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TRNG I HC BCH KHOA H NI VIN O TO SAU I HC

TIU LUN

CRACKING XC TC

Nhm hc vin: Phm Th Thanh Hiu Bi Th Thi Nguyn Quc t

H Ni, nm 2011

MC LC MC LC......................................................................................2

M u
Du m c coi nh l ngun nhin liu chnh cho mi phng tin giao thng v cho nn kinh t quc dn. Hin nay, du m tr thnh ngun nng lng quan trng nht ca mi quc gia trn th gii v l nguyn liu cho cng nghip tng hp ha du nh : sn xut cao su, cht do, t si tng hp... Ngoi ra, cc sn phm phi nhin liu ca du m nh du m bi trn, nha ng...cng l mt phn quan trng trong s pht trin ca cng nghip ng c, my mc. Mt trong s nhng qu trnh quan trng nht ca nh my lc du l qu trnh cracking xc tc. C th ni, cng ngh cracking xc tc l mt trong nhng cng ngh quan trng nht ca cng ngh hu c ha du. Ngy nay, Vit Nam ang trn con ng cng nghip ha, hin i ha, ngnh cng nghip ha du c xp vo mt trong nhng ngnh mi nhn cng nghip ca quc gia. T khi xut hin n nay, cracking xc tc cung cp nhng sn phm ng qu cho cng nghip, c bit l xng. Qu trnh cracking xc tc ngy cng c ci tin gii quyt nhng bi ton v ngun nguyn liu du m ngy cng c cht lng xu, nhng yu cu bc xc v xng c tr s octan cao, thay v s dng xng pha ch ...

Chng I: Qu trnh cracking xc tc


I.Mc ch v ngha ca cracking xc tc: - Mc ch ca qu trnh cracking xc tc l nhn c cc cu t c ch s octan cao cho xng t hay xng my bay. Ngoi ra, thu thm mt s sn phm ph khc nh gasoil nh, gasoil nng, kh... y l cc nguyn liu qu, c gi tr trong cng nghip tng hp hu c ha du. - Qu trnh cracking xc tc (FCC) l mt qu trnh khng th thiu c trong bt k nh my ch bin du no trn Th gii, v qu trnh ny l mt trong cc qu trnh chnh sn xut xng c tr s octan cao. II.Nguyn liu cho cracking xc tc: 1.Cc c trng v nguyn liu cho cracking xc tc: Cc nh my lc du phi ch bin nhiu loi du th khc nhau. Cht lng ca du th thng b bin i theo tng vng khc nhau, do , ngi ta phi xc nh r cc tnh cht c trng ca tng loi nguyn liu m bo s vn hnh n nh ca cc cng on ch bin (cracking, reforming...) trong mt nh my lc du. Da vo c trng v nguyn liu FCC, ngi ta c th la chn cht xc tc, x l cc s c, ti u ha qu trnh cracking xc tc. Hai yu t quan trng nht nh hng n cht lng ca nguyn liu FCC: + Cc hydrocacbon . + Cc tp cht. C cha trong nguyn liu FCC. 1.1.Phn loi cc hydrocacbon:

Cc hydrocacbon trong nguyn liu FCC thng c phn thnh: parafin, olefin, naphten v aromat. - Nguyn liu FCC cha ch yu l parafin. Chng d b cracking v to ra sn phm lng nhiu nht. ng thi, lm tng hiu sut to kh t nhng lm gim tr s octan nhiu nht. - Cc olefin khng tn ti trong t nhin, n c mt trong nguyn liu FCC l do cc qu trnh x l trc (cracking nhit....). Chng thng b polime ha to ra cc sn phm khng mong mun nh cc v nha. - Nguyn liu giu cu t naphten rt c a chung trong cracking xc tc, do chng c cc sn phm xng c tr s octan cao. - Cc aromat cng lm tng tr s octan nhng do chng c cha cc vng benzen bn nn khng thch hp cho qu trnh cracking xc tc. Do khi cracking aromat thng b b gy cc mch nhnh, lm tng hiu sut kh. Ngoi ra, mt s t hp cht aromat a vng c th to ra cc v nha, lm gim hot tnh xc tc. 1.2 Cc tp cht: Trong nhng nm gn y khi ngun nguyn liu cht lng tt ngy mt cn dn, cc nh my lc du phi ch bin cc ngun du th nng hn, cht lng xu hn. Cc ngun nguyn liu FCC hin nay u l nguyn liu nng v cha nhiu tp cht. Hu ht cc tp cht trong nguyn liu FCC u nm trong thnh phn cc cht hu c phn t ln, di dng cc hp cht cha: + Nit + Lu Hunh + Kim loi (Niken, Vanadi, Natri...) Cc tp cht nh hng xu n s hot ng ca thit b, gy ra nhim c xc tc FCC, lm mt hot tnh i vi cc phn ng to ra cc sn phm c gi tr, lm tng gi thnh ch bin v phi x l nguyn liu v sn phm. 1.2.1 Nit: + Gy ng c xc tc tm thi. + Trong thit b hon nguyn xc tc, Nit trong cc c chuyn thnh N2, phn cn li c chuyn thnh oxit nit (NOx). NOx thot ra mi trng cng vi kh thi gy nhim mi trng. + To hp cht n mn cc thit b, cc chi tit thit b kim loi. + To hp cht d b oxi ha, lm i mu sn phm. 1.2.2 Lu hunh:

Tc ng xu ca lu hunh l rt nh trong qu trnh ch bin du m. 1.2.3 Cc kim loi: Cc kim loi l cht xc tc v tr xc tc cho nhiu phn ng khng mong mun nh ehydro ha v ngng t, lm cho hiu sut hydro v cc tng ln, hiu sut to xng gim. 2. La chn nguyn liu cho qu trnh cracking xc tc: Da theo thnh phn phn on c th chia nguyn liu cho qu trnh cracking xc tc thnh 4 nhm sau: +Nhm 1 : nhm nguyn liu nh, l phn on kerosen-xola ly t qu trnh chng ct trc tip. Gii hn nhit si trung bnh l 260-380 0C. T trng trung bnh: 0,830,86. Trng lng phn t trung bnh: 190-220 vc. y l nguyn liu tt nht sn xut xng my bay v t. +Nhm 2 : nhm nguyn liu l phn on Gasoil nng. Gii hn nhit si trung bnh l 300-500 0C. T trng trung bnh: 0,88- 0,92. Trng lng phn t trung bnh: 280-330 vc. y l nguyn liu tt nht sn xut xng t v xe my. +Nhm 3 : nhm nguyn liu c thnh phn phn on rng, l hn hp ca hai nhm trn. Gii hn nhit si trung bnh l 210-5500C, c th l phn on ly t chng ct trc tip hay l phn chit ca qu trnh lm sch du nhn bng dung mi chn lc. y l nguyn liu tt nht sn xut xng t v my bay. +Nhm 4 : nhm nguyn liu phn on trung gian l hn hp phn on kerosen nng v xola nh. Gii hn nhit si trung bnh l 300-430 0C. y l nguyn liu tt nht sn xut xng t v my bay. Nguyn liu t c gi tr nht l cc phn chit ca qu trnh lm sch du nhn bng dung mi chn lc, cn mazut, gasoil nng ca cc qu trnh ch bin th cp khc cho hiu sut khng cao v to nhiu cc. Ngoi ra, trong cc nguyn liu ny cha nhiu hp cht ca S, N v cc kim loi nng d lm ng c xc tc. Trong cc nhm nguyn liu trn, nguyn liu tt nht dng cho cracking xc tc l phn on kerosen-xola gasoil nng, thu c t chng ct trc tip. Phn on ny cho hiu sut xng cao, t to cc nn thi gian lm vic xc tc ko di. Lu : Trong nguyn liu cracking xc tc khng cho php c mt phn on nh c nhit si nh hn hoc bng 2000C, v trong iu kin cracking phn on ny m b phn hy th to ra nhiu kh lm cho hiu sut xng v tr s octan gim. Mt khc, trong nguyn liu khng cho php cha lng ln cc hydrocacbon thm a vng (v trong qu trnh d ngng t cc bm trn b mt xc tc), nha, asphanten v cc hp

cht cha N, S... Nu qu trnh cracking xc tc cho php s dng cc nguyn liu ny mt gii hn nht nh th cn tin hnh lm sch nguyn liu (loi b bt cc tp cht trn) trc khi a nguyn liu vo s dng. *Hin nay, Vit Nam c 3 m du quan trng c xc tin khai thc, l: + M Bch H: cch b bin Vng Tu khong 120 km, c bt u khai thc t nm 1986 n nay. Tr lng du m y ang gim dn, c th khai thc vi ba nm na. Tuy nhin, nu c bin php u t cng ngh cao khai thc th cp c th tng thm sn lng v ko di thm thi gian khai thc ca m. + M Rng: cch m Bch H khong 30km v pha Ty Nam, bt u c khai thc t nm 1994. Nhng sn lng ban u cha ng k. + M Nam Cn Sn: nm vng trng Nam Cn Sn, cch b bin 280km v cch m Bch H 160km, c tin hnh khai thc t thng 10/1994. Nhng thun li cho qu trnh craking xc tc nh mt s c tnh ca du th Vit Nam : - Du th Vit Nam thuc loi du nh, tng hiu sut sn phm trng thu c nhiu (50-60%trng lng du th). Hiu sut cc sn phm trc tip t du th Vit Nam Hiu sut % th tch t du m Bch H i Hng Naphta 17,81 22,55 Kerosen 13,91 14,70 DO 19,51 27,15 Cn (chng ct kh quyn trn 3450C)-FO 48,27 39,45 0 Cn (chng ct chn khng trn 550 C) 14,2 5,0 - Du th Vit Nam l loi du th rt sch cha rt t cc c t, rt t lu hunh, rt t kim loi nng v cc hp cht ca nit. Nh vy m trong qu trnh ch bin khng phi thc hin cc gii php tn km loi b cc tp cht. Nhng cng trnh nghin cu ca UOP (M) xut gii php dng ton b cn du th Vit Nam (chng ct kh quyn, chng ct chn khng) cracking xc tc sn xut xng vi hiu sut cao m khng ng c cht xc tc, mt gii php cng ngh rt kinh t so vi khi ch bin cc loi du th khc trn th gii. Trong s cc phn on ca du th Bch H v i Hng u l nguyn liu tt cho qu trnh cracking xc tc. Theo bng, hiu sut % th tch t du th Bch H ca phn on gasoil nng (cn chng ct chn khng) cao hn so vi du th i Hng. Tuy nhin, do m du Bch H ang cn dn, cn nghin cu thm v du th i Hng s dng v khai thc mt cc hp l. Cc phn on

