A . Phn m u.

Cng vi s pht trin ca cc ngnh cng nghip hng u th ngnh cng nghip ho du cng pht trin mnh v c nhng vai tr quan trng trong cuc sng. Trong cng nghip ha du mi qu trnh u c nhng ng gp khng nh cho s pht trin ca ngnh xc tc hc khng ngng tng ln khi ngy cng c nhng i hi cao v cht lng ca sn phm, khi tin hnh phn ng. Xc tc rt cn thit cho phn ng, xc tc lm cho cc phn ng c tin hnh mt cch nhanh chng, chnh xc nht, ng thi em li hiu qu cao cho sn phm thu c do c tnh chn lc. c c nh vy nn xc tc khng ngng ci tin em li hiu qu cao hn trong cng nghip lc ho du. c bit trong cng nghip lc ho du xut hin qu trnh Refocrming xc tc, qu trnh ny cng em li nhng kt qu cao thc y s pht trin cho ngnh cng nghip ch bin du. Trong cc loi nhin liu, xng l nhin liu quan trng nht, xng c tr s octan cao cho php ng c hot ng tt hn nhiu, do cc nh khoa hc tm kim nhng phng php tt nht sn xut xng c tr s octan cao ngay t nhng nm u th k ny. Nm 1911 Zekisky v cc cng s pht hin ra phn ng chuyn ho cycloancan su cnh thnh aren trn xc tc platin v paladi phn ng ny t c s khoa hc cho qu trnh Reforming xc tc. Trc i chin th gii do nhu cu v cc

hp cht thm v xng my bay cho mc ch qun s th qu tring Reforming u tin c tin hnh quy m cng nghip, s dng nguyn liu l phn on gasoie. Tuy nhin, n nm 1950 khi Hasensel v cc ng nghip cng ty Universal Oil Produets chng minh rng xc tc platin c th s dng trong cng nghip ri n nm 1955, Reforming nhit. Qu trnh xc tc khng ch cho pht lng sn phm m cn cho hiu sut cao. Ngy nay, Reforming xc tc l mt trong nhng qu trnh quan trng trong cc nh my ch bin du m hin ti. Vai tr ca qu trnh ny khng ngng c tng ln do nhu cu v xng c cht cao v nguyn liu cho qu trnh tng hp ha du ngy cng pht trin nhanh trn th gii. Qu trnh ny cho php ch loi xng c tr s octan cao v sn xut cc loi hydro cacbon thm ( Bezen, Toluen, Xilen ), lm nguyn liu cho cng nghip tng hp ho du. Qu trnh Reforming thng dng nguyn liu l phn on xng c tr s octan thp khng tiu chun cu nhin liu cho ng c xng. Do l phn on xng ca qu trnh chng ct trc tip du th hay t phn on xng ca qa trnh cracking nhit, cc ho hay hay vibicking. Cc phn ng xy ra trong qa trnh isome ho, hydro ha, dehydro to vng cho sn phm chnh l cc hp cht thm c tr s octan cao. Xc tc cho phn ng l Pt hoc hp kim ca Pt mang trn cht mang oxy nhm xp v c hot ho. y l nhng xc tc hai chc nng v c kim loi v oxy nhm u ng vai tr tm hot tnh.

Do c vai tr quan trng trong cng nghip ch bin du nn qu trnh Reforming xc tc ngy cng c nghin cu v p dng rng ri trn th gii. Hin nay lng xng thu c t qa trnh Reforming xc tc chim 25% ton b lng xng thu c tiu th trn th gii. Trong cng nghip ch bin ho du hin i, qu trnh ny cng c ngha ln lao khi to ra sn phm c tr s octan cao m khng cn pha thm ch, trnh nhim mi trng. Cho nn qu trnh Reforming xc tc trong ch bin du c quy m rt ln, to nn nhng bc tin quan trng cho s pht trin cu ngnh cng nghip lc ho du ngy cng phc v nhiu hn cho i sng. Chnh v vy m n nhm gii thiu v ton b qu trnh Reforming xc tc. C s ho hc, xc tc nguyn liu, sn phm, c ch, ng hc ca qa trnh, cc quy trnh cng ngh in hnh s dng trong cng nghip. ng thi n ny nh gi ton b qu trn v vai tr ca n.

B. Tng quan l thuyt.

I. Mc ch ca qu trnh. Theo lch s pht trin ca qu trnh Reforming xc tc th ngay t nm u xut hin qu trnh em li hiu qu rt cao trong lc ho du m c bit l hiu sut xng tng ln ng thi cht lng ca xng c ci thin mt cch r rt.

Mc ch chnh ca qu trnh Reforming xc tc l nng cao tr s octan ca xng do dn n nng cao hiu sut s dng du m t trong cng nghip lc ho du, em li vai tr quan trng trong i sng, v d: Khi tng tr s octan ca xng t 66 ln 88 th chi ph xng cho mt nm gim i 22%. ng thi qu trng Reforming xc tc l sn xut hydro cacbon thm trong gm c Bezen, Toluen, Xylen ... lm nguyn liu cho cng nghip ho du v tng hp hu c. Ngoi ra, qu trnh Reforming xc tc cn thu c kh hydro k thut vi gi r nht so vi cc qu trnh iu ch hydro khc. Mt khc y chnh l ngun thu H2 cn c ng dng trong nhiu qu trnh lm sch sn phm du m v ch bin du. Qua ta thy rng, cc mc ch ca qu trnh Reforming xc tc c vai tr rt quan trng trong cc nh my ch bin du m. II. C s ho hc.

Reforming xc tc l mt qu trnh chuyn ho ho hc phc tp s dng nguyn liu l xng chng ct trc tip v gn y nh s pht trin ca cc qu trnh lm sch bng hydro m ta c th s dng xng ca cc qu trnh lc du khc ( xng ca qu trnh cc ho, xng caracking nhit ... ). Qu trng ny c tin hnh trn xc tc hai chc nng, thng cha Pt c mang trn oxyt nhm. Trong qu trnh Reforming

cc parafin mch thng v cc cyclo parafin b chuyn ho thnh cc hp cht thm v isoparafin lm tng tr s octan ca xng. Mc ch ca qu trnh sn xut xng c tr s octan cao ( RON trong khong t 95 102 ) m khng phi pha thm ch. ng thi, do sn phm ch yu trong qu trng l hydro cacbon thm nn qu trnh cn c ng dng thu BTX ( kh nguyn liu l phn on naphta nh c nhit si t 310 3400F ) l nhng nguyn liu qu cho tng hp hu ho du. Do cc phn ng xy ra trong qu trnh Reforming xc tc l nhng phn ng isome ho, hydro ho, dehydro ho ng vng, dehydro ho v cc phn ng ph khc. 1. Phn ng dehydro ho. y l phn ng nhm to ra hydro cacbon thm, ng thi phn ng dehydro ha cn thu nhit mnh v phn ng xy ra vi Naphten chim t 18 50% trong nguyn liu. Phn ng dehydro ho cyclohexan v dn xut ca n c tc kh ln khi ta dng xc tc c cha Pt Hp cht ch yu ca Naphten l cyclopetan v cyclohexan ( trong cyclopetan nhiu hn cyclohexan ) Cyclohexan b dehydro ho trc tip to thnh hp cht thm.

CH3 CH3
5

+ 3H2

(1).

Sau phn ng RON tng v tr s octan ca cyclohexan l 75 cn tr s octan ca Toluen l >100. Cn cyclopetan khi b tc phn ng dehydro ho xy ra nhanh m cn bng ca phn ng isome ho c iu kin chuyn ho thnh cyclopetan l 95% cn cyclohexan ch l 5%. Do phn ng dehydro ho naphten c tc ln m trong qu trnh Reforming s nhn c nhiu RH thm v hydro.
2. Phn ng dehydro ho ng vng.

Phn ng ny xy ra vi cc parafin, xy ra kh hn so vi phn ng ca naphten. Ch c nhit cao mi c th nhn c hiu xut RH thm ng k Dehydro ho parafin to ra hydrocacbon thm. Khi tng chiu di ca cc mch cacbon trong parafin, hng s cn bng to RH thm cng c tng ln.

CH3 n C8H18 +4H2 (2).

CH3

Sau phn ng tr s octan nghin cu tng t 0 ( tr s octan ca n-octan ) ln >100 ( tr s octan ca xylen ). Phn ng to vng nm cnh cng xy ra, nhng sau sn phm li tip tc bin i thnh vng thm.

C2H5 n C7H16 + H2 (3).

Nhng phn ng xy ra chm, c xc tc bi c thnh phn kim loi v thnh phn c tnh axit ca xc tc. Phn ng thu nhit ny thng xy ra t thit b gia cho n thit b cui cng ca qu trnh. ng thi dehydro ho ng vng parafin to RH thm l mt trong nhng phn ng quan trng nht ca Reforming xc tc, nh phn ng ny m cho php

bin i mt lng ln cc hp cht c tr s octan thp ca nguyn li thnh cc RH thm l cu t cao octan. 3. Phn ng isome ho. y l phn ng nhm bin i isome ho n-parafin isoparafin. Trong c t 15 75% parafin mch thng c tr s octan nghin cu < 50. Parafin mch thng c th b isome ho to thnh mch nhnh.

CH3 n C5H12 CH2CH2CHCH3 (4).

Vi cc n-parafin nh, s isome ho lm ci thin tr s octan phn ng chuyn ho n-pentan thnh iso-pentan, lm tng tr s octan t 62 ln 92. Phn ng isome ho parafin xy ra kh nhanh v c xc tc ch yu bng chc nng axit ca xc tc. Ngoi ra trong phn ng olefin cng c th b isome ho nhng thng l hydro isome ho do s c mt ca hydro trong mi trng phn ng. Hepten-1 + H2 CH3CH2CH2CH2CHCH3 (5).

CH3

Phn ng isome ho naphten cng c tin hnh nhanh chng bi c thnh phn axit v kim loi ( mc nh hn ) ca xc tc. Phn ng ny sp xp li phn t m khng kt hp hoc tch hydro do n khng b nh hng bi p sut. 4. Phn ng Hydro ho. Phn ng hydro ho xy ra vi olefin trong nguyn liu to thnh parafin. Phn ng c thc hin d dng trong iu kin ca qu trnh Reforming, thnh phn olefin cng c th chuyn ho trc tip thnh Aromatic. Phn ng ny nhm chuyn ho cc hydro cacbon cha no thnh no, lm gim s to cc gy nn s kh hot tnh ca xc tc.
5. Phn ng Hydro cracking.

y l phn ng cracking vi s c mt ca hydro. Phn ng ny b mch parafin to thnh mt parafin khc v mt olefin. Di s c mt ca hydro phn ng b bo ho ngay lp tc. n - C9H20 + H2 C4H10 (6). n C5H12 + n

n-parafin b chia nh thnh n-parafin khc c mch ngn hn do phn ng khng lm tng c tr s octan. Khng nhng th, phn ng cn lm mt mt xng do s b gy cc parafin c s cacbon di 8 thnh cc sn phm kh. Do vy,

hiu sut xng s gim, phn ng xy ra kh chm v ch yu c xc tc bi chc nng axit ca xc tc. Naphten cng c th tham gia phn ng hydro cracking. Giai on u tin ca phn ng ny l t vng vi s c mt ca hyro to thnh parafin.

C2H5 + H2 CH3(CH2)5CH3 (7).

6. Nhng phn ng ph trong qu trnh Reforming xc tc. Phn ng ca cc hydro cacbon thm c thay th xy ra nh sau:

CH3 CH3 + (8). CH3 Hydricacbon thm cng c th b hydroalkyl ho. 2

10

CH3 C2H5 + H2 + C2H6 (9).

CH3

Cc phn ng ph ca hp cht thm khng mong mun l phn ng to cc, to ra nhng hp cht a vng ngng t trn tm hot tnh ca xc tc. Cc hp cht d vng cha N v S b hydrosulfua ho v hydronit ho to ra H2S hoc NH3.

+ 4H2 (10). S CH3

C5H12

H2S

y l nhng phn ng lm gim hm lnglu hunh trong xng, do n l phn ng ph c li. *. Phn ng to cc. S to cc trong qu trnh l khng mong mun, nhng do s tng tc ca olefin v diolefin, cc hp cht thm a vng m to thnh cc. Cc s kh to ra nu ta thao tc iu kin

11

nhit thp, p sut cao v t l H2/RH cao. y l mt phn ng phc tp. S to thnh cc ph thuc vo nhiu yu t: - Nhit phn ng.
-

p sut hydro. nng ca nguyn liu v chnh l cc hp cht phi hydro

cacbon, olefin v cc cht thm a vng l cc hp cht gp phn thc y nhanh qu trnh to cc. hn ch s to cc, ngi ta phi s dng p sut hydro va sao cho cc ch to ra khong 3 4% so vi lng xc tc trong khong thi gian 6 thng n 1nm. Nhng nu tng p sut hydro s lm cn tr qu trnh to thnh RH thm, cn tr phn ng. *. Trong iu kin tin hnh qu trnh Reforming cn xy ra cc phn ng ph, tuy khng lm nh hng nhiu n cn bng ca cc phn ng chnh nhng li c nh hng ln n hot ng, bn ca xc tc. + Phn ng phn hu v kh cc hp cht cha oxy, nit, lu hunh to thnh H2S, NH3, H2O. + Phn ng ngng t ca cc hp cht trung gian khng bn nh olefin, diolefin vi RH thm dn n to thnh cc cht nha v cc bm trn b mt xc tc.

III.

Xc tc cho qu trnh.

12

Xc tc cho qu trnh c s dng l loi xc tc a chc, chc nng oxy ho- kh v chc axit baz. Chc nng oxy ho kh c tc dng xc tin cho cc phn ng hydro ho- kh hydro. Cn chc nng axit c tc dng thc y cc phn ng xy ra theo c ch ioncacboni nh ng phn ho v hydro cracking. Bng 1: Nhng thnh phn ca xc tc

Cht mang xc tc. oxit nhm. oxit nhm. oxit nhm. oxit nhm. oxitslic-oxit nhm.

Thnh phn dehydro ho. Molipden. Platin. Crm. Molipdat coban. Platin.

% 10 15 0,3 0, 6

Thnh phn khc.

10 15 Halogen.

