Thit k phn xng reforming xc tc ti: Thit k phn xng Refeforming xc tc nng xut 2,2 triu tn/ nm vi s thit

it b xc tc c nh.

Mai Ngc Chin KTHH5 K54

Thit k phn xng reforming xc tc

Mc lc
PHN CNG NGH ........................................................................................................ 18 II. Cng ngh Reforming ............................................................................................... 18 II.1 Cc yu t nh hng n qu trnh .................................................................... 18 II.1.1. nh hng ca nhit ................................................................................ 19 II.1.2. nh hng ca p sut ................................................................................. 20 II.1.3. Tc np liu ............................................................................................. 21 II.1.4. T l hydro/hydrocacbon nguyn liu .......................................................... 21 II.2. Gii thiu mt s s cng ngh ..................................................................... 22 II.2.1. Gii thiu chung ........................................................................................... 22 II.2.2 Mt s s dy chuyn cng ngh ............................................................. 28 II.2.2.1 S cng ngh qu trnh platforming ca hng UOP vi lp xc tc c nh....................................................................................................................... 28 II.2.2.2 S cng ngh qu trnh magnaformig do hng Chevron, s dng xc tc Pt - Re ............................................................................................................. 30 II.2.2.3 Dy chuyn reforming vi lp xc tc chuyn ng .............................. 32 II.2.2.4 Qu trnh New reforming ........................................................................ 36

Mai Ngc Chin KTHH5 K54

Thit k phn xng reforming xc tc

M U
Vo nhng nm 1859 ngnh cng nghip ch bin du m ra i v t sn lng du m khai thc ngy cng c pht trin mnh v s lng cng nh v cht lng . Ngy nay vi s pht trin v tin b ca khoa hc k thut, du m tr thnh nguyn liu quan trng trong cng ngh ho hc. Trn c s nguyn liu du m, ngi ta sn xut c hng nghn cc ho cht khc nhau, lm nguyn liu cho ng c, nguyn liu cho cc ngnh cng nghip khc . Ngnh cng nghip ch bin du nc ta ra i tuy cha lu, nhng n c nh gi l mt ngnh cng nghip mi nhn, c bit l trong giai on t nc ta ang bc vo giai on cng nghip ha - hin i ha. t c nhng mc tiu m s nghip cng nghip ha - hin i ha ra th cn phi p ng mt nhu cu rt ln v nguyn liu, nhin liu cho pht trin cng nghip v kinh t. Trong cng nghip ch bin du m cc qu trnh chuyn ho ho hc di tc dng ca cht xc tc chim mt t l rt ln v ng vai tr v cng quan trng. Cht xc tc trong qu trnh chuyn ho c kh nng lm gim nng lng hot ho ca phn ng v vy tng tc phn ng ln rt nhiu. Mt khc khi c mt ca xc tc th c kh nng tin hnh phn ng nhit thp hn. iu ny c tm quan trng i vi cc phn ng nhit dng (phn ng hydro ho ankyl ho , polyme ho ) v nhit cao v mt nhit ng khng thun li cho phn ng ny. S c mt ca cht xc tc trong qu trnh chuyn ho ho hc va c tc dng thc y nhanh qu trnh chuyn ho , va c kh nng to ra nhng nng cn bng cao nht, c ngha l tng hiu sut sn phm ca qu trnh. Trong qu trnh chuyn ho ho hc di tc dng ca xc tc th qu trnh reforming xc tc chim mt v tr quan trng trong cng nghip ch bin du m, lng du m c ch bin bng qu trnh reforming chim t l ln hn so vi cc qu trnh khc. Qu trnh reforming xc tc

Mai Ngc Chin KTHH5 K54

Thit k phn xng reforming xc tc c xem l mt qu trnh ch yu sn xut xng cho ng c, l mt qu trnh quan trng khng th thiu trong cng nghip ch bin du. C th ni qu trnh reforming ra i l mt bc ngoc ln trong cng ngh ch bin du. Trc y ngi ta dng xng chng ct trc tip c pha trn thm ph gia (ch ) lm tng tr s octan. Ngy nay ngi ta s dng xng ca qu trnh reforming cho ng c th cht lng m bo hn ,t nh hng n mi trng hn.

Mai Ngc Chin KTHH5 K54

Thit k phn xng reforming xc tc

PHN TNG QUAN

I. C S HA HC CA QU TRNH REFORMING XC TC
Reforming xc tc l mt qu trnh chuyn i cc thnh phn hydrocacbon ca nguyn liu m ch yu l naphten v parafin thnh hydrocacbon thm c tr s octan cao, 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 (nh xng ca qu trnh cc ha, xng cracking nhit...). Qu trnh ny c tin hnh trn xc tc hai chc nng thng cha platin (trong hn hp vi cc kim loi qu khc v mt halogen) c mang trn cht mang xit nhm tinh khit. Mc ch ca qu trnh l 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 ca qu trnh l hydrocacbon thm nn qu trnh cn c ng dng sn xut BTX (khi nguyn liu v phn on naphta nh c nhit si t 310 - 340oF) l nhng nguyn liu qu cho tng hp ha du. Ngoi ra, qu trnh cn l ngun thu hydro nhiu nht v r nht. I.1. Cc phn ng xy ra trong qu trnh Reforming xc tc Bao gm cc phn ng: dehydro ha cc hydrocacbon naphten, dehydro vng ha cc hydrocacbon parafin, ng phn ha, hydrocracking. Ngoi ra cn cc phn ng ph, tuy khng lm nh nhiu n cn bng ca phn ng chnh nhng li nh hng ln n hot ng v bn ca xc tc. l cc phn ng : Phn ng phn hu v kh cc hp cht c cha oxy, nit , lu hunh thnh H2S ,NH3 , H2O. Phn ng phn hu cc hp cht cha kim loi v halogen. Phn ng ngng t cc hp cht trung gian khng bn nh olefin, diolefin vi cc hydrocacbon thm, dn n to thnh hp cht nha v cc bm trn b mt xc tc .

Mai Ngc Chin KTHH5 K54

Thit k phn xng reforming xc tc V th pht trin qu trnh reforming xc tc, ngi ta phi hn ch ti mc ti a qu trnh to cc. Trong thc t sn xut ngi ta thng dng p sut v nng hydro cao hoc tin hnh ti sinh lin tc xc tc (RCC) I.1.1. Cc phn ng dehydro ho - Dehydro ho cyclo alkal to hydro cacbon thm:
5000C + 3 H2 >5000C CH3 CH3 + 3 H2

5000C th nng lng hot ho ca phn ng to benzen l 51,6 Kcal/mol, cn to Cyclo hexan l 72,1 Kcal/mol. V vy 5000C ch xy ra phn ng to benzen. y l nhng phn ng thu nhit v vy khi tng nhit v gim p sut th hiu sut hydrocacbon thm tng ln. Ngoi ra khi hm lng hydrocacbon naphten tng ln trong nguyn liu th qu trnh Reforming s tng r rng hm lng hydrocacbon thm. Phn ng tng tr s octan ca xng cn ph thuc hm lng n-parafin cha bin i trong sn phm v chng c tr s octan kh thp (NO ca n-heptan bng 0). Do , ngoi phn ng hydro ho naphten cn phi tin hnh phn ng khc sao cho t hiu qu qu trnh Reforming. - Dehydro ho parafin to olefin:

C9 H20

C 9H18 + H2

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Thit k phn xng reforming xc tc Dehydro ho vng ho parafin hoc olfin to cht thm:
CH3

n C7H16

+ 4 H2 CH3

n C7H14

+ 3 H2

Phn ng dehydro vng ho n-parafin xy ra kh khn hn so vi naphten. Ch c nhit cao mi thu nhn c hiu sut hydro cacbon tng, hng s cn bng to hydro cacbon thm cng tng ln . Bng 1: nh hng ca nhit v chiu di mch cacbon ti hng s cn bng ca phn ng dehydro vng parafin. Phn ng n - C6H14 n - C7H16 n - C8H18 n - C9H20 C6H6 + 4H2 C7H8 + 4H2 C6H5 - C2H5 + 4H2 C6H5 C3H5 +4H2 4000K 3,82.10-12 6,54.10-10 7,18.10-10 1,42.10-9 6000K 0,67 31,77 39,54 65,02 8500K 3,68.105 9,03.105 1,17.107 1,81.107

Khi tng nhit hng s cn bng ca phn ng dehydro vng ho tng rt nhanh, nhanh hn naphten. Nhng tc hydro ho li rt nhy so vi s thay i p sut hoc t s H2/RH nguyn liu.

Mai Ngc Chin KTHH5 K54

Thit k phn xng reforming xc tc

100 80 60 40 20 n C6 445

100 18kg/cm H2/RH=4

2

80 H2 /RH=10 60

H2/RH=4 P=18kg/cm2 H2/RH=10

40 t0C 500
Hnh 1

n-C7

20 0 400

550

450
Hnh 2

500

Hnh 1: Cn bng n - C6 benzen trong phn ng dehydro vng ho. Hnh 2: Cn bng n - C7 toluen trong phn ng dehydro vng ho. Dehydro vng ho to hydro cacbon thm l mt trong nhng phn ng quan trng nht ca Reforming xc tc v n 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 tr s octan cao. I.1.2. Cc phn ng izome ho - Izome ho : n - parafin izo - parafin V d: - Hydro Izome ho: V d: - Izome ho alkyl: Heptan -1 + H2 2 metyl hexan xyclopetan xyclohexan
CH3 Mai Ngc Chin KTHH5 K54 8

n - C7H14 metyl hexan.

Thit k phn xng reforming xc tc

-Izome ho alkyl thm

C2H5

CH3 CH3

I.1.3. Cc phn ng hydro cracking parafin v naphten. i vi paraffin thng xy ra phn ng hydro cracking v hydrogemolyse: R-C-C-R1 R- C-C-R1 i vi naphten: R-CH3(izo) + R1 - CH3(izo) + Q=11Kcal/mol R2-CH3 + CH4 : phn ng hydrogenolyse

R1

+ H2

R3H

+H2

R 4 H + R3 H +

Q = 20 Kcal/mol

R2
Ngoi ra cng cn c cc phn ng hydrodealkyl ho cc hydrocacbon thm:

R
+ H2

C6H6 + RH + Q = 12 - 13 Kcal/mol

I.1.4. Cc phn ng tch nguyn t d th Hydro denit:

R
+ 5H2 C5H12 + NH3

N
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Thit k phn xng reforming xc tc Hydro desunfua:

+ 4H2
S CH3

C5H12 + H2S

Tch oxy: ROH +H2 RH +H2O

Ngoi ra cn c cc phn ng phn hu cc hp cht kim loi halogen. I.1.5. Cc phn ng to cc y l cc phn ng khng mong mun xy ra trong qu trnh Reforming nhng do s tng tc ca olefin, diolefin v cc hp cht thm a vng m to thnh cc. Cc s kh to ra hn iu kin nhit thp, p sut cao v t l H2/RH cao. Phn ng to cc l phn ng phc tp 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 trng lng ca cc xc tc trong khong thi gian t 6 thng n 1 nm nhng nu tng p sut th cn tr to cc hydrocacbon thm.iu ny i hi cc nh sn xut phi ch iu kin cc chc hoc tnh ca xc tc gp phn iu khin c qu trnh to cc ca qu trnh reforming. I.2. C ch phn ng Reforming xc tc I.2.1.C ch phn ng reforming hydrocacbon parafin: Nhiu nh nghin cu cho rng phn ng Reforming hydrocacbon parafin xy ra theo 3 giai on: Dehydro ho parafin. ng vng. Dehydro ho hydro cacbon vng thnh hydro cacbon thm. Giai on u v cui xy ra trn tm xc tc kim loi, cn giai on gia xy ra trn tm axit. Cc giai on c th xy ra xen k nhau. C ngha l trong khi giai on ny cha kt thc th giai on khc bt u nh s tn ti tm xc tc axit bn cnh

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10

Thit k phn xng reforming xc tc nhng tm xc tc kim loi m cc giai on c th xy ra ni tip hoc gn nh ng thi xy ra. V d nh phn t n - heptan (n - C7H16) chuyn ho thnh Toluen nh sau:
- H2 M +H
+

- H2 A + - H+ - H2 M A + - H+ + H+

- H2 M + H+

- H2 M A + - H+

- H2

- H2

Vi A l tm axit, M l tm kim loi C ch ng vng ca cacbocation bc ba cho thy khi Reforming n -C6 th khng phi vng 6 cnh u tin c to ra m chnh l hp cht vng nm cnh (metyl cyclopetan) to ra u tin:
- H2 M A A H A - H2 M +H+

- H2

C1 - C5
M

+A

+A

- H2

Tc giai on ng vng nh hn nhiu so vi giai on dehydro nn khi Reforming naphten th d hn nhiu so vi parafin. I.2.2. C ch phn ng Reforming hydro cacbon naphten. Qu trnh chuyn ho cyclohexan thnh benzen.
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Thit k phn xng reforming xc tc

I.3. Nhit ng hc ca phn ng v iu kin phn ng Xt thng s nhit ng hc ca mt s phn ng quan trng trong qu trnh reforming xc tc qua cc phn ng ca hydrocacbon C6. Bng 2: Cc thng s nhit ng hc cc phn ng hydrocacbon C6 Phn ng Cyclohexan C6H6 + 3H2 Metyl cyclo pentan Cyclohexan n - hexan C6H6 + 4H2 n - hexan Hexen - 1 + H2 n - hexan 2 - metyl pentan Kp 500oC 6.105 0,086 0,78.105 1,1 0,037 H Kcal/mol 52,8 - 3,8 63,8 - 1,4 31,0