III.Cc c trng ca sn phm cracking xc tc : Sau khi cracking, cc sn phm ca cng on FCC c phn ring theo khong nhit si : kh, xng, gasoil nh, gasoil nng. Trong , phn on xng l sn phm quan trng v c gi tr nht. Hiu sut cc sn phm FCC ph thuc vo nhiu yu t: ngun nguyn liu, bn cht xc tc, ch cng ngh v mc ch kinh t cng ngh ca nh lc du. 1.Sn phm kh cracking xc tc: Hiu sut ca sn phm kh chim 10-15% nguyn liu em cracking. Nu tin hnh iu kin cng th hiu sut s ln v ngc li. - Cc kh nh (C2 v nh hn) thot ra t thp hp th du c gi l kh kh. Cc cu t chnh ca kh kh l: hydro, metan, etan, etylen v H2S. Nu nguyn liu c hm lng Lu hunh cao th kh cracking cha nhiu H2S. Nu nguyn liu cha nhiu Nit trong kh s c NH3. Kh kh l mt sn phm khng mong mun ca phn xng FCC, kh kh nhiu qu gy ra qu ti my nn kh t. - Sn phm propan-propen lm nguyn liu cho qu trnh polyme ha v cho qu trnh sn xut cc cht hot ng b mt. - Phn on kh propan-propen, butan-buten l nguyn liu cho qu trnh sn xut kh ha lng LPG, nguyn liu cho ankyl ha, lm nguyn liu cho tng hp ha du. 2.Sn phm xng cracking xc tc: Xng l sn phm chnh ca qu trnh, hiu sut xng cracking xc tc thng thu c t 30-55% lng nguyn liu em cracking. Hiu sut xng v cht lng xng ph thuc vo cht lng nguyn liu, xc tc v ch cng ngh. - Nu nguyn liu c hm lng hydrocacbon naphten th cho hiu sut v cht lng xng cao. Nu nguyn liu c hm lng ln parafin th nhn c xng c tr s octan thp. Trong nguyn liu c hm lng Lu hunh cao th xng nhn c c hm lng Lu hunh ln, thng chim khong 15% trng lng Lu hunh cha trong nguyn liu. - Xng nhn c t qu trnh cracking xc tc c t trng khong 0,72-0,77. Tr s octan theo phng php nghin cu (RON) khong 87-91. - Thnh phn ha hc ca xng cracking xc tc khc hn vi xng cracking nhit v xng chng ct trc tip. Xng cracking xc tc c tr s octan cao hn, c cha 9-10% trng lng hydrocacbon thm. Ni chung, xng cracking xc tc l cu t c bn ch to xng thng phm cho t v my bay. Thnh phn xng cracking:

+ Hydrocacbon thm : 25-40% + Olefin + Naphten + Parafin : 15-30% : 2-10% : 35-60% (iso-parafin l ch yu)

tng tr s octan cho xng cracking xc tc, ngi ta pha thm nc ch (TEL). Mc tip nhn nc ch ph thuc vo thnh phn ha hc ca xng. Tuy nhin, xng c pha ch rt c, gy nhim mi trng. Phn on xng cc dy chuyn cng ngh Lin bang Nga thng c nhit si cui l 1950C, cn cc nc khc thay i c th l 204 hoc l 2200C. 3.Sn phm gasoil nh: - Gasoil nh ca qu trnh c nhit si 175-3500C. So snh vi nhin liu diezen th n c tr s xetan thp v hm lng lu hunh kh cao. - Vi nguyn liu l phn on xola t du h parafin th gasoil nh nhn c, c tr s octan xetan tng i cao (45 46). Vi nguyn liu cha nhiu hydrocacbon thm, naphten th tr s xetan thp (25 35). - Cht lng gasoil nh khng ch ph thuc vo cht lng ca xc tc v ch cng ngh cracking xc tc. iu kin cng: hiu sut, cht lng gasoil nh thp v ngc li. - Sn phm gasoil nh dng lm cu t pha cho nhin liu diezen, lm nguyn liu sn xut b hng, hay lm cu t pha long mazut. - Gasoil nh c c tnh: T trng: 0,83 0,94. Thnh phn ha hc:

+ Lu hunh 1,7 2,4% trng lng. + Hydrocacbon olefin 6% trng lng. + Hydrocacbon thm 30 50% trng lng. Cn li l hydrocacbon parafin v naphten. 4.Sn phm gasoil nng: - L sn phm cn ca qu trnh. Cht lng ca n ph thuc ch cng ngh, ngun nguyn liu v cht lng gasoil nh. - Gasoil nng c nhit si > 3500C, c t trng: 0,89 0,99. - Gasoil nng cha mt lng kh ln tp cht c hc. Hm lng lu hunh trong cao hn khong 1,5 ln so vi nguyn liu ban u.

- HCO l sn phm nhn c t thp chng ct sn phm FCC, c khong nhit si nm gia gasoil nh v du gn (DO). HCO l du cha nhiu vng thm nng, thng c s dng nh dng hi lu ca thp chng ct nhm truyn nhit cho nguyn liu mi hoc cho b phn gia nhit ca thp tch C4. HCO c th c x l tip trong cng on hyro cracking, hoc dng pha trn vi du gn. - DO-du gn l sn phm nng nht ca qu trnh cracking xc tc. DO cn c gi l du st, du y v du cn FCC. DO l sn phm c gi tr kinh t thp nht, nn ngi ta thng c gng hn ch hiu sut DO. - Cc l sn phm c to thnh do mt phn nguyn liu b chuyn ha t cc phn ng cracking th cp, polime ha, ngng t... Cc bm trn b mt xc tc, lm gim hot tnh cht xc tc. Khi t chy cc trong thit b hon nguyn, hot tnh ca xc tc c hon nguyn, nhit thot ra t phn ng t chy cc li bo m ch nhit cho reacto cracking. - Sn phm gasoil nng lm nguyn liu cho cracking nhit v cc ha hoc lm nhin liu t l. Ngy nay, ngi ta cn dng n lm nguyn liu sn xut b hng.