0 1

< 10.

u tin vo nm 1940 ngi ta p dng qu trnh Reforming u tin vi cht xc tc l axit molipden c mang trn oxit nhm. Xc tc tt phi c chuyn ho chn lc tt c hydro cacbon thnh hp cht thm mt cch nhanh chng ch vi mt lng nh xc tc. Xc tc Platin c chn lc cao nht v hot tnh ln nht nhng gi thnh t. Thnh phn akylcyclohexan chuyn ho nu iu kin phn ng thch hp v ng hc thnh phn
13

akylcyclopen tan chuyn ho thnh hp cht thm phi qua giai on isome ho nn chuyn ho ca thnh phn ny ph thuc vo hot tnh ca xc tc cho phn ng isome ho cao nht cn xc tc crm thp nht, xc tc ny c chn lc tt v n nh cao. Xc tc cho phn ng Reforming c 2 chc nng: Chc nng hydro ho - dehydro ho cho phn ng chuyn ho parafin thnh olefin, cc hp cht vng no thnh cc hp cht thm c xc tc bi kim loi v chc nng isome ho, c xc tc nh tnh axit ca cht mang theo c ch ion cacboni. Nhng xc tc nh tnh axit ca cht mang theo c ch ion cacboni. Nhng xc tc nh oxit crm v oxit molipden trn cht mang l oxit nhm th hin c 2 chc nng ny trn b mt kim loi cn xc tc Pt trn cht mang axit th th hin hai chc nng nhng hn hp kim loi. C hot tnh vi phn ng hydro ho v dehydro ha cn oxit nhm c hot ho c tnh axit ( bng mui flo hoc clo ) c hot tnh vi phn ng isome ho v hydro cracking. Nhng xc tc a kim loi lm gim p sut ca qu trnh. S kh hot tnh xc tc do to thnh cc lin quan n c cht mang v kim loi. Cc to ra do nhng phn ng ph ca hydrocacbon c bit l olefin. S kh hot tnh xc tc nhanh nu p sut ring phn ca hydro thp v nhit cao. Xc tc b kh hot tnh d ti snh bng cch t chy t cc. Trc y ngi ta s dng cc cht xc tc oxit trong qu trnh Reforming nh MnO/Al2O3. Loi xc tc ny r tin, bn vi lu
14

hunh, song n c nhc im l c hot tnh thp, nn trong qu trnh Reforming phi c th hin ch cng ( vn tc th tch thp ~0,5h-1, nhit cao ~3400C ), iu kin ny cc phn ng hydro cracking xy ra mnh. tng chon lc ca qu trnh cn phi thc hin p sut 14 20 atm. Nhng s gim p sut li thc y qu trnh to cc, do vy khng ko di c thi gian lm vic ca xc tc, lm gim cht lng xng thu c. Do c tt c nhng l do trn dn n khng s dng loi xc tc ny. Bng 2: Kt lun v hot tnh vi phn ng dehydro ho ca mt vi xc tc kim loi v oxit kim loi. Xc tc, % khi lng. Hot tnh cho phn ng dehydro ha mol, C6H6 xc tc. 34% Cr2O3 ng to gen vi Al2O3 10% MoO3 ng kt ta vi Al2O3 5% Ni trn Al2O3 hoc SiO2 Al2O3 1%Co trn Al2O3 5% Ni trn SiO2 1% Ph trn Al2O3 SiO2 - Al2O3 13 200 320 13 3 0,5

0,5 Pht trin trn Al2O3 hoc 1400-4000.

15

Xc tc Pt/ Al2O3 Vo nm 1949, hng UOP (Universal Oil Co, M ) s dng xc tc Pht trin v Al2O3 lm thnh phn chnh to thnh mt dng xc tc c hot tnh v chn lc cao (90 95% ). Xc tc ny c s dng, cho n nm 1970. Hm lng Pht trin trong xc tc l 0,3 0,8% trng lng, nhit phn ng l 5000C v p sut l 30 35 at. Trong Pht trin xc tin cho qu trnh oxi ho kh cn Al2O3 l axit rn, ng thi Pht trin mang chc nng xc tc cho phn ng hydro ho v kh hydro. in hnh l trong Reforming chng lm tng tc phn ng kh H2 ca naphten, kh hydro ng vng cc parrrafin, c ngha l ng vai tr thc y qu trnh hydro cacbon thm. Ngoi ra n cn thc y qu trnh hydro ha lin tc cc sn phm trung gian ( hydro ho cc hp cht khng no to ra trong qu trnh ) cho nn hn ch c qu trnh to cc, ko di tui th v tng cht lng sn phm. Kim loi Platin ( Pt ). Pt c a vo xc tc dng khc nhau, ph bin l dng dung dch ca axit platin cydodric H2 ( PtCl6 ). Pt l cu t tuyt vi cho xc tc Reforming, ng thi n c kh nng hot tnh rt tt cho phn ng dehydro-hydro ho. Trong qa trnh Reforming, Pt lm tc ca ph ng kh hydro, cc hydro cacbon naphten, kh hydro vng ho cc hydro cacbon parafin to thnh RH thm. Ngoi ra n cn thc y qu

16

trnh no ha cc hp cht trung gian l olephin, diolephin, lm gim tc to thnh cc bm trn xc tc m l nguyn nhn chnh lm gim hot tnh ca xc tc. Hm lng Pt trn xc tc chim khong 0.3 0,7% khi lng. Cht lng tt ca mt cht xc tc Reforming c cc tnh cht : hot tnh, chn lc cao v n nh cao. Nu hm lng Pt ln hn 0,6% th xc tc d b thiu kt. Pt thng c phn tn trn cht mang di dng nhng tinh th nh c ng knh t 8 1000A. Khi nguyn liu cha hm lng parafin cao v dng xc tc cha 0,35% Pt th xng thu c c tr s octan cao ln ti 102 ( RON ) m khng cn pha nc ch. Khi c pha thm 0,8ml nc ch nhng vn mun t tr s RON=102 th xc tc phi c 0,8%Pt. Khi a thm cc nguyn t t him vo s c tc dng km hm s thiu kt ca cc vi tinh th Pt v xc tc c n nh, bn nhit cao hn hn xc tc ch c Pt nguyn cht. Cht mang oxit nhm. Al2O3 trong xc tc l cu t mang chc nng axit ca cht xc tc. Tnh axit ca oxit nhm l do trn b mt c cha nhm OH. Al2O3 xc tc cho phn ng isome ho d xy ra nh phn ng thay i v tr ni i trong Buten. N kh xc tc cho nhng phn ng isome ho xy ra, kh v axit ca n yu.Do phi tng axit ca oxit nhm trong xc tc bng cch hot ho n.

17

 tng axit, ngi ta thm vo halogen hu c ( cc hp cht cha Clo hu c ) ( C2H4Cl2 ) v do ngoi tc dng tng axit n cn tc dng lm n nh phn tn Pt nh n to ra cc phc hp Pt Al2O3, ngoi ra cc cht xc tc t thc y cc phn ng cracking trong iu kin phn ng: Hm lng cho thm vo 0.5 1% trng lng. axit ca n c vai tr c bit quan trng khi ch bin nguyn liu vi hm lng Pt ln: Cc tm axit kch ng phn ng hydro cracking ca cc parafin v phn ng ng phn ho hydro cacbon napten 5 cnh thnh 6 cnh v tip theo l cc napten 6 cnh b kh hydro to thnh hydro cacbon thm. Cht mang Al2O3 cn phi c tinh khit trong hm lng Fe v Na khng qa 0,02% trnglng. Al2O3 c s dng lm cht mang ch yu 2 dng tinh th eta v gama. Dng eta c tnh axit v din tch b mt ban u cao hn gama nhng sau khi ti sinh hoc s dng mt thi gian th b mt gim i v ch dng c vi ln ti sinh. Cn dng gama bn nhit hn m vn duy tr c din tch b mt ban u sau khi ti sinh v s dng, n c th s dng sau vi trm ln ti sinh v ti sinh yu ca n c khc phc bng cch a hologen vo, theo phng php phn tch o c th din tch b mt cu xc tc l 175 300m2/g. Th tch l xp l 0,45 0.50 cm3/g ht xc tc c dng phi hoc cu c ng knh t 1/12 1/16in.

18

Do vy cht lng tt ca mt cht xc tc Refoming phi c nhng tnh cht: chn lc, hot tnh v n nh cao. Bng 3: Mt s c trng v tnh cht ca xc tc Reforming. Cc ch s. Xt ( Lin X c ) ATT0,65. % Pt ( % trng lng). ng knh ht (m/in). V mt ring (m2/g). Ch s bn (kg/mm) ng knh l (A0) Th tch l (ml/g) Cht Cl F Cl Cl Cl 0,75 0, 88 40 120 40 120 80 100 0,97 1,2 180 240 28 0 160 20 0 1,8 2,2 1,5 1,5 3,0 0,6 o,6 5 o,35 0,58 0,37 0,55 8815 TOR RY- 302 France. RD-150 M- c. R-16 M.

19

kch ng.

Trong thc t, cc ch tiu c bn c dng nh gi cht lng ca xc tc. Hiu sut xng n nh, tr s octan ca xng, hiu sut RH thm, hiu sut v thnh phn ca sn phm kh v thi gian lm vic ca xc tc. Bt u t nhng nm 1960, ngi ta thit k cc dy chuyn Reforming vi p sut H2 thp nht c th xy ra nhiu RH thm hn, nng cao tr s octan m cn tng hiu sut xng, iu ny rt ngn thi gian ti sinh xc tc. ng thi vi nghin cu thay i ch cng ngh ngi ta cn thc y vic nghin cu tm kim xc tc mi, hon thin hn, c bn cao hn. l xc tc a kim loi. Ngoi Pt, hin nay cn s dng cc xc tc khc nh nguyn t I2, Re, Mioxen ( xc tc nhiu kim loi) v mt s cht kch hot nh Mo, Sn, Co, kim loi kim v kim th hoc nhiu kim loi lm tng hot tnh xc tc v lm cho Pt phn b u khng b thiu kt Sn (thic) khng lm tng hot tnh xc tc nhng cng khng lm gim m li gim gi thnh xc tc. Trong xc tc cn c b sung thm cc nguyn t thuc phn nhm Na v Ca nhm hn ch tm hydro genolise parafin v ngng t cc hp cht khng no to nha, cc nguyn t khc lm cht kch ng nh C, Xi, Ge nhm khng ch axit ca cht mang. Nng Pt v cc cht kch ng thng c khong 1 3%.
20

Trong nhng nm 90 ca th k ny, hng UOP xy dng dy chuyn vi lp xc tc chuyn ng UOP lm vic vi p sut thp, ch khon 3,5at (50psi). Khi p sut thp th chn lc ca xc tc tng cao, nht l khi ch bin nguyn liu c hm lng RH parafin ln. Khi lm tng vai tr ca phn ng dehydro vng ho parafin: 50 60%RH thm nhn c t chuyn ho parafin. Do tr s octan ca sn phm c th t c RON >100. Ngoi ra, hng Philips nghin cu phn ng dehydro ho trn xc tc Pt vi s c mt ca Sn trn Zn Al2O3 hoc Ca Al2O4 vi hm lng cc hnh thnh trn b mt xc tc rt t. Thnh xc tc bao gm 0,05 5%Pt, 0,1 0,5%Sn, 80 98% Zn Al2O4, hoc l Ca Al2O4. Nhit tin hnh l 500 5700C. Bng 4: Cc giai on ci tin ti Lin Bang Nga. Cc giai on ci tin thay i v thnh phn xc tc. Cht mang. Kim loi chnh. Cht kch ng. axit Kim loi khc. Tn xc tc. Ch cng ngh.
21

Al2O3 Pt F

Al2O3 Pt Cl

Al2O3 Pt Cl Re,Ge,Pb, Sn.

ATT. 56

ATT. 64

KP. 102104.

p sut trong h thng Mpa.

3,5 4

3 3,5

1,2 2

Cc xc tc KP. 102,104 c bn c cao hn so vi xc tc ATT 64 ti ba ln trong khi hm lng ca Pt li nh hn 1 1,5 ln. Ngoi ra cng c nhng cng trnh nghin cu s dng phc ( PtCl2 C[nCl3]2) mang trn cht mang Al2O3 trong phn ng dehydro ho parafin. Hm lng Pt chim khong 0,3 0,8% trng lng, nhit phn ng l 5000C, p sut 30 35at. ng thi hin nay c nhiu s ci tin xc tc nh bin tnh chng cho thm mt kim loi na hoc thay i cht mang ( axit rn ) cht mang ( axit rn ) xc tin cho phn ng ng phn ho, cracking nh: Pht trin/ FO2, Pt/ Al2O3, Pt/FO2Al2O3Pt-O2. axit rn. Pt-Re, cn cc axit rn l cc axit , Al2O3, FO2, alumino silicat, zeolit. Vic cho thm kim loi ny nhm mc ch tng hot tnh ca xc tc v gim gi thnh. 1. Chun b xc tc. Xc tc kim loi c th c ch to bng phng php ngm tm hoc trao i ion trn cht mang c b mt ring ln nh oxit nhm hoc oxit silic. Trong phng php ngm tm, cht mang c tm dung dch mui kim loi. Sau ht xc tc c lm kh v c nung nng khng kh chuyn mui kim loi thnh oxit kim loi, oxit ny b kh bng nc kh ion ra mui v ion kim loi cn li trn b mt, ri xc tc c mang v kh .
22

Phng php trao i ion to ra nhiu tinh th v kch thc tinh th cng nh hn phng php ngm tm, phng php ny to ra nhng xc tc bn hn, trong iu kin nung v kh cng nh hng n hot tnh, nhng xc tc rt hot ng, nhng phn bn trong c th khng c tc dng v phn ng xy ra trc khi cht phn ng thm vo li. Trong trng hp ny hot tnh ca xc tc tng, kch thc ht gim vi nhng xc tc Pht trin, nh hng ny ng k. Vi nhng xc tc c hot tnh km hn Pt, th nh hng ca kch thc ht l khng ng k. Trong vic chn kch thc ht xc tc phi la chn cn bng gia hot tnh v gim p sut trong lp xc tc, cn lp xc tc c nh th chiu di ht xc tc thng bng hoc ln hn ng knh mt cht.
2. Ng c xc tc.

