QU TRNH REFORMING XC TC I.

Gii thiu chung

Ngy nay vic s dng cc ng c c h s nn cao i hi cht lng nhin liu, c bit l ch s octan cao. p ng yu cu , ngi ta pha trn vo xng cc ph gia hoc tng cng cc hp phn hydrocacbon cho ch s octan cao. Hin ti vi cc tiu chun nghim ngt v mi trng mt loi ph gia truyn thng l tetraetyl ch, tuy lm tng ch s octan ln 15-20 s nhng li gy c hi i vi sc khe con ngi, nn gn nh c loi b hon ton. i vi cc ph gia thay th hu hiu nh MTBE, TAME cng c mt s kin nghi ng v kh nng chm phn hy ca chng trong mi trng. Hin ti Vit nam xut hin mt s ph gia mi cha Mn, Fe c th thay th tm thi cc ph gia truyn thng. Nhng cc ph gia trn c s kim loi ny cng cn gy nhiu tranh lun, cn c tip tc lm sng t v kh nng nhim mi trng. Ngi ta c xu hng la chn phng n th hai, tng cng cc hp phn pha ch t cc qu trnh ch bin su nh cracking, reforming, ng phn haCc hp phn ny cho ch s octan cao hn nhiu so vi xng t chng ct trc tip, m li t gy nhim mi trng. Xng pha trn nhm mc ch t nhng ch tiu quan trng sau : p sut hi bo ha (RVP- Reid Vapor Pressure) : o p sut hi ca cc hydrocacbon, cn thit cho s khi ng ca ng c. Ch s octan : o mc chng kch n ca xng, ch tiu quan trng v ng c kch n thp s hot ng hiu qu hn v tit kim c nng lng. c hi : o cc hp phn c hi trong xng. Cc nh my lc du thng ch n hm lng benzen, olefin, lu hunh. Ch s octan l i lng c quan tm hn c v thng c la chn nh gi v iu chnh cht lng xng. Ty thuc vo ch s octan m ngi ta c th chia thnh xng thng (regular) hoc xng cht lng cao (premium). nhiu nc, cc phng tin vn ti la chn mc cht lng xng theo ch s octan theo s hng dn ca cc nh ch to ng c. C 2 mc cht lng 87 v 89, thng s dng mc 87 hn. Cn hiu y l gi tri trung bnh gia ch s octan o theo phng php nghin cu v ch s octan o theo phng php m t: (RON+MON)/2. cc cy xng VN ngi ta nim yt gi xng theo ch s RON. C th thy i vi phn on xng nh (ts-80oC) tng i kh c th ci thin ch s octan bng cc chuyn ha ho hc, ngoi tr mt qu trnh duy nht c th p dng, l ng phn ha, trong cc n-parafin c chuyn thnh cc isoparafin, lm tng ng k ch s octan. Vi cc phn a xng nng (ts > 800C) giu parafin v naphten c th lm tng ch s octan nu chuyn ha chng thnh cc hydrocacbon thm (aromatics). y chnh l nguyn tc ca qu trnh reforming xc tc.
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Reforming xc tc l qu trnh lc du nhm chuyn ha phn on naphta nng c chng ct trc tip t du th hoc t mt s qu trnh ch bin th cp khc nh FCC, hidrocracking, visbreaking, c ch s octan thp (RON =30-50) thnh hp phn c s ca xng thng phm c ch s octan cao (RON =95-104). V mt bn cht ha hc y l qu trnh chuyn ha cc n-parafin v naphten c mt trong phn on thnh cc hydrocacbon thm. Chnh cc hydrocacbon thm vi ch s octan rt cao lm cho xng reforming c ch s octan cao ng hng u trong s cc xng thnh phn.

Hnh 1: Cc phn ng chnh trong qu trnh reforming

Thnh phn xng thng dng hin nay trn th gii thng cha : Xng cracking xc tc : 35% t.t Xng reforming xc tc : 30% t.t Xng alkyl ha : 20% t.t Xng isomer ha : 15% t.t T cc s liu trn cho thy, xng reforming ng th hai trong xng thng phm, ch sau xng cracking. Thm ch mt s khu vc nh M, Ty u, xng reforming c phn vt tri. Phn b thnh phn xng thng mi M Mt s tnh cht ca reformat : - Thnh phn ct: thng thng t 35 190C - T trng : 0,76 0,78 - Ch s octan RON : 94 103 (tu thuc iu kin cng ngh) Do v tr quan trng ca xng reforming trong thnh phn xng thng phm, c bit l xng cht lng cao m hin nay trong mi nh my lc du trn th gii thng c ti
Hnh 2: Phn b thnh phn xng thng mi

ti m.

thiu l mt phn xng reforming xc tc. Cng sut ch bin nm trong khong 40 tn/gi n 150 tn/gi. Tng cng sut ca cc phn xng reforming xc tc trong tt c cc nh my lc du Php ln ti 18 triu tn trong mt nm. Ngoi ra, reforming cn cung cp nguyn liu BTX cho ho du v cung cp H2 cho qu trnh x l v chuyn ho bng H2 trong nh my lc du. Mc ch ca qu trnh RC l chuyn ha cc hydrocarbon paraffin v naphthene c trong phn on xng thnh aromatic c tr s octane cao cho xng, cc hp cht hydrocarbon thm (B, T, X) cho tng hp ha du v ha hc, ngoi ra cn cho php nhn c kh hydro k thut (hm lng H2 n 85%) II. Nguyn liu v sn phm

