PHN II

1. QU TRNH CRACKING XC TC 2. QU TRNH REFORMING XC TC 3. QU TRNH ALKYLE HA

CHNG I QU TRNH CRACKING XC TC

I. MC CH II. QU TRNH PHT TRIN III. NGUYN LIU IV. SN PHM V. XNG CA QU TRNH FCC VI. HIU SUT CHUYN HA CA QU TRNH VII. IU KIN CNG NGH CA QU TRNH VIII. CC PHN NG XY RA IX. CHT XC TC X. S CNG NGH XI. CRACKING XC TC NGUYN LIU NNG

I- MC CH
Phn hy cc phn on nng, vi s c mt ca cht xc tc, nhm thu c xng (mc ch chnh), gasoil v GPL

II- QU TRNH PHT TRIN

1. Cng ngh cracking xc tc tng c nh 2. Cng ngh cracking xc tc tng di ng (TCC : Thermofor Catalytic Cracking) 3. Cng ngh cracking xc tc tng si (FCC : Fluid Catalytic Cracking)

Spray water

Torch oil

III- NGUYN LIU

Ch yu: gasoil chn khng (DSV) vi khong nhit si 350 550oC (hoc 380 550oC) Tuy nhin, ngi ta thng trn thm cc ngun nguyn liu nng khc tng hiu sut thu xng nh : distillat nh ca qu trnh chng ct kh quyn (DA) c khong nhit si 380410oC distillat ca qu trnh cc ha hoc gim nht cn goudron (RSV) tch nha asphantne 550oC+,. .. Gn y, do tnh trng d tha cc sn phm nng trn thm cn RA 380+ (10 50%). d 0,9 0,98 ; Nu hm lng cc tp cht nh : Ni, V, cc hp cht ca S, N, .. ln th phi tin hnh x l bng hydro.

IV- SN PHM
1. 2. 3. 4. 5. 6. 7. Kh t Kh ha lng Xng Gasoil nh Gasoil nng Slurry Cc

V- XNG CA QU TRNH FCC

V.1- Thnh phn - ch s octane

V.2- S x l phn on xng trung tm ca qu trnh FCC

V.3- Tnh n nh ca xng FCC

Xng FCC cha mt hm lng ng k cc olfine v c c cc diolfine. Cc HC khng no ny rt km n nh. Khi tip xc vi khng kh, chng d dng b oxy ha v polymer ho to ra cc hp cht mi dng kt ta thng gi l nha thng to cn trong nhin liu, lm tc nghn cc ng phun nhin liu v soupape. Xng FCC trong qu trnh tn cha thng phi thm vo cc loi ph gia chng oxy ha khong vi ppm c ch qu trnh to nha v tho mn tnh n nh ca xng thng phm

V.4- Cc tp cht trong xng FCC

Cc hp cht ca lu hunh Cc hp cht ca oxy Cc hp cht ca nit

V.5- S x l xng FCC

VI- HIU SUT CHUYN HA CA QU TRNH

Conv = (kh + xng + cc) % masse = 100 - (LCO+HCO+Slurry) Conv = 50 75%

VII- IU KIN CNG NGH CA QU TRNH

Nhn chung, cc phn ng xy ra trong qu trnh cracking xc tc l phn ng thu nhit v tng s phn t. Do , cc phn ng xy ra thun li iu kin T cao v P thp. Nhng iu kin cng ngh ca qu trnh : T = 470 550 oC ; P = 1,5 2,5 bar tng i ; khng c mt ca H2 trong mi trng phn ng (H2 lm nhanh hot tnh ca CXT)

VIII- CC PHN NG XY RA TRONG QU TRNH CRACKING XC TC

1. Cc phn ng nhit 2. Cc phn ng xy ra di tc dng ca xc tc
khng th trnh khi theo c ch chui gc. l nhng phn ng ng th, xy ra pha kh. khng c tnh chn la to thnh mt lng ln cc HC nh nh C1, C2, C2= trong phn on C1 - C4. ng thi, sn phm xng thu c c cht lng xu (IO thp v km n nh ha hc) hn ch cc phn ng ny E* cc phn ng ny cao nn xy ra thun li iu kin T cao