Trong iu kin Refoming xc tc, nhng thnh phn nh lu hunh, nit, halogen, oxy cng b hydro ho to ra nhng cht kh gy c xc tc nh H2S, H2O m in hnh l: CH2-S-CH2CH2CH3 + 2H2 CH4 + CH3CH2CH3 + H2S. a. Ng c cc hp cht lu hunh. Cc hp cht lu hunh d lm ng c xc tc platin, n lm c ch phn ng dehydro ho v hot ho cho phn ng hydro cracking, l lm ng c thnh phn kim loi ca xc tc. Tu vo mc nh hng khc nhau m cc hp cht lu hunh nh hng n kim loi Pht trin: Cc hp cht mercaptan v sunpht lm gim hot tnh mnh hn cc hp
23

cht tiophen v H2S hay S nguyn t. Do m bo thi gian lm vic lu di cho xc tc th hp cht S cn c loi b khi nguyn liu trc khi a vo l phn ng. T thc t Reforming, nu hm lng lu hunh qu ln s lm gim hiu sut v cht lng ca xng, ng thi nng lu hunh cao cng lm tng tc phn ng kh hot tnh ca xc tc, c bit l p sut hydro thp khi i hi phi tng H2/RH. Nu c mt H2S trong kh tun hon s lm tng kh nng n mn thit b b phn ng xon ca l t nng. Khi xc tc tip xc vi nguyn liu cha lu hunh, khng ch kim loi trn xc tc b ng c m ngay c Al2O3 cng b bin i n c tc dng vi hp cht lu hunh to thnh sunfat nhm Al2(SO4)3. Do vy lm cho qu trnh ti sinh xc tc phc tp hn v i hi mc ti sinh su hn. Ngay c khi ti sinh chuyn Al2(SO4)3 v Al2O3 nhng hot tnh ca xc tc vn gim xung ng k so vi khi nguyn liu khng cha lu hunh. b. S ng c ca hp cht nit. Cc hp cht nit c trong nguyn liu cng nh hng xu n hot tnh ca xc tc khi tip xc vi cc cht cha nit nh NH3, hot tnh ca xc tc gim nhanh, c bit l chnh chc axit. V NH3 mang tnh baz v lm trung ho cc tm axit ca xc tc, do n s lm gim tc cc phn ng ng phn ho, vng ho v hydro cracking. Hm lng cho php ca Nit trong nguyn liu ch l 1ppm, nn a

24

s cc qu trnh Reforming u p dng qu trnh hyro ho lm sch nguyn liu.

c. nh hng ca nc.

Hm lng ca nc nh hng ti xc tc rt r rng. N khng ch lm gim nhanh hot tnh ca chc axit ca xc tc m cn lm tng qu trnh n mn thit b, trong hm lng nc c khng ch trong gii hn 10 15ppm. Bin php tch nc l phi s l trc bng qu trnh lm kh khi dng hoc l phun kh clorua vo khi nguyn liu cha nc. Chng hn nh qu trnh UHa forming, vi nguyn liu cha 15ppm nc, ngi ta phun clorua vo xc tc ti sinh trong mt thi gian cn thit khi phc li hot tnh ban u ca xc tc. Trong mt s trng hp khc, ngi ta s dng 1,5ppm hp cht ciclo propylen phun vo khi hm lng nc trong nguyn liu ti 50ppm. Ngi ta thy rng xc tc trn cht mang SiO2 - Al2O3 ( v d catforming ) l loi rt nhy vi nc, th bin php trn rt hu hiu.
d. nh hng ca kim loi.

Cc kim loi nh asen, ch ... c mt trong nguyn liu l cc cht lm ng c xc tc. S c mt ca ch trong nguyn liu c th do nhiu nguyn nhn khc nhau, nhng thng do nguyn liu, do vn chuyn hoc lu kho. Cc hp cht ch tch ng dn trn xc tc gy nn s kh hot tnh xc tc bng cch lm mt chc nng hydro ho v dehydro ho ca xc tc. Biu hin ca ng c ch c th quan st d dng
25

v c s gim nhit thit b phn ng u tin. Mc d c th loi b s kh hot tnh thm na nhng hot tnh mt khng khi phc li c na. Do s thay th xc tc nhng lp u tin thng l do ng c ch nn hm lng cho php thng nh hn 0,02ppm v ca asen thm ch cn nh hn 0,001ppm m trong asen cn gy c hn c ch.
e. nh hng ca hm lng olephin v cc.

Cc hp cht olephin thc y nhanh qu trnh to cc, hm lng ca n trong nguyn liu cn phi nh hn 2%. Cc lng li trn xc tc v lm gim kh nng to sn phm mong mun ca xc tc, nguyn nhn ca s gim hot tnh ny l do s khc nhau v cu trc ca sn phm cc, thay i v phn b khi lng ca cc trn kim loi v cht mang khi thay i iu kin to cc ph thuc vo cht lng nguyn liu, iu kin hot ng ca qu trnh nh p sut, vn tc, th tch. Phn ng to cc l nhng phn ng vng ho v polime ho c xc tc bi axit ca olephin to thnh hp cht a phn c khi lng phn t cao hn. Nhng hp cht ny li tip tc phn ng dehydro ho v polime ho su hn, cc phn ng ny xy ra nhanh chng nu p sut ring phn hydro thp. gim lng cc to thnh trn b mt kim loi ngi ta tm cch loi b cc tm axit mnh trnh phn ng ngng t ( bng cch thm Sn, Re ) hoc loi b cc sn phm giu

26

cacbon bng cch hydro ho. S kh hot tnh xc tc cng c th do Pt b thiu kt nhit cao lm gim phn tn. Thay i cc tnh cht cc xc tc khi lm vic. Trong qu trnh lm vic xc tc cn b thay i cc tnh cht vt l khi tip xc vi nhit cao v thng xuyn phi tip xc vi cc c t trn. S thay i ny ca xc tc Reforming c phn thnh cc loi nh sau: - Nhng thay i c tnh cht tm thi, ngha l khi phc li cc tnh cht ban u ca n bng qu trnh ti sinh xc tc. l cc thay i do s to cc hay ng c thun nghch bi cc hp cht ca oxy, nit. lu hunh.
-

Nhng thay i vnh vin, l nhng thay i khng c kh nng ti sinh. V d do s thiu kt nhit cao m b mt ring ca xc tc v cu trc Al2O3 cng nh phn tn ca kim loi Pt gim i. S thay i ny cn d xy ra hn nu xc tc l n kim loi hay khi ti sinh xc tc nhit khng c khng ch cht ch. Do nhng thay i ny s lm gi ho nhanh xc tc, v n mt thi gian no th phn xc tc gi ho ny phi c thay th bng xc tc mi c hot tnh cao hn nhm gi cho hot tnh chung ca xc tc khng thay i ngha l hiu sut v cht lng ca xng c n nh trong qu trnh.

3. Ti sinh xc tc.

27

Ti sinh xc tc l qu trnh phc hi hot tnh ban u ca xc tc bng cch loi b cc lng ng trn xc tc. Trong qu trnh ti sinh xc tc cc phng php c th la chn c thc hin khc phc nhng nh hng ca s ng c xctc tm thi nu thit b ngng lm vic trc khi nh hng ca s kh hot tnh c loi b. chnh l mc ch ti sinh xc tc. hot tnh v hot ng ca xc tc sau thi gian lm vic thng b gim ng k so vi xc tc mi. Hm lng Pt trong xc tc mi v xc tc lm vic ging nhau nhng phn tn khc nhau v nht l hm lng Clo thay i ng k. xc tc lm vic hm lng Clo gim rt nhiu. Hnh 5: nh hng ca thi gian lm vic ti hiu sut v cht lng sn phm ca qu trnh Reforming xc tc. Bng thc nghim vi cc phn ng mu chun cho thy hot tnh dehydro ca xc tc lm vic gim 1,5 ln so vi xc tc mi, cn kh nng ng phn ho gim rt nhiu. S gim hot tnh dehydro c gii thch bng s bin i trng thi ca Pt trong xc tc ( do tnh ng, ng t cc tinh th Pt t 10 15A0 tng ln 200A0 v ln hn na v gim s tm hot ng. Mc d hm lng Pt trn xc tc mi v xc tc lm vic nh nhau. Do khi phc tnh cht ca xc tc, xc tc lm vic phi c ti sinh, m mi mt qu trnh Reforming yu cu mt iu kin ti sinh ring.

28

Trong cng nghip ngi ta p dng nhng bin php ti sinh sau: a. Dng phng php oxy ho. Phng php ny nhm t chy cc bm trn xc tc bng oxy ca khng kh nhit 300 5000C. Qu trnh ny nhiu giai on, cc giai on c th hin nh sau: Sau khi ngng cp liu, mt lung kh tun hon c thi vo xc tc loi b nhng hydro cacbon nng cn li trong thit b, thit b gia nhit, thit b phn ng, h thng tun hon kh c tch ra khi nhng thit b khc. Cc qu trnh u a oxy vo thit b u tin v ln lt n thit b phn ng cui cng, nhng mt s qu trnh a oxy vo thit b u v cui cng mt lc tit kim thi gian v mt lng ln cc trong thit b cui cng phi mt nhiu thi gian loi b. Tuy nhin lng oxy a vo thit b cui cng cn c kim tra. Trong qu trnh bn ti sinh oxy ly t khng kh hoc oxy ho lng: Nh ti sinh p sut 100psi vi khng kh l phng php ph bin nht. Bng cch s dng oxy nguyn cht trong mi trng nit, thit b ti sinh c th ti sinh xc tc p sut cao hn. b. B sung hp cht Clo. Trong qu trnh lm vic hm lng Clo trn cht mang gim dn. khc phc ngi ta b sung cc hp cht hu c cha Clo vo sau khi ti sinh oxy ho - kh ( sau khi t cc). Qu trnh ti sinh bng Clo khng nhng tc dng lm hot

29

tnh axit tng ln m cn tc dng tch cho cc hp cht kim loi lng ng trn xc tc. Hm lng st, ch v bitmut gim r rng. Phng php ny thch hp cho xc tc b gim axit, ng thi hm lng Clo trn xc tc c khng ch sao cho mc 1% khi lng, l nng ti u cho chc axit ca xc tc. Pt/` Al2O3. c. Dng phng php kh. Phng php ny thch hp vi nhng xc tc b lu hunh v nit lm ng c. Sau khi t cc, xc tc c kh bng H2 hon nguyn cc tm kim loi v gii phng cc hp cht lu hunh tch ng trn xc tc. Qu trnh ny thng c tin hnh p sut cao ( p 200 atm v nng H2 > 10% ). Ngoi ra cn c phng php ti sinh ngoi thit b l nhng xc tc b lng ng cc c a ra khi thit b v c a n mt thit b ti sinh xc tc ring, thit b ny cacbon b loi b nh qu trnh oxy ho. Xc tc c ti sinh sau c a li thit b. Phng php ny c u im l c kh nng iu khin nhit tt hn so vi trng hp ti sinh ngay ti thit b. 4. Tui th xc tc. chn lc ca hu ht ca cc xc tc gim theo thi gian s dng. Xc tc mt hot tnh dehydro ho to thnh cc hoc do nhng thay i vt l trong cc thnh phn v cu trc ca xc tc. S gim hot tnh hydro ho mnh hn s gim hot tnh hydro cracking do khi nhit c thay i b
30

vo s mt mt hot tnh, t l hydro cracking tng lm cho hiu sut kh tng, hydro gim v hiu sut lng gim. S gim chn lc theo nhit , chn lc ca xc tc Pt Rh nh hn xc tc Pht trin. Thi gian sng ca xc tc ny ln hn ca xc tc Pt n 4 ln. Trong nhng thit b tun hon th xc tc thng c th s dng c sau vi trm ln ti sinh trc khi phi thay th hon ton. Sau mt s ln ti sinh, nu c xc nh l khng cn hot tnh na th xc tc c thay th. Nhng xc tc ny c a n nh my thu hi kim loi, thu hi nhng Pt v cc kim loi qu khc nh Re. Kim loi c thu hi c th li c a i sn xut xc tc a thm vo nhng nguyn liu lm xc tc cha c s dng. IV. C ch ca qu trnh.

Phn ng chnh ca Reforming l: Napten aren + H2 nC7 aren +H2 nC7 isoC7 nC6 bezen + H2 Nng lng hot ho ca cc phn ng nh sau:

CH3 CH3

+ 3H2
31

EA = 20kal/mol. n C7 n C7 C1 C6 iso C7 EA = 45kcal/mol. EA = 25kcal/mol.

Cc kcal/mol.

EA = 30

S c ch phn ng N Hecxan ( C6H14 ). ...................................... Trong nguyn liu cha nhiu H2-C vng no th xng thu c c tr s octan cng cao. Cc hydro cacbon c phn t lng ln d b hydro cracking hn cc hydro cacbon c phn t lng nh. Cc phn ng ny cng c tc dng tch cc lm tng hiu sut xng v tr s octan ca xng ( do isoparafin ) cn khi iu kin cng, cc hydro cacbon c phn t lng nh cng b hydro cracking, lc ny cho hiu sut kh v cc tng ln v vy nhng phn ng li c tc dng tiu cc. ng thi axit ca xc tc c nh hng ln n phn ng hydro cracking. axit cng ln th phn ng hydro cracking cng xy ra mnh ( chnh l ti

32

sao ngi ta khng dng aluminosilicat ) l cht mang m dng Al2O3. V Al2O3 c axit nh hn. Ngoi ra trong qu trnh cn c cc phn ng ph, cc phn ng ny va mang li hiu qu, va lm c hi. C li l cc phn ng hydro ho cc hp cht cha O, N, S, d dng xy ra trn cc xc tc c hot tnh hydro ho nhit 300 5000C v 14 17atm to thnh cc hp cht H2S, NH3, H2O v tch c chng ra khi sn phm. RSH + H2 RH + H2S

Nu hm lng S cha trong nguyn liu t 0,1 0,5% bng cch dng phn ng trn. Cn li l cc phn ng ngng t, trng hp cc hydro khng no v thm, hydro cracking to nhiu kh v cc. Parafin - H2 Olephin T/H. Piliolephin.

Trong nhit cng cao lng olephin to ra cng nhiu dn n phn ng trng hp cng tng, cn nu tng p sut th c th hn ch phn ng ngng t v to cc, tuy nhin nu p sut H2 qu ln, phn ng hydro cracking li xy ra mnh v cn bng phn ng xiclohecxan bezen s chuyn dch v bn tri, tc l gim bt hm lng hydro cacbon thm. V nhng l do trn, phi la chn iu kin, ch Reforming cho thch hp hn ch sn phm thu c hi.

