2 CH * C CH C2H2 C2H2 C2H2 * * C + CH=CH2 * C3H2=CH CH CH CH C C CH + H * C* * C2H2 CH C

CH

* CCH=CH

CCH=CH2 + CH * CCH=CHCH=CH

o la s chuyn hoa cua acetylen quy vao nhiu hp cht khng bao hoa n khi lng phn t cao va la nhiu arene.
5.

Chuyn hoa nhit(Hydro cacbon thm Aromatic)

 n nh nhit cua aren thay i tuy vao cu truc cua no.Benzen va naphtalen khng thay th nhom methyl th n nh cach xa so vi alcan. Nhiu aren , alcoyle ma chi phi lin kt C_C trong lin kt vi vong t phn li rt nhanh so vi alcan.iu o do s phn chia nng lng gia lin kt cua cac phn t :
H
325 375

C
271

CH2CH2R

Trong qua trnh nhit , nhiu aren khng thay th dehydr hoa ngng tu hoc ngng tu phu thuc c ch gc . Qua trnh ngng tu benzen c m ta nh sau :

+
* H*

+ H*
H2

Biphenyl va hydrogen la san phm cau cua phan ng nay . Toluen c tach bi qua trnh cracking cai tin :
CH3 * CH2

+ +

H* * CH2 H CH3

* H

CH3

H2

+ CH3
* CH2

* CH3

+
* CH2

CH3

CH4

+
CH2CH2

Gc benzyl C 6 H 5 CH 2 la t hoat ng. Trong mt s trng hp , vn tc cua phan ng tach nhit cua Toluen la bng vn tc be gay lin kt C 6 H 5 CH 2 H .

Nhiu phan ng tng chuyn hoa cua toluen co th c sinh ra bng phan ng dehyro ngng tu vi vic hnh thanh dibenzyl va demethyl hoa thanh methal va benzen . V vy nhit cua phan ng cracking cua toluen la rt cao , nng cua gc benzyl tng bi qua trnh be gay lin kt C_C beo cua dibenzyl. Vn tc phat trin mach la rt cao so vi phan ng tach toluen , va qua trnh nay theo c ch mach :
C6H5CH2 * C6H5CH2 CH3 C6H5CH2C6H4CH3 + H *

C6H5CH3 C6H5CH2 H3C * C6H5CH2C6H5 + CH3

Nhiu aren alcoyle mach dai nhn thy bn canh se t tach mach alcoyle trong iu kin cua qua trnh nhit. Nhng phan ng khi u c lam bi s ct mach cua lin kt C C lin kt vi nhn aromatic :
C6H5 CH2 CH2 R * * C6H5CH2 + CH2R

Nhiu san phm u tin la toluen , styren va alcan . VI. Thit b :

1. Lo ng: Trong cng ngh cracking nhit , ngi ta hay dung lo ng 2 bc :bc xa i lu loai bung . S cu truc cua lo gm 2 bung bc xa va 1 bung i lu . Trong bung bc xa nhin liu c t chay, cp nhit cho lo . Ngi ta b tr cac ng pha trn ngon la nhn trc tip nhit bc xa,con bung i lu la nhn nhit cua kh khoi chu yu do truyn nhit i lu . Nguyn liu c trn trong lo doc theo ng, chung c gia nhit nh nhit lng thu c khi t chay nhin liu (kh hoc long). Phan ng cracking nhit xay ra trc tip trong ng nay. Vi khoang T0< 5500C, s ct mach c thc hin nhng cha xay ra qua trnh ngng kt va thm hoa . t , ngi ta b tr nhng mo t bn hng doc theo chiu dai cua bung bc xa, c nap nhin liu kh hay long .Vic b tr cac mo t ngn hay dai tuy thuc nhin liu s dung kh hoc long .Thng th b tr ngn thch hp cho nhin liu la Fuel gas (thanh phn kh hn hp C1,C2,C3) hoc

nhng thanh phn nhin liu co ham lng long t . ng t ng gia nhit 2 mt . y, phng phap gia nhit gradien trong mi phn cua ng c thit lp nhit ti u tng ng tai v tr cho trc hay ch nhit c khng ch cht che . Nhng ng thng ng trong bung bc xa c gia nhit nh hiu ng truyn nhit t nhng mo t cua lo va kh lo t . Kh lo t sau khi c lam lanh mt phn c a vao bung i lu, tai y s truyn nhit c thc hin nh s i lu nhit hiu ng . Nh s phn b b phn ng y, nguyn liu c t nong n nhit bt buc sau o chung chuyn xung ng thng ng , thc hin qua trnh va san phm cracking nhit thoat ra khoi lo chuyn n bnh tach . Kh lo t c chuyn n b phn tn dung nhit lng ri thai ra ngoai khng kh. S dung ng thng tranh ti a vic ong cau cn va dan n nhit t0cao nh ng xon rut ga . bung i lu ng t nm ngang tranh tr lc va giam chiu cao cua lo . bung bc xa, ng thng ng nhm thu hep khoang khng gian, han ch ti a vic ong cau va dan n v nhit, khc phuc sc bn cua ng . Vic s dung lo lin hp nay manh, co ng sut nhit cao, ch lam vic cht che, thi gian trong lo cua nguyn liu nho tranh c cracking su. tranh nhng phan ng bc 2 ,ngi ta thc hin cracking mc chuyn hoa nguyn liu (v du la parafin) khng ln lm (20-25%) ri cho no quay vong tr lai sau khi a tach nhng phn oan nhe . Ky thut nhit phn . Cac ng truyn nhit c t bi cac ngon la muc ch nng cao nhit nhanh ti a , nhit san phm ra cao nht co th at c thi gian lu la ngn nht. Cng ngh : Nhit lng mang vao c tnh : H * W = * D * L (1) Trong o : + H :nhit lng mang vao + W : lu lng trong lng + : nhit trao i + D : ng knh + L : chiu dai ng truyn nhit Thi gian lu c tnh theo cng thc sau :