2- Cc phn ng xy ra di tc dng ca xc tc
l cc phn ng d th xy ra vi s tham gia phn ng ca cc ion carboni trung gian khng bn. Cc phn ng chnh xy ra theo c ch ny : phn ng isomer ha phn ng ct mch v tr phn ng chuyn v hydro phn ng kh hydro cc phn ng ngng t khc

S to thnh ion carboni

C 3 gi thuyt c a ra : Proton ha mt olfine c mt trong cht phn ng hay c to thnh trc bi qu trnh cracking nhit :

Proton ha 1 P (hay 1 N) to thnh ion carbonium tip tc phn hy ion carbonium ny to thnh ion carbnium = cch loi b mt phn t H :

Tm acide Lewis s ly mt ion H+ ca paraffine :

Cc ion carboni mi to thnh s c kh nng t bin i t dng km n nh sang dng n nh nht v chng s tc dng vi cc phn t trung ha ca nguyn liu to ra sn phm mi v ion carboni mi. Qu trnh c tip tc nh vy

IX- CHT XC TC
Cc phn ng trong qu trnh cracking xc tc l cc phn ng d th, ch yu xy ra trn b mt cht xc tc rn di dng bi, tr, bt mn, ... Lng cht xc tc ca qu trnh FCC chim mt t l ln so vi tng lng cht xc tc rn c s dng trong cng nghip lc du (khong 80%)

Cht xc tc Zolithe
Cht xc tc zolithe thuc loi CXT acide dng rn, hn hp ca hai cu t ch yu l : zolithe l tc nhn acide ng c hot ha trn mt cht mang, hm lng zolithe 10 50 % khi lng. Ngoi ra, cn c cc cht ph khc. Cht xc tc ny nm di dng bt mn vi nhng ht nh c kch thc trung bnh t 50 60 m vi c ht t 20 100 m. Gm cc cu t ch yu sau : Zolithe Cht mang

S lo ha ca cht xc tc
Xc tc trng thi cn bng Nguyn nhn s lo ha ca cht xc tc Cc bin php ngn nga s lo ha ca cht xc tc

Cc bin php ngn nga s lo ha ca cht xc tc

Gm 3 bin php chnh : Gim hm lng Na trong zolithe Gim tc dng ph hy cu trc mng ca acide V bng cch cho vo cc loi oxyde khc to hp cht bn vng vi V2O5. Cc oxyde c hiu qu nht l cc oxyde kim loi kim th (MgO, CaO), oxyde t him Re2O3 v cc oxyde hn hp khc nh : TiO2 v CaO, SrO v BaO Trung ha hoc lm mt hot tnh ca Ni bng cch thm vo cc hp cht ca Ch hoc bng cch s dng cht mang

Trong qu trnh FCC, CXT lm vic c mt thi gian th s b mt lp cc (to thnh do cc phn ng ngng t c hi xy ra trong qu trnh cracking) bm trn b mt CXT, lm che ph cc tm hot ng ca XT lm gim hot tnh ca CXT hiu sut ca qu trnh chuyn ha cng gim theo. khc phc phi tin hnh ti sinh XT. Bn cht ca qu trnh ti sinh xc tc l t chy cc bm trn b mt cht xc tc bng oxy ca khng kh. Cc phn ng xy ra u l phn ng ta nhit : C + O2 CO + 2200 kcal/kgC CO + O2 CO2 + 5620 kcal/kgC C + O2 CO2 + 7820 kcal/kgC 2H + O2 H2O (hi) + 28600 kcal/kgH2

Ti sinh cht xc tc

X- S CNG NGH
Phn xng FCC bao gm 4 khu vc : 1. khu vc phn ng ; 2. khu vc phn tch sn phm ; 3. khu vc iu phi cht xc tc ; 4. khu vc x l khi thi.