33

Ngoi ra trong c ch ca qu trnh Reforming xc tc th c ch phn ng c a ra vi xc tc ph bin nht ca qu trnh. Xc tc Pt/ Al2O3. Lng Pt c s dng sao cho hot tnh dehydro ho ln hn isome ho olephin l hp cht trung gian ca phn ng, nhng trong iu kin Reforming c mt dng vt. C naphten v parafin u b dehydro ho thnh olephin trn tm dehydro ho cu xc tc. Cyclohecxen tip tc b hydro ho nhanh chng thnh cromatic, ankyl cyclopenten b isome ho thnh cyclohexen trn tm cc hot tnh axit. Cyclohexen li tip tc phn ng ca n trn tm dehydro ho to thnh nhng cu trc alkyl hoc b vng ho thnh naphten. Khi p sut thp n-heptan d chuyn thnh aromatic hn dng iso ca n, t l ca nhng phn ng cao ( n- heptan chim u th ) ln hn chuyn ho thp. Parafin c s nguyn t cacbon ln hn 7 b chuyn ho thnh hp cht thm d dng hn heptan. iu ny cho thy hp cht trung gian naphten khng c to thnh t parafin trn xc tc Pt bng cch ni hai u nguyn t cacbon li. Xc tc Pt to ra nhng dn xut ca cyclopentan bng cch ni nguyn t cacbon th hai hoc th su li, alkyl cyclopentan c to thnh nh vy b isome ho thnh alkyl cyclohexan. i vi phn ng hydro ho v dehydro ha, c ch n gin nht l c ch ca Bonhoeffer-farkas da trn c s s hp th ho hc ca cc cht phn ng. Theo c ch ny, mt phn t hydro b hp th trn 2 tm hot tnh kim loi lm
34

phn ly lin kt H-H. Trong phn ng hydro ho nguyn t hydro trn b mt nh vo olephin b hp th theo 2 giai on, giai on to thnh hp cht trung gian b hp th, thng l cc gc alkyl. Phn ng hydro ho thng l bc 1 vi p sut ring phn ca hydro, l bc 0 hoc m vi p sut ring phn ca olephin. Cc phn ng to hp cht thm to ra ch yu trn thnh phn kim loi ca xc tc hai chc nng. Phn ng dehydro ho metyl cyclohexan l bc 0 i vi metyl cyclohexan v hydro nhit nh hn 3720C. Trong nhng iu kin giai on gii hn vn tc l giai on gii hp toluen trn b mt. C ch phn ng dehydro ho cyclohexan qua giai on hp th cyclohexan ng thi phn ly hoc sau khi hp th phn ly nhanh chng 6 nguyn t hydro. Phn ng to thnh lin kt ca hp cht thm thng qua tng tc vi orbital ca kim loi. Cc bc phn ng nh sau: ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Mt lng nh ca dien pha kh v cyclohexan c mt trong sn phm chng t phn ng dehydro ho xy ra theo tng bc v mt lng nh sn phm trung gian b gii hp. Cyclopentan khng b dehydro ho to ra cc dien tr khi tin hnh nhit cao nhng n b hydro cracking d dng to ra pentan. iu ny ch rng cc dien kh c to thnh do vn hnh hc trn b mt xc tc, cc alkyl cyclopentan v alkyl cyclohexan c nhng v tr b chn ( gem-dialkyl, spiran ) khng b dehydro ho, nhit m cyclohexan c th phn ng d

35

dng. Nhng chng c th b dehydro ho nhit cao khi c s sp xp li phn t. ...................... y cho thy phn t phi nm ngang bng trn b mt kim loi phn ng xy ra trng thi hp ph ban u. Phn ng isome ho cng c th xy ra trn b mt kim loi, nhng c ch khc vi phn ng xy ra trn tm xc tc axit. Parafin c hp ph trn 2 nguyn t cacbon k nhau v c th tch 2 nguyn t hydro v hp ph nh loi olephin. S gii hp khng gn 2 nguyn t hydro v to ra olephin pha kh. .................. ng thi parafin c th hp th trn nhng nguyn t C khng gn k, to thnh lin kt C-C mi, vng 5 hoc 6 cnh. Phn ng ny yu cu nhng nguyn t C lin kt vi b mt b tch ring bi 4 hoc 5 nguyn t C lin kt vi cc nguyn t kim loi gn k. Cc bc ca phn ng nh sau: + 2 lin kt C-C khng ph v, hydrocacbon hp ph trn b mt nguyn t C lin kt vi tm kim loi bn cnh: ,,,,,,,,,,,,, + 1 lin kt C-C to thnh gia 2 nguyn t C-* to thnh vng cyclopentan hoc cyclohexan. ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,

36

S gii hp vng 5 hoc 6 cnh c th xy ra- vng c th hp ph li trn b mt hoc thay i nhng nguyn t C thc t lin kt vi b mt m khng cn gii hp lin kt C-C gia 2 nguyn t b hp ph c th b v. - Nguyn t H c nh tr li phn t b hp th sau gii hp th ta c 1 isoparafin. Ti cn bng. Phn ng isome ho trn cht mang oxit nhm c thc hin theo c ch ion cacboni. S isome ho alkan kh hn nhiu alken, xc tc axit mnh v nhit cao c nh hng n phn ng ny. Alkan kh kt hp vi proton ca nhm oxit xc tc nhng nhng vt ca alken th c th kt hp vi proton d dng to ra ion cacboni lm tng tc qu trnh isome ho parafin. S vn chuyn hydro ni b phn t nh cc ion cacboni nh sau: .............. Do vy, cc parafin mch thng u tin b hydro ho to thnh olephin, olephin ny b isome ho trn tm axit ca xc tc to thnh iso-olephin li b hydro ho to thnh isoparafin. C ch ny cho php ng dng nhng xc tc c axit km mnh hn v c th iu khin c, khng xc tin cho nhng phn ng khng mong mun ( phn ng hydrocracking ) v phn ng to cc, so vi nhng tm axit mnh ca xc tc cracking. S isome ho olephin xy ra nhanh chng trn tm axit ca xc tc.

37

Olephin c th b vng ho trn nhng tm axit. C ch ny vn cha c nghin cu nhng s vng ho ca olephin khng xy ra theo c ch ion cacboni trn axit nhm hot ho v s to ra cacboni vng khng thy xut hin trong iu kin Reforming. Do c th phn ng ny lin quan n s kt hp proton v lin kt li nh tm axit. Vy phn ng c th xy ra trn 2 nhm axit baz cnh nhau trn b mt xc tc. .......................................... Phn ng m vng trn xc tc axit ca metyl cyclopentan xy ra bng cch kt hp trc tip proton vo mch vng to ion cacboni khng vng. ,,,,,,,,,,,,,,,,,,,,,,, C ch tng t c th gii thch cho phn ng vi dien to thnh metyl cyclopentan: V d 1,5 hexadien to ra metyl cyclopentan, metyl cyclopentan v bezen trong metyl cyclopenten chim u th. Phn ng xy ra do s alkyl ho ni phn t khi trung tm cation ang pht trin xa lin kt i to thnh vng 5 hoc 6 cnh. Phn ng hydrocracking xy ra trn tm axit ca xc tc tun theo c ch ion cacboni nh phn ng hydro cracking tng nhanh ca cht phn ng tng do d dng b gy mch cc parafin. Hydrocarcking b gy mnh c parafin mch thng v mch nhnh. S phn ng Reforming ca nhng hydro cacbon 6C.
38

,,,,,,,,,,,,,,,,,,,,,,,,,,, Qua s , nhng phn ng song song vi honh xy ra trn tm axit ca xc tc v nhng phn ng song song vi tung xy ra trn nhng tm kim loi cht phn ng, nhexan c dehydro ho u tin trn kim loi to ra hexan mch thng. Hexen ny ti tm axit bn cnh, n v nh hp isohexen v i ti trung tm kim loi, y n c th b hp th v b hydro to thnh isohexen. ng thi ion cacboni th cp cng c th phn ng to thnh metyl cyclopentan. Cht ny tip tc phn ng to thnh cyclohexen v sau thnh bezen.

V.

Nguyn liu v sn phm.

1. Nguyn liu. Ngi ta thng dng phn on xng cht lng thp c khong si t 62 1800C lm nguyn liu cho qu trnh Reforming. Trong thc t cng nghip ch bin du, nhn cc cu t cao octan cho xng, ngi ta dng phn on si t 85 1800C hay 105 1800C. Phn on xng c im si nh hn 600C l khng thch hp v n khng cha cyclo ankan v ankan c kh nng chuyn ho thnh aren, m ch cha cc hydro cacbon c s cacbon nh hn 6, ch c kh nng chuyn ho thnh cc hydro cacbon kh. Nhng nu im si cao hn 1800C, nhiu cc lng ng trn xc tc lm gim thi gian sng ca xc tc trong iu kin phn ng.

39

Tu thuc vo mc ch ca qu trnh m la chn cc phn on thch hp. Nu nhm mc ch thu xng c tr s octan cao, v gim lng kh v cc khng mong mun th thng s dng xng c phn on 85 1800C v 105 1800C. Phn on c nhit si u l 1050C c th sn xut xng c tr s octan n 95 100, ng thi lm tng hiu xut xng v hydro-Cn nhn RH thm ring bit, ngi ta dng nguyn liu l cc phn on hp. Gii hn si t 62 850C nhn Bezen. Gii hn si t 62 11050C nhn Bezen v Toluen. Khong nhit si t 62 1400C c s dng sn xut hn hp Bezen, Toluen, Xylen trong khi phn on c khong nhit si 62 1800C sn xut ng thi c aren v xng c tr s octan cao. Do vy, t c nhng sn phm mong mun, mt s qu trnh cn tin hnh tch phn on. nh hng n qu trnh Reforming xc tc khng ch l thnh phn ct m quan trng l thnh phn ho hc ca phn on nguyn liu. Trong nguyn liu c cha cc loi hp cht khc nhau ca parafin, ca naphten, ca RH thm v cc hp cht phihydro cacbon khc nh hp cht oxy, nit, lu hunh. V cc hp cht ny u lm tng tc cc phn ng ngng t to nha v cc gy ng c xc tc, lm gim nhanh hot tnh ca xc tc, c bit l vi xc tc Pt/Al2O3 th hp cht cha lu hunh nguy him nht.
40

Nu hm lng ca naphten trong nguyn liu cng cao, nht l cyclohexan v dn xut ca n cng nhiu, th phn ng dehydro ho xy ra cng trit v hm lng RH thm s cng nhiu. c trng cho ch tiu v cht lng cho nguyn liu v xng Reforming c trnh by trong bng 5 di y. Bng 5: Tnh cht v thnh phn ca nguyn liu v sn phm trong qu trnh Reforning ca phn on 85 1800C v 105 1800C cho xng c tr s octan l 95.

Cc tnh cht.

Phn on 85 1800C I II III

Phn on 105 1800C I III IV 0,7 72

Nguyn liu. Trng lng ring, d204 thnh phn cacbon % hydro 0,73 0,73 0,74 0,75 0,7 8 66 2 0 50

Aren. Cyclo ankan. Ankan. Tr s octan.

6,5

7,4

10,0 7,4

12, 2

11, 0 48, 0 41, 0 55,

26,0 27,4 27,0 23,1 26, 0 67,5 65,2 63,0 69,5 61, 8 39,5 25,5 39,

41

0 Xng Reforming. Trng lng ring, d204 thnh phn hydro cacbon % Cha no. Aren No Hiu sut % Xng n nh Hydro 75,0 76,5 77,7 76,0 81, 0 1,2 1,2 1,3 1,3 1,6 1,2 0,9 0,8 0,9 0,7 5 34,5 34,4 33,7 33,7 31, 8 0,78 0,78 0,79 0,79 0,7 5 9 6 8 95

0 0,8 04

0,5 68, 5 31, 0 88, 3 2,2

6,45 64,7 65,5 65,4 67,

Hm lng tp cht c trong nguyn liu cng phi c khng ch trc khi thc hin qu trnh trnh ng c xc tc. nh gi cht lng nguyn liu Reforming xc tc thng qua thnh phn ho hc ca nguyn liu, hng UOP a ra mt s chun tng quan KUOP c xc nh theo biu thc sau: KUOP = 12,6 ( N + 2Ar )/100. Trong : N: l hm lng % ca naphten. Ar: l hm lng % ca RH thm.

42

Trong nguyn liu Reforming xc tc, KUOP v c bit l tng s N + 2Ar thay i trong khong rng ( tng N + 2Ar c th t 30 80). Nu KUOP = 10 th nguyn liu cha nhiu RH thm hn, nu KUOP = 11 th nguyn liu cha nhiu naphten v RH thm mt vng. Cn nu KUOP = 12 l nguyn liu cha mt hn hp bng nhau gia RH vng v RH parafin v nu KUOP = 13 th nguyn liu ch yu l RH parafinic. Do vy, nu KUOP thp hay tng N+2Ar c trong nguyn liu cng cao th nguyn liu cng cha nhiu naphten v nguyn liu cng thun li nhn xng Reforming c tr s octan cao. Ngoi ra, thnh phn phn on cng nh hng ln n cc ch tiu ca qu trnh Reforming xc tc. Cc hp cht phihydro cacbon, c bit l cc hp cht ca lu hunh v nit trong nguyn liu phi gim ti cc tiu v nh hn gii hn cho php. V cc hp cht ny ch lm tng tc cc phn ng ngng t to cc, to nha, u c xc tc v lm gim nhanh hot tnh ca xc tc. Do nguyn liu trc khi a vo Reforming xc tc u c qu cng on x l bng hydro ha lm sch loi b cc hp cht phihydro cacbon, cc hp cht olephin, diolephin v c kim loi do nhim bn vo nguyn liu Reforming trong qu trnh ch bin. Cc hp cht phihydro cacbon s c loi ra dng hi nh: NH3 , H2S v H2O nh qu trnh hydro ho lm sch. Tu thuc vo ch cng ngh v nht l xc tc m qu trnh hydro ho lm sch s t c cc ch tiu v cht lng cho nguyn liu Reforming xc tc.
43