* Nguyn liu ca qu trnh Xut x: Xng t chng ct trc tip, Xng t qu trnh Visbreaking, Hydrocracking, phn on gia ca sn phm FCC. Thnh phn: Hn hp hydrocarbon t C7 n C11 (trong trng hp nh my khng c phn xng isomerisation c th s dng phn on C5 n C11). Tnh cht: Khong chng ct: 60-180C T trng: 0.7-0.8 g/cm3 Trng lng phn t trung bnh: 100-110 RON: 40-60 Thnh phn nhm: Paraffin : 40-60 wt% Olefin : 0 wt% Naphtene : 20-30 wt% Aromatic : 10-15 wt% Hm lng tp cht: Xc tc rt nhy vi cc cht c c trong nguyn liu, do cn thit phi lm sch nguyn liu (dng cc cng ngh lm sch HDS, HDN, HDM). Gii hn tp cht cho php trong nguyn liu (sau khi lm sch): S < 1ppm N (hu c) 1 ppm H2O (v cc hp cht cha oxy) 4 ppm Kim loi (As, Cu, Pb...) 15 ppb Olefin v cc diolefin = 0 Halogen (F) 1 ppm Metals (Pb, As, Sb, Cu...) < 1ppb V nguyn tc ngi ta c th s dng phn on naphta t 60180oC tin hnh qu trnh reforming. Nhng ngy nay ngi ta thng s dng cc phn on c gii hn si u 80oC lm nguyn liu. Gii hn si u uc thit lp nh vy nhm loi bt
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cc hp phn C6 d chuyn ha thnh benzen l mt hp cht c hi, cn tin ti loi b theo tiu chun mi v mi trng. Gii hn si cui ca nguyn liu thng c chn trong khong 165180 Gii hn si cui ca nguyn liu khng nn cao qu 180 oC v xng reforming cha nhiu hydrocacbon thm, c nhit si ln hn nguyn liu khong 20C. M gii hn si cui ca xng thnh phm (cha t 40-50% reformat) theo tiu chun th gii ch cho php n 200-2050C. Ngoi ra nu im si cui ca nguyn liu qu cao s dn ti qu trnh cc ha cc hydrocacbon nng, lm gim hot tnh xc tc.
C.

nh hng chiu di mch cacbon (lin quan n im si cui ca nguyn liu) n chuyn ha naphten t thy r v phn ng xy ra nhanh. i vi parafin, chiu di mch cng tang (trong phn t cng cao) th qu trnh dehydro vng ha cng thun li. Tuy nhin mch cacbon cng cng d gy hn do cracking. Phn ng dehydro ha naphten vng ha parafin thnh hp cht thm. Nh vy, nguyn liu cng giu parafin cng kh chuyn ha thnh reformet so vi nguyn liu giu naphten. C th m t nh tnh s chuyn ha trn hai phn on nh hnh sau: V vy, t uc cht lng sn phm mong mun (v d, vi RON nh trc) nguyn liu giu parafin i hi nhit phn ng cao hn ( tng khc nghit ha ca qu trnh). Trong cng nghip ngi ta thng nh gi kh nng chuyn ha ca nguyn liu thnh sn phm thm da vo gi tr N+2A (N, A Hnh 3: nh tnh s chuyn ha trn 2 phn on % trng lng ca naphten v aromat tng ng c trong nguyn liu). Gi tr ny cng cao th kh nng thm ha cng ln, khc nghit ca qu trnh vn hnh cng gim. Ch s N+2A bin thin trong khong 3080. Hng UOP (M) c a ra h s KUOP c lin quan n ch s N+2A theo cng thc sau: KUOP = 12,6 (N+2A)/100. Vi mc ch sn xut BTX cho ha du th vic la chn ngun nguyn liu v gii hn im ct phn on ng vai tr quan trng. thu tng BTX ngi ta thng chn phn on 60- 145C. Nu ch thu benzen chn phn on 65-85C. Thu toluen chn phn on 85-120C. Thu xylen chn phn on 120-145C.

Bng 1: Thnh phn v tnh cht ca mt s nguyn liu reforming

Naphta trung Naphta Trung Naphta bnh t ng parafin hydrocracking rp) ASDTM D86, C IBP 10% 30% 50% 70% 90% FBP Thnh phn,% V Parafin Naphten Aromatic N+2A RON d415

giu Naphta ( giu naphten (Nigeria)

98 115 127 140 157 180 201

81 105 113 119 129 143 166

92 106 115 123 132 147 155

88 107 115 123 132 145 161

33 55 12 79 62 0,775

45 45 10 65 55 0,754

66,8 21,8 11,4 44,6 50 0,716

29,3 61,9 8,8 79,6 66 0,779

Trong cng nghip nguyn liu cn c x l nhm mc ch loi tr cc cht u c xc tc reforming (hp cht S, N, nc, cc kim loi), iu chnh im ct nguyn liu ph hp C th tm tt cc bc x l s b nguyn liu nh sau: Cho nguyn liu v hidro i qua l phn ng c cha xc tc NiMo (hoc CoMo) nhm loi tr cc kim loi, cc hp cht cha lu hunh v hp cht cha nit (gi chung l cc qu trnh x l dng hidro). Trong trng hp nguyn liu l cc phn on xng cracking cn thm giai on x l lm no ha olefin nhm loi tr kh nng to nha. Tip theo cho nguyn liu qua ct tch loi H2S v nc. Trong nhiu trng hp, cn tch phn on xng nh ( a vo phn xng isomer C5/C6) ra khi phn on xng nng (dng cho reforming xc tc). * Hydro ha lm sch nguyn liu - Tch lu hunh: - Mercaptan: - Sunfit: - Disunfit: - Sunfit vng: - Thiophen:
S

- Tch nit: - Pyridin:

N

- Quinolin:
N

- Pyrol:
OH

- Tch oxy: - Phenol: - Phn ng vi olefin:

+ H2 O

Olefin vng (Naphten) - Tch kim loi: Cc kim loi trong hp cht c kim c tch ra bi s phn hy cc kim loi, b gi li trong xc tc hoc do hp ph hoc phn ng ha hc vi xc tc. - Tch halogen: Cc halogen hu c c phn hy hon ton trn xc tc to thnh cc mui v c, chng c tch ra khi ta phun nc hn ch ti a s n mn thit b. - S ti hp ca sunfua hydro vi olefin to mercaptan: Hm lc ca cc hp cht cn tch s c khng ch bng iu kin cng ngh ca qu trnh.