1- Khu vc phn ng
Thit b phn ng Thit b ti sinh

XI- CRACKING XC TC NGUYN LIU NNG

Nguyn liu : cn ca qu trnh chng ct kh quyn (RA); T cao v c mt ca hi nc CXT s b ph hu thu nhit do hm lng ng k ca V c trong nguyn liu ; T ca xc tc c ti sinh rt ln nhit ca hn hp nguyn liu v cht xc tc ng riser ln, dn n qu trnh cracking su, to ra nhiu kh v cc l cc sn phm khng mong mun. gii quyt vn trn, ngi ta nghin cu v a ra hai cng ngh chnh sau : Cng ngh trch bt nhit t TBTS xc tc Cng ngh R2R

Cng ngh R2R

Cng ngh R2R s dng cho qu trnh cracking xc tc cn p dng cc k thut mi sau : S dng 2 tng ti sinh S dng h thng MTC X l kh CO, NOx, SOx cho kh thi S dng thit b tch nhanh xc tc ra khi hn hp sn phm RTD Thit b phun sng nguyn liu

H thng MTC

Thit b phun sng nguyn liu

Chng II: QU TRNH REFORMING XC TC

1. 2. 3. 4. 5. 6. 7. 8. 9. 10. MC CH LCH S PHT TRIN NGUYN LIU SN PHM CHT XC TC CC PHN NG CA QU TRNH C CH PHN NG NG HC QU TRNH CC IU KIN TIN HNH QU TRNH S CNG NGH

I- MC CH
Bin i thnh phn HC cc phn on nh ca du m, ch yu l cc P v N c t 6 10 nguyn t C (thng l 7, 8, 9) thnh cc HC thm c s C tng ng

V tr ca phn xng RC trong nh my lc du

III- NGUYN LIU

sn xut ra cc HC thm c t 6 10 C (thng l 7, 8, 9), qu trnh RC cn cc loi nguyn liu cha cc P hoc N c s C tng ng. Thnh phn nguyn liu : Gm 2 loi nguyn liu : loi P : c P = 6070%, N =15 25%, A = 10 15% . loi N : c P = 2030%, N = 60 70%, A = 8 15% . c bit khng c olfine thu cc loi hydrocarbon thm ring l, ta chn cc phn on xng c gii hn si hp nh sau : sn xut Benzne : dng phn on xng c gii hn nhit si : 62 85oC ; sn xut Tolune : dng phn on xng c gii hn nhit si : 85 120oC ; sn xut Xylne : dng phn on xng c gii hn nhit si : 120 140oC

IV- SN PHM
Kh giu H2 : 2 4% m, mt phn c s dng cho tun hon li qu trnh, cn phn ln c a ra khi h thng s dng cho qu trnh lm sch sn phm v cho qu trnh hydrocracking ; Kh t C1 - C2 : 1 4% m lm nhin liu t Phn on C3 - C4 : 5 14% m sn xut GPL : hiu sut thu C4 max khi s dng cht xc tc Pt/ Aluminosilicat ; hiu sut thu C4 min khi s dng cht xc tc Pt/ Al2O3, ng thi gim ppH. Xng Reformat : 80 90% khi lng, c : RON = 98 100 ; S = RON - MON = 10 ; Giu hydrocarbon aromatic ( 60%)

V- CHT XC TC
Tt c cc cht xc tc c s dng hin nay u l dn xut ca cht xc tc Pt trn cht mang alumine c chlore ho do hng UOP p dng t nm 1949 ; Gi thnh tng i t : 35 F/kg so vi 2 F/kg zolithe xc tc cho qu trnh FCC ; Gm 2 loi cht xc tc : Cht xc tc Pt trn cht mang alumine Cht xc tc 2 chc kim loi (bimtallique)

Chu k ti sinh v tui th ca cht xc tc

i vi cng ngh ti sinh bn lin tc : chu k ti sinh khong 6 15 thng, trung bnh l 1 nm. Tui th ca cht xc tc khong 5 7 nm ; i vi cng ngh ti sinh lin tc : chu k ti sinh khong 2 10 ngy, trung bnh cht xc tc c ti sinh khong 100 ln/ nm. Tui th ca cht xc tc khong 2 4 nm, ngn hn do b mi mn v ph hu trong cc tng xc tc di ng.