Chng II:

Ha hc ca qu trnh cracking xc tc

I.Nguyn l ca qu trnh cracking xc tc : C th biu din bng s sau: Nguyn liu Chun b x l L phn ng Xc tc lm vic Sn phm qua Xc tcchng tch

ti sinh

L ti sinh xc tc II.C s ha hc chnh: Trong iu kin tin hnh qu trnh cracking xc tc xy ra mt s lng ln cc phn ng ha hc. Cht lng v hiu sut ca qu trnh c quyt nh bi cc phn ng ny. 1.Phn ng phn hy cc mch C- C, phn ng cracking : L phn ng phn hy b gy mch nhng phn t c kch thc ln (trng lng phn t ln) thnh nhng phn t c kch thc nh hn. y l phn ng chnh ca qu trnh. - Parafin b cracking to olefin v parafin nh. CnH2n+2 CmH2m + CpH2p+2 Vi n= m+p - Olefin b cracking to olefin nh hn. CnH2n CmH2m + CpH2p Vi n= m+p Cc alkyl hyrocacbon aromat (cc hyrocacbon vng thm, vit tt ArCnH2n+1, vi Ar: gc hyrocacbon aromat, CnH2n+1: gc alkyl). ArCnH2n+1 ArH + CnH2n Aromat olefin Cracking mch nhnh ca vng thm to thnh parafin v hyrocacbon thm c nhnh nh hn. ArCnH2n+1 ArCmH2m+1 + CpH2p , Vi n= m+p - Cracking naphten to ra cc olefin. CnH2n CmH2m + CpH2p Vi n= m+p Nu parafin mch c cha mt vng xyclohexan th vng khng b ph v: CnH2n C6H12 + CmH2m + CpH2p

Naphten xyclohexan olefin Vi n= m + p + 6 2.Phn ng ng phn ha (izome ha): n- olefin n- parafin iso- olefin iso-parafin

olefin

L phn ng to ra nhng hyrocacbon c cu trc mch nhnh.

3.Phn ng chuyn dch hyro: L qu trnh chuyn i H- trong v gia cc phn t phn ng, nn cn gi l s chuyn dch hyrua. Nh c xc tc m c s phn b li hyro, cho nn lm no c mt s hyrocacbon i, lm tng tnh n nh ha hc ca sn phm nhn c. Naphten + olefin hyrocacbon thm + parafin. Tin cht cc aromat + olefin cc + parafin. 4.Phn ng alkyl ha v kh alkyl ha: - Phn ng alkyl ha xy ra nhit thp, lm gim hiu sut kh. ArH + CnH2n Ar CnH2n+1 - Phn ng kh alkyl ha ngc vi phn ng alkyl ha, xy ra nhit cao v to nhiu kh. 5.Phn ng trng hp: Ch yu xy ra vi hyrocacbon i: CnH2n + CmH2m CpH2p Vi n + m=p 6.Phn ng ngng t to cc: Ch yu xy ra i vi cc hyrocacbon thm a vng, xy ra khi nhit cao.
CH=CH2

R1CH=CHR2 R2 R1

H2

S to cc trong qu trnh cracking xc tc l khng mong mun, v cc bm trn b mt xc tc, gim hot tnh xc tc, gim thi gian lm vic ca xc tc. Trong iu kin cng nghip, cc phn ng cracking chnh (phn ng phn hy cc mch C- C) khng b hn ch bi cn bng nhit ng hc, ti cn bng cc hyrocacbon u c th phn hy hon ton thnh cacbon graphit (C) v hyro. Ngc li, cc phn ng ph nh isome ha, alkyl ha cc aromat c th xy ra ch mc nh trong iu kin cracking cng nghip. Cc phn ng ankyl ha parafin-olefin,

hydro ha aromat v polyme ha olefin (ngoi tr polyme ha etylen) u hon ton khng xy ra. Cc phn ng cracking thu nhit mnh, isome ha c hiu ng nhit nh, cong phn ng chuyn dch hydro th ta nhit trong qu trnh cracking, cc phn ng thu nhit lun lun chim u th, hiu ng nhit ca qu trnh ph thuc vo ngun nguyn liu, cht xc tc v iu kin phn ng . III. C ch phn ng cracking xc tc : C ch ca qu trnh cracking xc tc l c ch ion cacboni. C s ca l thuyt ny da vo tm hot tnh l cc ion cacboni, chng c to ra khi cc phn t hyrocacbon ca nguyn liu tc dng vi tm axit ca xc tc loi Bronsted (H+) hay Lewis (L). Theo c ch ny, qu trnh cracking trn xc tc aluminosilicat xy ra theo cc giai on sau : 1.Giai on to ion cacboni: 1.1.T hyrocacbon parafin:

CnH2n+2 + H+

CnH2n+3
+

C+H2n+1 n

+ H2 +
+2

CnH2n+2 + L(H )
+

CnH2n+1 + LH

CmH2m+1

Cn-mH2(n-m)

- Ion cacboni c th c to thnh do s tc dng ca parafin vi tm axit Bronted ca xc tc :