Cc s liu nhit ng hc cho thy ti cn bng cyclo hexan chuyn ha thnh aromatic p sut ca hydro v ch mt lng nh olefin tn ti vi parafin. Nhng phn ng chnh ca reforming l thu nhit. Phn ng isome ho l trung ha nhit trong khi phn ng hydro cracking to nhit , cc s liu cng cho thy hiu ng nhit ca phn ng ph thuc chnh vo nng xyclonapatran trong nguyn liu v n hp th nhit mnh nht, v nhit ca phn ng c ly t hn hp nguyn liu v khi nn nhit ca hn hp ny gim. Phn ng dehydro to vng ca parafin v phn ng dehydro ha ca naphtan l nhng phn ng chnh lm tng tr s octan. Cn bng nhit ng ca nhng phn ng
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Thit k phn xng reforming xc tc ny dch chuyn v pha sn phm phn ng khi p sut ring phn ca hydro thp v nhit phn ng cao (500oC).Tuy nhin iu kin ny thch hp to thnh cc v s to cc ch c th ngn chn bng cch thc hin phn ng trong mi trng hydro, nu p sut hydro cng cao, s lng ng cc trn b mt xc tc cng t. Vic tng p sut hydro cng khng lm chm phn ng hydro ha to ra aromatic. Vy qu trnh reforming xc tc phi c thc hin di p sut cao v hydro sn phm c hon li vng phn ng . Phn ng hydrocracking thch hp nhit v p sut ring phn ca hydro cao, phn ng ny thng khng mong mun trong qu trnh reforming v chng tiu th hydro v to ra hydrocacbon pha lng. (Hnh 8) minh ha s ph thuc ca hiu sut phn ng vo p sut phn ng ti nhng tr s octan khc nhau.

Hiu sut phn ng >100%

9 0 8 0 7 0 6 0

10 0

RON85 RON95 RON102 RON104

0 1 2 3 4 5

p sut thit b

Hnh 3: Hiu sut phn ng v p sut ti nhng tr s octan khc nhau. Ti p sut cao cho trc, tr s octan c th c tng khi tng nhit mc d iu ny gy ra s mt mt hiu sut do phn ng hydrocracking tng ln. Nh vy qu trnh thng c thc hin p sut thp t c hiu sut pha lng tng ln. Tuy nhin, p sut ring phn ca hydro phi cao trnh s to thnh nhng hp cht khng no c kh nng b polime ha to thnh cc. Trong thc t, qu trnh c th c tin hnh trong khong nhit 455 510oC v p sut 6,5 50 atm. iu kin ch chuyn ha mt phn aromatic cn nu thc
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Thit k phn xng reforming xc tc hin nhit cao hn v p sut khong 10 atm th c th chuyn ha gn nh hon ton naphten thnh aromatic ti cn bng vi nhng qu trnh lm vic p sut cao t 34 50 atm th vn tc phn ng hydrocracking cao, mc chuyn ha thnh hp cht thm gim (bng 5), vn tc phn ng kh hot tnh xc tc v hiu sut hydro thp. Ngc li, p sut thp (8,5 20,5 atm) chuyn ho cc hp cht thm cao, hiu sut hydro cao, phn ng hydrocracking gim, nhng li nhanh chng kh hot tnh xc tc do s to thnh cc. Bng 3: c trng vn tc v hiu ng nhit ca nhng phn ng reforming quan trng Loi phn ng Hydrocracking Vn tc tng i Thp nht nh hng ca s tng p Hiu ng sut tng cng nhit Vn tc tng Ta nhit va phi

Dehydro ha to Thp vng isome ha ca Nhanh parafin isome naphten Dehydro parafin Dehydro naphten ha Nhanh

Khng nh hng ti s Thu nhit gim nh trong vn tc Gim vn tc Gim vn tc Gim chuyn ha Gim chuyn ha Ta nhit t Ta nhit t Thu nhit Rt thu nhit

ha

Kh nhanh Rt nhanh

ha

Nhit phn ng c chn lm cn bng gia s tng hot tnh xc tc v s tng vn tc phn ng kh hot tnh khi nhit tng. Khong nhit t 460 525oC v thng l gia 482 v 500oC. Nhng qu trnh hot ng p sut thp v nhit kh cao to ra sn phm c tr s octan cao
Mai Ngc Chin KTHH5 K54 14

Thit k phn xng reforming xc tc nht. Khi xc tc b mt hot tnh trong qu trnh hot ng nhit thng c gim t t duy tr tr s octan khng i. Khong vn tc th tch l t 0,9 n 5 phn th tch nguyn liu lng trn th tch xc tc trong mt gi, thng dng nht l t 1 2 . Nn la chn vn tc sao cho nhng phn ng hydro cracking xy ra trong gii hn cho php v nhng phn ng dehydro ha to vng xy ra t yu cu mong mun. Phn ng thm ha v isomeho khng b nh hng bi vn tc khng gian nn nhng phn ng ny t cn bng ngay c khi vn tc khng gian cao. T l mol gia hydro v hydrocacbon nguyn liu thay i t 3 n 10, nhng ph bin nht l t 5 n 8. T l ny th nh hng bt li n phn ng thm ha, tng phn ng hydro cracking v lm gim vn tlc phn ng nh hot tnh xc tc. Gi tr la chn thng gii hn thp phn ng hydro cracking xy ra t yu cu v s kh hot tnh xc tc l thp. Nhng naphtan c nhnh thng l thnh phn chnh ca nguyn liu. Nguyn liu c hm lng hydrocacbon khng no cao phi c hydro ha trc khi phn ng gim tiu th hydro trong phn ng v s kh hot tnh xc tc. Nng ca tp cht trong nguyn liu ng vai tr cht gy ng c xc tc phi c iu khin nghim ngt. Sunfua lm ng c chc nng kim loi ca xc tc nn phi duy tr nng nh hn 1 ppm i vi nguyn liu cho xc tc mi. Nguyn liu c hm lng sunfua cao phi c hydro sunfua ha trc phn ng. Cc hp cht nit hu c b chuyn thnh amoniac lm ng c chc nng axit ca xc tc. Nng ca n phi nh hn 2 ppm. Nit thng c loi ra khi nguyn liu x l hydro xc tc, ng thi vi hydro desunfua ha. Nc v cc hp cht cha Clo cng l thnh phn khng mong mun trong nguyn liu v n thay i axit ca cht mang v lm o ln cn bng ca nhng phn ng ang xy ra v nhng hp cht ny loi b, hm lng ca chng cn phi iu khin cn thn duy tr axit ca xc tc. Nhng kim loi nh ASipb, Cu phi gi nng rt thp v chng to hp kim vi ch lm kh hot tnh ca xc tc. Hm lng asen trong nguyn liu phi thp hn 30 phn t.