Cc cht ng c xc tc
Nc Nit Lu hunh Cc kim loi Pb, As, Hg, Si

VI- CC PHN NG CA QU TRNH

Cc phn ng chnh Cc phn ng ph

Bng 2 : Nhit ca cc phn ng ch yu ca qu trnh reforming xc tc

Loi phn ng Phn ng kh hydro cc P Phn ng kh hydro cc N Phn ng kh hydro v khp vng cc P Phn ng isomer ha cc nP Phn ng isomer ha cc N Nhit phn ng, kJ/mol + 125 + 210 + 250 -10 -15

VII- C CH PHN NG
Phn ng Kh hydro P, N Kh hydro v khp vng Isomer ha Hydrocracking Alkyle ha Cc ho C ch 1 chc 1 chc v 2 chc 2 chc 2 chc 1 chc 1 chc v 2 chc Tm ng Pt Pt Pt + cht mang acide Pt + cht mang acide Pt + cht mang acide cht mang acide Pt hoc cht mang acide Pt + cht mang acide

Hnh 2 : Cc hng phn ng chnh chuyn ha thnh aromatic

Hnh 3: Cc qu trnh chuyn ha ch yu ca cc paraffine xy ra trn b mt CXT

VIII- NG HC QU TRNH
Qua bng 2, qu trnh RC nhn chung thu nhit mnh nn xy ra thun li iu kin nhit cao. V vy, cn phi cung cp nhit cn thit cho qu trnh bng cch chia thnh 3 hoc 4 tng xc tc lin tip c cc l t xen k. Vic chn 3 hoc 4 tng xc tc lin tip hoc 3, 4 thit b phn ng lin tip ph thuc vo bn cht ca nguyn liu : 3 i vi nguyn liu thuc loi P 4 i vi nguyn liu thuc loi N

IX- CC IU KIN TIN HNH QU TRNH

T = 490 525 oC ; P = 12 25 bar nu l tng XT c nh ; = 3 10 bar nu l tng XT di ng. T l H2/HC = 5 7 nu l tng XT c nh = 1,5 4 nu l tng XT di ng Vn tc truyn nguyn liu : PPH (t nguyn liu / t xc tc / h) = 1 3 h-1

X- CNG NGH CA QU TRNH

Cc cng ngh khc nhau ch yu dng TBPW : dc trc hay xuyn tm tng XT c nh hay di ng ; Trc y, qu trnh cn vn hnh P cao (> 50 bar) th P do TBPW xem nh khng nh hng ng k. Do vy, trong nhng nm ny thng s dng TBPW dc trc vi cu to n gin v gi thnh r. n nm 1960, khi xut hin CXT 2 chc kim loi (bimtallique) v gim P vn hnh cn 10 bar th P do TBPW tr nn ng k TBPW dng xuyn tm tr thnh mt s la chn duy nht vi P nh hn nhiu so vi dng dc trc

Hin nay qu trnh RC gm 2 cng ngh chnh : Cng ngh ti sinh bn lin tc vi tng xc tc c nh (semi-rgnratif) : lm vic bn lin tc ; cht xc tc c ti sinh vi chu k t 6 15 thng khi hm lng cc bm trn b mt cht xc tc ln (15 20%); Cng ngh ti sinh lin tc vi tng xc tc di ng (rgnratif) : lm vic lin tc ; chu k ti sinh cht xc tc t 2 10 ngy : cht xc tc lm vic i qua ln lt cc thit b phn ng ni tip nhau, sau cht xc tc c ti sinh v quay li thit b phn ng u tin.

XI- S cng ngh

Gm 3 khu vc chnh : Khu vc x l nguyn liu Khu vc phn ng Khu vc n nh sn phm

QU TRNH ALKYLE HA
1. 2. 3. 4. 5. 6. Mc ch Nguyn liu Sn phm Cc phn ng xy ra Cht xc tc C ch phn ng

Chng III

I- Mc ch
Sn xut xng c thnh phn ch yu l cc hydrocarbon nhiu nhnh c ch s octane cao (ch yu l iso-octane) bng cch alkyle ha cc iso-paraffine (ch yu l iso-butane) bi cc olfine (ch yu l butne). Xng ny c gi l alkylat, l cu t tt nht pha trn xng cao cp v n c ch s octane cao v nhy nh (RON 96, MON 94). iu cho php ch to c xng theo bt k cng thc pha trn no