* Sn phm ca qu trnh RC C th m t mi theo gin sau :

Bng 2: tng quan gia nguyn liu v sn phm ca qu trnh reforming xc tc

Nh vy, t naphta nng ban u vi ch s octan thp sau khi tin hnh reforming xc tc, ngi ta thu c cc sn phm vi hiu sut sau: Reformat (xng C5+ ) : 80 - 92% C4 : 3 - 11% C3 : 2 - 9% Kh nhin liu C1-C2 : 2 - 4% Hidro : 1,5 - 3,5 % Trong cc sn phm quan trng hn c l reformat (xng C5+), cc hydrocacbon thm - m ch yu l benzen, toluen, xylen (BTX) v kh hydro k thut. 1. Sn phm xng reforming xc tc Mt s tnh cht ca xng (reformat) : Thnh phn ct: thng thng t 35190oC T trng: 0,76 0,78 Ch s octan RON: 94 103 Thnh phn hydrocacbon: ch yu l aromatic v paraffin, naphten ch chim < 10%, olefin khng ng k. Do c cht lng cao (ch s octan cao nht trong s cc xng thnh phn, thu c t qu trnh lc du), hm lng olefin li rt thp nn xng reforming c th s dng lm xng my bay. S thay i thnh phn v tnh cht ca xng reformat trong cc gii hn nu trn ph thuc vo nguyn liu ban u, iu kin cng ngh, cht xc tc. V d tng quan gia nguyn liu l naptha Trung ng v sn phm reforming trnh by trn bng sau.

Bng 3:So snh Nguyn liu Sn phm reforming t du th Trung ng:

d415 IBP Nguyn liu Sn phm C5+ 0,754 0,701 81 60

ASTM D86 10 % 105 93 50 % 119 118 90 % 143 152 166 185 FBP

Thnh phn , %V P N A N+2A 65 115

RON

45 45 10 40 5 55

55 95

* Thnh phn parafin trong nguyn liu kh nh hng n cht lng xng C5+. Nu ch s dng ton b reformat lm xng thng phm s khng kinh t, do hm lng hydrocacbon thm qu cao, to nhiu cn trong ng c v gy nhim mi trng. Xng ny li c p sut hi bo ha thp, lm cho ng c kh khi ng. Chnh v vy ngi ta a vo xng thng phm cc hp phn khc nh xng ng phn ha, xng alkylat, butan, MTBE... 2. Kh hydro k thut y l sn phm kh quan trng ca qu trnh reforming xc tc. Hm lng hydro trong kh chim 70 90%. Thnh phn nguyn liu, cht xc tc v iu kin cng ngh cng nh hng n hm lng hydro trong kh. Kh ny mt phn c s dng li cho qu trnh reforming, cn phn ln c s dng cho cc qu trnh lm sch bng hydro (HDS, HDN, HDM...) hoc cc qu trnh chuyn ha c hydro (hydrocracking, hydroisomer ha). y l ngun thu hydro kh r, hiu sut cao ( thu c khong 90 120 Nm3/m3 nguyn liu) v c th lm sch tu mc ch s dng. Vic ci tin cng ngh, xc tc cho qu trnh reforming nhm lm tng hiu sut xng th cng ko theo s gia tng hm lng H2 trong sn phm v thc y thm s pht trin cc qu trnh s dng hydro. 3. Kh ho lng LPG Kh ha lng thu c sau khi cho sn phm i qua thp n nh xng, bao gm ch yu propan v butan. Hiu sut kh ph thuc vo tnh cht ca cht xc tc m trc tin l axit. y l sn phm khng mong mun trong iu kin reforming, v s lm gim hiu sut ca sn phm chnh l reformat. 4. Sn phm hydrocacbon thm Qu trnh reforming cn cung cp ngun nguyn liu BTX (benzen- toluen-xylen) cho ha du. Cc sn phm thm trong qu trnh ny chim ti 65-75% trong tng sn phm lng hoc c th cao hn na vi cc cng ngh v xc tc hin i. Trong c bit quan trng l paraxylen- nguyn liu cho sn xut cht do, si tng hp, cao su nhn to, nguyn liu cho cng nghip dc phm, m phm, thuc nhum III. Cc phn ng ha hc
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Nguyn liu ban u cho reforming ch yu l phn on naphta nng, c nhit si nm trong khong 80-180oC, cha nhiu parafin v naphten, di tc ng ca nhit cao (khong 480-540oC), xc tc a chc nng v mt p sut va phi (530 atm ), c th xy ra cc hng chuyn ha c bn sau: 1. Dehydro ha naphten thnh hydrocacbon thm.
R R

3 H2

(+50 kcal/mol)

y l phn ng thu nhit mnh. Khi tng nhit v gim p sut hiu sut Hydrocacbon thm s tng ln. 2. Phn ng dehydro vng ha n-parafin.
R

4 H2

Phn ng ny xy ra kh hn so vi phn ng ca naphten. Ch nhit cao mi c th nhn c hiu sut hydrocacbon thm ng k. Khi tng chiu di mch cacbon trong parafin, hng s cn bng to hydrocacbon thm cng tng ln. Phn ng ny l mt trong nhng phn ng quan trng nht ca reforming xc tc. Cho php bin i mt lng ln cc hp cht c tr s octan thp ca nguyn liu thnh cc hydrocacbon thm l cc cu t c ch s octan cao. 3. Hydroizome ha. a. Phn ng izome ha n-parafin.