R 1CH 2-CH 2R 2

- Ion cacboni cng c th c to ra do s tc dng ca parafin vi tm Lewis :


O RH O O S i R
+

+ H (xt )
+

R1CH2-C+HR2 + H2 +xt

A l O

l H: A O

S i

1.2.T hyrocacbon olefin:

CnH2n + H

CnH2n + L
R 1 CH=C H
O RH

- Ion cacboni to ra do s tc dng ca olefin vi tm acid Bronsted ca xc tc:


R2

CnH2n+1 + CnH2n+1 LH
+
+

H(xt)

C R 1 CH-C H
O R

R 2 + xt

- Ion cacboni to thnh O s tc dng ca olefin vi tm acid Lewis ca xc tc: do Si +

Al

H : Al

Si

Trong nguyn liu ban u thng khng c hyrocacbon olefin, nhng olefin c th to ra do s phn hy cc hyrocacbon parafin c phn t lng ln. Cc olefin to thnh lp tc tc dng vi tm acid ri to ra ion cacboni. Khi olefin tc dng vi H+ (xt) th xc sut to alkyl bc 2 ln hn alkyl bc1. Khi olefin c lin kt i cacbon bc 3 th ion cacboni bc 3 d to thnh hn cacbon bc 2.
CH3 CH3-CH C-CH3 CH3

+ H(xt)

CH3-CH2 C+-CH 3 CH3-CH C-CH3 CH3


+

1.3.T hydrocacbon naphten: Khi hydrocacbon naphten tc dng vi tm axit ca xc tc hay ion cacboni khc s to ra cac ion cacboni mi tng t nh qu trnh ny xy ra vi parafin. 1.4.T hyrocacbon thm : H+ kt hp trc tip vo nhn thm.
H H

+
trng hp parafin.

HX

Cc hyrocacbon thm c mch bn di th to thnh ion cacboni cng ging nh 2.Giai on bin i ion cacboni: Cc ion cacboni c to ra t giai on trn li nhanh chng tham gia vo cc phn ng bin i khc nhau nh : - Phn ng ng phn ha: R-C-C-C-C+ C-C+-C-C-R - Phn ng cracking theo qui tc: Ion cacboni chuyn ha theo qui tc phn ct lin kt i vi tm C+ to ra mt olefin v mt ion cacboni mi, nh hn.

C
(1)

C C
(2)

R C

C =C

+ C H3 + C R

(3) C

Nu ba lin kt C- C v tr th lin kt C- C v tr (1) l c xc sut t mch ln nht, sau n v tr (2) v cui cng n v tr (3). Cc ion cacboni nhanh chng tc dng vi olefin hay vi parafin theo phn ng vn chuyn ion hydrit:
+ +

CnH2n+1 + CmH2m CnH2n +

CmH2m +1
+

CnH2n+1 + CmH2m +2 CnH2n +2 +

CmH2m +1

+ i vi qu trnh phn ct ca ion cacboni mch thng xy ra vi tc cn chm hn, kh khn hn so vi phn ng ct ca ion cacboni mch nhnh, v n to ra mt ion cacboni bc 1. + i vi ion cacboni l ng ng ca benzen, s phn ct cc lin kt C- C trong mch vng l mt phn ng kh khn. Trc khi phn hy, proton c kt hp vi mt trong nhng lin kt C- C trong nhn thm to thnh nhng hp cht trung gian, sau in tch ion cacboni s dch chuyn theo s sau: +

CH3 - CH- CH2

CH3 - CH = CH2

+R
Cc ion ny c th tham gia cc phn ng ng phn, cracking, alkyl ha hay ngng t. Bin i ca ion cacboni tip din cho n khi n c cu trc bn vng nht, c bn cao nht. C th sp xp bn ca c ion cacboni theo th t sau: Ion cacboni bc 3 > ion cacboni bc 2 > ion cacboni bc 1. V d:
R1 C
+

R2

R1 C

R2

R1 C

bn ca ion cacboni s quyt nh mc tham gia cc phn ng tip theo ca chng. V ion cacboni bc 3 c bn cao nht nn s cho php nhn hiu sut cao cc hp cht izo-parafin. Cht lng sn phm c quyt nh bi cc phn ng ca ion cacboni m c bit l cc phn ng phn hy, ng phn ha v chuyn v hydro. 3.Giai on dng phn ng: Giai on ny xy ra khi cc ion cacboni kt hp vi nhau hoc chng nhng hay nhn nguyn t hydro ca xc tc to yhnh cc phn t trung ha.
C OH C C C O O S O OH

R3

O C C C
+

S O

C th so snh qu trnh cracking nhit v cracking xc tc nh sau: Thnh phn nguyn liu - Vi n-parafin. Cracking nhit - Phn ln thu C2 olefin v C4C5 mch thng. - Phn ng ng phn ha khng nhiu. - Kh thu sn phm vng. - Vi vng no. - Cracking kh khn. - Vi alkyl thm. - i mch alkyl. IV.ng hc cho qu trnh cracking xc tc: Cracking xc tc - Thu C3 C6 olefin mch nhnh. - ng phn ha rt nhiu. - Thu sn phm vng, to aren. - Cracking d dng. - Tch nhm alkyl ra khi vng thm.