So snh tnh cht ca cc loi xng thu c t cc qu trnh khc nhau

RON MON TVR 0,50 0,37 0,55 % vol % vol A O 30 70 0,4 20 0,7 0,5

Xng FCC 89 93 78 81 Reformat 96 105 87 92 92 97 90 94 alkylat

II- Nguyn liu

Ngun nguyn liu giu olfine ch yu thu c t qu trnh cracking xc tc ; Ngun nguyn liu giu iso-Paraffine ch yu thu c t qu trnh issomer ha; 3 phn on nguyn liu giu olfine chnh :
Phn on C4 Phn on C3 + C4 Phn on C4 c cha C5

Cc tp cht c hi trong nguyn liu

Cc tp cht c hi trong nguyn liu : nc, cc diolfine, cc hp cht ca oxy, S, .. lng tiu tn cht XT v RON ca xng alkylat. c bit, hm lng C2= trong nguyn liu phi rt thp : v C2= l 1 cht lm ng c XT, lng tiu tn XT cho C2= l ln nht (30,6 kg xc tc / kg C2= )

Lng tiu tn CXT do cc tp cht c trnh by trong bng sau

Tp cht Nc Butadine Ethylne Mercaptan(cho 1 kg S) Disulfure(cho 1 kg S) Mthanol Dimthylther MTBE kg xc tc/kg tp cht 10,6 13,4 30,6 17,6 12,8 26,8 11,1 17,3

III- Sn phm
Sn phm alkylat l mt hn hp v cng phc tp ca cc paraffine t C5 C12 v c trnh by trong bng 7.4. Alkylat cha ch yu cc iso paraffine nhiu nhnh, trong hm lng phn on C8 chim t 62 74 % th tch. V 6 trong s 18 ng phn ca C8 chim 90% phn on ny, gm : 2,3 DMH ; 2,4 DMH ; 2,5 DMH ; 2,2,4 TMP ; 2,3,4 TMP ; 2,3,3 TMP

IV- Cc phn ng xy ra
Phn ng chnh l phn ng gia 1 mol iso-butane v 1 mol olfine, ch yu l butne to thnh 1 mol iso-paraffine, ch yu l iso-octane : i-C4H10 + C4H8 i-C8H18 Theo qui c : iso-octane c RON = 100

Phn ng alkyle ha ta nhit v km theo s gim s mol nn xy ra thun li iu kin nhit thp v p sut cao. Nhit phn ng ph thuc vo bn cht ca olfine s dng v c c lng nh sau :
195 kcal/kg alkylat 175 kcal/kg alkylat 140 kcal/kg alkylat : vi propne ; : vi butne ; : vi pentne

V- Cht xc tc
Phn ng alkyle ha iso-butane bng cc olfine c th thc hin c m khng cn cc cht xc tc nhng vi nhng iu kin tin hnh qu trnh rt khc nghit : nhit khong 500 oC, p sut t 200 400 bar ; Khi c mt cht xc tc acide, phn ng c th xy ra nhit thp ( 50 oC) v p sut thp ( 30 bar) ; Hai cht xc tc thng c s dng nht trong cng nghip sn xut alkylat l : HF v H2SO4 trng thi lng ;

Phn ng alkyle ha xy ra hoc b mt phn chia pha hoc trong pha acide, v vy ha tan ca cc cht phn ng khc nhau l mt yu t rt quan trng. Cc olfine thng ha tan rt tt trong pha acide, nhng ngc li, cc isobutane li ha tan rt t trong acide. C th trong : H2SO4 99,5 %, ch ha tan 0,1 % iso-butane ; HF 99,5 %, ch ha tan 2,4 3,6 % iso-butane

Tnh cht ho l ca 2 loi acide

HF H2SO4 Khi lng phn t 20,01 98,08 Nhit si, oC 19,4 290 -82,8 10 im chy, oC 0,99 1,84 T trng d154 0,256 (0oC) 33 (15oC) nht ng lc, cP Tnh tan, % trng lng i-C4H10 / acide 100% (27 oC) 2,7 i-C4H10 / acide 99,5% (13 oC) 0,1 HF / i-C4H10 (27 oC) 0,44 0,90 HF / C3H8 (27 oC)