Bng 6: Hm lng cho php cc hp cht phihydro cacbon c mt trong nguyn liu Reforming xc tc. Hm lng S Hm lng Nit Hm lng Oxy Hm lng Clo Hm lng kim loi. Hm lng Asenic Hm lng Ch Hm lng ng. 2. Sn phm. Sn phm chnh thu c trong qu trnh Reforming xc tc bao gm xng c tr s octan cao, cc hydro cacbon thm ( BTX ). Qu trnh Reforming xc tc cng l mt qu trnh ng k sn xut ra sn phm ph l hydro c bit l trong qu trnh s dng nguyn liu giu naphten sn xut hydro cacbon thm. a. Xng c tr s octan cao. Xng Reforming xc tc l loi xng quan trng nht v n c hm lng cc hp cht thm v tr s octan rt cao v n nh hm lng sunfua v nha thp. Xng Reforming l thnh phn chnh sn xut xng khng ch, c tnh ca n ph thuc vo nguyn liu u vo v cht lng ca xc tc, ch cng ngh ca qu trnh. Tu theo thnh phn ho max 1ppm max 20 ppm max 5 ppm max 0,5 ppm max 0,5 ppm max 2 ppm max 0,5 ppm

44

hc v thnh phn ct ca nguyn liu ban u m ta c th nhn xng vi cht lng khc nhau. Xng Reforming c thnh phn ho hi ch yu l cc hydrocacbon thm v RH parafin, cn hm lng olephin rt nh ( khong 3% hm lng naphten khng vt qu 10% v vy n c n nh cao. Cc hp cht thm li thng tp chung phn on c nhit si cao do s phn b tr s octan l khng u. Khong nhit si ca xng sn phm l rng hn ca nguyn liu. Nhng thnh phn c nhit si thp c to ra nhng phn ng hydro cracking, thnh phn ny c nhit si cao hn t hydro ho (Cc hp cht thm thng c nhit si cao hn khong 500F so vi cc hp cht parafin v naphten to thnh n ). Mt s t hp cht thm v olephin c th b ngng t to ra nhng hp cht c nhit si rt cao. Do p sut cao thch hp cho phn ng hydro cracking lm thp khong nhit si, cn phn ng dehydro ho lm tng nn hm lng hp cht thm tp chung phn c nhit si cao. Do vy, phn c nhit si cao hn c tr s octan cao hn. Butan to trong qa trnh thng cha t 40 50% isobutan. u im ca xng Reforming xc tc l c tr s octan cao, lng olphin thp nn n nh oxy ho cao (1700 1800 pht ) thun li cho qu trnh bo qun, tn cha v vn chuyn. ng thi n cng c nhc im l t phn nh, trong qu trnh khng xy ra s ct mch cacbon to ra hydro cacbon nn t trng ca xng cao, p sut hi bo ho thp, s
45

phn b thnh phn phn on khng u nn ng c s kh khi ng nu nhit thp v ch lm vic khng n nh. b. Cc hydrocacbon thm: Cc hydro cacbon thm thu c bao gm Benzen, Toluen, Xylen... l nhng sn phm rt cn thit cho cng nghip ho du v tng hp hu c. Sn phm thng l hn hp ToluenXylen, Benzen-Toluen c th c thu hi v tinh ch bng cc qu trnh hp ph ( cht hp ph l silicagen ), chng ct trch ly ( phenol ), chng ct ng ph hoc trch ly bng dung mi ( dietylen glycol lu hunh ). Benzen: Trong qu trnh Reforming, Benzen thng c to ra di dng hn hp vi cc hyro Cacbon thm khc v c tch ra bng cch trch ly dung mi hoc chng ct ng ph v n to hn hp ng ph vi cc hydro cacbon khc. Benzen thu c c tinh khit cao, thng c s dng trn vi xng v n c c tnh chng kch n cao, c xu hng lm gim s kh n my. Ngoi ra Bezen cn l ngun nguyn liu sn xut rt nhiu hp cht hu c l dung mi cho nhiu sn phm cng nghip. Tluen: Thu c vng vi bezen trong qu trnh Hydro Forming v platforming, nhng s dehydro ho ca naphten thnh Toluen d dng hn Bezen. Lng Toluen thu c nh Reforming rt ln c ng dng lm thnh phn ca xng v lm dung mi cho nhiu qu trnh.

46

Bng 7: Cht lng xng Platforming. Cc thng s Hm lng parafin trong nguyn liu % 65% Trng lng ring 200C (g/cm2) Thnh phn ct phn on ( 0C ) Nhit si u Nhit si 10% Nhit si 50% Nhit si 90% Nhit si cui Thnh phn ho hc ( %, TL ) Hydro cacbon khng no Hydro cacbon thm Paraphin + Naphten Tr s octan, MON Tr s octan, RON 2,2 59,0 38,8 80 89 0,9 65,4 33,7 85 95 1,0 62,0 37,0 80 89 0,5 685 31,0 85 95 49 82 135 172 202 42 76 138 171 215 58 96 140 170 198 58 110 140 168 205 0,785 < 40% 0,738 0,796 0,722

Xylen: Thu c sau qu trnh l hn hp cc ng phn ca Xylen. Hiu sut Xylen hn hp sau khi tch Bezen v Aren nh trch ly trong dung mi chn lc cao ( 799% ). Xylen cng c s dng pha trn vi xng ( c th dng ngay hn hp BTX ) hoc dung mi. Ngoi ra cn thu c sn phm kh hydro Trong kh ny cha 70 90% th tch hydro.
47

VI Cc yu t nh hng n qu trnh. C nhiu loi Reforming khc nhau nhng vn c nhng yu t chung nh hng n qu trnh l: 1. Loi c tnh xc tc: Xc tc phi c la chn sao cho ph hp vi tng qu trnh hiu sut, hot tnh v bn ca n i vi qu trnh phi l ti u. Do vy, ta c th thay i thnh phn ca xc tc nh hm lng Clo, hm lng Platin ...Cn i vi xc tc hai kim loi th loi v lng kim loi th hai l nhn t chnh trong vic la chn xc tc. Hot tnh xc tc c th thay i bng cch thay i loi xc tc hoc cn bng Clo - nc trong xc tc. chn lc ca xc tc l kh nng xc tc to ra sn phm mong mun ti iu kin cho. chn lc cng thay i theo loi xc tc v cn bng Clo nc trong xc tc. bn ca xc tc c xc nh bi nhit v p sut qu trnh, s tin s l nguyn liu loi b lu hunh, nit v oxy. Xc tc Pt trong oxit nhm hot ho c bn tt nhng xc tc Pt trong oxit nhm oxit silic li kh hot tnh rt nhanh v n c hot tnh axt mnh v xc tc cho phn ng hydro cracking rt nhanh. Trong nhng nm gn y, tng bn ca xc tc ngi ta s dng xc tc Pt- Re hoc xc tc nhiu kim loi. Xc tc Pt-Re. Al2O3 c u im l c bn cao vi s kh hot tnh xc tc bi cc, cho php lm vic kh lu p sut hot ng kh thp. Do s bin i axt ca cht mang di
48

tc dng ca Re, Re cng lm bn thnh phn Pt nn s mt mt b mt trong ti sinh gim v xc tc nhiu kim loa bn hn v c hot tnh cao hn do s tng hot tnh kim loi. ................................................. Hnh 1: Hot tnh v bn ca xc tc pht trin / Al2O3 + SiO2 v Pt/ Al2O3. S thay i hot tnh ca 2 kim loi trong xc tc kim loi nh hng r rt n thnh phn v cht lng sn phm. Do Cl lin tc b tch khi b mt, lng cht lng ca xc tc phi c duy tr bng cc h thng thm nhng hp cht Cl hu c vo nguyn liu. ..................................................... Hnh 2: nh hng ca hm lng Cl n hot tnh v bn xc tc Pt/ Al2O3 trong qu trnh Reforming. Do phn ng vng ho c xc tc chn lc bng Pt c phn tn cao, bt k qu trnh no gy ra s mt mt b mt u bt li cho hot tnh v chn lc ca Reforming. S thay i ca cn bng phn ng Reforming khi kch thc tinh th Pt tng do s thiu kt nhit cao. Vn tc phn ng dehydro ho gim ng k trong khi vn tc phn ng isome ho tng nhanh. Bng 8: nh hng s thay i kch thc tinh th n phn ng. Kch thc nC7 cn li Phn ng
49

Phn ng

Phn ng

tnh th trung bnh A0 10 12 33 73 158 44452 Pt trn cht mang t do

dehydro ho v ng vng %

isome ho %

hydro cracking

3,0 3,5 4,6 7,0 9,8 23,4 74

37,4 32,8 26,8 21,6 17,7 12,4 0,4

9,0 10,6 14,2 21,7 24,3 28,9 0,1

50,6 53,1 54,4 49,7 48,2 35,3 25,5

Vn tc phn ng dehydro ho ph thuc vo din tch b mt ca Pt. Hm lng Pt trnh by hnh sau: ............................................................................................
2. nh hng ca p sut.

Cc qu trnh Reforming u km theo qu trnh tng th tch nh kh H2 ca naphten, vng ho. p sut ca qu trnh l nhn t chnh nh hng n hiu sut v s quay vng xc tc, p sut t 400 n 500psi thch hp thi gian quay vng xc tc di.

50

Do s gim p sut, cn bng phn ng dehydro ho chuyn v pha lm tng hiu sut sn phm thm v hydro, s gim p sut lm gim kh nng hydro cracking. Vic tng phn ng dehydro ho v gim phn ng hydro cracking lm tng hiu sut C5 v sn phm Reforming do s gim p sut lm tng t l cc. p sut thp th s kh hot tnh xy ra nhanh n mc thi gian sng ca xc tc l 1 nm. Cc thit b bn ti sinh khng thun li cho hot ng p sut thp cho n khi a vo xc tc hai v nhiu kim loi lm gim mc to cc. Trong nhng h thng nhiu thit b hoc thm tr trong cng mt thit b gim p sut c th thay i theo s thay i t l cp liu v t l kh tun hon. p sut cn c quyt nh bi hot tnh v chn lc xc tc. V d: Trc y s dng xc tc Mo/ Al2O3 , P=15 20 at. Cn by gi dng xc tc pht trin / Al2O3 duy tr P =20 40 at trong h thng m hot tnh to cht thm vn m bo. p sut trong h thng nh hng n hiu sut to hydro cng nh hng ng k n qu trnh. Khi khng c hydro th khng xy ra phn ng v b mt kim loi b che ph bi cc, khi tng p sut hydro, b mt kim loi c lm sch mt phn v c phn ng dehdyro v dehydro ng vng u xy ra.

51

p sut ring phn hydro cng nh hng n phn ng isome ho v dehydro isome ho. Nu trong iu kin lm vic khc ca qu trnh l khng i, khi tng p sut th vn tc cc phn ng hydro cracking v kh ankyl s tng ln, trong trng hp ny cn bng s dch chuyn v pha to parafin. Khi gim P trong h thng, dn n gim P ring phn ca H2 lm tng mc thm ho cc parafin v naphten. 3. Vn tc th tch. Vn tc th tch l i lng o lng naphta phn ng trn mt lng xc tc cho trc trong thi gian cho trc. Khi vn tc cp liu ca naphta c tnh theo th tch trn gi v lng xc tc c tnh theo th tch th gi l vn tc th tch ( CHSV ) khi lng cht phn ng v xc tc tnh theo khi lng th gi vn tc th tnh theo khi lng ( WHSV ). Vn tc th tch nh hng n cht lng sn phm ( tr s octan ). Vn tc th tch cng ln, tr s octan cng cao, nh hng ca nhit thit b c th thay th vn tc th tch v cng xc nh cht lng sm phm. Vn tc th tch c nh hng nh n hiu sut sn phm v bn xc tc. Gi tr ca CHSV trong khong t 1 3h. Tr nhng gi tr thp ca vn tc th tch (<1) thun li cho phn ng hydro cracking, gi tr ln nh hng n chn lc t hn nhiu nhng thng s khc. S ph thuc ca thnh phn sn phm vo vn tc th tch c trnh by hnh sau: ..............................................

52

Hnh 4: Thnh phn sn phm ca phn ng ca 2 metyl pentan trn xc tc Pt trn cht mang oxit nhm khng axit. iu kin phn ng : t0=4400C, p=9,5at, t l H2/2-MP=4, xc tc cha 0,3%Pt.
4. T l mol H2/HC.

Tl mol H2/HC l mt gi tr o vn tc dng hydro tun hon cn thit cho qu trnh lm bn xc tc v n qut nhng sn phm phn ng v nhng vt liu ngng t trn xc tc s tng t l H2/HC s loi b tp cht ra khi thit b phn ng nhanh hn v cung cp nhng ch tiu nhit to ra ca phn ng ln hn. N cng lm tng p sut ring phn hydro v do lm tng bn ca xc tc m khng nh hng nhiu n hiu sut hoc cht lng sn phm. Hin nay xu hng lm gim t l H2/HC t 8 :1 10:1 n 3:1 5:1. S gim t l H2/HC lm tng vn tc to cc v gim thi gian tun hon xc tc ( t l tng t 5:1 4:1 lm gim thi gian tun hon khong 20% trong khi cc iu kin khc vn gi nguyn ). nh hng ln n hiu sut khi gim t l H2/HC t 8 :1 10:1 n 3:1 5:1 khng ln nh nh hng ca s gim p sut t 500 n 200psi.
5. nh hng ca nhit .

