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GVHD: PGS.TS. Nguyn Hu Trnh

Li cm n
Li u tin, em xin trn trng gi li cm n ti cc thy c gio B mn Cng ngh
tng hp hu c ha du trng i hc Bch Khoa H Ni to iu kin thun li
v gip cho em hon thnh bn n ny.
c bit em xin gi li cm n ti PGS.TS Nguyn Hu Trnh, ngi tn tnh gip
v trc tip hng dn em. Qua vic thc hin n, gip em hiu r hn v qu trnh
isome ha cng nh cc qu trnh khc trong nh my lc-ha du. Tuy nhin, do thi
gian v kin thc c hn, nn bn n khng th trnh khi nhng thiu st.
Em rt mong c thy ch bo, gip em hon thin bn n v kin thc ca mnh
c th phc v cho qu trnh lm n tt nghip quan trng pha trc.
Em xin chn thnh cm n.

Sinh vin thc hin

Lng Ngc Thi

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Mc Lc
Li cm n........................................................................................................................ 1
Mc Lc............................................................................................................................ 2
Li m u........................................................................................................................ 4
Chng 1. Tng quan v qu trnh isome ho...............................................................5
1.1. C s ho hc ca qu trnh isome ho...............................................................5
1.2. C ch ca phn ng isome ho............................................................................6
1.3. Xc tc ca qu trnh ...........................................................................................9
1.3.1. Xc tc pha lng..............................................................................................9
1.3.2. Xc tc axit rn................................................................................................9
1.3.3. Xc tc lng chc..........................................................................................9
1.4. c im ca nguyn liu naphta nh................................................................10
1.5. Sn phm qu trnh isome ha............................................................................11
Chng 2. Cc cng ngh isome ho cng nghip......................................................13
2.1. Cc qu trnh pha lng vi xc tc AlCl3...........................................................13
2.1.1. Qu trnh isomate (Standart Oil Co.Indiana) ............................................14
2.1.2. Qu trnh ca hng Shell Development Co..................................................14
2.1.3. Qu trnh ca hng Esso Rearch & Engineering Co..................................15
2.2. Cc qu trnh xc tc pha hi.............................................................................16
2.2.1. Qu trnh Butamer ca UOP........................................................................17
2.2.2. Qu trnh isome ho ca hng BP (British Petroleum) ..............................18
2.2.3. Qu trnh isome ho ca hng Shell ............................................................19
2.2.4. Qu trnh isome ho ca hng IFP...............................................................21
2.2.5. Cng ngh TIP ca UOP (Total isomerization process)..............................22
2.2.5. Cng ngh Penex ca UOP...........................................................................25
2.3. La chn s cng ngh v thuyt minh.........................................................26
Chng 3. Tnh ton cng ngh v thit b chnh.......................................................30
3.1. Cc s liu cn thit cho trc...........................................................................30
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3.2. Tnh ton cn bng vt cht v cn bng nng lng......................................30

3.2.1. Tnh ton cho l phn ng th nht.............................................................38
3.2.1.1. Tnh ton cn bng vt cht...................................................................38
3.2.1.2. Tnh ton cn bng nhit lng.............................................................42
3.2.2. Tnh ton cho l phn ng th 2..................................................................47
3.2.2.1. Tnh ton cn bng vt cht...................................................................47
3.2.2.2. Tnh ton cn bng nhit lng.............................................................52
Kt Lun......................................................................................................................... 56
Ti liu tham kho.........................................................................................................57

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Li m u
Hin nay du m tr thnh ngun nng lng quan trng nht ca mi quc gia
trn th gii. Hiu qu s dng ca du m ph thuc vo cht lng ca cc qu
trnh ch bin, trong cc qu trnh xc tc gi vai tr quan trng. Vic a du m
qua cc qu trnh ch bin s nng cao c hiu qu s dng v tit kim c
ngun ti nguyn qu him ny.
Xng l hn hp cc hydrocacbon t C5 n C10 c nhit si t 35C n
180C, d bay hi v c tnh t chy km. c dng lm nhin liu cho ng c t
trong l ch yu, ngoi ra cn dng lm dung mi cho cng nghip trch ly du v pha
ch m phm. Trong cng nghip sn xut xng, nhn chung cc quc gia u c xu
hng ci thin v nng cao cht lng xng nhm p ng yu cu k thut ca
ng c v bo v mi tng trong sch. V vy vic nng cao cht lng xng
trong quan trng nht l nng cao tr s octan, gim hm lng benzen, hm lng
cc hp cht cha oxy, hm lng olefin ang l vn t ln hng u.
Cng nghip ch bin du dng hai qu trnh ch o nhn xng c tr s octan cao
l qu trnh reforming xc tc v qu trnh cracking xc tc. Tuy nhin, do nhu cu v
xng cht lng cao ngy cng tng trong khi phn C5 v C6 ca cng nghip ch bin
du ngy cng c s lng ln m li khng th t c tr s octan cao khi p dng cc
qu trnh trn. Trc y phn on ny ch c dng pha trn vo xng vi mc
ch t p sut ca xng v thnh phn ct, cn tr s octan ca phn ny khng
cao v a s cc cu t ny ch yu l cc parafin mch thng. V th cn thit phi c
dy chuyn ch bin v s dng iso-parafin C5 C6, cc cu t ny c tr s octan
cao. nhn c iso-parafin C5 C6 ngi ta dng qu trnh isome ha. u im ca
qu trnh ny: Bin i hydrocacbon mch thng thnh cu t c cu trc nhnh l cu t
c tr s octan cao. Nh th nng cao ng k hiu sut v cht lng ca xng.
Qu trnh isome ha n-parafin c dng nng cao tr s octan ca phn on C5
v C6 ca xng si n 70 0C, ng thi cho php nhn cc iso-parafin ring bit nh isopentan v iso-butan t nguyn liu l n-pentan v butan tng ng, nhm p ng ngun
nguyn liu cho qu trnh tng hp isopren v isobutan l ngun nguyn liu tt cho qu
trnh alkyl ha hoc nhn isobuten cho qu trnh tng hp MTBE.
Chnh v tm quan trng ny m qu trnh c nhiu hng ln trn th gii nh
Shell, UOP, nghin cu v pht trin. Vi ti ny s gip e tm hiu k hn v vai
tr cng nh s pht trin ca qu trnh isome ho.

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Chng 1. Tng quan v qu trnh isome ho

1.1. C s ho hc ca qu trnh isome ho
Isome ho l qu trnh nhm bin i cc hydrocacbon mch thng thnh mch
nhnh. Qu trnh ny thng p dng nng cao octan pha vo xng nhm nng cao cht
lng.
Cc phn ng isome ho n-pentan v n-hexan l cc phn ng c to nhit nh. Do cc
phn ng isome ho to nhit nn v mt nhit ng, phn ng s khng thun li khi
tng nhit . Mt khc, phn ng isome ho n-parafin l phn ng thun nghch v
khng c s tng th tch, v th cn bng ca phn ng ch ph thuc vo nhit .
Bng 1.1. Nhit to thnh ca mt s cu t [2]
Cu t
C5: 2-metylbutan (iso-pentan)
2,2-dimetylpropan (neo-pentan)
C6: 2-metyl pentan (iso-hexan)
3-metylpentan
2,2-dimetyl butan (neo-hexan)
2,3-dimetylbutan

H298 Kcal/ml
- 1,92
- 4.67
- 1,70
- 1,06
- 4,39
- 2,53

Nhit thp to iu kin to thnh cc isome v cho php nhn c hn hp

iu kin cn bng v c tr s octan cao. th di y cho thy s ph thuc gia
nng cn bng ca cc isome vo nhit ca phn ng isome ho n-pentan v nhexan c xy dng t tnh ton v thc nghim. T th cho thy, khi tng nhit ,
nng cc isome u gim, cn nng cc n-parafin tng. Cng t th, nu t<
200C s thit lp c mt hn hp cn bng c tr s octan cao.