Phn ng t cn bng trong vng lm vic ca reactor iu kin 5000C vi xc tc Pt/Al2O3 nh sau: Vi n-C6 l 30%; n-C5 l 40%; n-C4 l 60% b. Phn ng dehydroizome ha cc alkyl zyclopentan
R R
1

4. Hydrocracking parafin v naphten. i vi parafin, thng xy ra cc phn ng hydrocracking v hydrogenolyse: (Phn ng hydrogenolyse) Vi naphten:
R1

+ H2
R2

R3H

R4H

R3H

Ngoi ra cn phn ng hydrodealkyl ha cc hydrocacbon thm:

H2

Tc dng ca cc phn ng ny trong qu trnh reforming l gp phn lm tng NO cho sn phm, v to ra nhiu izo-parafin. 5. Phn ng to cc S to cc trong qu trnh reforming l khng mong mun, nhng do s tng tc ca olefin, diolefin v cc hp cht thm a vng m to thnh cc. Cc s kh to ra nu ta thao tc iu kin nhit thp, p sut cao v t l H 2/RH cao. Phn ng to cc l mt loi phn ng phc tp, cc nghin cu v thc t sn xut u cho thy, s to cc ph thuc vo nhiu yu t : Nhit phn ng p sut ca hydro nng ca nguyn liu v chnh l cc hp cht phi hydrocacbon, olefin v cc hp cht thm a vng l cc hp cht gp phn thc y nhanh qu trnh to cc.

IV.

C ch phn ng qu trnh RC

nh hng nhit ng hc n c ch phn ng: Nhit phn ng ca mt s phn ng chnh trong qu trnh reforming c nu trong bng sau:
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Bng 4: Nhit phn ng ca mt s qu trnh STT Phn ng H (Kcal/mol) 1 2 3 4 5 Dehydro ha parafin Dehydro ha naphten Dehydro vng ha parafin ng phn ha parafin Hydrocracking 31,5 52,8 63,6 -1 -5 -10

Dehydro ha naphten v dehydro vng ha parafin l cc phn ng thu nhit mnh (endothermic), dehyro ha parafin thu nhit va phi, cn ng phn ha parafin to nhit nh (exothermic). Ba phn ng u xy ra thun nghch, c s gia tng s phn t trong sn phm phn ng (do hnh thnh H2), nn thun li nhit cao, p sut thp.
Bng 5: Ph thuc nhit cn bng t chuyn ha 90% vo p sut

Phn ng

Nhit cn bng chuyn ha 90%, oC 1 atm 10 atm 355 391 487 428 391 15 atm 443 492 562 496 492 50 atm 487 540 623 550 540

1. Dehydro ha : Cyclohexan Benzene + 3H2 MethylCyclohexan Toluene + 3H2 2. Dehydro vng ha : n-Hexan n-Heptan Benzene + 4H2 Toluene + 4H2

294 315 354 305 315

3. Dehydro ng phn ho : MethylCyclopentane Benzene+ 3H2

T bng trn, iu kin l thuyt thun li v p sut v nhit c th t chuyn ha 90% cho cc phn ng thm ha l 1atm v khng qu 350oC. Tuy nhin trong thc t ngi ta khng tin hnh qu trnh reforming iu kin trn, l do ti sao chng ta s xem xt tip theo trong phn ng hc. nh hng ca nhit v p sut n cn bng nhit ng gia parafin v aromatic t C6 n C9 c biu din trn hnh sau:

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T hnh chng ta thy, nu tng p sut H2 ln qu cao (30atm) s lm gim hm lng cc hydrocacbon thm to thnh, c bit i vi cc hydocacbon c s C thp hn. Chng ta cng thy, i vi hydrocacbon no c trng lng phn t cng cao th hiu ng thun li ca nhit v p sut cng r rt. Ngha l trong cng mt iu kin, cc hydrocacbon mch di hn (c s nguyn t cacbon cao hn) s d chuyn ha thnh sn phm thm hn.
Hnh 4: Cn bng nhit ng hc cc phn ng ca qu trnh reforming

Nghin cu nh hng nhit v p sut n tc cc phn ng khng mong mun l cc ha v cracking, ngi ta nhn thy: Tc hnh thnh cc gim khi tng p sut H2 v gim nhit phn ng, tc cracking gim khi gim p sut H2 v gim nhit phn ng. Mt khc, nh phn nhit ng hc nu, vic tng p sut hoc lm gim nhit u nh hng khng thun li n qu trnh chnh to cc sn phm thm. V vy, trong thc t ngi ta cn c s la chn cc thng s vn hnh ti u tha mn c hai yu t nhit ng hc v ng hc, ngha l bo m cho hiu sut cc phn ng thm ha cao ng thi hn ch cc sn phm cracking v cc ha (v d t 3 -4% cc trn trng lng xc tc trong khong 6-12 thng). Trong cng ngh bn ti sinh ngi ta chn p sut vn hnh khong 10-20 atm, trong cng ngh CCR chn p sut t 3,5-4 atm v nhit phn ng l 500oC. Nh trn nu, trong iu kin reforming, thun li cho cc phn ng chnh l dehydro ha naphten, dehydro ng vng ha parafin, dehydro ng phn ha naphten v ng phn ha parafin. Ba phn ng u to nn cc sn phm l hydrocacbon thm v phn ng cui cho sn phm l cc parafin mch nhnh. Chnh cc sn phm ny ng gp vai tr chnh lm cho ch s octan ca xng thu c sau qu trnh reforming (cn gi l reformat) tng ln rt nhiu so vi nguyn liu naphta ban u. RON nguyn liu = 40-60 RON sn phm = 95-105 Ty thuc vo hiu sut reformat thu c m ch s octan c th cao hn hay thp hn. V d, reforming vi cng ngh bn ti sinh cho hiu sut xng ~ 80% th RON t ~90 cng ngh ti sinh lin tc cho hiu sut reformat ~ 90% cho RON ~100.

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V.