1.ng hc phn ng cracking xc tc gasoil l mt vn kh phc tp. Thnh phn nguyn liu v sn phm lun thay i theo chiu dc lp xc tc n nh, ngay c thnh phn cht xc tc cng b bin i theo thi gian do hin tng ng c, to cc...Trong cc thit b cracking cng nghip hoc trong thit b c lp xc tc linh ng, cc cu t d b cracking nht c chuyn ha trong phn u ca reacto, trong cc phn tip theo khng ch l sn phm m bao gm c phn nguyn liu d kh cracking. V vy, cc nguyn liu quay vng t cc thit b cracking bao gi cng kh cracking hn nguyn liu gc ban u. Cn c vo cc c im phc tp , Kemp v Wojciechouski a ra mt phng trnh ng hc cho cracking xc tc du kh nh sau:

Trong :

dCA =k0. CS. C. ki0. A Xi i=1 d

+ ki0: hng s tc cracking ca cc cu t trong nguyn liu. + Xi: phn mol ca cu t th i. + k0: hng s tc ban u biu kin. + CS: nng tm xc tc. + CA: nng tng cng ca gasoil. S hng ki0 Xi biu din s nh hng ca thnh phn gasoil n tc cracking. 2.Qu trnh cracking xc tc l mt th d in hnh v xc tc d th, n c th xy ra cc giai on sau : - Qu trnh khuch tn nguyn liu n b mt xc tc (khuch tn ngoi).

- Khuch tn hi nguyn liu n cc tm hot tnh trong l xp ca xc tc (khuch tn trong ). - Hp ph nguyn liu trn tm hot tnh xc tc. - Cc phn ng ha hc trn b mt xc tc . - Kh hp ph cc sn phm cracking v nguyn liu cha tham gia phn ng ra khi b mt v ra khi l xp ca xc tc . - Tch cc sn phm cracking v nguyn liu cha tham gia phn ng ra khi vng phn ng . Tc chung ca qu trnh s c quyt nh bi giai on no chm nht. Tc ca phn ng cracking xc tc, trong a s cc trng hp c miu t bng phng trnh bc 1 sau : K = v0 . n . ln(1-x) (n 1) .x Trong : + K : tc ca phn ng(mol/g.h) + vo : tc truyn nguyn liu (mol/h). + n : s mol sn phm c to thnh t mt mol nguyn liu. + x : mc chuyn ha (phn mol) i vi phn on du trn xc tc zeolic, phng trnh bc 1 :

K=

v0

1-x
Vi vo l tc th tch khng gian truyn nguyn liu (m3/h). Phn ng xy ra trong vng ng hc hay vng khuch tn hon ton ph thuc vo bn cht ca nguyn liu v vo ch cng ngh ca qu trnh.

Chng III: Xc tc cho qu trnh cracking xc tc


I. Gii thiu chung v cht xc tc cracking cng nghip 1. Cc loi xc tc S pht trin v ci tin qu trnh cracking xc tc trong cng nghip ch bin du m, ngoi vic ci thin v nguyn liu, h thng thit b, ch cng ngh ...th ta thy

ci chnh l do s ci tin trong vic s dng cc cht xc tc. Phn ng cracking xc tc ch yu xy ra trn b mt cht xc tc, chiu hng ca phn ng ph thuc vo bn cht ca xc tc. Xc tc dng trong qu trnh cracking thng l xc tc rn, xp, c ngun gc t thin nhin hay tng hp, vi b mt ring ln. - u tin xc tc cracking c dng l t st thin nhin c tnh axit. V d: Xc tc tri-clorua nhm AlCl3 tin hnh nhit thp 200 3000C, nhc im ca xc tc ny l xc tc mt mt nhiu do to phc vi cc hyrocacbon ca nguyn liu, iu kin tip xc gia xc tc v nguyn liu l khng tt, cho hiu sut v cht lng xng thp. - Sau , ngi ta s dng aluminosilicat v nh hnh. u tin, ngi ta dng t st bentonit, song hiu sut chuyn ha thp nn tin hnh s dng aluminosilicat tng hp. Xc tc ny c hot tnh v chn lc tng i cao. - Hin nay, ch yu s dng zeolit hoc xc tc aluminosilicat cha zeolit. Vi u im ca loi xc tc cha zeolit l gim c gi thnh ca xc tc, d dng ti sinh xc tc. 2.Xc tc trong cng nghip: - Xc tc trong cng nghip thng c iu ch t 3 25% khi lng ca zeolit tinh th (ng knh ca ht zeolit tinh th c 1m) trong mt cht nn (mantrix) l aluminosilicat v nh hnh hoc khong st. - m bo ch lm vic trng thi lu th trong dng hi hyrocacbon, kch thc ht xc tc thng khong 2060m. Zeolit phi c phn tn vo trong pha nn aluminosilicat v nh hnh trnh cc hiu ng nhit cc b, n nh hot tnh xc tc ca zeolit, nh cu trc xp v axit khc nhau gia zeolit v pha v nh hnh. Hin nay, trong cng nghip s dng ch yu l zeolit X, Y c kch thc mao qun rng (810A0) ch to xc tc dng cho cracking cc phn on rng v nng. Ngoi ra, cn c th s dng loi zeolit mao qun trung bnh nh ZSM-5, ZSM-11. Cc loi xc tc trn c ch to di dng ht vi cu s dng cho qu trnh cracking vi lp gi si (FCC) hoc dng cu ln cho thit b c lp xc tc chuyn ng (RCC). Mt khc, trong cht xc tc FCC, ngoi cc hp phn c bn l zeolit Y dng US Y v pha nn aluminosilicat v nh hnh, ngi ta cn thm vo cc zeolit ph gia (vi hm lng t 1 10% khi lng) nh: H-ZSM-5, H-ZSM-11, H-beta .... gia tng tr s