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Hnh 1.1. s ph thuc nng cc cu t vo nhit phn ng

Khi isome ho cc n-parafin cn xy ra mt s phn ng ph nh phn ng
cracking v phn ng phn b li:
2C5H12
C4H10 + C6H14
gim tc ca phn ng ph ny v duy tr hot tnh ca xc tc, ngi ta phi
PH 2

thc hin qu trnh p sut hydro

= 2 4 MPa v tun hon kh cha hydro.
ng hc v c ch phn ng isome ho ph thuc vo iu kin tin hnh qu
trnh v ph thuc vo xc tc.
1.2. C ch ca phn ng isome ho
Cc qu trnh ch bin du c th c thc hin trong pha lng hoc pha hi. Qu
trnh thc hin trong pha lng vi xc tc Friedel-Crafts (AlCl 3) nhit 80-100 C
t c ph bin. Qu trnh thc hin trong pha hi l qu trnh ph bin vi xc tc
axit, axit rn hoc xc tc lng chc nhit cao, do vy ta xt c ch ca qu trnh
ny.
V d:
Phn ng bin i n-butan thnh isobutan v isobuten [1]:

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Cch 1:

Cch 2:
CH3 CH2 CH2

A(H+) H2

CH3 C+H

CH3

CH2 CH3
A(H+)

CH3 CH

M - H2

Trun g tm
axitA(H+)

CH3 CH

CH

CH3

-H2

CH

CH3
CH3

CH3

CH

CH2
CH

H
+

C + H2

CH3 CH

CH2

CH3

C ch
xyclopropan
M, + H2
CH

CH3

C+ CH3

- H+

CH3

CH3
A(H+)

CH 3

-H2

CH2

CH 3
C ch xyclopropan mi gii thch c s to thnh iso-parafin v iso-olefin.
Theo c ch trn, xyclopropan khi m vng to thnh C + bc 1, tuy nhin tc
to thnh rt nh sau chuyn sang C+ bc 3 vi tc rt ln:
CH2
H+

CH3

CH
CH3

CH2
CH

CH2+

CH3

CH3

C+ CH3
CH3
CH
+ H2
CH3
CH3

CH3 + H+

Ngoi cc phn ng trn cn xy ra phn ng to dime (c ch lng phn t):

C C C+ C + C C C C
C C C C C C C
2C 4
t mch

C
+
C
C

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C
Trong hai c ch trn, c ch lng phn t d xy ra hn. Tuy nhin sn phm
trung gian ca c ch ny (dime) c kch thc ln hn, nn nu cht xc tc c l kch
thc nh hn kch thc ca dime th phn ng ny khng xy ra. Do vy, mun tng
chn lc, phi chn xc tc c chn lc ph hp. Xc tc thng dng trong cng
nghip l zeolit feriorit (d=5Ao, axit tng ng vi ZMS-5).
Isobutan l cu t rt quan trng v t , bng cch dehydro ha thu isobuten, l nguyn
liu sn xut MTBE. S phn ng nh sau:
n- butan
iso- butan
iso- buten
MTBE
Phn ng c th xy ra trn xc tc axit rn, in hnh l zeolit.
Isome ha n- hexan thnh isohexan:
C ch phn ng ny xy ra qua hai giai on nh sau:
+ Giai on 1: To olefin, xc tin cho qu trnh ny l cc tm kim loi trong xc
tc Pt.
C

-H2

+ Giai on 2: ng phn ha, xy ra trn tm axit Lewis:

A

C
C

C
C

C
C

+H2
A

C
C

C+ C
C C

C+

M, H2

C
C

C
C

C+
C C C
C C C C C
-H

C
C
Tm li, xc tc cho isome ha tng t nh nh xc tc cho reforming, xc tc hai
chc nng,v isome ha thng xy qua hai giai on:
Giai on 1: Tch hydro ( lc ny vai tr xc tc l tm kim loi M)
Giai on 2: ng phn ha ( vai tr xc tc l cc tm axit A).
C

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1.3. Xc tc ca qu trnh [1]

Xc tc cho qu trnh isome ho thuc loi xc tc thc y phn ng to thnh ion
cacboni, tc l cc xc tc c tnh axit. C th chia lm 3 loi:
1.3.1. Xc tc pha lng
Xc tc cho qu trnh isome ho thuc loi xc tc thc y phn ng to thnh ion
cacboni tc l xc tc mang tnh axit. Trc y ngi ta dng xc tc Lewis nh AlCl 3
c hot ho bng HCl. Gn y ngi ta vn s dng xc tc trn c s AlBr 3 v hn
hp AlCl3 + SbCl3, u im ca loi xc tc mi ny l hot tnh rt cao, nhit 93 C
hu nh chuyn ha hon ton cc parafin C 5 - C6 thnh iso parafin. Nhc im ca
loi xc tc ny l mau mt hot tnh, chn lc thp v d b phn hu [1]. axit
mnh ca xc tc d gy n mn thit b. Ngoi cc xc tc trn th cng cn s dng
mt s xc tc nh:
H3PO4 26-1350C
C6H5SO3H 760C isome ha buten-1v buten-2
H3PO4/cht mang l t nung 325-3600C isome ho n-anken v iso-anken [2]
1.3.2. Xc tc axit rn
BeO: Dng bin i xyclohexan thnh metylxyclopentan 450C.
Cr2O3: Dng bin i hexadien-1,5 thnh hexadien-2,4 225-250oC
ThO2: Isome ha olefin 398- 440C
TiO2 : Dng bin i heptylen thnh metylxyclohexen 450C
Al2O3-Cr2O3, Al2O3-Fe2O3 , Al2O3-Co, Al2O3-MnO2 (tt c u trn theo t l khi
lng l 4:1) dng isome ho metylbutylen 294-370C.
Al2O3 Mo2O3: Bin i n-pentan thnh iso-pentan 460C
Cr 2O3-Fe2O3 : Chuyn v tr ni i, ni ba trong hp cht khng no 220-300 C
m khng thay i cu trc mch cacbon.
MoS3 : Dng bin i n-parafin thnh iso-parafin.
Al2O3-V2O5: c dng bin i xyclohexan thnh metylxyclopentan.
Zeolit cc loi: isome ha hydrocacbon thm.
1.3.3. Xc tc lng chc
l cc loi xc tc tng t nh xc tc reforming Pt/Al 2O3. Vi xc tc ny c th
to ran gay R+ 50C ( nhit phn ng ni chung nh hn 150C). Sau ny ngi ta
dng xc tc Pt/mordenit, hoc Pt/zeolit khc. Vi xc tc , phn ng phi thc hin

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250C. Nhng ph bin vn l loi xc tc Pt/Al2O3, c 7% trn xc tc. Dng CCl4

clo ho.
S khc nhau gia xc tc izome ho v xc tc reforming ch:
Xc tc reforming Pt/Al2O3.Cl (Pt 0,3%, lng clo t)
Xc tc izome ho Pt/Al2O3.Cl (Pt 0,3%, lng clo nhiu hn).
Reforming
Izome ho
Al- Cl
Cl-Al-Cl
Lc axit yu hn
lc axit mnh hn
( 1 nguyn t clo cho 1 nguyn t Al)
(2 nguyn t clo cho 1 nguyn t Al)
Zeolit l mt trong cc axit rn, n c tnh rt qu: axit cao, l xp ln, l mt ry
phn t, do vy cho php ta tch c cc phn t c kch thc khc nhau. Tt hn c l
dng xc tc zeolite ZMS-5 ca hng Mobile Oil (M).
Bng 1.2. c trng ca xc tc isome ho [1]

Nhit phn ng
khi s dng

Nhit phn ng khi s

dng

FiedelCrafts AlCl3.AlBr3

80-100C

Pha lng gy n mn

Oxit Al2O3,Cr2O3,BeO

200-450C

Pt/Al2O3

350-500C

Pt/Al2O3 clo ho

80-150C

Pt/zeolite

250-300C

Pt/zeolite-X

300-330C

Pt/zeolite-Y

300-330C

Pt/ZSM5

300-330C

Xc tc

Pha hi

1.4. c im ca nguyn liu naphta nh

Isome ho thng dng nguyn liu l phn on light naphta, c ly t phn
xng naphta hydrotreating. c trng ca nguyn liu s quyt nh ch cng ngh
v cht lng sn phm. Thnh phn ca nguyn liu tiu biu c ngun gc khc nhau
c trnh by bng 1 di y.