Xc tc s dng cho qu trnh Reforming

Xc tc reforming l xc tc lng chc nng do trong thnh phn ca n cha hai pha c th thc hin hai chc nng chnh sau: Chc nng hydro-dehydro ha c thc hin bi cc kim loi dng phn tn Chc nng axit nhm sp xp li cc mch cacbon (ng phn ha, ng vng ..) c thc hin bi oxyt nhm c b mt ring ln v c clo ha iu chnh lc axit thch hp. Chc nng kim loi ng vai tr chnh, gip hnh thnh cc hp cht hydrocacbon khng no v dehydro ho cc naphten. Cn thit lp c s cn bng gia hai chc nng c th c hot tnh xc tc cao v la chn tt. Nu xc tc qu axt s d xy ra cracking lm gim nhanh hot tnh xc tc. Trong cng nghip ngi ta lun kim tra hm lng Cl- a vo m bo cn bng trn lun n nh. S di y m t tng qut cc phn ng chnh xy ra trong qu trnh reforming vi s tham gia ca hai loi tm xc tc: Nghin cu cc phn ng dehydro ha v dehydro ng vng ha cc hydrocacbon ring r nh cyclohexan, n-heptan ... ngi ta thy vic a cc kim loi ph gia nh Re, Sn, Ir, Ge (cn gi l cc cht xc tin) lm tng tc phn ng dehydro ha v dehydro vng ha (nht l vng p sut thp) ca h xc tc lng kim so vi xc tc ch cha Pt. vng p sut thp, cc kim loi ph gia cng ng vai tr quan trng trong vic gim tc cracking v hydro phn (hydrogenolysis) t lm gim kh nng to cc v tng hiu sut sn phm chnh. nh hung ca kim loi th 2 n qu trnh dehydro ha Cyclohexan. Trong s cc h xc tc CH4 + C3H6 C4H10 o lng kim, chng ta thy hai h xc tc Pt-Sn v t C, xc tc C2H6 + C2H4 Pt-Re t ra u vit hn c, chng cho php lm C4H10 o vic p sut thp (<10 atm) m vn bo m t C, xc tc C4H10 hot tnh dehydro ha v dehydro ng vng ha C4H8 + H2 cao. Ring h xc tc Pt-Sn hi c bit, ch th hin hot tnh cao vng p sut thp. Ln hn 5 atm, h xc tc ny khng pht huy c tc dng tch cc so vi Pt v cc h lng kim khc trong phn ng dehydro v dehydrovng ha.
toC, xc tc

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Nu nh thp nin 70 ch khong 30% reformat thu c t h xc tc lng kim th n nhng nm 80 th phn ln ti 80%. Chng ta xem xt k hn v vai tr ca 2 kim loi ph gia c a vo xc tc reforming cng nghip hin nay l Re (Renium) v Sn (Thic). Ngi ta nhn thy Re c cc chc nng sau: thay i c ch to cc v c tc dng bo v kim loi chnh Pt v lm tng bn v tui th xc tc, t lm tng chu k hot ng ca xc tc. Cn Sn th li c cc vai tr nh lin kt vi Pt lm thay i c ch phn ng theo hng c li. Cho hiu sut v la chn theo reformat cao iu kin p sut thp (< 5 atm). Tuy nhin loi xc tc ny km bn hn so vi xc tc cha Re. Vi cc c im trn, ngi ta thng s dng Re trong cng ngh bn ti sinh v Sn trong cng ngh ti sinh lin tc (CCR). C th lit k mt s mc xc tc lng kim mi ca cc hng xc tc tn tui trn th gii : UOP (M) IFP (Php) CCR: CR- 201 Criterion (M) Bn ti sinh: PR- 8, PR- 28 CCR: PS- 20, PS- 40 Exxon KX-120, KX-130, KX-190, KX-200 Amoco PHF-5, PRHP-30, PRHP-35, PRHP-50, PRHP-58 Engelhard (M) RD- 150, E- 501, E- 601 IMP (Mexico) RNA- 1, RNA- 2, RNA- 4, RNA- 4M Lin x (c) A- 56, A- 64, KP-108, KP-110 S mt hot tnh xc tc nh hng u c xc tc
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Bn ti sinh: R-56, R-62, R-72 Bn ti sinh: RG-102, RG-104, RG- 482

Ti sinh lin tc (CCR): R-132, R-134

Cc cht xc tc reforming rt nhy vi cc tp cht c trong nguyn liu v kh tun hon (H2, N2). nh hng u c c th l thun nghch v khng thun nghch. nh hng thun nghch l sau khi cht c thi tc dng, bng bin php x l c bit (qu trnh ti sinh xc tc), b mt v tnh cht xc tc c phc hi tr li. nh hng khng thun nghch l b mt v tnh cht xc tc khng th khi phc li c. Cc cht u c thun nghch Nc v cc hp cht cha oxy: Tc dng vi clo c trong xc tc lm gim tnh axit ca xc tc, t dn ti lm gim hot tnh xc tc. Cc hp cht cha oxy th li d dng to thnh nc trong iu kin reforming. Cn bng H2O/Cl cn c quan tm gi axit n nh cho xc tc. vic a thm Cl vo h trong qu trnh vn hnh l cn thit. Ngoi ra nc cn gy n mn thit b. C th s b loi b nc bng cch cho qua cc ct hp ph cha ry phn t (zeolit 5A). Lng nc cho php trong nguyn liu ti a l 4 ppm. Hp cht cha lu hunh: Trong iu kin reforming s d dng chuyn ha thnh H2S, u c chc nng kim loi do hnh thnh sulfua platin: Pt + H2S Pt S + H2 T , chc nng quan trng nht ca xc tc l dehydro, dehydro ng vng ha b u c. Trong s cc hp cht cha lu hunh th mecaptan (R-S-H) v H2S c nh hng u c ln hn c, lm gim hiu sut v cht lng reformat, lm tng t trng kh cha hydro, tng mc lng ng cc. H2S c tnh axit nn cn gy n mn thit b (Hm lng cho php < 0,5 ppm). Cc hp cht cha nit: Cc hp cht nit hu c d dng chuyn ha thnh amoniac trong iu kin reforming. Cht ny s tc dng vi Cl trong xc tc to NH4Cl, lm gim chc nng axit ca cht xc tc, ko theo s gim hot tnh xc tc, lm tng s hnh thnh hydro. NH4Cl li d bay hi trong vng phn ng lm tng nhit thit b. Mt khc, NH4Cl d kt tinh nhng phn lnh hn ca h thng, gy h hng thit b:

Cc cht u c khng thun nghch:

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a. Cc kim loi kim v kim th lm trung ha tnh axit ca cht mang (Al2O3), to thnh hp cht aluminat kh bn. b. Cc kim loi As, Cu, Pb, Zn, Hg, Si, Fe kt hp vi Pt to mi lin kt bn, u c vnh vin tm kim loi khng phc hi li c.T d lm mt chc nng chnh l hydo-dehydro ho ca xc tc. Cc kim loi ny cn tch t trong c 4 l phn ng, lm gim nhit vng phn ng, dn ti mt hot tnh xc tc tng th (hm lng cho php i vi mi kim loi l 5 ppb). bo v hu hiu cc cht xc tc reforming bin php bt buc v hiu qu trong cng ngh l phi c phn xng x l s b nguyn liu bng hydro (hydrotreating) nhm loi b cc cht c thun nghch v khng thun nghch trn, nht l trong trng hp c s dng nguyn liu t cc ngun ch bin th cp khc (hydrocracking, FCC, visbreaking...) c hm lng ng k cc cht u c trn so vi nguyn liu naphta t ngun du th. VI. Cc phng php hot ha (ti sinh) xc tc Trong qu trnh lm vic xc tc c th b mt mt phn hot tnh xc tc do nh hng ca s lng ng cc trn b mt xc tc, do nh hng ca cc cht u c... Mt iu cn lu l, chng ta cng c gng la chn iu kin vn hnh cho hiu sut xng cao nht hoc ch s octan tt nht (v d, tng nhit hoc gim p sut) th s lng ng cc cng tr nn trm trng hn (xem phn c trng ng hc ca qu trnh reforming). Vi mt lng cc qu ln, s che ph v lm gim ng k s lng cc tm hot ng. Lc , tu thuc vo cu to cht xc tc, s mt i mt phn hoc ton b cc chc nng xc tc. Cn thit phi c qu trnh ti sinh xc tc tr v trng thi hot ng ban u. Qu trnh ny c th c tin hnh bng mt s phng php sau: + Phng php oxy ha (phng php t): Cc lng ng trn b mt cht xc tc c loi b bng cch t chy trong dng khng kh pha long vi Nit nhit 350 500oC. cn ch trnh hin tng qu nhit cc b lm gim b mt, gim bn c hc ca cht mang hoc lm tng qu trnh thiu kt lm gim phn tn kim loi. Chu k ti sinh xc tc ph thuc vo iu kin vn hnh h thng, nhng thng khong 6 thng mt ln. Sau mi ln ti sinh, hot tnh xc tc tr v trng thi ban u, nhng sau nhiu chu k ti sinh xc tc s gi ha v gim kh nng xc tc. Vic ti sinh xc tc s tr nn thng xuyn hn., cho n khi cn phi thay th xc tc mi. Thi gian tn ti ca xc tc reforming thng khong vi nm. Qu trnh t cc c biu din bng phong trnh sau : CnHm + O2 CO2 + H2O + Q y l qu trnh ta nhit, nhng khi nh hng n cht lng xc tc cn gim thiu lng nhit ta ra ( T 0oC ). iu ny cn thit v nhit cao lm gim