octanca xng hoc gia tng hm lng olefin nh trong thnh phn kh cracking v thm mt s ph gia th ng ha kim loi. II. Vai tr ca xc tc cracking: Xc tc trong qu trnh cracking c tm quan trng rt ln. N c tc dng lm gim nng lng hot ha, t dn n tng tc phn ng. Ngoi ra, xc tc cn c tnh chn lc, n c kh nng lm tng hoc chm khng ng u cc loi phn ng, c ngha l hng phn ng theo chiu c li nhm thu c sn phm phn ng c cht lng v hiu sut cao. III. c tnh ca xc tc cracking: Xc tc cracking phi m bo cc yu cu sau: 1. Hot tnh xc tc phi cao: - Hot tnh xc tc l yu cu quan trng nht i vi xc tc dng trong cracking. V mc ch ca qu trnh cracking l nhn xng, nn phng php dng hiu sut xng nh gi hot ng ca xc tc s n gin hn, hot tnh xc tc cng cao th cho hiu sut xng cng ln. + Xc tc c hot tnh cao, hiu sut xng >45% + Xc tc c hot tnh trung bnh, hiu sut xng 30 40% + Xc tc c hot tnh thp, hiu sut xng l <30% - Hot tnh xc tc ph thuc vo tnh cht vt l, ha hc ca xc tc, m trc ht l ph thuc vo thnh phn ha hc ca xc tc v ph thuc vo iu kin cng ngh ca qu trnh . 2. chn lc phi cao: - Xc tc cn c chn lc cao cho xng c cht lng cao v hiu sut ln. - L kh nng ca xc tc lm tng tc ca cc phn ng c li, ng thi lm gim tc ca cc phn ng khng mong mun. - chn lc ca xc tc quyt nh kh nng to cc sn phm c gi tr ca n, l cc cu t xng c tr s octan cao. - chn lc c th c nh gi bng cch xc nh t l gia hiu sut xng v cc (hay kh) cng mt su bin i. T s gia hiu sut xng v cc (hay kh) cng ln th chn lc xc tc cng cao. Xc tc thng c nh gi ng thi hot tnh v chn lc ca n so vi xc tc mu khi tin hnh trong cng mt iu kin cracking . 3. n nh phi ln:

Xc tc phi gi c nhng c tnh ch yu (hot tnh, chn lc) sau mt thi gian lam vic lu di. n nh xc tc c trng cho kh nng khng thay i cc tnh cht trong qu trnh lm vic. Xc tc c n nh cng cao th cng tt trong qu trnh s dng. 4. m bo bn c, bn nhit: - Trong qu trnh lm vic, xc tc c st vi thnh thit b lm cho xc tc d b v, do lm tn tht p sut qua lp xc tc tng ln, lm mt mt xc tc ln. V vy, xc tc phi m bo bn c. - Khi lm vic nhit thay i, khi nhit cao qu m nu xc tc khng c bn nhit th c th b bin i cu trc dn n lm gim cc tnh cht ca xc tc. 5. Xc tc phi m bo thun nht cao: Xc tc cn ng nht v thnh phn, v cu trc, v hnh dng v v kch thc. - Kch thc khng ng u s to ra nhng vng phn lp v c tr lc khc nhau. ng thi, do s phn lp theo kch thc nn s ph v ch lm vic bnh thng ca thit b. Mt khc, khi kch thc khng ng u lm tng kh nng v vn, dn n mt mt xc tc. - Cu trc l xp khng ng u s lm gim b mt tip xc dn n lm gim hot tnh xc tc . 6. Xc tc phi bn vi cc cht lm ng c xc tc: Xc tc phi chng li tc dng gy ng c ca cc hp cht ca Nit, Lu hunh v ca cc kim loi nng ko di thi gian lm vic cho xc tc. 7. Xc tc phi c kh nng ti sinh: Xc tc c kh nng ti sinh tt s nng cao hiu qu v nng sut ca qu trnh, lng tiu hao xc tc cng gim xung. 8. Xc tc phi d sn xut v gi thnh r: y cng l yu t quan trng, gp phn nh hng cho cc nh nghin cu v sn xut.

Chng IV. Qui trnh cng ngh cracking xc tc


I.S nguyn tc ca qu trnh cracking xc tc cng nghip:

Hnh 1.1 S nguyn tc ca qu trnh cracking xc tc cng nghip

S gm mt reacto cha lp xc tc chuyn ng, cng vi mt b phn tch ht xc tc v sn phm (thit b phn ng xc tc), mt thit b hon nguyn xc tc, trong cc-sn phm cacbon phn t lng cao, c t chy phc hi hot tnh xc tc v mt thit b chng ct tch sn phm cracking thnh cc phn on c nhit si khc nhau v mt phn du nng c hi lu tr li reacto cracking. Hin nay, cc thit b cracking xc tc c nhiu hng ch to v ci tin. II. Cc yu t nh hng n qu trnh cracking xc tc: nh hng n cc ch tiu lm vic ca qu trnh cracking xc tc khng ch l nguyn liu v cht xc tc m cn c cc thng s cng ngh ca qu trnh. Cc thng s cng ngh bao gm: 1. nh hng ca nhit : Nhit thch hp 450 520 0C. y l khong nhit thch hp nht to xng. Khi tin hnh tng nhit , lc u hiu sut xng tng v sau t n cc i ri gim xung. iu ny l do qu trnh phn hy tng, lm phn hy cc cu t xng va c to thnh. Khi tng nhit , phn ng phn hy tng nhng ng thi cc phn ng bc 2 nh dehydro cng tng, lm tng hiu sut hydrocacbon thm v olefin. Khi trong sn phm kh hm lng C 1 C3 tng cn C4 gim, t trng v tr s octan tng ln. 2. nh hng ca p sut: Ti p sut 1,4 1,8 at, qu trnh cracking xc tc xy ra trong pha hi. Khi tng p sut hiu sut xng tng ln, hiu sut kh C 1 C3 gim, hm lng olefin v hyrocacbon thm gim, hm lng hyrocacbon no tng v do vy cht lng xng gim ( tr s octan ON gim).