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Bng 1.3. Thnh phn nguyn liu tiu biu [2]

Ngun nguyn liu

Kuwait

C5: n-pentan
2-metylbutan
2,2-dimetylpropan
Xyclopentan
C6: n-hexan
2-metylpentan
3-metylpentan
2,2-dimetyl butan
2,3-dimetyl butan
Metylxyclopentan
Xyclohexan
Benzen
RON ca C5
RON ca C6

58.5
41.5
0.1
43.2
22.4
16.9
2.0
4.2
5.1
4.2
2.0
74.4
55.9

Mid
continent
3.0
36.2
0.8
41.6
26.3
14.3
0.5
0.5
14.0
2.2
0.6
72.9
57.7

Xng
ct
42.2
56.2
1.2
27.7
32.5
12.5
0.75
0.75
17.0
4.5
79.2
76.4

Arabia

Wyoming

64.3
33.3
2.4
46.6
40.5

59.8
36.4
3.8
37.8
38.2

3.9

3.8

7.3
2.0
72.1
55.1

18.8
1.4
73
61.1

T cc s liu trong bng thy rng, hm lng n-parafin thng khng vt qu

65% trong nguyn liu. Do , nu cho ton b nguyn liu qua bin i isome ho l
khng hp l m cn phi tch cc isome khi n-parafin v ch cho bin i n-parafin.
hn ch cc phn ng ph v s km hm qu trnh nn tin hnh phn ng mc
bin i va phi, ri sau khi tch cho tun hon tr li nguyn liu cha bin i. Khi
tin hnh thao tc nh vy, cho php tng cao tr s octan ca phn on ln ti thiu
l 20 n v.[1]
Trong thc t cng nghip, ngi ta thng em isome ho phn on C 5 -C6 cn nheptan em isome ho khng tin li v trong iu kin tin hnh qu trnh, cc parafin
cao (>C6) d b cracking v d to cn nha lm cho sn phm c tr s octan tng i
thp. ng tic l khi tin hnh isome ho phn on C 5 - C6, tr s octan ca xng ch
tng ln n mt gii hn nht nh v thng l khng vt qu 100 n v theo phng
php nghin cu. V th n khng phi l qu trnh ch o thu cc cu t cho xng.
Song nh trn ni n l qu trnh chnh nhn iso-pentan sn xut isopren.
1.5. Sn phm qu trnh izome ha
c trng sn phm ca qu trnh isome ho l cc iso-parafin y l nhng cu t
cao octan, rt thch hp cho vic sn xut xng cht lng cao. Sn phm thu c t qu
trnh isome ho c tr s octan c th t ti 88 - 99 (theo RON). Vi mi hng khc nhau
th sn phm thu c c cha %V ca cc cu t khc nhau nhng nhn chung n khng
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c s chnh lch nhiu v tr s octan, c th nh sn phm ca qu trnh isome ho ca

hng Essoresearch v Engineering Co tin hnh trong pha lng c kt qu nh trong bng
sau
Bng 1.4. Thnh phn sn phm t cc nguyn liu khc nhau [2]
Cu t
%V
n-pentan
Isopentan
n-pentan
2,2-dimetylbutan
2,3-dimetylbutan
2-metylpentan
3-metylpentan
Xyclopentan
Xyclohexan
Metylcyclopentan
Benzen
Tr s octan
RON + 3ml
TEP/Gal
Hiu sut, % V

Nguyn liu Lousianna

Nguyn liu
Sn phm

Arbian
Nguyn liu

16.3
11.6
19.0
1.9
2.1
15.3
9.4
2.3
6.4
10.8
4.8

29.1
11.3
30.4
0.0
0.7
11.3
6.6
0.7
1.5
5.4
1.0

4.8
23.1
4.4
20.7
5.0
11.4
6.2
1.8
15.5
2.2
4.8
98

>99

Sn phm
7.1
33.3
4.1
25.2
4.6
12.0
5.1
0.1
6.6
0.9
1.0
98.5

99

T s liu trong bng thy rng trong qu trnh bin i isome ho i t nguyn liu
l n-C5,n-C6 th sn phm chnh thu c l iso-pentan v 2,2 dimetylbutan. Sn phm
thu c t qu trnh isome ho c cht lng cao, chnh v u im ny nn c nhiu
hng tham gia nghin cu v thit k dy chuyn isome ho x l phn on C 5, C6 c
tr s octan thp thnh phn on cao octan cho xng, p ng nhu cu s dng xng
cht lng cao nh hin nay.

Chng 2. Cc cng ngh isome ho cng nghip

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Trong cng nghip hin nay, c rt nhiu cng ngh isome ha sn xut xng c tr
s octan cao. Nhng nhn chung da vo xc tc c th phn ra thnh hai nhm l qu
trnh isome ha s dng xc tc rn xy ra trong pha hi v isome ha s dng xc tc
pha lng. Qu trnh pha lng tin hnh vi xc tc c axit mnh nh xc tc Friden
Craf. Nhit qu trnh thng nm trong khong 90 150 0C. Cn qu trnh izome ha
xy ra trong pha hi thng s dng xc tc lng chc v nhit cao.
2.1. Cc qu trnh pha lng vi xc tc AlCl3
Cc qu trnh izome ho ny c t rt lu i v loi ph bin izome ho n-butan
thnh izo-butan. S nguyn l ca loi ny c trnh by hnh di.

Hnh 2.1. S isome ho xc tc trong pha lng.

1: reactor; 2: thit b tch xc tc v kh; 3,4: thp phn on

Nguyn l hot ng:

Nguyn liu c bo ha bng HCl v kh H 2 trong thit b hp th, sau c
a trc tip vo thit b phn ng Reactor (1). ng thi xc tc cng c bm vo
Reactor. Ti y phn ng isome ha xy ra, sau phn ng ton b c a sang thit b
tch xc tc v kh, cn cn nha xc tc (2) c tho ra t pha di Reactor. Sau khi
xc tc c tch cho tun hon li. Sn phm v nguyn liu cha phn ng c a
sang thit b phn on (3,4), sau khi phn on ta thu c sn phm v phn nguyn
liu cha phn ng c tun hon li tip tc phn ng.
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GVHD: PGS.TS. Nguyn Hu Trnh