VI- C ch phn ng
Qu trnh alkyle ha i-C4H10 bi cc olfine l mt qu trnh ht sc phc tp vi rt nhiu cc phn ng ph c th xy ra ; Vi cc cht xc tc l HF v H2SO4, phn ng xy ra theo c ch ion carbonium

Phn ng chnh
L phn ng alkyle ha i-C4 bi C4= 3 giai on : Giai on khi u mch : Olfine, butne-1 hoc butne-2, c proton ho bi acide (HF , H2SO4) to thnh 1 ion carbonium bc 2

CH3 CH = CH CH3 + H+ CH3 C+H CH2 CH3 1-C=4 + H+X- n-C+4Xn-C+4X 2-C=4 + H+X-

Cc ion carbonium bc 2 c to thnh s cn bng vi hn hp butne-1 v butne-2 (butne-2 chim a s): Cc ion carbonium bc 2 ny ng thi s phn ng vi cc i-C4 = cch trao i 1 nguyn t H iC4++ n-C4H10 :
CH3 CH3 H

H3C

C CH3

H3C

C H CH2 CH3

H3C

H3C CH2 CH2 CH3

CH3

Giai on pht trin mch : Bao gm 3 phn ng lin tip nhau : phn ng alkyle ha, isomer ha v trao i H Phn ng alkyle ha : Khi nng ca carbocation tertiobutyle iC4+ ln, butne-2 s tin hnh phn ng alkyle ha vi chng to thnh cc 2,2,3TMP+ :

CH3 H3C C
+

H3C H3C CH CH CH3 H3C C H3C

CH3 CH C H CH3
+

CH3

Phn ng isomer ha : Trn y l mt ion carbonium bc 2, n c xu hng t chuyn ha sang dng cc ion carbonium bc 3 bn vng hn bng cch di chuyn nhm CH3 dc theo chiu di ca mch C
CH3 H3C C CH3 CH2 CH3 C
+

CH3 CH3 H3C CH CH CH3

CH3 C
+

CH3 CH3 CH3 H3C CH2 C CH3 C

+

CH3

iC8+ Vi cht xc tc l H2SO4 , hu ht cc butne-1 s tin hnh isomer ha thnh butne-2 trc khi phn ng vi carbocation tertiobutyle iC4+ . Cn i vi cht xc tc HF, qu trnh isomer ha ny xy ra khng hon ton.

Phn ng trao i H : Qu trnh kh proton c tin hnh khi ibutane trao i mt nguyn t H vi iC8+ to thnh C8H v carbocation tertiobutyle iC4+ :
CH3 iC8
+

CH3 iC 8H

H3C

CH CH3

+ H3C

CH3

iC8H = 2,2,4TMP (2,2,4-trimthylpentane) hoc 2,3,4TMP (2,3,4-trimthylpentane) hoc 2,3,3TMP (2,3,3-trimthylpentane)

Giai on t mch : Bao gm nhng phn ng lm gim nng ca cc carbocation tertiobutyle iC4+ . Trong , c th k n phn ng kh proton cc carbocation tertiobutyle iC4+ to thnh isobutne :
CH3 H3C C
+

CH3 H2C C CH3

H2

CH3

(iso-butne)

Cc iso-butne c to thnh li tham gia vo qu trnh alkyle ha cc iso-butane, tip tc to thnh sn phm, do , lm tng vt lng tiu th isobutane ln rt nhiu :
CH3 H3C C
+

CH3

CH3 CH3 H3C C CH3 CH2

CH3 C
+

H2C

CH3

CH3
CH3 H3C C CH2 CH3 C
+

CH3 CH3

CH3 H3C C CH2

+ H3C

CH3 CH CH3

CH3

CH CH3

H3C

CH3

CH3

CH3

Trn y l c ch ca qu trnh alkyle ha i-C4 bng nC4=. Nu xt qu trnh alkyle ha bi C3=, bi i-C4= v bi C5= s phc tp hn nhiu v c xem l cc phn ng ph v sn phm ca cc phn ng ny ch t 30% m ca alkylat.