Khi tng p sut ca qu trnh cracking xc tc khng c hiu qu kinh t cao. V vy, ch tin hnh p sut thng. 3. Mc chuyn ha: i vi hyrocacbon tinh khit, khi tham gia phn ng mc chuyn ha c o bng lng sn phm to thnh theo thi gian. Nhng i vi phn on phc tp nh phn on du m, trong cracking xc tc ngi ta li o lng xng l sn phm chnh v sn phm kh, cc. Nu gi y l % th tch ca sn phm vi im si cui cao hn im si cui ca xng, th chuyn ha C c tnh theo cng thc: C = 100 y ng nhin cch xc nh nh vy cha st vi thc t, hiu chnh theo s bin i ha, l trong qu trnh to xng v kh, ngi ta xc nh mc bin i theo cng thc sau : C= 100 y (100 z ) Vi z l phn % xng trong nguyn liu. 4. Tc np liu ring: Tc np liu ring (hay tc khng gian np liu) l t l gia lng nguyn liu c np trong mt n v thi gian trn lng xc tc trong reacto (hay t l v th tch ca chng) v c k hiu bng M/H/M hay V/H/V (V/V/H). Nu P l p sut trong reacto v c tnh bng at th chuyn ha C c lin quan vi M/H/M theo biu thc:

P.K C = 100 - C M/H/M

Phng trnh bin din trn ch p dng vi trng hp xc tc c nh. Trong trng hp cracking xc tc c nh. Trong trng hp cracking xc tc vi lp tng si ca xc tc FCC ta c chuyn ha C li ph hp vi cng thc sau:

C P.K = 100(1M/H/M 2 Vi K lC/100)tc tng hp ca qu trnh. hng s


Khi tng tc np liu ring s lm gim chuyn ha v ngc li, v rng tc np liu l i lng ngc li vi thi gian phn ng. Khi s dng xc tc c hot tnh cao, ta c th tng tc np liu. Nh vy s tng nng sut ca thit b. Khi tng tc np liu, nu ta tng nhit phn ng, th tr s octan ca xng v tng hiu sut olefin trong kh. l phng php chnh iu khin ch sn xut propylen v buten trong qu trnh cracking xc tc. 5. Bi s tun hon xc tc: L t l gia lng xc tc trn nguyn liu (X/RH).

- Khi dng xc tc zeolit, cho php gim t l X/RH xung cn 10/1 so vi xc tc v nh hnh l 20/1. - Khi dng cng ngh xc tc chuyn ng vi kch thc ht t 3 5 mm, t l X/RH cn thp hn na, ch khong 2 5/1. - Khi tng t l X/RH s lm tng chuyn ha, tng hiu sut cc trn nguyn liu nhng hm lng cc bm trn xc tc li gim xung. - Khi gi tc np liu M/H/M l khng i, nu tng t l X/RH th thi gian tip xc gi xc tc v nguyn liu gim, khi hot tnh trung bnh ca xc tc tng ln. l l do t hiu qu cao ca qu trnh vi lp xc tc si FCC. Nh t hiu qu cao m cho php gim kch thc thit b. Tuy nhin, nu tng qu cao mc tun hon xc tc v lm nh hng n qu trnh ti sinh l ti sinh v cc trang thit b km theo. Nh vy, thng s bi s tun hon xc tc rt quan trng trong qu trnh cracking xc tc, n nh hng khng nhng ln hiu sut v cht lng sn phm n cc thng s khc, m cn nh hng n vic xc nh kch thc cc thit b chnh ca qu trnh. Cho nn, cn phi chn c thng s ny mt cch ti u. 6. Hiu ng nhit: Hiu ng nhit ca qu trnh bng tng hiu ng nh ca cc phn ng ring bit ca qu trnh, hiu ng nhit ph thuc vo su chuyn ha.

Ti liu tham kho [1]- PGS. TS. inh Th Ng. Ho hc du m. Nh xut bn khoa hc v k thut H ni. 2005. [2]- GS. TS. Nguyn Hu Ph. Cracking xc tc. Nh xut bn khoa hc v k thut H ni. 2005. [3]- TS. L Vn Hiu. Cng ngh ch bin du m. Nh xut bn khoa hc v k thut H ni. 2001. [4]- B mn nhin liu. Cng ngh ch bin du m. Trng i hc Bch Khoa H Ni. 1983. [5]- Trn Mnh Tr. Du kh v du kh Vit Nam. Nh xut bn khoa hc v k thut H ni. 1996. [6]- B mn qu trnh thit b cng ngh Ho v thc phm. C s cc qu trnh v thit b cng ngh ho hc. Tp 1. Trng i hc Bch khoa H Ni. 1999.