Mai Ngc Chin KTHH5 K54

15

Thit k phn xng reforming xc tc I.4. Xc tc Reforming Xc tc s dng trong qu trnh Reforming l loi xc tc lng chc nng. Chc nng oxy ho - kh c tc dng lm tng tc ca phn ng hydro

ho - kh hydro. Chc nng axit: c tc dng thc y cc phn ng theo c ch ion cacbon

nh ng phn ho v hydro cracking vng ho. I.4.1 Vai tr ca xc tc hai chc nng I.4.1.1 Platin Platin l cu t rt tt, l kim loi c dng ch yu trong qu trnh reforming xc tc. Palatin khng nhng xc tc cho phn ng dehydro ha cc naphten v phn ng dehydro - vng ho cc parafin to ra hydro cacbon thm m platin cn c tc dng thc y c phn ng no ha cc hp cht trung gian: olefin, diolefin... lm gim tc to cc trn b mt cht xc tc l mt nguyn nhn chnh dn ti vic gim hot tnh cht xc tc. Hm lng platin trong cht xc tc reforming chim khong 0,3 0,7 (% khi lng) . Hm lng pt c nh hng n hot tnh ca xc tc . v d khinguyn liu cha hm lng parafin ln m dng xc tc cha 0,35 % trng lng pt trong xc tc th nhn c xng c tr s octan l 102 m khng cn pha thm nc ch . phn tn ca pt trn cht mang AL2O3 cng nh hng n hot tnh ca xc tc . Trong qu trnh lm vic ca xc tc hm lng pt hu nh khng thay i nhng ta vn thy hot tnh kh hydro li gim xung l do cc tinh th pt b thiu kt t li thnh cc tinh th ln . V vy tm hot ng b gim xung . Vy hot tnh ph thuc ch yu vo hm lng kim loi pt v c bit l phan tn ca n trn cht mang Axt . ngi ta thy rng nu cc ht phn tn c kch thc nh hn 10A0 th l tm hot ng mnh , cn kch thc ht phn tn ln 70A0 th xc tc khng c hot tnh i vi cc phn ng chnh ca qu trnh reforming . iu chnh tng quan gia hai xc tc th pt ch nn chim 1% b mt ca cht mang .

Mai Ngc Chin KTHH5 K54

16

Thit k phn xng reforming xc tc Khi nghin cu ngi ta thy rng nu cho thm nguyn t Re vo c tc dng km hm s thiu kt ca cc tinh th pt v nguyn t Re s kt hp vi pt to thnh hp kim c n nh cao hn pt nguyn th . Do xc tc ca qu trnh reforming ngy nay l AL2O3 c thm nguyn t Re c hot tnh cao hn , n nh v bn nhit cao hn. I.4.1.2 Cht mang Cht mang trong xc tc reforming c th l Al2O3 hoc l SiO2, thng th ngi ta hay dng Al2O3. l mt Oxit c b mt ring ln (250 m2/g), chu nhit cao. Bn thn Al2O3 l mt axt lewis v nguyn t nhm cn c mt lng t t do, cn Al2O3 cha nc l mt axit Bronsted v mang H+.

Cht mang AL2O3 cn phi tinh khit ( hm lng Fe , Na khng qu 0,02% trng lng ) tng cng tnh axit ngi ta thng halogenua ha ri ch ha nhit. y thng dng clo. Nu s dng cht mang - AL2O3 hay- AL2O3 vi din tch b mt khong 250 m2/g th c b sung thm cc hp cht halogen nh flo ,clo, hay hn hp ca chng . Axt tng khi tng hm lng ca halogen , thc t cho thy ch nn khng ch hm lng ca halogen khong 1% so vi xc tc trnh phn hu mnh . Halogen c a vo xc tc khi ch to hoc khi ti sinh xc tc . Khi c clo th qu trnh xy ra nh sau :

Al - OH O Al - OH
Mai Ngc Chin KTHH5 K54

+ Cl

Al - OH O Al - Cl
17

+ OH -

Thit k phn xng reforming xc tc

Chc nng Axt c th hin bi cht mang . Axt ca n c vai tr c bit quan trng khi ch bin nguyn liu parafin c trng lng phn t ln : cc tm Axt kch ng phn ng hydrocracking ca cc parafin , phn ng ng phn ho hydrocacbon naphten 5cnh thnh 6 cnh , tip theo l cc naphten 6 cnh b kh hydro to thnh cc hydrocacbon thm . I.4.2. Nhng yu cu i vi xc tc reforming: Xc tc cn c hot tnh cao i vi phn ng to hydro cacbon thm c hot tnh i vi phn ng ng phn ho parafin v c hot tnh thp i vi phn ng hydro cracking. Xc tc phi c chn lc cao Xc tc phi c bn nhit v kh nng ti sinh tt. Xc tc phi bn vi cc tc nhn gy ng c (cc hp cht ca lu hunh,

nit, xy, nc mui ca kim loi nng v cc tp cht khc). Xc tc phi c n nh cao (kh nng bo ton hot tnh ban u trong

sut thi gian lm vic). Xc tc c gi thnh r.

PHN CNG NGH

II. Cng ngh Reforming
II.1 Cc yu t nh hng n qu trnh Qu trnh reforming c cc thng s cng ngh chnh nh : nhit , tc np liu, p sut v t l mol gia H2/RH ca nguyn liu.
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Thit k phn xng reforming xc tc II.1.1. nh hng ca nhit Qu trnh reforming xc tc tin hnh trong iu kin nhit nm trong khong 479 5250C, khi iu kin p sut v tc th tch khng i. Nu gim nhit th s tng hiu xut xng, hiu sut kh gim, lng hydrocacbon thm khng nhiu nn tr s octan ca xng khng cao, tuy nhin t to cc bm trn b mt xc tc nn thi gian lm vic ca xc tc di hn. Ngc li khi tng nhit qu trnh th hm lng kh tng ln, thnh phn lng gim xung dn n hiu sut xng gim , tuy nhin lng hydrocacbon thm tng nn tr s octan ca xng tng . khi nhit tng th kh nng to cc cao nn d lm mt hot tnh ca xc tc .V vy, iu chnh nhit sao cho ph hp vi cc thng s k thut khc m bo hiu sut , cht lng ca sn phm yu cu . Bng 4: nh hng ca nhit ti mt s ch tiu ca sn phm Nhit (oC) Ch tiu 435 Hiu sut xng kh propan (%) Hm lng phn on c Tos n 100oC (% TT) Hm lng hydrocacbon thm trong xng (% TT) p sut hi bo ha ca xng (mmHg) Tr octan theo phng php nghin cu (khng pha nc ch) 67,5 74 80,5 89 19 27 35 45 34 36 41 46 98 450 96,8 465 95 480 91,6