Qu trnh Reforming xc tc tin hnh trong iu kin nhit nm trong gii hn 470 5250C. Khi iu kin p sut v tc th tch khng i, nu gim nhit th s dn

53

n tng hiu sut xng, gim hiu xut kh gim vic to cc, ng thi gim lng hydro cacbon thm. Ngc li nu tng nhit th tng s to thnh hydro cacbon thm, gim hiu sut xng, gim nng H2 trong kh tun hon ( v nhit cao thun li cho cc phn ng hydro ha v kh hydro vng ho, to cht thm. Song bn cnh cng lm tng cng cc phn ng hydro cracking v vy lm cho hiu sut kh tng ln v mc cc ho cng tng ln. Nh vy khi nhit tng ln th hydro thm cng ch tng n gii hn cho php, nu tng qu cao th vic to cc tng lm cho xc tc gim hot tnh v thi gian lm vic ca xctc cng gim). Bng 9: S ph thuc hiu sut v cht lng ca sn phm Reforming xc tc vo nhit . Cc ch tiu Hiu sut xng kh propan Hm lng phn on c t0 si n 1000C, % th tch. p sut hi bo ho ca xng ( mmHg ) RON khng pha nc ch Hm lng hydro cacbon thm trong xng, % th tch
6. nh hng ca nguyn liu

Nhit ( 0C ) 435 98,0 34,0 310 67,5 19,0 450 96,8 36,0 350 74 27,0 465 95,0 41,0 430 80,5 35,0 480 91,6 46,0 59,0 89 45,0 6

54

Tu theo mc ch ca qu trnh Reforming m chn nguyn liu cho thch hp. nhn xng c tr s octan cao th phi chn nguyn liu c nhit si 85 1800C. Nu nhit si thp hn 850C ( Nguyn liu nh ) th khi b hydro cracking s to thnh nhiu kh, l sn phm khng mong mun ca qu trnh. Cn nu chn xng c nhit si t 180 2200C th s tng cng phn ng trng hp to cc bm trn xc tc, lm gim hiu qu ca xc tc. Ngoi ra thnh phn hydro trong nguyn liu cng nh hng rt ln, nu tng hm lng naphten v thm cng nhiu th hiu sut xng cng cao. ................................................ Hnh 5: nh hng thnh phn hydro cacbon ca nguyn liu n hiu sut xng. nhn hydro cacbon thm BTX lm nguyn liu cho tng hp ho du th ta chn xng nguyn liu c t0 si hp: sn xut Bezen: Nguyn liu c t0 si 62 850C sn xut Toluen: Nguyn liu c t0 si 85 1200C sn xut Xylen: Nguyn liu c t0 si 120 1400C Nhng thnh phn khc c mt trong nguyn liu nh hm lng Clo... cng nh hng n qu trnh, c bit l n hot tnh v bn xc tc. nh hng ca hm lng nc trong dng hydro tun hon n hot tnh v bn xc tc c trnh by trong hnh.
55

............................... 7. Hiu ng nhit ca qu trnh. Cc phn ng ch yu ca qu trnh Reforming xc tc l phn ng kh hydro cc hydrocacbon Naphten 6 cnh thnh hydrocacbon thm v kh hydro vng ho cc hydrocacbon Parafin thnh hydrocacbon thm. Cc phn ng ny u km theo s thu nhit. Ngoi ra cn c phn ng hydrocracking, phn ng ny km theo s to nhit v cn c mt s phn ng ph xy ra yu v hiu ng nhit c th b qua. V vy hiu ng nhit ca qu trnh c xc nh bi su ca cc phn ng kh hydro, kh hydro vng ho v hydro cracking. Qu trnh chuyn ho nguyn liu giai on u ch yu xy ra cc phn ng kh hydro, kh hydro vng ho nn hiu ng nhit ca giai on ny quyt nh ch yu su ca 2 dng phn ng trn. Nhng do cc phn ng kh hydro cc Naphten xy ra nhanh hn nhiu so vi phn ng hydro vng ho cc hydrocacbon Parafin v vy gi tr hiu ng nhit y ph thuc ch yu vo hm lng cc hydrocacbon Naphten trong nguyn liu. Qu trnh chuyn ho nguyn liu giai on cui, khi cc phn ng thm ho hu nh cn bng th vai tr ca phn ng hydrocracking quyt nh hiu ng nhit ca giai on ny. Ngi ta thy rng tt nhit gim i r rt cc thit b phn ng trong cc h thng Reforming xc tc.

56

Trong tnh ton k thut, hiu ng nhit ca qu trnh thng c tnh cho 1kg nguyn liu. Ni chung hiu ng nhit ca qu trnh Reforming xc tc trong mi trng hp u c gi tr m ln. Ngi ta thy rng gi tr hiu ng nhit s dng nguyn liu khc nhau th khc nhau. V d khi s dng nguyn liu c hm lng Naphten cao hn s khc khi s dng nguyn liu xng Parafin cao. Gi tr trung bnh ca hiu ng nhit i vi nguyn liu xng Parafin th nm trong gii hn t - 50 - 70 kcal/kg. Cn i vi nguyn liu xng nhiu Naphten th nm trong gii hn -100 -140kcal/kg. Ta thy rng khi ch bin xng nguyn liu cc phn on hp vi mc ch nhn hydrocacbon thm BTX th gi tr hiu ng nhit cn cao hn, c bit l nguyn liu cha nhiu Naphten. 8. nh hng ca lu lng nguyn liu. Khi tng lu lng nguyn liu hay gim lng cht xc tc trong cc thit b phn ng n s lm gim thi gian tip xc ca cc cht tham gia phn ng cht trung gian vi cht xc tc v lm tng hiu sut xng n nh, tng hm lng hydro trong kh tun hon, gim hiu sut hydro cacbon thm v tr s octan gim. ng thi khi tng tc th tch ( hay tng lu lng ) ca phn ng hydro ca naphten. hydro cracking cc parafin nng, ng phn ho butan v pentan s chim u th v xy ra nhanh hn cn cc phn ng i hi thi gian ln nh kh

57

hydro vng ho parafin kh ankyl, v hydro cracking cc hydro cacbon nh xy ra yu hn. T thy rng vi mc ch ca qu trnh Reforming xc tc s nhn BTX, qu trnh phi c tin hnh trong iu kin thi gian lu lng nguyn liu trong vng phn ng t, ng thi c ngha l tc th tch khi s dng nguyn liu v naphten ln, nhit si s dng trung bnh v p sut thp t 10 20 at. 9. c tnh ca thit b. Cc thit b phn ng c phn loi thnh 2 loi chy xung v chy xuyn tm. Trong thit b xuyn tm i vo nh v chy xung qua lp xc tc, sn phm i ra t y . ........................................................................... Trong thit b xuyn tm, nguyn liu i vo t nh v sn phm i ra t y nhng nguyn liu chy ngang qua 1 lp xc tc vng n dng nguyn liu r nhnh i vo xc tc. Thit b bn ti sinh thng l mt dy gm 3 n 4 thit b. Kch thc ca thit b u tin thng nh hn so vi thit b cui cng. Nhng phn ng thu nhit rt nhanh, xy ra thit b u tin c th lm gim nhit thit b n mc m nhng phn ng tip theo b ngng li, lp xc tc nm di im c nhit ny hot ng khng c hiu qu. Do vy nn s dng thit b c kch thc nh, ng thi nhng phn ng xy ra thit b cui cng tng i chm, do kch thc thit b phi ln. S phn chia kch thc thit b c a ra trong bng 10.
58

Bng 10: Kch thc thng thng ca thit b. H thng 3 thit b Thit b s 1 2 3 phn trm 20 230 50 H thng 4 thit b Thit b s 1 2 3 4 phn trm 12 20 28 40

Ngoi ra, c khi nng sut ca thit b bn ti sinh c th c m rng, 2 thit b sn c c ni song song v 1 thit b mi thng nh hn c thm vo. Thng thng nhng thit b song song thng c t nhng v tr cui cng. H thng tun hon thng s dng 5 hoc 6 thit bi. H thng lp xc tc chuyn ng thng s dng 3 hoc 4 thit b.

VII Ci tin xc tc v cng ngh.

Qu trnh Reforming xc tc vi lp xc tc c nh u tin c p dng trong cng nghip vo nm 1940 v khi dng xc tc Molipden. Song n cng khng c pht trin v s to cc qu nhanh trn xc tc. Vo nm 1949 Reforming xc tc s dng xc tc trn c s Pt ra i v qu trnh ny lin tc c ci tin. Cng vi qu trnh ci tin xc tc, cng ngh cng c ci tin theo v ngi ta p dng cng ngh p sut ca qu trnh ngy mt thp. Nhng ci tin cho php tng c hiu sut v cht lng ca xng. V p dng qu trnh p sut thp, m lm tng

59

tc to cc t cng ngh c s ln ti sinh xc tc tng ln. V d hng ESSO p dng qu trnh Reforming xc tc vi p sut bng 6 Kg/cm2 trong Reator vi lp xctc c nh nhng c b sung thm 1 l phn ng ph. Thay i mi nht l t nm 1971 hng UOP a ra cng ngh xc tc chuyn ng vi qu trnh ti sinh xc tc lin tc ( CCR ) cng ngh ny cho php gim p sut t 20 Kg/cm2 xung cn 10 12 Kg/cm2 v khi c xc tc th h mi cng ngh ny cho php gim p sut xung cn 3 3,5 Kg/cm2 ( Hng UOP v FIN ). ng nhin xc tc th h mi c gi thnh cao hn ( ngay cht mang cng t hn: 35F/kg so vi 2F/kg ca xc tc FCC ). Nhng n c p dng v ch tiu kinh t: Tng tr s octan, tng hiu sut xng v lng kh H2. S ci tin theo hai hng: Ci tin xc tc v ci tin cng ngh. Bng 11: Trnh t ci tin xc tc v cng ngh 194 0 194 0 Thp nin 1950 rt nhiu qu trnh Reforming xc tc c pht trin t xc tc Pt. 196 0 197 Pht trin xc tc a kim loi ( ngoi Pt cn c cc kim loi khc ) Qu trnh Reforming ti sinh xc tc lin tc ra i. Pht trin xc tc Pt. Reforming xc tc u tin s dng xc tc Molipden.

60

0 198 0 199 0 Qu trnh Reforming ti sinh xc tc sn xut RH thm. Ra i qu trnh Reforming xc tc mi ( New Reforming )

Vo nm 1950, nhiu qu trnh Reforming xc tc s dng xc tc Pt c pht trin v nh my Reforming trong khu lc du l cha kho chnh sn xut xng c tr s octan cao cng vi qu trnh Cracking vi vic ti sinh xc tc si ( FCC ). Qu trnh Reforming xc tc khi s dng Reator vic ti sinh xc tc b cc ho. Mt s qu trnh s dng Reator c ng van song song ti sinh xc tc tng Reator ring m khng cn phi dng lm vic ton b h thng ( qu trnh Powerformer ). Vo thp nin 1960, xc tc bi v a kim loi c pht trin. Xc tc bi v a kim loi c ci tin c bn cao, chng li s to cc, gp phn nng cao cht lng ca sn phm. Sn phm c RON = 100 m vn u t, gi thao tc khng cao. u nm 1970 c mt s ci tin ni bt l qu trnh Reforming xc tc, l qu trnh c ti sinh lin tc xc tc ca hng UOP v tip theo l ca TFP. Xc tc b cc ha c tho ra lin tc khi Reator v c a quay tr li Reator sau khi c ti sinh trong mt thit b ti sinh ring. Qu trnh ny c gi l qa trnh ti sinh lin tc xc tc ( CCR). Nh
61

kh nng ti sinh lin tc xc tc b cc ho, qa trnh CCR cho php dng p sut thp v thao tc lin tc, hng nm cha phi thay xc tc mi. Cng nh gim p sut m hiu sut RH thm v H2 tng ln ng k. Ngy nay, qu trnh CCR vi p sut siu thp v c th lm vic p sut 3,5 at. Hu nh tt c cc qu trnh Reforming xc tc mi c xy dng u l qu trnh CCR. Bng 12: Cc hng i u trong qu trnh ci tin Reforming xc tc. Tn qu trnh Hng thit k Policyastor UOP mer Xc tc c nh R.11-R12 Pt = 0,375 0,75 Powerform err Xc tc c nh KX, RO, Bo ( Pht trin, Re ) TFP Reforming MAONA former Engla nd TFP Xc tc c nh Xc tc c nh RG400 Pt=0,2 0,6 RD 150, (Pt=0,6)E50 0 Ti sinh gin on Ti sinh gin on Ti sinh gin on Ti sinh gin on Loi reator Loi xc tc Loi l ti sinh

Reniormer

CRC

Xc tc c
62

F(Pt,Re)

Ti sinh gin

nh CCR Potformer UOP Xc tc chuyn ng, reator chng ln nhau Aromi TEP Xc tc chuyn ng, reator cnh nhau Pht trin, Re

on R16,20Pt, Re Ti sinh lin tc

Ti sinh lin tc

Pht trin qu trnh CCR ch c hai hng : UOP v TFP(FIN). n nm 1996, UOP c 139 nh my v FIN c 48 nh my CCR. Trong cng nghip ch bin du, qu trnh Reforming vi lp xc tc c nh vn cn kh ph bin, y iu kin tin hnh qu trnh c chn m bo b bt thi gian ln gia cc ln ti sinh ln ( thng 7 6 thng n 1nm). Qa trnh ti sinh xc tc c tin hnh ng thi trong tt c cc Reator thi gian tng cng dng ti sinh v bo dng thit b l 20 40 ngy/nm m in hnh l cng ngh ca qu trnh ny l (Plat Reforming). Qu trnh New Reforming.

63

Sau mt thi gian di pht trin, cng ngh lc ho du thit lp c cng ngh mi c kh nng Reforming chn lc LPG v Naphta nh thnh cc cu t cao octan cho php pha trn to xng c cht lng cao v cc sn phm khc l cc RH thm. LPG ln u tin c s dng lm nguyn liu dn dng v nguyn liu sn xut olephin nh bng cch dehydro ho hay craking mi. Sau , SPG tr thnh mt vn ln ca lc du v LPG vt qu mc tiu th v tr ln kh bn trn th trng. Tip theo chnh Naphta nh cng tha do s lng trn vo xng cao octan ngy mt gim xung do tr s octan ca naphta nh qu thp. T nm 1996 n nay, cng ngh ho du sn xut thay i s dng naphta nh v LPG lm nguyn liu cho sn xut xng c tr s octan cao v RH thm. Trong nm 1997 qu trnh New Reforming c pht trin nhm mc ch ny. Cc phn ng xy ra trong qu trnh New Reforming. - Dehydro ho to parafin to olephin. - Oligomer ho olephin to thnh trimer v dimer. - Vng ho dimer v trimer. - Dehydro ho hp cht vng to RH thm. Ngoi cc phn ng chnh trn cn xy ra cc phn ng ph: Hydro cracking to metan, etan hay phn ng ngng t to cc bm trn xc tc.

VIII- Mt s dy truyn Reforming in hnh.

64

Qu trnh Reforming xc tc xut hin vo nhng nm 1970. Trong nhng nm 1940 1949 ngi ta s dng cht xc tc trong qu trnh l oxit nh ( MoO3/Al2O3 Co2O3/ Al2O3) cc xc tc oxit trong iu kin Reforming b mt hot tnh rt nhanh do vic to cc bm trn b mt xc tc. Xc tc sau vi chc gi lm vic l hot tnh gim hn v cc loi ny phi ti sinh thng xuyn. Cc h thng ti sinh xc tc bng cch dng nh k (ch sau 10 20 gi l phi ti sinh), cc xc tc oxit cn c im yu l c hot tnh v chn lc thp. V sau ngi ta xy dng h thng ti sinh xc tc lin tc trong thit b ti sinh v lin tc quay li thit b phn ng. Bin php ny cho php ko di thi gian lm vic ca xc tc v tng cng sut lm vic ca thit b. I. Cc loi s chnh.