2.1.1. Qu trnh isomate (Standart Oil Co.Indiana) [2]

Qu trnh ny c thc hin c th khng cn tun hon n-parafin. Chng ch khc
nhau ct tch (4). Qu trnh hot ng lin tc v khng cn ti sinh xc tc. Xc tc
c dng l hn hp AlCl3 v HCl khan. Vng phn ng c duy tr p sut H 2
ngn chn cc phn ng ph nh phn ng Craking v a t.
Ch cng ngh ca qu trnh:
ToC= 120oC;
P = 50- 60at
3
3
H2/RH= 10-18 m / m nguyn liu.
Nguyn liu c bo ha bng HCl khan v kh H 2 trong thit b hp th, sau
c t nng n nhit cn thit v c np vo reactor. Xc tc dng c tch
ra cng cn nha v phn ng isome ha xy ra trong pha lng.
Sn phm phn ng sau khi qua thits b tch xc tc v tch kh, c qua thp tch
vt axit, ri vo ct phn on tch ring n-parafin v cho tun hon tr li vi nguyn
liu.
2.1.2. Qu trnh ca hng Shell Development Co
Qu trnh ny c dng ch bin phn on n-butan thnh iso-butan v cng
c dng ch bin phn on C 5. Trong cc ti liu hin c, cha thy ni n s liu
p dng cho phn on C6 v nng hn. y cng l mt qu trnh lin tc v khng ti
sinh xc tc. Xc tc l mt dung dch ca HCl khan v tricloantimoan c hot ho
bng HCl khan. Vng phn ng c gi p sut hydro hn ch cc phn ng ph.
iu kin thao tc ca qu trnh cng ngh ny nh sau:
Bng 2.1. Ch cng ngh ca cng ngh Shell Devlopment Co [2]
Nhit (0C)

80 - 100

p sut reactor, at

21

p sut ring phn ca hydro, at

4,3

H2/nguyn liu, %mol

1,3

% khi lng ca H2/nguyn liu

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% khi lng ca AlCl3 trong xc tc

T l xc tc/RH (V)

Thi gian tip xc (pht)

15 (~ V/H/V = 2,5)

2.1.3. Qu trnh ca hng Esso Rearch & Engineering Co

Qu trnh ny thc hin nhit t 25-500C. c im chnh ca qu trnh l tin
hnh chuyn ho cao nn khng cn phi tun hon li nguyn liu cha phn ng.
Sn phm ca qu trnh t cc loi nguyn liu khc nhau c dn ra bng di y.
Ngoi ra hng ABB Lumunus Global thit k dy chuyn isome ho x l phn
on C5- C6 c tr s octan thp thnh phn on c tr s octan cao cho xng. Xc tc
dng l AlCl3 hot ho nn xc tc c hot tnh rt cao v chn lc cng ln, do
vy m khng cn phi tch iso-parafin khi n-parafin nhng vn t c sn phm c
tr s octan cao v hiu sut t n 99,5% t nguyn liu c RON bng 68 - 70.
Bng 2.2. Nguyn liu v sn phm ca hng Esso Research & Engineering Co [2]
Nguyn liu Louisiana

Arbian

Nguyn liu Sn phm

Nguyn liu Sn phm

n-pentan

16.3

4.8

29.1

7.1

Iso-hexan

11.6

23.1

11.3

33.3

n-hexan

19.0

4.4

30.4

4.1

2.2- dimetylbutan

1.9

20.7

0.0

25.2

2.3-dimetylbutan

2.1

5.0

0.7

4.6

2- metyl pentan

15.3

11.4

11.3

12.0

3- metyl pentan

9.4

6.2

8.6

5.1

Xyclopentan

2.3

1.8

0.7

0.1

Xyclohexan

6.4

15.5

1.5

6.6

Metyl xyclopenyan

10.8

2.2

5.4

0.9

Cu t
%V

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GVHD: PGS.TS. Nguyn Hu Trnh

Benzen

4.8

4.8

Tr s octan

1.0

1.0

98

98.5

> 99

99

RON + 3ml TEP/Gal

Hiu sut, % V

2.2. Cc qu trnh isome ha pha hi

i vi qu trnh isome ha pha hi, xc tc s dng l xc tc rn, lng chc kim
loi qu trn cht mang oxit (nh Al 2O3, t st hay zeolit). Qu trnh ny c thc hin
nhit cao hn so vi qu trnh isome ha trong pha lng nhng b li qu trnh ny
khng to ra mi trng n mn, chn lc rt cao v xc tc c th ti sinh c. V
vy m tnh kinh t ca qu trnh s cao hn. Di y l nguyn l chung ca qu trnh
ny:
H2

Tun hon H2

Iso-parafin

Reactor
Nguyn liu

l gia nhit

B phn
tch

Hnh 2.2. S izome ho pha lng

2.2.1. Qu trnh Butamer ca UOP

Mc ch ca qu trnh ny l sn xut isobutan t n-butan cung cp nguyn liu
cho cng ngh alkyl ho v sn xut MTBE. Nguyn liu ca qu trnh chnh l n- butan.
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Qu trnh ny s dng xc tc l aluminoplatin hot ho bng Clo. Qu trnh isome

ho c tin hnh trong pha hi, vi s c mt ca hydro vi lp xc tc c nh nhit
t 120-240oC. Sau mt chu trnh s nhn c hiu sut isobutan ln hn 50%. Do
xc tc c chn lc cao nn hn ch c cc sn phm ph. Hiu sut sn phm
t c trn 90% v tiu hao H2 tng i thp, hn na do t xy ra cc phn ng ph
nn khng cn t l H 2/RH cao m vn khng nh hng n thi gian lm vic ca xc
tc [2].

Hnh 2.3. Dy chuyn cng ngh izome ho n-butan

1. Ct tch iso-butan
3. L phn ng
5. My nn
I. Nguyn liu
III. Kh t

Cc thng s v cng ngh:

- Nhit phn ng
- p sut lm vic
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2. Ct n nh;
4. L t nng;
6. Thit b tch;
II. H2
IV. Sn phm

:
:

150-200oC
3,8Mpa

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- Vn tc np liu
- Xc tc
- Thi gian lm vic ca xc tc

GVHD: PGS.TS. Nguyn Hu Trnh

:
:
:

1-3h-1
Pt/Al2O3
>12 thng

Nguyn tc hot ng: Hn hp nguyn liu mi v sn phm ca phn ng n

nh c a vo thp tch isobutan (1), ti y sn phm tch ra c tinh khit cao,
n-butan c trn vi kh cha H 2 tun hon qua thit b t nng (4) n nhit phn
ng ri c np vo l phn ng (3) bn trong c cha xc tc. Sn phm ca phn ng
c lm lnh ri c dn vo thit b tch p sut cao (6). Kh H 2 tch ra c b sung
mt lng nh H2 ri qua my nn quay li l phn ng. Sn phm lng sau khi tch
c a vo ct n nh (2), ti y s tch mt phn tip kh H 2 v C1, C2. Sn phm
chnh c cho qua thp tch (1).
u, nhc im ca cng ngh:
u im:
- Xc tc c hot tnh v chn lc cao, c th iu chnh c hot ca n
nn hiu sut phn ng l kh cao, t phn ng ph to cc to cn nn lng kh H 2
khng cn s dng nhiu.
- Qu trnh lm vic pha hi nn kh nng n mn l khng ng k
- Nhit , p sut phn ng khng qu cao nn t tiu tn nng lng cho qu
trnh.
- Xc tc c kh nng ti sinh nn m bo c tnh kinh t ca qu trnh.
Nhc im:
Tn nhiu thit b bm, my nn. i vi s dng mt phn ng s gp kh
khn trong vn bo m c mc chuyn ha khi ti sinh xc tc.
2.2.2. Qu trnh izome ho ca hng BP (British Petroleum) [2]
Qu trnh ny s dng nguyn liu l phn on C5/C6 hay hn hp ca chng.
Nguyn liu l C5- C6 hay hn hp ca chng c hydro ha lm sch cc tp cht lu
hunh v sy kh trc khi a vo thit b phn ng.
Xc tc dng cho qu trnh l alumoplatin c hot ho bng clo hu c nn c
hot tnh v chn lc cao, thi gian lm vic ko di. duy tr hot tnh v
chn lc ta b sung mt lng nh halogen hu c vo nguyn liu, chnh v th m lm
tng kh nng n mn kim loi ( c 0.0013mm/nm), nn ta cn ch ti vn n mn
thit b.
Sn phm ca qu trnh c tr s octan kh cao (trn 80). Ngoi ra cn thu c mt
lng ln kh C1, C2, C3 a i lm kh nhin liu.