Trong o : : thi gian lu. T (1) va (2) ta co :

* W = D 2 * L (2) =
H *D

Mun giam thi gian lu th giam ng knh D nhng ma chung ta khng th giam ng knh qua nhiu v tr lc cao , nhiu ng truyn nhit tn kem , tc cua cht lu tng gy xoa mon. 2 . Ct tinh ct : Muc ch : Ct tinh ct hay ct tach hoan thin tin hanh tach phn oan kh giau butan , xng nhe khng n nh , xng nng , gasoil. Cu tao: Ct tinh ct la mt thit b hnh tru thng ng c ch tao t thep cacbon pha ngoai , con pha trong c lot bng thep mm , bn trong thap co b tr cac a va c chia lam hai phn bi mt a ic . Phn pha trn lam nhim vu chng luyn con phn mm pha di ch chng tach cac cu t nhe cha trong cn nng. Vo ngoai con co lp cach nhit va cac ca kim tra s lam vic cua thap , lam v sinh , lp rap va thay th cac a. Khac ct tinh ct th , thap tinh ct nay lam vic iu kin ap sut cao ( 0.8 - 1.0 Mpa).

KT LUN
Trn y la toan b qua trnh nghin cu cua nhom v tai cracking nhit . Qua qua trnh tm hiu , nghin cu nhn thy : Cracking nhit la mt qua trnh quan trong trong nha may hoa du. Qua trnh nay tuy khng u vit bng qua trnh cracking xuc tac ( phan ng chon loc , ch s octan cao) nhng vn c s dung nhm ch bin cac phn rt nng cua cn du thanh nhng san phm nng lng va phi nng lng .

PHU LUC
Tn sach tham khao:
1.Cng ngh ch bin du mo inh Th Ngo 2.Hoa hoc du mo va kh L Ming Hiu 3.Cac san phm thng phm du mo 4.C s cac qua trnh va thit b cng ngh hoa hoc Nguyn Trong Khung 5.Procedes de petrochimie A.Chauvel - G. Lefebvre - L . Castex 6.Raffinage et genie chimique Pierre Wuithier

Muc luc
A.Li gii thiu B.Ni dung tai I.Gii thiu chung 1.t vn 2.Chon phng phap 3.Qua trnh cracking nhit +Muc ch +iu kin vn hanh +Nguyn liu +c trng san phm II. S cng ngh Thuyt minh s . III. Cac thng s anh hng 1.Nguyn liu 2.Nhit . 3.Ap sut 4.Thi gian phan ng. IV. Thit b. 1.Lo ng 2.Ct tinh ct. C. Kt lun D. Phu luc.

S cng ngh Thuyt minh s S chung cua qua trnh x ly bng nhit gm co qua trnh x ly cn bng Hydro Trong chng ct du th ta thu

c san phm ay cua ct chng ct gm nhng Hydrocacbon co khi lng phn t rt ln va phn cn cha nhiu tap cht (kim loai,hp cht lu huynh, hp cht cua Nit...) Charge (bitume hoc RSV...) trc khi vao lo Hydro cracking c gia nhit trc bng hi nong trong thit b trao i nhit E 01 . Dong H2 (c tao ra va dong H2 tun hoan ) cung c gia nhit ng thi trong E 02 ri trn vi charge trc khi vao thit b hydrocracking . Dong nguyn liu + c gia nhit ln n t0 phan ng trong lo va i t nh xung di xuyn qua lp xuc tac c nh trong thit b phan ng . Dong H 2 lanh thm c a vao 1 khu vc khac cua thit b phan ng . San phm sau khi ra khoi thit b phan ng i qua bnh tach nong (Hot flash drum). y du nhe ra nh qua thit b trao i nhit vi charge sau o c ngng tu lam lanh bng khng kh hay bng H2O (Nng lng khng kh va H2O nhn c em cung cp cho thit b khac hay lam quay turbin ). Sau khi c lam lanh hn hp long hi c cho vao bnh tach vn hanh vi ap sut thp hn TBPW. Dong kh i ra khoi bnh tach giau Hydro c a qua x ly bng amine (loai bo kh axit bng amine ) va quay hi lu lai qua trnh . Du long nng t ay bnh tach tip tuc qua 1 thit b tach nong tach tip phn long con lai. Hi ra nh qua thit b trao i nhit vi dong H2 ri kt hp vi dong long t balon 1 ri vao balon 2 . Kh thu c a qua x ly bng H2 (HDC).Long thu c t ay balon cung a i qua HDC x ly . (phn du nng ra ay c a vao thit b Cracking nhit) San phm kh co th qua 1 thap hp thu hoc mt qua trnh khac thch hp thu hi Naphta nhe va LPG . Phn long a qua 1 thap tach Butan va sau o n 1 phn oan tach khac thu cac san phm ct thng thng nh: naphta, kerosen, diesel