Cc phn ng ph
L cc phn ng to thnh cc phn on nh C5 C7 v cc phn on nng C9 C14 Gm cc phn ng chnh sau :
Polyalkyle ha Cracking Trao i hydro

Polyalkyle ha : to thnh cc phn on nng C9 C14 i-C4+ + C4= iC8+ i-C8+ + C4= iC12+ iC12+ + i-C4H i-C12H + i-C4+ iC16+ i-C12+ + C4= Cracking : xy ra theo c ch t mch , to thnh cc phn on nh C5 C7 C12+ C5+ + C7= C5+ + i-C4H C5H + i-C4+ C7= + H+ C7+ C7+ + i-C4H C7H + i-C4+

Trao i hydro :
l phn ng khng mong mun v : lm tng lng tiu tn iso-butane v to thnh cc paraffine nh ; to thnh iso-butne, vi cht xc tc H2SO4 s lm tng lng sn phm nng. Thng xy ra theo c ch xc tc acide :

C3= + i-C4H C3H + i-C4= i-C4=+ i-C4H 224 TMP

Tm li, ta c : C3= + 2 i-C4H C3H + 224 TMP

VII- iu kin tin hnh qu trnh

Vi cht xc tc H2SO4 C 5 y t quan trng nh hng n cht lng alkylat v lng tiu tn cht xc tc l :
thnh phn ca cht xc tc ; nhit v p sut tin hnh phn ng ; t s mol gia iso-butane/olfine ; mc khuy trn ; thi gian lu.

nh hng ca hm lng nc v du ha tan trong H2SO4 n cht lng ca alkylat

T s mol gia iso-butane/olfine

T s ny khong = 5 15 ; Nu < 5 : s lm gim rt nhiu cht lng ca alkylat Nu > 15 : thc t khng mang li hiu qu g

nh hng ca nng iso-butane trong vng phn ng n MON ca alkylat

nh hng ca nng iso-butane trong vng phn ng n lng tiu tn H2SO4

Mc khuy trn : Yu t ny nh hng rt ln i vi qu trnh s dng CXT H2SO4 (t hn i vi qu trnh s dng CXT HF do H2SO4 c hn HF) ; qu trnh khuy trn phi t hiu qu m bo s tip xc gia 2 pha l tt nht ; Nu tc khuy trn 1000 3000 rpm s tng RON cho xng ln 7,5 n v Thi gian lu. trnh cc phn ng ph xy ra, i hi thi gian lu trong TBPW cng ngn cng tt. Tuy nhin, trong trng hp alkyle ha vi CXT H2SO4 th thi gian lu tng i di 20 30 pht. Nguyn nhn l do mi khi kt thc phn ng, cn phi c thi gian pha acide t c trng thi bo ho iC4 do ha tan << ca HC ny trong H2SO4

Vi cht xc tc HF
C 4 y t quan trng nh hng n cht lng alkylat v lng tiu tn cht xc tc l : thnh phn ca cht xc tc ; nhit v p sut tin hnh phn ng ; t s mol gia iso-butane/olfine ; thi gian lu

nh hng ca nhit phn ng n RON ca alkylat vi nguyn liu l phn on C4 ca FCC

nh hng ca t s mol iso-butane / butne n RON v MON ca alkylat

nh hng ca t s mol iso-butane / butne n lng tiu tn HF

Thi gian lu
Tng i ngn hn, khong 10 20 pht

VIII- S cng ngh

Vi cht xc tc l H2SO4
Cng ngh Stratco Cng ngh Exxon/Kellogg Cng ngh Phillips Cng ngh UOP

Vi cht xc tc l HF

S cng ngh vi cht xc tc l H2SO4

Bao gm 2 cng ngh chnh : Stratco v Exxon/Kellogg ; 2 cng ngh ny gm cc im chung sau : s gm 3 khu vc : khu vc phn ng : to thnh nh tng hydrocarbon trong acide v ti y xy ra qu trnh alkyle ha ; khu vc lng v tch 2 pha : acide cho hi lu li u qu trnh, cn hydrocarbon c a sang khu vc phn tch ; khu vc phn tch : tch iso-butane tha/nbutane/ alkylat, iso-butane tha cho hi lu li khu vc phn ng