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Hnh 2.4. Dy chuyn cng ngh izome ho ca hng BP

1 L gia nhit nguyn liu
3. Tch kh
5. My nn kh

2. L phn ng
4. Ct n nh
6. Ngng t

2.2.3. Qu trnh izome ho ca hng Shell [2]

Qu trnh c dng izome ha phn on C 5- C6 ca xng ct trc tip nhm mc
ch nhn cc hp phn c tr s octan cao trong khi tr s octan ca nguyn liu nh hn
73 m cho php pha trn to sn phm c tr s octan cao hn 83 (theo RON).
Xc tc cho qu trnh thuc loi xc tc a chc nng vi kim loi qu him trn cht
mang zeolit vi hm lng natri nh nht.
Nguyn liu sau khi c cho qua qu trnh hydro ha lm sch khi cc tp cht ca
lu hunh v c sy kh loi hi nc nhm hn ch kh nng n mn thit b ca
cc hp cht ny mi cho vo izome ha. Xc tc ca qu trnh ny khng nhy vi cc
loi hp cht ca lu hunh v nc. Do vy m hm lng lu hunh cho php trong
nguyn liu l 35ppm v khi lng, v hm lng nc cho php l 10-20ppm.
Ngoi cc phn ng chnh ra qu trnh ny cn c cc phn ng ph:
Aromatic b chuyn ho thnh cc naphtenic.
Naphtenic b hydro ho thnh parafin.
C7+ phn ng cracking thnh cc phn t nh hn.
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S cng ngh c miu t nh di y:

Hnh 2.5. S cng ngh izome ho ca hng Shell

1. Thit b phn ng 2. Thp tch 3. My nn
4.Thp n nh.
iu kin ca cng ngh:
- Nhit ca qu trnh
: 245-2470C
- p sut ca qu trnh
: 300-500 Psi
- T l H2/RH
: 1/4
- Thi gian lm vic xc tc l : 5-10 nm
- Tc np liu
: 1- 3h-1
Hiu sut ca qu trnh t 97 n 98 % (theo LV).
u, nhc im ca cng ngh:
u im:
- Nhit v p sut khng qu cao nn thun li v mt nhit ng, thun li cho
vic gia cng thit b, khng s dng nhiu cc my nn t tin.
- Dy chuyn hot ng lin tc nn c kh nng t ng ha, gim c s nhn
cng s dng trong phn xng.
- Xc tc c thi gian lm vic kh lu, hot tnh cao.
Nhc im:
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GVHD: PGS.TS. Nguyn Hu Trnh

- Xc tc kh hot tnh cao, thi gian lm vic lu nhng kh nng ti sinh rt

km.
- Qu trnh lm vic trong mi trng axit nn kh nng n mn thit b cao. Do
vy phi s dng vt liu t tin.
2.2.4. Qu trnh izome ho ca hng IFP [2]
Qu trnh ny s dng xc tc zeolit hoc Al- Cl. S la chn loi xc tc ph thuc
vo yu cu nng cao tr s octan. Qu trnh ny c tun hon cc cu t n-parafin cha
chuyn ho bng sng phn t tr li thit b ban u. Tr s octan c ci thin mt
cch r rt. iu ny c minh ha bng 9 di y.
im c bit ca cng ngh ny l c dng thit b kh isopentan ra khi nguyn
liu. Hp ph v nh hp ph pha hi v dng isopentan kh hp ph.
Ch cng ngh:
- Nhit phn ng :
230 - 290oC
- p sut
:
14 - 42kg/cm2
- Tc np liu th tch : 14- 22h-1
- T l H2/nguyn liu

1
4

Hnh 2.6. S cng ngh izome ha ca IFP

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GVHD: PGS.TS. Nguyn Hu Trnh

Bng 2.3. Tr s octan ca sn phm izome ha theo cng ngh IFP cc ch v

xc tc khc nhau [2]
Cng ngh
Khng tun hon nguyn liu cha
chuyn ho
Tch isopentan v khng tun hon
n-parafin
C tch v tun hon cc cu t cha
chuyn ho
C tun hon cc cu t
n-parafin
Tch isopentan v n-parafin, c tun
hon n-parafin

Zeolit

Al-Cl

80

83

82

84

86

88

88

90

92

92

u, nhc im ca cng ngh:

u im ca cng ngh ny l xc tc c hot tnh cao v bn c nhit, qu trnh
thc hin pha hi nn trnh c s n mn thit b, qu trnh lm vic lin tc
nn d t ng ha c kh nng lin hp c vi cc phn xng khc trong khu
lc du, lng hydro np vo khng yu cu tinh khit qu cao.
Nhc im ca cng ngh l nhit phn ng cao nn d xy ra cc phn ng
ph to cc to nha.
2.2.5. Cng ngh TIP ca UOP (Total isomerization process)
Qu trnh thc hin isome ha nguyn liu thuc phn on t C 5 C6 chim 40 n
50% ( mch thng). Trong nguyn liu nu c mt ca benzen th n s b hydro ho
thnh xyclohexan.
Cng ngh ny c s dng qu trnh hp ph vo tch cu t mch nhnh v mch
thng ra khi nhau. Cht hp ph thng dng trong qu trnh ny dng sng phn t.
Trong n ch cho php n-parafin i qua, cn cc cu t khc b gi li. Sau khi tch ra
khi hn hp cc cu t c tr s octan cao c em i pha trn xng. Cn phn b hp
ph c em i tch v tun hon tr li thit b phn ng. Qu trnh nh dng hydro
nh hp ph
Qu trnh ny khi tin hnh cn phi c mt ca kh hydro trnh s to cc trn
xc tc v trnh mt hot tnh xc tc.

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Hnh 2.7. Cng ngh TIP ca hng UOP [3]

iu kin ca cng ngh:
Nhit ca qu trnh: 200-3700C
iu kin p sut ca cng ngh l: 1365- 3415 Kpa
Nguyn l: Nguyn liu sch c a qua thit b hp ph thay v a trc tip
vo thit b phn ng. Nh vy, cc hp cht mch nhnh c a trc tip vo b cha
sn phm. Do s lm gim c qu trnh cracking to cc sn phm nh.
i vi nhng nguyn liu cha t n-parafin th vic a thit b hp ph vo s gim
c kch thc thit b phn ng.
i vi nguyn liu c hm lng benzen cao th c th tin hnh trong c hai thit b
(thit b phn ng v thit b hp ph), benzen trong thit b phn ng s c chuyn
ha thnh xyclohexan, v th sn phm s cha t benzen.
u, nhc im ca cng ngh:
u im:
- Xc tc c hot tnh cao, bn c, c kh nng ti sinh nn hiu qu kinh t cao.
- S dng xc tc trong pha hi nn mi trng lm vic c nng axit nh nn
kh nng n mn khng ng k.
- Qu trnh thc hin lin tc nn c kh nng t ng ha cao.

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Nhc im:
Nhit phn ng tng i cao cn to cc, to cn nn lm gim hot tnh xc
tc.
Bng 2.4. Cc c trng chung ca qu trnh TIP ca UOP v IFP
Hng thit k

UOP
C tun hon n-parafin

IFP
C tun hon n-parafin

c im

Tch n-parafin bng

sng phn t

Tch n-parafin bng

sng phn t

Hp ph v kh hp ph
pha hi
Dng H2 nng kh hp
ph
Nhit phn ng
p sut
Tc np liu th tch

230 2900C
14 42 kg/cm2
14 22 h-1

T l H2/nguyn liu
Nguyn liu v sn
phm

1-4

Tr s octan ca nguyn
liu RON

68

Tr s octan ca sn
phm RON/MON

89/97

Nng sut xng

98% kl

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Hp ph v kh hp ph
pha hi
Dng isopentan

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GVHD: PGS.TS. Nguyn Hu Trnh

2.2.5. Cng ngh Penex ca UOP

Qu trnh ny nhm thu sn phm c tr s octan cao t nguyn liu l phn on
naphta nh c tr s octan thp.
S izome ho Penex bao gm mt ct tin phn on dng tch nguyn liu
thnh hai phn ring bit: phn on C5 v phn on C6. Phn on C5 c a i
tch izo-pentan, cn n-pentan c cho qua l phn ng cha xc tc izome, sau sn
phm quay li ct tch izo-pentan. Tng t cho khi x l vi phn on C6, phn on
ny cng c cho qua ct tch izo-hexan, cn n-hexan cho qua xc tc izome ho. Sn
phm cho quay tr li ct tch khi s dng sang phn t ( Qu trnh Molex).
Xc tc s dng tng t nh xc tc reforming nhng khng cn ti sinh.