310

350

430

590

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Thit k phn xng reforming xc tc II.1.2. nh hng ca p sut Phn ln cc phn ng chnh ca qu trnh reforming xc tc u km theo qu trnh tng th tch .Theo quan im nhit ng hc th p sut cao s cn tr qu trnh ca cc phn ng tng th tch c ngha l cn tr qu trnh to hydrocacbon thm. Nhng nu p sut thp th phn ng cracking xy ra mnh, dn n to cc nhiu v vy ngi ta phi duy tr p sut cao trong h thng. p sut trong h thng c quyt nh ch yu bi hot tnh v chn lc ca cht xc tc. V d trc s dng xc tc Mo/Al2O3 th p sut trong h thng chn 15 20 at. Nhng hin nay thng dng xc tc Pt/Al2O3 th duy tr p sut 20 40 at trong h thng m hot tnh to hydrocacbon thm vn m bo. p sut ca qu trnh l nhn t chnh nh hng n hiu sut v s quay vng xc tc, p sut t 400 500 psi thch hp thi gian quay vng xc tc di, do vy s gim p sut, cn bng phn ng dehydro ha chuyn v pha lm gim hiu sut sn phm thm v hydro. S gim p sut lm gim kh nng hydrocracking. Vic tng phn ng dehydro ha v phn ng hydrocracking lm tng hiu sut C5 v sn phm reforming. Nhng s gim p sut thp s kh hot tnh xy ra nhanh n mc thi gian rng ca xc tc ch vi ngy, trong khi p sut cao thi gian sng ca xc tc c th n 1 nm. Cc thit b bn ti sinh khng thun li cho hot ng p sut thp cho n khi s a vo xc tc hai hay nhiu kim loi lm gim mc to cc. Nh vy c th s dng p sut 200 250 psig m vn duy tr c thi gian quay vng xc tc kh khi hot ng p sut cao. Vi thit b tun hon v thit b lp xc tc chuyn ng th p sut c th gim n 85 psig. Trong nhng h thng nhiu thit b hoc thm ch 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 ring phn ca hydro cng nh hng ng k n qu trnh, nh hng ny c minh ho bng s ph thuc vn tc phn ng dehydro ha ng vng ca n heptan c xc tc bi Pt/Al2O3 vo p sut ring phn hydro.

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Thit k phn xng reforming xc tc 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 dehydro ho ng vng u xy ra. Nu p sut ring phn ca hydro vt qu 10 atm th c th loi b cc hu nh hon ton. Nhng nu tng hn na th hn ch vn tc phn ng dehydro ha, p sut ring phn cng nh hng n phn ng isomeho v dehydroisome ha. II.1.3. Tc np liu Khi tng lu lng nguyn liu (hay gim cht xc tc trong cc thit b phn ng ) s lm gim thi gian tip xc ca cc cht tham gia phn ng vi cht xc tc dn n lm tng hiu sut xng n nh v tng hm lng hydro trong kh tun hon , gim hiu sut hydrocacbon thm dn n tr s octan gim . Ngha l khi tng tc th tch th cc phn ng kh hydro ca napten , hydro cracking, ng phn ho butan v pentan s chim u th v xy ra nhanh hn. Cn cc phn ng i hi thi gian nh kh hydro , vng ho parafin, kh alkyl ,hydrocracking , hydrocacbon nh xy ra yu hn . v vy tnh ton tc np liu ring sao cho ph hp .Trong qu trnh reforming xc tc th tc np liu ring thng c duy tr trong khong 1,5 gi (h-1) II.1.4. T l hydro/hydrocacbon nguyn liu T l mol hydro trong kh tun hon trn mol nguyn liu trong qu trnh reforming xc tc thay i trong mt gii hn rt rng tu theo mc ch ca qu trnh. p sut hydro l yu t rt quan trng trnh s to cc . T l mol H2/RH xc nh nng ca hydrocacbon trong vng phn ng .t l mol hydro s dng n nh do np kh cha hydro cho tun hon tr li t qu trnh phn ng. Chn t s tun hon kh cha hydro c quyt nh bi cc yu t : thnh phn phn on ca nguyn liu, khc khe ca qu trnh v tr s octan ca sn phm xng. T l hydro trn nguyn liu cng cao th tc to cc trn xc tc cng nh v thi gian lm vic ca xc tc cng ko di . song nu tng t l s dn ti tiu tn mt lng nhit ng k , ng thi lm tng tr lc thu ng v th tch ca thit b , ng dn.V

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Thit k phn xng reforming xc tc vy cn phi iu chnh t l hydro trn nguyn liu sao cho ph hp vi yu cu sn phm II.2. Gii thiu mt s s cng ngh II.2.1. Gii thiu chung 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 qu trnh ny 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,ci tin theo hng xc tc v ci tin theo hng cng ngh v mang li nhng kt qu ng k (bng 5) cho ta thy s ci tin v xc tc v cng ngh. Bng 5: S lc tin hnh ci tin xc tc v cng ngh reforming xc tc trn th gii. 1940 1949 1950-1960 1960 1970 1980 1990 Reforming xc tc u tin s dng xc tc molipden Pht trin xc tc Pt Rt nhiu qu trnh Reforming xc tc c pht trin t xc tc Pt 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. Qu trnh reforming ti sinh xc tc sn sut hydrocacbon thm. Ra i qu trnh reforming xc tc mi (new reforming).

T nm 1950, nhiu qu trnh reforming xc tc s dng xc tc Pt c pht trin v qu trnh reforming trong khu lc du l cha kho chnh sn sut xng c tr s
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Thit k phn xng reforming xc tc octan cao cng vi qu trnh cracking vi lp xc tc si (FCC). Qu trnh reforming xc tc khi s dng thit b vi lp xc tc c nh nn n phi nh k dng lm vic ti sinh xc tc b cc ha. Mt s qu trnh s dng l phn ng c ng van song song d ti sinh xc tc tng l phn ng ring m khng cn phi dng lm vic ton b h thng (qu trnh powerformer). Vo thp nin 1960, xc tc hai v a kim loi c pht trin. Xc tc hai 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, chi ph vn hnh khng cao . u nhng nm 1970 mt ci tin ni bt v qu trnh reforming xc tc ra i l qu trnh c ti sinh lin tc xc tc ca UOP v tip theo l ca IFP, xc tc b cc ha c tho ra lin tc khi l phn ng v c a quay tr li l phn ng sau khi c ti sinh trong thit b ti sinh ring. Qu trnh ny c gi l qu trnh ti sinh lin tc xc tc (CCR). Nh kh nng ti sinh lin tc xc tc b cc ha, qu trnh CCR cho php dng p sut thp v tho lin tc, hng nm cha phi thay xc tc mi, cng nh gim p sut m hiu sut hydrocacbon 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 6. Cc hng i u trong qu trnh ci tin reforming xc tc

Tn qu trnh

Hng thit Loi thit b k phn ng

Loi xc tc

Loi l ti sinh Ti sinh

(Platformer) Platreforming

UOP

Xc tc c nh

R11 - R12

Pt = 0,375 gin on
23

Mai Ngc Chin KTHH5 K54

Thit k phn xng reforming xc tc 0,75 Powerforming (Powerformer) IFP reforming (IFP reforming) Maonaforming (Maonaformier) ReNiforming (Reniformier) CCR plat-forming (CCR platFormer) EXXO Xc tc c nh N IFP Xc tc c nh KX, RO, Ti sinh BO(Pt, Re) gin on RG 400 Pt (0,2 -0,6) Ti sinh gin on

Engelh Xc tc c nh ard CRC Xc tc c nh

RD.150(pt = Ti sinh 0,6);E500 gin on FC (pt, Re) Ti sinh gin on Ti sinh lin tc Ti sinh lin tc

UOP

Xc tc chuyn ng, thit b phn R16 : 20 ng chng ln nhau pt, Re Xc tc chuyn ng, thit b phn Pt, Re ng chng ln nhau

AromiZer

IFP

Phng php ti sinh xc tc ca qu trnh reforming xc tc thng c chia lm 3 loi : Thit b bn ti sinh (xc tc c nh), thit b ti sinh tun hon (c lp t 1 thit b phn ng ph) v thit b lp xc tc chuyn ng. y vn c bn trong thit k thit b xc tc l cn bng nhit. Nhng phn ng to ra nhng sn phm thm l thu nhit. Mc d nhng phn ng ny c b li bi phn ng ta nhit hydrocracking, vn cn phi cung cp mt lng ln nhit vo vng phn ng. Trong thit b lp xc tc c nh, nhit c cung cp bi vic s dng mt s thit b ni tip vi s gia nhit li gia nhng phn ng. V nhng hp cht c kh nng phn ng cao, phn ng u tin nn gim nhit ln xy ra thit b u tin. Mi thit b tip theo c gim nhit thp hn thit b trc.