S cu to ca loi TBPW theo cng ngh Stratco

A : chm ng hnh ch U D : Turbine B : khu vc ngoi bin dc theo thnh E : u thy lc thit b F : b phn phn tn C : V TBPW

S qu trnh alkyle ha theo cng ngh Stratco s dng cht xc tc H2SO4

S cu to ca loi thit b phn ng theo cng ngh Exxon/Kellogg

S qu trnh alkyle ha theo cng ngh Exxon/Kellogg s dng cht xc tc H2SO4

Qu trnh alkyle ha s dng CXT l H2SO4 lun to thnh ng thi mt lng rt ln bn acide (trong , H2SO4 chim 90% m. Qu trnh x l bn ny rt phc tp v tn km v H2SO4 khng th tch ra khi cc hp cht du ha tan bng cc phng php vt l, m trc ht phi tin hnh phn hy bn acide ny, sau H2SO4 s c ti to li t SO2 l sn phm ca qu trnh kh H2SO4 bng cc hp cht du ha tan. Nguyn tc ca qu trnh ti sinh H2SO4 gm 3 bc sau : phn hy acide v cc du hu c thnh SO2, H2O, CO2 v N2 di tc ng ca khng kh ; chuyn ha SO2 thnh SO3 ; cho SO3 hp vi nc to thnh H2SO4 vi nng 98,5 % m

Qu trnh ti sinh H2SO4

S cng ngh vi cht xc tc l HF

Bao gm 2 cng ngh chnh :Phillips v UOP ; Cng ngh vi CXT l HF khc vi cng ngh CXT H2SO4 ch l khng s dng h thng khuy trn c hc bng turbine nn n gin hn (do HF < H2SO4, ng thi ha tan ca iso-butane trong HF ln hn nhiu) Hn hp nh tng to thnh vi cc ht nh HC khuych tn trong pha lin tc l acide HF, s c bm vo phn di ca TBPW qua h thng cc ng nh v s i t di ln trn, sau qu trnh tch 2 pha acide / HC cng c thc hin nh i vi H2SO4 bng phng php lng. T phn ng duy tr 30 oC cho php s dng nc lm tc nhn lm lnh cho TBPW

S nguyn tc thit b phn ng dng ng theo cng ngh Phillips

S qu trnh alkyle ha theo cng ngh Phillips s dng cht xc tc HF

S nguyn l TBPW thng ng theo cng ngh UOP

S 2 TBPW thng ng lm vic lin tc theo cng ngh UOP

S qu trnh alkyle ha theo cng ngh UOP s dng cht xc tc HF

Cc tiu chun la chn H2SO4 hoc HF

Gm 4 tiu chun : 1. Cht lng ca alkylat v bn cht nguyn liu cn x l : Cht lng ca alkylat gn nh l nh nhau i vi cc cng ngh khc nhau s dng cc cht xc tc khc nhau ; Tuy nhin, vi nguyn liu khng cha iso-butne (n t phn xng MTBE) chng hn th alkylat thu c t qu trnh s dng H2SO4 c RON cao hn. 2. Gi thnh cht xc tc : Tuy gi thnh ca HF t hn H2SO4 nhng nhn chung chi ph cho cht xc tc / gi thnh sn phm chim n 33% i vi H2SO4 v ch 5% i vi HF, do lng tiu th acide HF b hn v ngi ta c th tin hnh ti sinh HF ngay trong nh my

3. Gi thnh ca giai on phn tch v lm lnh : Gi thnh ca giai on lm lnh cng ln hn khi s dng cht xc tc H2SO4 do phi lp t cc my nn ln ; Ngc li, gi thnh ca giai on phn tch li ln hn khi s dng cht xc tc HF do t s isobutane / olfine cao hn, tr trng hp s dng cng ngh UOP vi nhiu thit b phn ng lm vic lin tc. 4. An ton nh my : y l mt tiu chun rt quan trng v c 2 loi acide u n mn rt mnh ; T mi trng, HF th hi (Ts = 19,4 oC), c bay hi ln ; Trong khi H2SO4 li th lng c p sut hi bo ha thp (Ts 300 oC)