Hnh 2.8. Qu trnh Penex ca UOP [3]

Ch cng ngh:
- Nhit phn ng :

370-480oC

- p sut

20-70atm

- Xc tc

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Pt/Al2O3 c b sung halogen.

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- Tc np liu

GVHD: PGS.TS. Nguyn Hu Trnh

:

2h-1

u, nhc im ca cng ngh:

u im:
- Xc tc c hot tnh v chn lc cao, bn c nhit, lm vic trong mt thi gian
di.
- Mi trng lm vic ca qu trnh l mi trng hi nn hn ch c kh nng
n mn thit b.
- Qu trnh thc hin lin tc nn c kh nng t ng ha cao.
- C kh nng lin hp vi cc qu trnh khc nh alkyl ha tn dng c cc
ngun nguyn liu.
Nhc im:
- Nhit phn ng cn qu cao nn rt d xy ra cc phn ng ph to cc, to
cn.
- Xc tc hu nh khng c kh nng ti sinh nn tnh kinh t cha cao.
2.3. La chn s cng ngh v thuyt minh
Mc tiu ca phn xng isome ho cn thit k l nhm thu c xng c tr s
octan cao t phn on xng ca qu trnh chng ct trc tip. Nguyn liu y l phn
on C5 - C6 , hay phn on C5, C6 ring bit. V y ta s dng nguyn liu l phn
on l n- C5, C6 nn ta chn cng ngh thch hp l cng ngh Penex ca UOP.
Qu trnh UOP Penex c thit k c bit cho xc tc ng phn ho pentan, hexan
v hn hp ca chng. Cc phn ng din ra vi s c mt ca hydro v c thc hin
trn b mt xc tc, ti iu kin thch hp m y mnh cc qu trnh ng phn
ho v qu trnh hydrocracking l b nht. iu kin thc hin phn ng th khng kht
khe, phn ng p sut lm vic va phi, nhit thp v yu cu p sut ring phn ca
hydro thp.
Xc tc qu trnh ng phn ho s chuyn ho tt c cc nguyn liu parafin chuyn
thnh cc cu trc mch nhnh c tr s octan cao: n-pentan (n-C 5) thnh isopentan (i-C5)
v n-hexan (n-C6) thnh 2,2 v 2,3-dimetylbutan. Phn ng c iu khin c s
cn bng nhit ng v thun li hn nhit thp. Vi cc parafin C 5 tham gia vo
qu trnh chuyn ho bi n-pentan v iso-pentan. Qu trnh isome ho parafin C 6 c phn
phc tp hn bi v s hnh thnh 2 v 3-metylpentan v 2,3-dimetylbutan c mt gii
hn bi s cn bng. Mng li phn ng bao gm ch yu l qu trnh chuyn ho nhexan thnh 2,2-dimetylbutan. Tt c benzen trong nguyn liu c hydro ho to

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xyclohexan v mt cn bng nhit ng c thit lp gia metylxyclopentan v

xyclohexan.

La chn dng chy ca Penex [3]:

Hnh 2.9. Chn la tun hon MeC5 v nC6

Hnh 2.10. Chn la tun hon MeC5 v nC6 thng qua UOP molex

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Hnh 2.11. La chn tun hon nC5, nC6 v MeC5

Thit k dy chuyn
V mc ch ca qu trnh l ta i isome ho phn on n-C 5, C6 c sn phm c tr
s octan cao pha vo xng do ta khng cn tch ring tng cu t. Nn em la chn
thit k dy chuyn cng ngh isome ho c tun hon n-C 5, C6. l s kt hp gia
Penex v Molex.
Thuyt minh dy chuyn cng ngh:
Nguyn liu u c bm t b cha qua thit b sy bng ry phn t tch nc.
H2 b sung cng c cho qua thit b sy tch nc. Dng kh H 2 c trn vi dng
nguyn liu, sau c trao i nhit vi dng sn phm y cc thit b phn ng
trc khi i vo thit b gia nhit. Hn hp nguyn liu c gia nhit n 370C ri i
vo thit b phn ng th nht. thit b phn ng th nht, xy ra cc phn ng hydro
ha cc aromatic v naphtenic. Dng sn phm ca thit b phn ng th nht c trao
i nhit n 400C ri tip tc i vo thit b phn ng th 2. thit b phn ng th 2,
xy ra cc phn ng ng phn ha. Ngoi ra cn xy ra phn ng hydrocracking. Sn
phm ra khi thit b phn ng th 2 c cho qua thit b lm lnh v vo thit b tch.
Dng H2 c tch ra v tun hon tr li thit b phn ng th nht, hn hp sn phm
i vo thit b n nh. Ti nh thp thu c kh nhin liu, sn phm isome y thp
c a sang h thng tch bng cng ngh Molex.
Cng ngh Molex lm vic nh mt sng phn t, s dng cht hp ph ZSM 5.
Sn phm isome lng c cho vo ct hp ph nh van quay. Trong ct hp ph xy ra
ng thi qu trnh hp ph v nh hp ph. Dng sn phm ra khi van quay gm: sn
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phm isome v cht nh hp ph i vo ct Rafinat, cc n parafin v cht nh hp ph

i vo thp chng tch. Ti ct Rafinat, sn phm isome c tch ra y i vo b
cha sn phm. Ti thp chng tch, cc n parafin tch ra y c hi lu li thit b
phn ng. Ton b cht nh hp ph tch ra nh ct Rafinat v thp chng tch c
hi lu li ct hp ph sau khi c gia nhit.

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Chng 3. Tnh ton cng ngh v thit b chnh

3.1. Cc s liu cn thit cho trc
Nguyn liu u: phn on naphta nh c nhit ct t 30-70C.
Nng sut 1.000.000 tn/nm.
Nhit phn ng 370-480C.
Xc tc Pt/Al2O3 c b sung xc tc halogen.
Cc s liu khc ly t ti liu tham kho hoc t nh my lc du.
3.2. Tnh ton cn bng vt cht v cn bng nng lng
Cc phn ng chnh xy ra trong thit b phn ng:
Phn ng ng phn ho:
n-C5

i- C5

(1)

n-C6

i- C6

(2)

Phn ng chuyn ha naphten thnh parafin.

CnH2n + H2

CnH2n+2

(3)

Phn ng chuyn ho hydrocacbon thm thnh naphten.

CnH2n- 6 + 3H2

CnH2n

(4)

Phn ng hydrocracking naphten.

CnH2n + n/3 H2

n/15(C1 + C2 + C3 + C4 + C5)

(5)

Phn ng hydrocracking parafin.