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din tch b mt v c th lm thay i pha ca oxyt nhm Al2O3, nhit cao cng lm xy ra qu trnh thiu kt lm gim phn tn ca Pt. Trong cng ngh CCR (ti sinh xc tc lin tc) qu trnh oxy ha c thc hin trong vng t (Burn Zone). + Phng php kh: Thc t cho thy, cc hp cht lu hunh khng c loi b hon ton bng qu trnh oxy ha, cn tn ti ch yu cc hp cht dng sunfat. Phng php kh c tin hnh nhm loi b trit cc dng hp cht ny v.cc kim loi tp c hi trong xc tc, quan trng hn c l kh Pt oxyt v dng Pt n cht. Trong cng ngh CCR, qu trnh kh xy ra ti vng kh (Reduction Zone). + Phng php clo ha: Trong qu trnh lm vic axit ca xc tc gim, mt phn do cc lng ng che ph b mt oxit nhm, mt phn do lng clo trong xc tc gim do nh hng ca H2O trong nguyn liu v trong kh tun hon. Clo cng c th mt do cun theo sn phm phn ng. Do cn phi b sung axit cho h xc tc bng cch bm thm mt lng nh Cl hu c. Lng Cl trn xc tc c gi mc 1% khi lng. Qui trnh ti sinh xc tc Qui trnh ti sinh hon chnh cht xc tc gm cc bc sau: Trng ra h thng: Dng dng nit thi sch cc hydrocacbon cn st li sau phn ng . t cc: t bng dng khng kh pha long vi N2 (c kim sot hm lng oxy trong kh) v nng dn nhit t theo chng trnh: - Nhit : t 370oC n 480oC - Oxy : t 0,5 n 2,0 % th tch Oxy-clo ha: Bm cc tc nhn cha Cl vo h nhm gi n nh lng Cl cn thit cho xc tc (1% trng lng ). - Nhit : 510oC - Oxy: 5% th tch Qu trnh nung: Mc ch lm kh xc tc v phn tn li platin - Nhit : 510oC - Lng oxy : 8% th tch - Thi gian: 4 gi Qu trnh kh: Mc ch nhm chuyn Pt t dng b oxit ha v dng kh (dng hot ng). Loi oxy bng cch trng vi nit. Sau a hydro vo h. - Nhit : 480oC.
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- Hm lng H2 ti thiu 50% th tch. - Thi gian: 4 gi. VII. Cc yu t nh hng. Cc yu t nh hng chnh n qu trnh reforming bao gm: Nhit thit b phn ng p sut thit b phn ng Tc np liu T l mol H2/ nguyn liu Cht lng nguyn liu 1. nh hng nhit Trong cng nghip ng nht vic nh gi hot tnh xc tc vi nhit c cung cp u vo thit b phn ng (i vi nguyn liu c th, RON cho trc). Nhit c th thay i nhm iu chnh cht lng sn phm, v d: Thay i ch s octan ca reformat. Ph thuc cht lng ca nguyn liu np. B tr s gi ha xc tc (gim hot tnh xc tc ) qua nhiu chu k hot ng. B tr mt hot tnh xc tc tm thi do cc tp cht gy ra. Nhit tng lm tng kh nng chuyn ha thnh sn phm thm dn ti tng ch s octan nhng li lm gim hiu sut xng. Ngc li nhit gim c li cho hiu sut xng, gim kh, gim hiu sut to cc. Nhit thng c chn trong cng ngh khong t 490-540oC. 2. Tc np liu c xc nh bng lu lng dng nguyn liu (th tch hoc trng lng) i qua trong 1gi trn 1 n v xc tc (trng lng hoc th tch lp xc tc). Khi tng lu lng nguyn liu hay gim lng xc tc u lm tng tc np liu, ni cch khc l lm gim thi gian tip xc ca cc cht tham gia phn ng vi lp xc tc. Hu qu dn ti lm tng hiu sut reformat (do gim kh), nhng ng thi lm gim cht lng reformat v gim ch s octan. iu ny cng d hiu v cc qu trnh c tc chm nh dehydro ng vng to thm, hydrocracking, dealkyl ha s kh xy ra hn nu thi gian tip xc t. Hiu ng ny c th c b tr nu tng nhit l phn ng. Trong thc t, hn ch bt hyrdrocracking v cc sn phn cc ha ngi ta thng p dng nguyn tc sau : gim tc th tch: gim nhit u vo cc l phn ng sau gim lu lng liu np .
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 tng tc th tch: tng lu lng liu np sau tng nhit l phn ng. C th gim tc th tch tng ch s octan. Tuy nhin trong vn hnh ngi ta khng c php gim tc trn nh hn mt na so vi thit k hoc < 0,75 h-1. V nh vy s khng kinh t, lm tng tc kh hot tnh xc tc. Tc c la chn ph thuc vo cc iu kin cng ngh c th: p sut vn hnh, t l mol H2/nguyn liu, thnh phn nguyn liu a vo v cht lng reformat mong mun. V d cng ngh CCR mi thng chn V = 1,5 -2,5 h-1. 3. p sut vn hnh Cc phn ng chnh c li cho reforming u xy ra thun li p sut thp. p sut cng thp hiu sut reformat v hidro cng cao. Tuy nhin nh hng cc s cng trm trng hn. Do cn la chn p sut thch hp va hn ch qu trnh to cc va t nh hng n hiu sut to xng. p sut vn hnh i vi mt phn xng cng ngh c th l gi tr c nh m ngi ta la chn trc nhm tho mn cht lng sn phm nht nh. Ngy nay nh ci tin cng ngh (s dng cng ngh ti sinh lin tc) v ci tin xc tc (tm c cc h xc tc c th lm vic p sut thp, cho hiu sut xng v RON cao) m ngi ta c th vn hnh qu trnh p sut thp nht m vn p ng yu cu v cht lng sn phm, vn u t v hiu qu kinh t. Cng ngh CCR tin tin nht (platforming, octanizing) s dng xc tc PtSn/Al2O3 cho php vn hnh p sut t 3-5 atm (trc y cn vi chc atm). 4. T l H2/ nguyn liu Xc nh bng t l gia lu lng (mol/h) hydro tun hon v lu lng nguyn liu np (mol/h). Thm mt lng ln kh tun hon cha H2 (80 -90% tl) nhm lm gim s lng ng ca cc trn b mt xc tc ( do tng qu trnh hydro ha cc hp cht khng no trung gian l tin cht to cc). T l H2/NL thay i trong khong rng (1-10). Gii hn di ph thuc lng H2 yu cu nh nht nhm duy tr p sut ring phn ca H2 trong h thng. Gii hn trn xc nh bi cng sut my nn, kch thc l phn ng v tnh kinh t qu trnh. Thay i t l ny t lm thay i cht lng sn phm. Mt khc vi cc cng ngh CCR hin nay p sut thc hin ch >3 atm, gim t l H2/NL trong trng hp ny tng ng vi vic lm gim p sut ring phn ca H2 nn c tc ng thun li n hiu sut sn phm.