Khi phn loi s cng ngh Reforming ngi ta ch yu da vo phng php v bn cht ca qu trnh ti sinh xc tc p dng trong s . Trong cng ngh tn ti cc loi sau:
1. Ph bin nht trong nhm ny l s Reforming vi lp

xc tc c nh, y iu kin lm vic ca h thng c chn sao cho m bo thi gian lm vic ca xc tc di ( thi gian gia hai ln ti sinh t 0,5 n 1 nm v ln hn ) thi gian ti sinh thit k khong 20 40 ngy trong nm v dng c h thng ti sinh.

65

2. Nhm th hai bao gm cc qu trnh vi thi gian lm vic ca xc tc ngn v ti sinh xc tc tin hnh tng thit b phn ng m khng ngng h thng. Vic thit k nh vy i hi cn phi c thit b phn ng d tr trong h thng. Tuy phc tp v c cu ng dn v b phn iu khin nhng li c th duy tr h thng lm vic p sut v nhit cao. 3. Nhm th ba l cc qu trnh vi lp xc tc chuyn ng. Vic ti sinh xc tc c tin hnh cc thit b ti sinh ring. 1. S cng ngh ca qa trnh Plat Reforming vi xc tc c nh. Trong cng nghip ch bin du, qu trnh Reforming vi lp xc tc c nh vn cn kh ph bin, y iu kin tin hnh qu trnh c chn m bo thi gian gia cc ln ti sinh ln ( thng 6 thng n 1nm ). Qu trnh ti sinh xc tc c tin hnh ng thi trong tt c cc Reator. Thi gian tng cng ti sinh v bo dng thit b l 20 40 ngy/nm. Hot ng ca s . Nguyn liu sau khi c lm sch s b phn xng lm sch bng hydro ho c cho sang trn vi kh cha hydro tun hon ri cho qua thit b trao i nhit (1) ri vo bung th nht ca l t (2) ti l t hn hp c t nng n 5200C ri a sang thit b phn ng ri a sang thit b th
66

nht (3) sau phn ng, quay li bung hai ca l (2) ri cho qua thit b phn ng th hai (4). Sau cho bung th ba ca l (2) ri cho qua thit b th ba (5), p sut hn hp ti ca vo thit b phn ng th nht(3) l 35at (cht xc tc dng trong thit b phn ng l p 64 ca Nga hoc xc tc RePt/Al2O3 ca Php ). Sn phm ca qa trnh reoming xc tc sau khi ra khi thit b phn ng th ba (5) x a qua thit b trao i nhit (1) v thit b trao i nhit (6) ri cho qua thit b lm lnh (7). Sau khi lm lnh hn hp n 350C cho qua thit b phn ly p sut cao (8) duy tr p sut 30at. Ti thit b ny xy ra qu trnh tch kh hydro ( khong 80%H2 ) ra khi hn hp, sn phm kh cha hydro sau khi tch a n my nn (17) mt phn kh cha hydro cn li a ra s dng lm sch nguyn liu hay dng cho mt s mc ch khc. Cn sn phm lng i ra y thit b phn ly p sut cao (8) s i vo thit b phn ly p sut (9) duy tr p sut 20at ti thit b ny tch kh kh ( C1 C3 ) ra khi hn hp, sn phm kh ny a sang phn xng tch kh. Xng cha n nh t y thit b tch kh p sut thp (9) c a qua bm v qua thit b trao i nhit (6), (10) v qua thit b t nng (11) i vo thp n nh (12) ta ly phn on hydro cacbon nh C4 C5 t y thp n nh v xng n nh cho qua thit b trao i nhit (10) v thit b lm lnh (14) v ta thu c xng thnh phm. Sn phm nh thp n nh c lm lnh bng thit b ngng t lm lnh (15) c a vo thng cha hi lu (16) ri cho
67

qua bm hi lu tr li nh thp n nh. Phn cn li a ra khi h thng a vo phn xng phn chia theo phn on kh. mi trng hydro v iu kin nhit 5250C d gy n mn kim loi. V vy, phn trong v kim loi ca thit b phn ng cn c mt lp lt bng b tng, ngoi ra phn trong thit b phn ng t mt ci cc bng thp t l gia hai thnh cc v thit b phn ng l mt lp kh ngn nhit b mt kim loi khng cao qu 1500C. Nhit ny phi kim tra cht ch bng pin nhit in. Nu nhit lp ny cao qa d gy n mn lm hng thit b phn ng. S Reforming xc tc c nh c th hin hnh: Loi s c bn ca Reforming xc tc s dng lin bang Nga c dn ra bng 16. Bng 13: S c bn Reforming xc tc ti Lin bang Nga. Loi Cng sut nghn tn/nm A35-5 A35-11/300 300 300 Thnh phn phn on ca nguyn liu ( 0C ) 85 180 85 180 105 140 A35-11/600 A35-11/30095 A35-11/600 85 180 Xng 600 300 85 180 85 180 Xng Xng Nilon-xng Xng Xng Sn phm c bn

68

Ak-6Y

1000

85 180 62 140

Xng Xng BT BT BT BT

A35-6 A35-12/300 A35-8/300 A35-13/300

300 300 300 300

62 105 62 105 62 105 105 140

Cc dy chuyn Reforming vi xc tc pht trin lp xc tc c nh thng p dng p sut ln (20 45at ) sau ny ngi ta thng dng qu trnh p sut thp hn ( 10 16at ) gim p sut lm cho qu trnh dehydro v dehydro vng ho c tng cng. Nh vy m cho php nhn sn phm c tr s octan cao hn, song s ln ti sinh cng tng ln. l cng ngh ca Etra forming v Mangna forming khi gim p sut lm vic v ng thi nng cao mc bin i nguyn liu th kinh t nht l nn chn s Reforming ti sinh xc tc lin tc ( CCR ). Ngy nay, loi Reforming xc tc lin tc tr thnh rt ph bin, nh ti sinh xc tc lin tc m khng phi dng qu trnh ti sinh xc tc nh cc dy truyn c v do vy, xc tc va mi c ti sinh c lin tc chuyn vo Reator. iu lm cho xc tc c hot tnh cao hn v n nh hn, lm vic iu kin kht khe hn m vn c hiu qu cao hn. 2. S Reforming xc tc lin tc CCR ca hng UOP.

69

c im ring bit ca s l cc Reator trng ln nhau thnh mt khi. Xc tc chuyn ng t chy t Reator trn xung Reator cui cng, sau xc tc lm vic c chuyn sang thit b ti sinh khi phc li hot tnh ri np tr li Reator th nht to thnh mt chu k kn. a. B phn Reator. Nguyn liu c trn vi kh H2 tun hon c t nng n nhit phn ng ( 526 5300C ), trong cc thit b trao i nhit v b phn th nht ca l ng ri c np vo reator th nht ( trn cng ). Sau khi tip xc vi xc tc n b bin i ( s ph thuc vo kht khe, cc iu kin cng ngh ca qu trnh ) to ln sn phm c tr s octan cao hn hay RH thm nhiu hn. Khi reator gm 4 thit b trng ln nhau theo trc thng ng. Kch thc tng dn t trn xung di v u l loi xuyn tm. S cu to ca reator trong mi reator c thit k v ng dn xc tc b phn phn phi, b phn cch ly v cc thit b khc sao cho ph hp vi qu trnh chuyn ng ca xc tc v cc phn ng ho hc xy ra. Lng xc tc cha trong reator rt khc nhau, khi m reator th nht ch cha 10 20% lng xc tc th reator cui cha 50% tng lng xc tc. T l phn b xc tc trong cc reator thng theo t s 11/1,5/2,5/5 ( vi s 4 reator ) xc tc lm vic c chuyn sang l ti sinh xc tc, hn hp khi phn ng i ra khi reator th nht c qua l t nung li n

70

nhit phn ng ri c np ngay vo reator th hai. C nh vy cho n reator th t. Sau reator th t hi kh sn phm c lm lnh do trao i nhit vi nguyn liu sau c ngng t v lm lnh tip bc chuyn sang b phn tch sn phm. thit b tch sn phm c chia thnh RH lng ngng t v hi kh giu H2. Phn ln kh ny c quay li reator nh my nn kh tun hon, phn kh cn li c trn vi b phn ti sinh ri i vo ct n nh sn phm. b. B phn l ti sinh xc tc. Xc tc lm vic chy t yl ca reator cui cng xung b phn khu xc tc bonke cha, sau n chy xung ng nng NO/. Ngi ta dng kh cha hydro tun hon t my nn tun hon y xc tc v vn chuyn n ln nh v b phn tch bi pha trn l ti sinh. b phn tch ny ngi ta b xung mt lng kh hydro tun hon tch cc ht bi mn ca xc tc ri xung y b phn tch bi ri chy xung l ti sinh. - Ti sinh xc tc gm 4 bc. Ba bc u l: + t chy cc. + Clo ho. + Lm kh ( sy kh ). Ba bc ny xy ra vng ti sinh, cn bc th t l kh xc tc xy ra trong b phn kh ring.

71

t chy cc bm trn xc tc c tin hnh trong vng chy nm nh ca l ti sinh. Xc tc a vo v chy xung pha di gia mng chn hnh tr t thng ng, khng kh nng c thi theo hng bn knh i t pha ngoi vo trong qua lp xc tc. Kh chy nng c thi nh bm, sau lm lnh v tun hon qua cc ng trong vng chy. t chy cc xy ra trong khi xc tc vn chuyn ng xung pha di, b phn lm lnh ti sinh s ly nhit khi t cc. Cn b phn t nng ti sinh s lm vic khi cn phi t nng kh m bo nhit pha trong cng thch hp. S oxy ho, phn tn kim loi trn xc tc v b sung thm Clo c thc hin trong vng Clo ho ca l ti sinh b tr pha di vng chy. Xc tc ri xung theo cc lp hnh tr, Kh Clo ho nng c thi qua lp xc tc v i ra vng chy. Kh Clo ho i t vng sy kh c thi qua cc ng vng trn i vo vng Clo ho. Hp cht Clo hu c c phun vo khng kh dn vo vng Clo ho v cng c t nng b phn gia nhit ring m bo nhit vo. c. B phn n nh. Reforming t b phn tch c np vo ct n nh iu chnh p sut hi ca n reformat s tch hydro cacbon nh v ta thu reformat n nh. iu chnh nhit ca ct n nh, ngi ta dng thit b t nng khi cn nhit b sung. Sn phm y s c bm qua vng i lu ca b phn t nng cho reactor v sau mi cho qua thit b trao i nhit tn dng nhit.
72

Ct n nh lm vic p sut cao c th phn hi lu v ch tch sn phm kh kh hydro metan, sn phm reformat n nh c cho qua thit b trao i nhit vi nguyn liu ri vo b cha. iu kin lm vic ca qu trnh nh sau: - B phn reactor v ct n nh. - Nng sut theo nguyn liu. 20.000 thng/ngy.
-

Nhit vo reactor: 520 5400C. H2/RH( mol ): 2,5. P trong reactor: 3,5kg/cm2C. P trong thit b tch: 2,5kg/cm2.

Hot ng ca s xc tc chuyn ng ca U.O.P. Cc l phn ng th cp t 1 3 c b tr ci n nm di ci kia v xc tc c chy t trn xung di theo ng cha xc tc l phn ng cp th 4, do y xy ra s to cc mnh nht iu kin Reforming th c b tr ring. Xc tc sau l (3), (4) c chy vo b phn cung cp ri c tc nhn vn chuyn a vo l ti sinh, xc tc c ti sinh li c a v l phn ng(1) v (4) nh vy c th iu chnh lng cc bm trn xc tc thp hn v cc iu kin Reforming nh nhit , p sut, t l mol hydro/nguyn liu thc t c th gi n nh trong sut thi gian h thng. iu cho php gi c cht lng v hiu sut cao ca sn phm v c hiu sut cao ca kh cha hydro cng nh nng cao ca
73

hydro trong kh. Qu trnh ny c trnh by trong hnh 2. Nguyn liu sau khi c lm sch phn xng lm sch bng hydro ho, c a qua thit b trao i nhit ri vo bung t th nht ri ln lt qua thit b phn ng chnh v cc bung t tip theo, sau t l phn ng chnh dng sn phm ln kh thng c i qua cc thit b trao i nhit v thit b tch, ti y mt phn hn hp kh c qua my nn n b phn chia kh. Ti y kh hydro c tch ra cn li cc kh bo c ho lng ri ho cng dng sn phm t y thit b tch qua bm vo ct n nh. Ti ct, phn nh ct ta thu c thnh phn nh - y ct thu c xng thnh phn l xng Reforming. Trong s qu trnh thuc nhm 1 ngoi Lin bang Nga ta cn k ti qu trnh Magna Reforming s cng ngh c trnh by hnh 3. Qu trnh ny l mt th d in hnh v ti u ho cc thng s cp 1 v cp 2 Reforming, tin hnh nhit tng i thp v tc th tch ln. iu cho php nng cao chn lc ca qu trnh bin i hydro naphten thnh thm, cp 3 v 4 c duy tr nhit cao v tc th tch thp nhm to iu kin cho qu trnh Reforming xy ra vi hm lng hydro cacbon thm v ch s octan d tnh trc, do u tin xy ra cc sn phm ng vi hydro vng ho, hydro cracking. m bo cc yu cu trn, th tch l phn ng c chn sao cho s phn b xc tc theo t l1:1:2:7 nhit thp v tc th tch ln cc cp 1
74

v 2 r rng cho php tng thi gian lm vic ca xc tc v gim c t l mol ca hydro/nguyn liu. Cn trong cp 3 v 4 cho php duy tr t l mol. H2/nguyn liu v nhit cao hn. Vi mc ch ny kh cha hydro tun hon c chia thnh 2 dng, khong 1/3 c trn vi nguyn liu vo cp 1, cn 2/3 a vo cp 3 ( l phn ng 3 ). Cc dy chuyn cng ngh Magna reforming u tin s dng xc tc pht trin/Al2O3 loi RD 150 v RD 1500C, sau ny i b phn cng ngh ny s dng xc tc a kim loi. Magna forming cng s dng 4 thit b phn ng thay v 3 thit b, nhit u vo mi thit b tng t thit b u tin n thit b cui cng t l mol kh tun hon/nguyn liu l 2,5 3 thit b u tin v 9 10 thit b cui cng. Hiu sut sn phm lng tng t nht 1 2% nhng gi u t cng tng 6,5% so vi h thng 3 thit b. Bng 14: Cc ch tiu c bn ca mt s qu trnh Ch tiu Cc qu trnh vi xc tc c nh Loi xc tc Loi R(UOP) E-500,E600 iu kin HR-71 E-601 a kim loi R-16,r-22 Magna Reforming Ultra Reforming Qu trnh UOP (lin tc)

75

Nhit (0C) p sut pa Tc th tch H1 T l mol/H2 nguyn liu Thi gian lm vic Tr s octan

470 525

470 490 490 570

470 520

500

2 3,5 1 3 5 7,5

1,4 1,8

1,4 2,1 1 3 2 4 2 3

2,5 3

3 5,5

360 95 100 100 102 40 102

153 95

S cng ngh Reforming vi thi gian gia hai ln ti sinh ngn ( Ultra forming, pecurerforming) qu trnh ny v nguyn tc l cc qu trnh tin hnh iu kin kht khe vi p sut thp v bi s tun hon kh cha hydro thp. Thnh phn nguyn liu vi nhit si cao hn. S cng ngh c ch ra hnh 4: ULtraforming l mt qu trnh Reforming ch kht khe, p sut, bi s tun hon hydro, nguyn liu c gii hn si cui cao hn 2000C. cc l phn ng (4) xy ra qu trnh Reforming th phn ng (8) bt u c thc hin ti sinh xc tc. Nh cc van chuyn hng m ngi ta thay i dng nguyn liu vo Reforming
76

hoc ti sinh. T dy chuyn ny ngi ta nhn xng vi tr s octan t ti 100 102 (RON). S ln ti sinh xc tc c nng cao hn so vi s c thi gian gia hai ln ti sinh di ( hng chc ln so vi 2 6 ln tng ng).