CnH2n+2 + (n-3)/3H2

n/15(C1 + C2 + C3 + C4 + C5)

(6)

Trong :
k1-6: Hng s tc ca phn ng thun 1- 6.
KP1-6: Hng s cn bng ca cc phn ng 1- 6.
Ta c th m t s gim hm lng ca cc hydrocacbon trong hn hp bng h
phng trnh vi phn sau:

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dN p
k
k1.PnC 1 .PiC
5 K P1
dVR
5

k
dN P
k 2 .PnC 2 .PiC
dVR
6
K P2
6

(8)

k
dN N
k3 PN .PH 3 .PP
2
dVR
K P3

(9)

dN A
k
k 4 PA .PH32 4 .PN
dVR
KP4

(7)

(10)

dN N
P
k5 N
dVR
P

(11)

dN P
P
k6 P
dVR
P

(12)

VR: i lng nghch o ca tc np liu theo mol, [kg xt/kmol/h]

NP, NA, NN: Phn mol ca parafin, aromatic, naphten trong hn hp nguyn liu.
P: p sut ton phn, Mpa.
PN, PP, PA: p sut ring phn ca naphten, parafin v aromatic, Mpa.
k3: Hng s tc ca phn ng (3) c xc nh theo th (3.1),
[kmol/h.Pa.kgxtc].
k4: Hng s tc ca phn ng (4) c xc nh theo th (3.2),
[kmol/h.Pa.kgxtc].

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k5, k6: Hng s tc ca phn ng (5), (6) c xc nh theo th (3.3),

kmol/h.Pa.kgxtc.
KP3, KP4: Hng s cn bng ca phn ng (3),(4) c xc nh theo phng trnh
sau:
1

K P 3 98,1 .10 .e

4450
7 ,12
T

( Pa 1 )
(13)

K P 4 9,81 .10 .e
3

12

46,15

25600
T

( Pa 3 )
(14)

th

Hnh 3.1. Hng s tc ca phn ng (3)

SVTH: Lng Ngc Thi

Hnh 3.2. Hng s tc ca phn ng (4)

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Hnh 3.3. Hng s tc ca phn ng hydrocracking naphten

v hydrocracking parafin.

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Hnh 3.4. S ph thuc ca nng mol vo nhit ca phn ng (1)

Hnh 3.5. S ph thuc ca nng mol vo nhit ca phn ng (2)

Bng 3.1. Thnh phn ca dng nguyn liu [4]

ST
T
1

Cu t

Thnh Phn mol (%)

Iso-Pentane

11,46

N-Pentane

20,16

2,2-Dimethylbutane

0,74

2,3-Dimethylbutane

1,62

2-Methylpentane

11,72

3-Methylpentane

6,34

n-hexan

29,64

Methylcyclopentane

6,21

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Cyclohexane

5,81

10

Benzene

6,30

Tng

100

Khi lng mol trung bnh: 80,48 kg/kmol

T trng ti 15C: 0,674
Khi lng ca cc hydrocacbon trong nguyn liu c tnh theo bng sau:
Bng 3.2. Khi lng phn t ca cc hp cht
Hydrocacbon

Cng thc ha hc

Cng thc khi lng

Parafin

CnH2n+1

MP = 14n + 2

Naphten

CnH2n

MN = 14n

Aromat

CnH2n-6

MA = 14n - 6

Bng 3.3. Phn khi lng ca cc cu t

Hm lng trong nguyn liu

Cu t

Mi

CnH2n+2

80,72

0,8146

0,8168

CnH2n

84

0,1247

0,1202

CnH2n-6

78

0,0607

0,0630

1,0000

1,0000

% khi lng, ai

Nng sut ca thit b tnh theo gi:

SVTH: Lng Ngc Thi

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L

G = 24 n
Vi L l nng sut tnh trn 1 nm,
n l s ngy thit b hot ng trong 1 nm, chn s ngy ngh bo dng, thay
mi xc tc trong 1 nm l 15 ngy. Vy s ngy hot ng trong 1 nm l 350 ngy.
T G =

1000000000
24 350

ng vi nc=

Gc
Mc

= 119047,6 (kg/h)

119047.6
= 80,48

= 1479,2 (kmol/h).

Bng 3.4. S mol ca cc h cu t trong hn hp nguyn liu trong 1h

Cu t

xi

nci= nc.xi (kmol/h)

CnH2n+2

0,8168

1208,23

CnH2n

0,1202

177,80

CnH2n-6

0,0630

93.20

Tng

1,0000

1479,23

Tnh lng kh tun hon cn thit

Chn t l H2/RH=4, t :
nH2= 4 1479,23= 5916,92 (kmol/h)
Bng 3.5. Thnh phn ca dng kh H2 (makeup gas) [4]
STT

Cu t

Phn mol (%)

H2

93,3

Methane

2,5

Ethane

2,4

Propane

1,4

i Butane

0,1

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6

n Butane

0,1

i Pentane

0,04

n Pentane

0,02

C6+

0,04

Lng cht xc tc cn thit

Th tch xc tc:

Vxt

GC
C .VO

Trong :
Vo: Tc th tch, chn Vo = 1,8 h-1.
c : Khi lng ring ca nguyn liu, kg/m3.
c = 0, 674.1000 = 674 kg/m3.

Vy th tch xc tc l :
Vxt=

119047,6
674 1,8

= 98,13 (m3).

Khi lng xc tc
mxt = Vxt. xt (kg).
Trong :
xt : Khi lng ring ca xc tc, ta c xt = 885, kg/m3 [4].
Vy : mxt = 98,13 885 = 86842,34 (kg).

y thc hin 2 l phn ng do ta c s phn b xc tc hai l nh sau: Chn

t l xc tc l 1v l 2 l 1:3.
Bng 3.6. Phn b xc tc trong hai l
L phn ng
SVTH: Lng Ngc Thi

Vxt (m3)
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24,53

21710,58

73,6

65131,76

Thnh phn v p sut ring phn:

Pi= P.yi
Trong :
Pi: p sut ring phn cu t i (Pa).
P: p sut chung ca l phn ng (Pa).
yi: nng phn mol ca cu t i trong hn hp.
P= 20x105 (Pa).

Bng 3.7. Thnh phn v p sut ring phn

ni, kmol/h

CnH2n+2

1208,23

0,1647

329400

CnH2n

117,8

0,0160

32000

CnH2n- 6

93,2

0,0127

25400

5916,92

0,8066

1613200

1,0000

20.105

H2

SVTH: Lng Ngc Thi

7336,15

yi = ni/ni

Pi = 20.105. yi ,(Pa)

Cu t

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3.2.1. Tnh ton cho l phn ng th nht

Vi gi thit l cc phn ng xy ra trong l phn ng ny c tc dng l lm no ho
cc hydrocacbon vng, v rng l phn ng hydro ho benzen ta nhit ln hn nhng
phn ng khc do ta phi thc hin nhit thp hn trnh xy ra nhng phn
ng reforming. Tht vy qu trnh hai l cho php phn ng xy ra l 1 gm phn ng
(3) v (4). nhit xy ra l ny l 370oC.
3.2.1.1. Tnh ton cn bng vt cht
Hng s tc ca phn ng chuyn ho hydrocacbon thm thnh naphten: k4
c tra th (3.2).
Tv: Nhit trung bnh trong l phn ng l 370oC.
Tv = 643K 1000/Tv = 1,555.
Theo th Hnh 3.1:
1000/Tv=1,3 tra c k= 2,55.10-7
1000/Tv=1,35 tra c k= 2,00.10-7.
Ngoi suy vi 1000/T=1,555, ta c k4=1,25.10-7 [kmol/h.Pa.kgxtc].
Tnh hng s cn bng KP4.

K P 4 9,81 .10 .e
3

12

46,15

25600
T

( Pa 3 )

= 9,813. 1012.e46,15-

- Theo (14) ta c:

25600
643

= 5.33. 1017 (Pa3).

gim tng i hm lng cc hydrocacbon thm do phn ng chuyn ho

aromatic thnh naphten.
SVTH: Lng Ngc Thi

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dN A
k
k 4 PA .PH32 4 .PN
dVR
KP4

= 1,25.10-7. 25200. 16000003

1,25.107
5.33 . 1017

. 48000= 1,29. 1016.

gim ny l rt ln iu chng t lng hydrocacbon thm chuyn ho thnh

naphten l gn nh hon ton. Ta coi ton b lng hydrocacbon thm chuyn ho
ton b thnh naphten.
Vy lng H2 phn ng phn ng (4) l:
H2(4) = 3. nar = 3. 93,2 = 279,6

(kmol/h).