VIII. Mt s cng ngh Reforming tiu biu Hin nay trn th gii tn ti 2 loi cng ngh reforming ch yu l cng ngh bn ti sinh v cng ngh ti sinh lin tc (CCR). Cng ngh bn ti sinh
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Mt s c im c bn l: Xc tc c nh. H thng dng nguyn liu c chuyn ng t thit b phn ng ny sang thit b phn ng khc. Ngng hot ng ton b h thng ti sinh cht xc tc ti ch, ngay trong thit b phn ng, khi lng cc trn lp xc tc chim 15-20% trng lng. Thng th chu k lm vic ca xc tc trong khong 6 thng n 1 nm. Thi gian ti sinh xc tc mt khong 2 tun l. Trong mt s cng ngh bn ti sinh ngi ta s dng cc thit b phn ng (reactor) c cc van ng m c lp, hoc lp thm mt thit b phn ng d tr, cho php ti sinh xc tc tng thit b ring bit m khng cn dng ton b h thng. Tuy nhin vn hnh cng ngh cng tr nn phc tp hn. Cng ngh bn ti sinh tng i lu i (cng ngh truyn thng), cc ci tin ch yu ch tp trung vo xc tc. T nhng nm 1949-1950 cht xc tc trn c s Pt (xc tc n kim loi) c a vo s dng cho xc tc tng c nh. Loi xc tc ny tuy cho hot tnh xc tc cao, nhng c nhc im l rt d b cc ha nn phi vn hnh trong iu kin p sut hidro kh cao (xp x 40 atm). Khong nhng nm 60, mt s kim loi ph gia c a thm vo h xc tc Pt (xc tc lng kim), khc phc tnh trng gim nhanh hot tnh xc tc. Cht xc tc tr nn bn hn vi qu trnh cc ha, gip qu trnh cng ngh c vn hnh p sut thp hn (khong t 15 n 30 atm). S n gin ca cng ngh bn ti sinh c trnh by trn hnh 19. M t hot ng ca s : Nguyn liu (phn on naphta nng ) c lm sch t qu trnh hydro ha, c trn vi kh hydro t my nn, sau khi qua cc thit b trao i nhit c dn ln lt vo cc l phn ng (c th t 3-4 l) c cha lp xc tc c nh . Cc sn phm c to thnh sau khi ra khi h thng phn ng , qua thit b trao i nhit, thit b t nng v thit b lm lnh. Qua thit b ngng t, sn phm lng gi li, kh khng ngng c s a vo thit b tch kh . Phn ln kh c nn li nh my nn kh v tun hon tr li l phn ng. Phn kh cn li c dn sang b phn tch kh. Hydro c tch ra t y c th c s dng cho cc qu trnh lm sch dng hydro. Phn lng tch ra c a vo thp n nh, thc cht l mt thp chng ct vi mc ch tch phn nh (LPG) nhm tng n Hnh 5: S n gin cng ngh Reforming nh ca xng v xc tc (lp xc tc c nh) gim p sut hi
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bo ha. LPG tch ra c a vo thit b ngng t. Xng sn phm ra y thp, mt phn c un nng v hi lu tr li thp n nh, phn ln c lm lnh v a vo b cha. Cng ngh bn ti sinh hin nay vn cn rt thnh hnh Php v mt s nc khc. V d, Vin du m Php (IFP) lp t c 600 phn xng bn ti sinh trn th gii so vi 120 phn xng CCR. IX. Cng ngh ti sinh lin tc (CCR): c im: Lp xc tc c chuyn dng nh nhng, lin tc trong h thng thit b phn ng vi vn tc va phi (trong khong 3- 10 ngy). Ton b h thng c vn hnh lin tc. Lp xc tc sau khi ra khi h thng phn ng c a ra ngoi ti sinh trong mt h thng ti sinh ring. Sau c quay tr li h thng phn ng. Cu to mt l phn ng dng ng th ng vi lp xc tc chuyn ng dng trong cng ngh CCR c m t trn hnh sau: Kch thc l phn ng thay i trong khong: ng knh 1,5 3,5m, Chiu cao 4 12m, Th tch lp xc tc 6 80 m3. Chi tit hn chng ta thy cm h thng thit b phn ng bao gm 3 - 4 l phn ng c kch thc, iu Hnh 6: Cu to theo mt ct dc l phn ng reforming xc tc kin vn hnh, lng xc tc np vo khng ging nhau, t phn b thnh phn sn phm ra t mi l cng khng ging nhau. H thng cu to t nhiu l phn ng gip cho dng hn hp nguyn liu v kh giu hidro (kh tun hon) t c nhit phn ng v b tr nhit nng t cc phn ng ha hc xy ra trong qu trnh reforming. Nhit gim nhanh trong l th nht do s xut hin ca cc phn ng thu nhit quan trng (ch yu l phn ng dehydro ha naphten), lng xc tc tiu th cho giai on ny chim 10-15% trng lng. l phn ng th 2
Hnh 7: S n gin cm h thng thit b phn ng bao gm 3 - 4 l phn ng v iu kin vn hnh cng tng xc tc np vo.

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nhit gim t hn, lng xc tc tiu th chim 20 -30%. Ti l phn ng cui cng, nhit gn nh n nh do c s b tr nhit gia cc phn ng thu nhit nh vi cc phn ng ta nhit kiu nh hydrocracking 1. S cng ngh PLATFORMING ca UOP: Thit b phn ng c xp chng ln nhau. Xc tc i t trn xung qua h thng thit b phn ng, sau tp trung li v c nng ln thit b ti sinh nh kh nng. Sau khi ti sinh, cht xc tc c a tr li thit b phn ng th nht. Nh c ly ra tng phn v ti sinh lin tc m hot tnh xc tc n nh cao hn so vi trong trng hp lp xc tc c nh (cng ngh bn ti sinh). Cng ngh ny hin nay c s dng ph bin hn c (chim 70% th phn cng ngh CCR trn th gii). Tuy nhin cng c nhc im l vn hnh kh khn do chiu cao h thng thit b phn ng. 2. S cng ngh OCTANIZING ca IFP (Php): H thng thit b phn ng c sp xp theo hng ngang.Tuy khc phc c nhc im v chiu cao nhng li tn din tch xy dng v ng ng dn ln dn n tng gi thnh xy dng v chi ph vn hnh cao. Ngoi ra c th k n cng ngh ti sinh lin tc POWERFORMING (Anh) v cng ngh hn hp DUALFORMING (Php), trong kt hp 2 h thng bn ti sinh v ti sinh lin tc vi 2 loi xc tc khc nhau. Phn xng reforming xc tc ca nh my lc du s 1 Dung qut Vit nam c lp t theo cng ngh Platforming ca UOP (M). Phn xng ny c nhim v cung cp hp phn pha xng (reformat) cht lng cao v p ng mt phn nguyn liu (BTX) cho ha du.

Vng ho

Dehydro ho

Hnh 8: Phn ng reforming parafin nh

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