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Thit k phn xng reforming xc tc Trong qu trnh xc tc chuyn ng nhit c cung cp bi dng kh tun hon. Trong hydroforming pha lng, dng kh tun hon c a vo y ca thit b v i qua lp xc tc tng si : Do s trn nhanh chng ca xc tc, nhit ca lp xc tc l hng s. Trong xc tc chuyn ng khng c s trn ca xc tc, do dng kh tun hon nng c a vo vi im trong lp xc tc. Xc tc c t nng khi n i qua mi im. Gia cc im nhit ca xc tc gim do tc dng ca nhng phn ng thu nhit. H thng bn ti sinh : Nguyn liu c s l trc khi i qua b phn trao i nhit vi dng sn phm, nguyn liu kt hp vi dng kh tun hon i vo thit b cp nhit tng nhit ln khong 900 980oF. Sau , nguyn liu i qua mt lot thit b phn ng. Cc l nung gia cc thit b b li s mt mt nhit do cc phn ng thu nhit. Sn phm sau khi trao i nhit vi nguyn liu c i vo mt my sy chn khng. Ti y, sn phm lng c ly ra y cn phn nh c phn chia thnh sn phm hydro v kh tun hon. Sn phm lng c a i n nh loi b phn nh. Thit b ny ngng lm vic theo chu k ti sinh xc tc. Thi gian gia hai ln ti sinh t nht l 6 thng. p sut trong thit b thng l t 500 550 psig (p sut cao). Vi thit b ny, tr s octan ln nht ca sn phm ch t khong RON = 100.vi cng ngh ny mt d tin hnh p sut cao nhng trong cng nghip ch bin du qu trnh ny vn cn kh ph bin , v quy trnh cng ngh kh n gin ,u t ban u va phi iu kin vn hnh khng qu kht khe. H thng tun hon: H thng ny khc h thng bn ti sinh ch n c thm mt s thit b phn ng d tr v mt h thng ng ng na xc tc trong mt thit b c th ti sinh trong khi cc thit b kia vn lm vic. Thit b ny c th thay th cho bt k thit b no trong h thng. u im ca qu trnh ny l p sut thit b thp nn c th t c hiu sut sn phm v tr s octancao (RON trn 100). Cc thit b cui cng thng nhiu hn cc thit b trc v nhit trung bnh cao hn do vy n thng c thay th thng xuyn hn. Do h thng ny lm vic p sut thp hn (200 400 psig) v iu kin khc nghit hn thit b phn ti sinh nn vic ti sinh tng
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Thit k phn xng reforming xc tc thit b thng xuyn ha v do hiu sut sn phm cao hn trong h thng bn ti sinh. H thng lp xc tc chuyn ng: Trong h thng ny, thit b thng c t chng ln nhau t thit b cui cng . Nguyn liu cng c nung nng bng trao i nhit. Thit b phn ng l loi thit b chy xuyn tm xc tc chuyn ng chm ti thit b u tin nh n thit b y. Xc tc b cc lng ng c a ti b phn ti sinh khi phc li hot tnh ri np tr li thit b phn ng th nht to thnh mt chu trnh kn . Vi cng ngh ny , nh ti sinh xc tc lin tc m khng phi dng qu trnh ti sinh xc tc nh cc dy chuyn c , v do vy xc tc va mi c ti sinh c chuyn lin tc vo thit b phn ng . iu lm cho xc tc c hot tnh cao v n nh hn ,v p sut thp thun li cho qu trnh . Mt loi khc t ph bin hn l cc thit b phn ng c ring nh bn ti sinh. Xc tc b lng cc c lng ra thit b cui cng v a i ti sinh. Xc tc mi v xc tc ti sinh c a vo nh ca thit b u tin duy tr lng xc tc khng i. V h thng ny hn ch s to cc trn xc tc nn n c th lm vic p sut thp 100 psig hoc iu kin khc nghit hn. S mt mt hiu sut sn phm c th hn ch ti a nu chn c t l tun hon xc tc thch hp. H thng xc tc tng si : H thng ny gm nhng thit b phn ng v thit b ti sinh t ni tip nhau. H thng lm vic p sut 200 300 psig nhit 900oF. duy tr nhit ny kh tun hon phi c un nng n nhit 1200oF (nhit nguyn liu nh hn 1100oF gim cracking nhit). Nhng ng ng xon lm ngui c lp trong thit b ti sinh lm gim s qu nhit do t chy v gin nhit 1100oF xc tc c th c tun hon vi t l 1 pound/pound nguyn liu. Nu t l tun hon cao hn, nhit t chy s c th truyn sang thit b phn ng v ng ng lm sch c th loi b. Tuy nhin, nu tng t l tun hon yu cu nn kh trong thit b ti sinh s tng v modipden trong xc tc tun hon s b kh trong thit b
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Thit k phn xng reforming xc tc phn ng v b oxy ha li trong thit b ti sinh. Mt phng php c s dng truyn tt c nhit ti sinh m khng lm tng lng khng kh. Theo phng php ny, mt vt liu tr cha tinh ch c tun hon gia thit b phn ng v thit b ti sinh vi t l ph thuc vo t l tun hon xc tc. Cc h thng kt hp: tr c octan ca mt qu trnh reforming c th c nng cao bng cch s dng nhng phng php chit, hp th hoc cracking nhit ph tr. S kt hp gia qu trnh platforming v chit gi l reforming, trong khi s kt hp gia hp th hoc reforming nhit vi Uareforming gi l iso - plus. C rt nhiu qu trnh feforming khc nhau do cc cng ty khc nhau a ra. iu kin hot ng ca mt s qu trnh c a ra trong bng 6 Bng 7: iu kin hot ng ca mt s qu trnh reforming Xc tc Pt Xc tc Hydroforming Platforming Ti sinh gin on Thnh phn xc tc trn cht mang 10% MnO3 Al2O3 Phn ng T, oF P, psig WHSP pound/pound Ti sinh Loi T, oF P, Psig Ring 1100 200 Vi nm Khng Gin on 1050 250 300 25 7,5 bbT
27