IX So snh cc loi xng.

Xng c a phn loi hoc theo phng php ch luyn t du m nh: Xng chng ct trc tip, xng cracking nhit, xng cracking xc tc, xng reforming. 1. Xng chng ct trc tip. L loi xng ly trc tip t du m trong cha 60 80% parafin thng, 12 13% naphten. 3 10% hydro cacbon thm, v c tr s octan t 43 53. Nhc im ca loi xng ny c tr s octan thp nn cht lng khng cao. 2. Xng Cracking nhit. L loi xng thu c do s b gy mnh cc cht c phn t lng ln c tr s octan 60 68 nhng cng yu cu v ch s octan cho xng thng dng. Nhc im ca xng cracking nhit mun s dng c th phi ch bin tip, pha thm ch hoc i ch bin ho hc. u im l c tr s octan va s dng. Xng cracking nhit chim mt lng ln olephin do vy khng tt. 3. Xng Cracking xc tc.
77

Xng cracking xc tc l ch yu thng thu t 30 35% nguyn liu em cracking. Cht lng ca xng thng ph thucvo cht lng ca nguyn liu, nu nguyn liu cha nhiu naphten th xng thu c c cht lng cao hn so vi nguyn liu cha nhiu parafin. Tr s octan l 87 91. Thnh phn 9 10% olephin. 20 30% aren cn li l naphten v parafin. u im ca xng ny dng trc tip lm xng t thng dng v mt s t cho xng my bay, v c ch s octan cao. Nhc im: Vn phi pha thm ph gia tng tr s octan, tch bt olephin hm lng ca n <3% ( Nu olephin nhiu th to cn, to tn khi chy ). 4. Xng reforming xc tc. c trng ca xng reforming xctc l: Tr s octan 100 105. Hm lng olephin <3%. Hm lng naphten <10% Cn li l thm v iso parafin. Xng reforming l loi xng tt nht s dng lm xng my bay v mt s t cho xng t.

78

Xng Reforming xctc l loi xng quan trng nht v n c hm lng cc hp cht thm v tr s octan rt cao v n nh, hm lng sunfua, nha thp. Xng Reforming thnh phn chnh l sn xut xng khng ch, c tnh ca n, ph thuc vo nguyn liu ban u v cht lng ca xc tc, ch cng ngh. u im: Tr s octan cao, lng olephin thp nn n nh oxy ho rt cao (1700 1800 pht) thun li cho qu trnh bo qun, tn cha v vn chuyn. Nhc im: t phn nh, trong qu trnh khng xy ra s ct mch cacbon to hydro cacbon nh nn t trng ca xng cao, p sut hi bo ho thp, s phn b thnh phn phn on khng u nn ng c s kh khi ng nu nhit thp v lm vic ch khng n nh.

X - c tnh du th Vit Nam & tim nng v cht lng sn phm thu c.
Du th Vit Nam thuc loi du ngt, t lu hunh ( 0,03 0,14%) c nhit ng c cao ( 15 350C) do hm lng parafin ln. Mt s thuc tnh nh nh DT-BHOligixen ( 38,2API), DT-BH y (37,3API) mt loi trung bnh nh DT-R- y(36,15API), DH-AX(36,9API) v loi nng c DT-BH-Mioxen (31,4API) DT-DH-IP, 2P, 3P v DT-R6. Hu ht cc du th c nht rt thp ( nht ng hc 500C < 10cts), ngoi ra du th cn c cc hm lng kim loi

79

gy nhim xc tc rt thp ( Vanadi v Niken<1ppm ). Mc d du th cc va ca cng mt m c tnh cht khc nhau nhng khi khai thc cng c trn ln tu theo sn lng ca cc va du. Du th BH ang c khai thc hin nay thuc 3 tng mioken, Oligoxen v tng y cn DT-DH l hn hp du t ging khoan 4X, 4P, 2P v 3P l hn hp du th BH tng i n nh v t l du ca cc tng d cht lng du th hn hp tng i n nh. Du th H hn hp c cht lng cha n nh v mi giai on khai thc ban u. Mc d khi thay i t l pha trn, gia cc loi du s thay i hiu sut cc phn on sn phm, nhng cc c tnh c bn ca hn hp du khng thay i nhiu. Bng 15: Mt s tnh cht c bn ca du th cc tng, cc ging khoan thuc m Bch H, i Hng v Rng. Tnh cht du T trng( API) Khi lng ring (150C,g/ml) Lu huynh %TL im chy ( 0C)
80
0

Bch H BH BH OHM 31.40 0,868 O 38.2 0 0,83 4 0,14 34 0,04 34 D 37.3 0 0,83 8 0,04 34

4X

i Hng 2P

3P

R-6 22.1 5 0,92 0

Rng R-7 37.3 2 0,83 8 0,04 33

R- 36.1 5 0,84 3 0,07 34

36.9 30.00 30.83 0 0,84 0,872 0,874 0 0,0 4 15 0,01 27 0,13 28

0,12 31

 nht 500C(sct) Nha Asphalten %TL

19,4 7 16,7 0

6,51 1,31

7,89 7,14

4,7 4 5,2 9

8,73 9,96

8,82 10,7 1

76,0 0 18,9

8,13 4,11

8,40 6,96

Thnh phn chng ct ca du th Vit Nam so vi c cu nhu cu sn phm ca th trng Vit Nam c s chnh lch: Thnh phn ct nh t hn nhu cu xng. Phn ct trung bnh t hn nhu cu DO + JetFuee + Du ho. Phn cn kh quyn nhiu hn nhu cu FO, nha ng, du nht. Ngoi ra gi tr du th Vit Nam trn th trng khu vc lun lun mc cao do cht lng tt, p ng nhu cu bo v mi trng cc nc cng nghip pht trin. Bng 16: c tnh du th Vit Nam Bch H T trng API Lu hunh (%TL) Nickel + Vanadium (ppm) Nitrogen(ppm) im ng c (0C) 300 30,6 400 33,5 300 26 40,9 0,03 1,1 i Hng 34,2 0,08 4,0 Rng 22,1 0,10 12,1

81

Trong cc m du ang khai thc hin nay Vit Nam, quan trng nht l m Bch H v i Hng du th khai thc thng mi t hai m ny chim 80 90% tng sn lng Vit Nam trong thi gian qua v c hin nay. V vy, du th Bch H v i Hng c xem l hai loi du tiu biu nht ca Vit Nam v c th gii bit n. Du th Bch H v i Hng thuc loi du nh n trung bnh, du th Bch H c t trng 60/600F l 0,8258 tc l 39,850 API thuc loi du nh trong khi du th i Hng c t trng 60/600F l 0,8822 tc l 26,060 API thuc loi du trung bnh. Du th Bch H v i Hng thuc h du parafin, c bit cha nhiu hydro cacbon n-parafin C10 Hm lng parafin du th Bch H v i Hng cha 29% v 17%. Bng 17: Tnh cht c bn ca du. Tnh cht du th Du th Bch H Du th i Hng Mioxen T trng d20/4 ( cst) Trng lng phn t Nhit ng c 0C Hm lng parafin %TL 362 34 21,3
82

Oligoxe n 0,8297 6,51 264 34 32,5

Tng y 0,8339 7,89 255 34 25,6

i Hng 1 0,8479 3,92 288 33,5 31,4

0,8645

nht ng hc 500C 19,47

Ch s cc %TL Hm lng nha %TL Hm lng asphalten %TL Nguyn t %TL Cacbon Hydro Nit Lu hunh Thnh phn chng ct %TL n 2000C n 3500C n 5000C Vanadium (ppm) Niken

5,2 14,0 2,7 85,96 13,40 0,22 0,14

0.77 1,14 0,17 83,24 14,29 0,04 0,04

0,53 6,50 0,64 83,89 14,00 0,035 0,04

0,52 2,02 0,15 83,44 13,86 0,037 0,08

14,10 37,80 67,60 2,50 21,00

18,89 46,56 77,50 <2 <2

18,54 48,64 79,88 <2 <2

20,78 55,51 89,53 <2 <2

Bng 18: c tnh tng qut ca du th Bch H va i Hng ( dng thng mi ) Cc c tnh T trong 0API T trng d60/600F Khi lng ring 150C (g/mml) Kh trong du C1C4 %TL Lu hunh %TL 0,03 0,01 0,08 Vt Bch H 39,85 0,8258 0,8254 i Hng 29,06 0,8822 0,8813

83

im chy, 0C Hng s c trng K(UOP) nht ng hc (cst) 500C 1000C

35 12,58 ` 5,34 0,44

25 11,90

8,76 5,60

Tim nng v cht lng cc sn phm chnh thu c. a. Cc phn on naphta: Naphta la thnh phn chnh sn xut xng t hiu sut naphta c tnh theo phn trm trng lng ca du. b. Phn on du ho Jet/kerosene: Kerosene t DT-BH v DT-H c hiu sut khng cao phn on si 140 2600C ca H-BH l 19%TL. c. Phn on Gasoil nh: Cc phn on gasoil nh l phn on ch yu sn xut nhin liu cho ng c diezel.
d. Phn on gasoil nng ( t chng ct chn khng VGO

360 5400C)
e. Cn chng ct kh quyn ( c nhit si >3600C).

Hiu sut cn chng ct kh quyn ca c hai loi du ny u kh cao. Cn ny ca du BH v H l nguyn liu tt cho qu trnh ch bin su.
84

Hiu sut cn chng ct kh quyn rt cao, c cht lng FO tt song gi vn thp hn gi ca du th do mun ch bin du th c hiu qu kinh t th khng th ch bin su.
f. Cn chng ct chn khng( t0 si >5400C)

C hm lng asphaten v ch s cc thp, c th dng lm nguyn liu sn xut nha ng. Qua , c hai du th BH v H u l loi c cht lng tt cho qu trnh cng ngh ch bin, nht l ch bin su. Vy du th Vit Nam cn qua phn xng Reforming xc tc tng cht lng ca sn phm.

85

C-Kt lun.
Nhu cu v xng c tr s octan cao m khng phi pha thm ch lm cho qu trnh Reforming tr thnh mt qu trnh lc du quan trng v cho ta thy tm quan trng ca bn n ny. Nhng kt lun c th tng kt t bn n ny nh sau: 1- Reforming l mt qu trnh phc tp gm mt lot cc phm ng to nhit v thu nhit, trong quan trng nht l phn ng dehydro ho naphta thnh cc hp cht thm. Qu trnh nhm mc ch thu xng c cht lng cao v cc sn phm BTX lm nguyn liu cho tng hp ho du, ngoi ra hydro thu c t qu trnh Reforming cung cp cho nhiu qu trnh cng nghip khc vi s lng nhiu nht, r nht.
2- Xc tc ca qu trnh l xc tc 2 chc nng. Chc nng

hydro ho - dehydro ho l nh kim loi, chc nng isome ho l nh tnh axit ca cht mang. Xc tc ph bin l Pt/Al2O3. Cn xc tc hai hoc nhiu kim loi trn mt s cht mang khc nh oxit sillic, zeolit cng t ra c tc dng tt.
3- Nguyn liu m qu trnh s dng tt nht l xng chng ct

trc tip c hm lng naphten cao. thu xng c tr s

86

octan cao s dng phn on c nhit si t 85 1800C cn thu BTX th s dng phn on hp hn c nhit si t 62 1400C.
4- iu kin tin hnh qu trnh l nhit v p sut cao

thng l 5000C v 30 35at. p sut ring phn ca hydro l mt nhn t nh hng quan trng n qu trnh. Cc nhn t vn tc th tch, t l H2/HC c tnh ca thit b cng nh hng quan trng n qu trnh. 5- S kh hot tnh xc tc ch yu l do s to cc trn b mt. Do vy, mt thi gian nht nh thng phi ti sinh xc tc bng cch oxy ho cc bng khng kh, cc phng php ti sinh khc nh kh bng hydro v Clo ho cng c p dng hp th nhng cht gy ng c (S,N...) v cp li axit cho xc tc. 6- Trong cng nghip, qu trnh c tin hnh trong nhng h thng bn ti sinh, tun hon, tng si hay lp xc tc chuyn ng. Qu trnh sn xut lin tc bng h thng xc tc chuyn ng l u vit hn c. Trong mi Cng ty u a ra nhng quy trnh cng ngh khc nhau nhng ni ting nht l Platforming ca hng UOP, M. 7- Bn n ny cng tnh ton c cn bng vt cht, cn bng nhit lng v s lc v kch thc ca thit b chnh trong phn xng Reforming xc tc vi cng sut 1,2 triu tn/nm.

87

88