Ti sinh tun hon Pt 850 950 200 - 400 1- 5

Pt thadogen

0,5% Pt 875 - 950

890 - 940 100 - 300 0,3 - 1

850 - 960 200 - 700 1- 4

200 - 600 1-5

Tun hon

Thi gian gia 2 Lin tc

Mai Ngc Chin KTHH5 K54

Thit k phn xng reforming xc tc ln ti sinh thng (1b)

II.2.2 Mt s s dy chuyn cng ngh II.2.2.1 S cng ngh qu trnh platforming ca hng UOP vi lp xc tc c nh Trong cng ngh ch bin du , qu trnh reforming vi lp xc tc c nh vn cn ph bin. y iu kin tin hnh qu trnh c chn m bo thi gian gia cc ln ti sinh ln (thng trn 6 thng n mt nm). Qu trnh ti sinh xc tc c tin hnh ng thi trong tc c thit b phn ng i vi h thng khng c cc thit b d tr. H thng trong qu trnh reforming xc tc thc hin phn ti sinh xc tc c tin hnh nh k ngay trong thit b phn ng. Loi h thng ny c th chia lm hai nhm : Nhm 1: Cc h thng trong qu trnh ti sinh xc tc c tin hnh ng thi trong tc c cc thit b phn ng. H thng ny c tin hnh ch cng va phi. Chu k lm vic ca xc tc ko di trong nhiu thng (c th 4-8 thng ). Thuc nhm ny c th k n cng ngh ca cc nc Lin X (c) v M nh qu trnh Katforming v Gudri-forming . Nhm 2: Cc h thng trong qu trnh ti sinh xc tc c thc hin trong mt s thit b d tr. N cho php khng cn dng ton b h thng reforming ti sinh xc tc, tuy nhin h thng li phc tp hn v mt cng ngh. H thng nay tin hnh ch cng v chu k lm vic ca xc tc ngn. Tiu biu cho nhm nay l cng ngh Ultraforming v Platforming.

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Thit k phn xng reforming xc tc

Hydro

Thit b phn ng

Kh nh

L gia nhit

Ngng t hi lu Thit b phn ng

Nguyn liu My bm Sn phm reformat

Hnh 4: Cng ngh reforming vi lp xc tc c nh UOP platforming

Nguyn tc hot ng: Nguyn liu l phn on naphta c sy kh v lm sch t b phn hydro ho lm sch c trn vi kh hydro t my nn sau khi qua cc thit b trao i nhit v c np ni tip vo l t nng v cc thit b phn ng t 1 n 3 (ngy nay thng dng n 4 l ). Sn phm ra khi l sau khi qua cc thit b trao i nhit c np tip
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Thit k phn xng reforming xc tc vo thit b t nng v thit b lm sch. Sau qua thit b ngng t, sn phm s gi nhit 38 0C. Kh khng ngng s c tch ra thit b tch kh. Phn ln kh ny c my nn v tip tc tun hon li. Phn cn li c dn sang b phn tch kh v s dng hydro sau khi tch cho cc qu trnh khc , v d cho hydro ho lm sch. Sn phm y ca thit b tch c a qua thit b trao i nhit vi sn phm nng ca y ct .Sn phm nh ca ct c dn sang thit b ngng t . hi s c tch ra khi dy chuyn . Sn phm lng c hi lu bng bm xng reforming n nh y c a qua thit b trao i nhit ri qua thit b lm sch, sau qua b cha. II.2.2.2 S cng ngh qu trnh magnaformig do hng Chevron, s dng xc tc Pt - Re y l qu trnh ci tin cng ngh reforming truyn thng c hiu qu nht. Qu trnh ny lm gim lng kh tun hon vo thit b reforming u tin v tng lng kh tun hon vo thit b cui cng

L phn ng

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Thit k phn xng reforming xc tc

L gia nhit

Hi Trao i nhit Lm lnh Hi

Thit b tch

Thp n nh

Nguyn liu

Bm My nn

lng

Hnh 5: S cng ngh xc tc c nh Magnaforming Trong thit b u tin, do nhng phn ng ta nhit nn phn ng dehydro ho gim so vi phn ng hydrocracking. V vy, s gim lng kh tun hon vo thit b ny lm gim nh hng sn phm kh do hydrocracking to ra. Magnaforming 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 tr u t cng tng 6,5% so vi h thng 3 thit b. Ti sinh xc tc: i vi h thng cng ngh ti sinh ng thi th cc bc tin hnh nh sau :
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Thit k phn xng reforming xc tc u tin ngng bm nguyn liu, cho thit b phn ng ngng hot ng xong vn tip tc bm kh ui ht cc hydrocacbon ng thi gim dn nguyn liu t l sau ngng hn. Nhit h xung 2000c th ngng bm kh hydro, thi ht kh hydro bng cch ht chn khng . Thi v thi kh tr sau bm kh tr n p sut khong 10 atm, un nng thit b phn ng t t, khi nhit vo khong 2500c th bm khng kh vo sao cho lng oxy vo khong 0,5% th tch v tng t t cho n 2% th tch th kt thc. Khi cc chy ht, nhit vo khong 4000c , gi nhit trong l khng qu 5000c sau lm lnh, thi kh tr qua v cui cng thi kh hydro qua. Bt u khi ng li h thng lm vic. Khi s cng ngh c s dng l d tr th vic ti sinh khng lm gin on thi gian lm vic v ch n gin l chuyn ng dn nguyn liu sang l phn ng lm vic thay th, qu trnh ti sinh i vi l phn ng lm vic tng t nh trnh by trn . II.2.2.3 Dy chuyn reforming vi lp xc tc chuyn ng Nm 1970 , mt ci tin ni bc v qu trnh reforming xc tc ra i l qu trnh c ti sinh lin tc xc tc ca UOP v IFP gi l qu trnh CCR . n nm 1996 , hng UOP xy dng c 139 nh my CCR cn IFP c 48 nh my CCR . c bit ca dy chuyn ny l cc l phn ng chng ln nhau thnh mt khi. Xc tc chuyn ng t chy t thit b phn ng trn cng xung thit b phn ng cui cng, sau xc tc lm vic c chuyn sang thit b ti sinh khi phc li hot tnh ri np tr li thit b phn th nht, to thnh chu trnh ln. Trong cc h thng ny qu trnh ti sinh xc tc c thc hin trong mt thit b ti sinh ring . y l h thng reforming xc tc hin i nht xut hin M nm1971. Trong cc h thng ny, cc thit b phn ng c b tr chng ln nhau lm thnh mt c cu chung nht. Xc tc i t thit b phn ng th 1 xung thit b phn ng th 2, ri ln lt xung thit b th 3,4 v cui cng xc tc c a sang thit b ti sinh. Sau khi xc tc ti sinh n li c a v thit b phn ng th nht. Nh vy qu trnh reforming xc tc c thc hin lin tc. Nh ly ra lin tc mt phn xc tc ti sinh nn c th duy tr mc hot tnh trung bnh ca cht xc tc cao hn v n nh hn so vi lp xc tc c nh. Do vy m p sut v bi s tun hon kh cha
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Thit k phn xng reforming xc tc hydro c th gim xung tng ng 3,5-12 at v 400-500 m3/m3. Vic gim p sut c nh hng tt n qu trnh, tng c hiu sut, tng nng hydro trong kh cha hydro. Ngy nay loi reforming ti sinh 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 dy chuyn c (dy chuyn reforming xc tc c nh). iu lm cho xc tc c hot tnh cao hn v n nh hn, lm vic iu kin kht khe hn v vn cho hiu qu cao hn. Sau y s cp mt cch chi tit qu trnh reforming xc tc chuyn ng ca hng UOP.

Xc tc ti sinh Kh nhin liu

kh

Thu hi phn nh

3 1 Phn lng

Nguyn Mai Ngc Chin KTHH5 K54 li u

Hydro tun hon

Sn phm reformat

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Thit k phn xng reforming xc tc

Hnh 6:S cng ngh qu trnh platforming ca hng UOP 1-thit b phn ng 3-thp tch 5-thit b ngng t Nguyn tc hot ng : S reforming ti sinh xc tc lin tc ca hng UOP c trnh by (hnh 6). c im ring bit ca s l cc thit b phn ng chng ln nhau thnh mt khi. Xc tc chuyn ng t thit b phn ng trn cng xung thit b phn ng cui cng. Xc tc lm vic c chuyn sang thit b ti sinh khi phc li hot tnh ri c np tr li thit b phn ng u to thnh mt chu trnh kn. Nh ly ra lin tc mt phn xc tc
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2-l gia nhit 4-thp n nh

Thit k phn xng reforming xc tc ti sinh nn n c th duy tr mc hot tnh trung bnh ca cht xc tc cao hn so vi h thng vi lp xc tc c nh. Do vy m p sut v bi s tun hon kh cha hydro c th gim xung tng ng c th 9 12 at v 400 500 m3/m3. Vic gim c p sut c nh hng tt n cht lng ca qu trnh, tng hiu sut, tng nng hydro trong kh cha hydro. Lng xc tc cha trong thit b phn ng rt khc nhau , thit b th nht ch cha 10-20% lng xc tc v cc thit b cui cha khong 50% khi lng xc tc . B phn ti sinh xc tc : Xc tc lm vic chy t thit b phn ng cui cng xung b phn thu xc tc bunke cha, sau chy xung ng nng. Ngi ta dng kh cha hydro tun hon t my nn tun hon y xc tc v vn chuyn n ln nh vo b phn tch bi pha trn l ti sinh. b phn ny ngi ta b sung kh hydro tun hon tch cc ht bi mn ca xc tc v mang chng ra ngoi vi kh i vo ng tp trung bi cn xc tc ri vo y b phn tch bi ri chy xung l ti sinh . Ti sinh xc tc gm c 4 bc, 3 bc u l :t chy,t chy cc clo ho v lm kh. Ba bc u xy ra vng ti sinh, v bc th 4 l kh xc tc xy ra trong b phn kh ring. t chy cc bm trn xc tc c tin hnh trong vng chy nm nh l ti sinh. Xc tc a vo v chy xung gia mng chn hnh tr ng thng, khng kh nng c thi theo hng bn knh i t ngoi vo trong qua lp xc tc sau lm lnh v tun hon qua cc ng trong vng chy, xc tc vn chuyn ng xung dn v b phn lm lnh ti sinh s ly nhit khi t cc. Vic t cc tun theo ch c bit nghim ngt m bo ht cc v khng nh hng xu n xc tc. Sau khi t chy cc th xc tc c cho qua vng clo ho clo ho v sau l sy. Cui cng xc tc c cho vo vng kh tch bit vi 3 khu vc t clo ho sy trn , sau khi kh xc tc c a theo ng dn xc tc vo ng xut xng, nu xt bin i nguyn liu th kinh t nht vn l dy chuyn CCR.
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Thit k phn xng reforming xc tc II.2.2.4 Qu trnh New reforming Sau mt thi gian di pht trin, cng nghip lc ha du thit lp c cng ngh mi c kh nng reforming chn lc kh ho lng v naphta nh thnh cc cu t c tr s octan cao, cho php pha trn xng c cht lng cao v cc sn phm hydrocacbon thm. T nm 1996 n nay, cng nghip du kh thay i cng ngh s dng naphta nh v kh ha lng lm nguyn liu cho sn sut xng cao tr s octan v hydrocacbon thm. Trong nm 1997, qu trnh Newreforming c pht trin nhm mc ch ny. Cc bc phn ng ca qu trnh c th tng qut ha nh hnh 7. NGUYN LIU Parafin nh HP CHT TRUNG GIAN SN PHM

Vng ha

Dehydro ha

Olefin Oligome

Hydrocacbon vng

Hydrocacbon thm

Hydrocracking

Sn phm cracking: metan, etan.

Hnh 7. S Phn ng Reforming parafin nh Cc phn ng xy ra trong qu trnh "New Reforming" gm: Dehydro ha olefin to ra olefin. Oligome ha olefin to thnh dime v trime. Vng ha dime v trime. Dehydro ha hp cht vng to thnh hydrocacbon thm.

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Thit k phn xng reforming xc tc Ngoi cc phn ng chnh trn, cn xy ra cc phn ng ph nh hydro cracking to metan, etan trong phn ng ngng t to cc bm trn xc tc. Trong s cng ngh reforming mi ca UOP, xc tc c s dng trong qu trnh l Zeolit c tnh chn lc hnh hc cho qu trnh vng ha. Tnh chn lc hnh hc ca Zeolit lm hn ch kch thc phn t ca cc hp cht sn phm trung gian v cho sn phm ch yu l hydrocacbon thm mt vng. So vi cc phn ng reforming bnh thng khc, qu trnh "New Reforming" to cc bm trn xc tc nhiu hn. Do vy vic ti sinh xc tc phi p dng cng ngh vi xc tc chuyn ng hay s dng l d tr. S pht trin ca "New Reforming" c khi qut bng 8: Bng8: Cc qu trnh New Reforming trn th gii Qu trnh Cyclar Z - Former Aromax Aroforming 2forming Hng thit k BP/UOP MitSubishi/Chiyod a CRC IFP Mobil Nguyn liu LPG LPG, Naphta nh Naphta nh Naphta nh Naphta nh, naphta

nhiu olefin

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Thit k phn xng reforming xc tc

PHN TNH TON

I.Cc s liu u : Cng sut : Nhit : 2.2 triu tn/nm. 743 8030K. 2 h-1. ? 40-45 at

Tc th tch LHSV: p sut :

Thi gian lm vic xc tc 1 nm Lng cc bm trn xc tc (% trng lng) : 3 5% T l H2/RH, (m3/m3) = 1500 Thit b phn ng chnh: l xuyn tm

Nguyn liu c nhng c tnh sau : Bng (17) c tnh ca nguyn liu : T trng (g/cm3) Ts u 0,733 358 Ts 50 395 Ts cui 438 P 62,61 N 26 A 11,39 Thnh phn phn on, K %, khi lng

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