Lng naphten to ra phn ng (4) l: nN(4) = nar= 93,2 (kmol/h).

Hng s tc ca phn ng chuyn ho naphten thnh parafin.
Tv = 643K 1000/Tv = 1,555.
Theo th Hnh 3.2
1000/Tv=1,25 tra c k= 2,45.10-15
1000/Tv=1,3 tra c k= 1,45.10-15
Ngoi suy vi 1000/ Tv=1,555, ta c k3 = 0,975.10-15 , [kmol/h.Pa.kgxtc].
Hng s cn bng KP3.
- Theo (13) ta c:
1

K P 3 98,1 .10 .e

= 98,1-1. 10-3.e

4450
7 ,12
T

4450
643

( Pa 1 )

-7,12

= 8,35 . 10-6.
iu chng t phn ng thun chuyn t naphten sang parafin chim u th hn.
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- S gim hm lng naphten do phn ng (3) l:

0.975.10-15
= 0,975. 10-15. 48000.1600000 -

. 326800

8,35.10 -6
=3,67. 10-5.

Mt khc, VR1= mxt

86842,34
7336,15

= 11,84 (kg/kmol.h).

nN(3) = -3,67.10-5.11,84 = - 4,34.10-4 (kmol/h).

Lng H2(3) tham gia phn ng (3) chnh bng lng naphten tham gia phn ng:
H2(3) = nN(3).nc= 4,34.10-4.1479,23= 0.642 (kmol/h).
Vy sau phn ng (3) th hm lng naphten s l:
nN(3) = (yN - nN(3)).nc = (0,1202 4,34.10-4). 1479,23
= 177,16 (kmol/h).
Vy hm lng naphten tng cng sau phn ng (4) l:
nN tng = nN(3) + ar = 177,16 + 93,2 = 270,36 (kmol/h).
Vy tng lng parafin C6 l:
nC6 = (0,5006+4,34.10-4). 1479,23 = 741,14 (kmol/h).
Khi lng phn t trung bnh ca parafin l:

Mp =

741,14.86+ 467,72.72
741,14+ 467,72

= 80,2 (kg/kmol)

M Mp = 14n+2 suy ra n= 5,86.

Bng 3.8. Cn bng vt cht cho l phn ng th nht
Cu t

ni (kmol/h)

SVTH: Lng Ngc Thi

yi

Mi
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u vo
P

1208,23

0,1647

80.6

96900,05

117,8

0,016

84

9895,2

93,2

0,0127

78

7269,6

H2

5916,92

0,8066

11833,84

7336,15

1,0000

130550,37

u ra
P5

467,72

0,0632

72

33665,76

P6

740,5

0,1043

86

58721,66

319,8

0,0387

84

26863,71

H2

5636,57

0,7938

11273,13

7164,6

1,0000

130524,26

Sai s gia lu lng dng vo v dng ra thit b th 1:

= 130550,37- 130524,26 = 26,11 (kg/h)

26,11
=
130550,37

.100% =0,02 %.

3.2.1.2. Tnh ton cn bng nhit lng

Ta c phng trnh cn bng nhit:
Q 1 + Q2 = Q3 + Q4 + Q5
Q1: Nhit lng mang vo bi nguyn liu v kh tun hon 25oC.
Q2: Nhit lng ca l t cn cung cp nng nhit ca nguyn liu v kh
tun hon t 25oC n 370oC.
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Q3: Nhit lng mang ra khi l phn ng do cc sn phm phn ng v kh tun

hon.
Q4: Nhit phn ng.
Q5: Nhit lng mt mt ra mi trng xung quanh.
Lng nhit c tnh theo cng thc:
Qi= nC-i.Ci.ti (KJ/h)
Trong :
nC-i : lu lng ca tng cu t i (kmol/h).
Ci : Nhit dung ring ca cu t i (J/mol.).
ti

: Nhit cu t i (0C).

Cc= nci. Ci (kJ/h.)

Trong ni: l cc thnh phn phn mol ca cu t th i.
Nhit dung ring ca mt cht c tnh theo.
Cp = a0+a1.T+ a2.T2 +a-2.T-2 (cal/mol.K)
Trong cc gi tr a0; a1; a2; a-2 : l cc hng s thc nghim.
T : Nhit tuyt i (K).

Bng 3.9. Gi tr ca nhit dung ring

Cu t
n-C5
Benzen
CycloC6
n-C6
H2

a0

a1.10

3,140
-5,040
-7,701
7,313
6,59

100,532
95,63
124,675
104,906
-0,2

a-2.10
-

-5

a2.10

-35,500
-40,600
-41,584
-32,397
0,48

Cp 250C

Cp 3700C

Cp 4000C

J/mol.
123,69
81,9990
105,75
147,67
26,29

J/mol.
221,98
164,70
231,04
255,67
26,64

J/mol.
228,73
171,09
239,81
264,35
26,69

Bng 3.10. Nhit dung ring ca cc cu t khc tra c

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Cp 250C

Cp 3700C

Cp 4000C

J/mol.
119,41

J/mol.
226,22

J/mol.
235,51

2,2-Dimetylbutan

142,63

272,27

283,54

2,3-Dimetylbutan

141,25

268,98

280,09

Metylpentan

143,00

267,20

278,00

Metylcyclopentan

110,71

240,83

252,15

Cu t
Iso-pentan

Bng 3.11. Nhit dung ring ca hn hp nguyn liu u vo v hydro tun hon
25C v 370C
Ci.nci 250C

Ci.nci 3700C

kj/h.

kj/h.

Cu t

nci,(kmol/h)

P
Iso pentan

169,51

20241,19

38346,55

n- pentan

298,21

36885,6

66196,65

2,2-dimetylbutan

10,95

1561,8

2981,36

2,3-dimetylbutan

23,96

3384,35

6444,76

Metylpentan

267,14

38201,02

71379,81

n- hexan

438,43

64742,96

112093,4

N
SVTH: Lng Ngc Thi

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Metylxyclopentan

91,86

10169,82

22122,64

Xyclohexan

85,94

9088,15

19855,58

Benzen

93,19

7641,48

15348,4

H2

5916,92

155555,83

157626,75

347472,2

512395,9

Tnh Q1:
Lng nhit mang vo ca nguyn liu v kh tun hon 25oC:
Q1= Qnl + QH
Trong :
Qnl = ni.Ci.t1 = nc.Cc.t1
QH =

nH.CH.t1

Q1 =347472,2. 25 = 8686805(kj/h)

Tnh Q2:
Lng nhit cn thit nng nhit ca nguyn liu t 25o n 370oC:
Q2 = Qt2 - Qt1
T bng thng k, ta c:
Q2= 512395,9. 370 347472,2. 25 = 180899678 (kj/h)
Tnh Q4:
Bng 3.12. Gi tr hiu ng nhit ca tng phn ng
Phn ng
1
SVTH: Lng Ngc Thi

Q, kcal/mol
2

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2
3
4
5
6

2
27
50
20
11

Lng nhit sinh ra do qu trnh phn ng. thit b phn ng 1 xy ra cc phn ng (3)
v phn ng (4).
Vy:

Q4 =

n3 .

Q3 +

n4 .

Q4

Ta c:

Q3 = 27 . 4,186 = 113,022 (kj/mol)

Q4 = 50 . 4,186 = 209,3

(kj/mol)

n3 = 0.0162

(kmol/h)

n4 = 23,85

(kmol/h)

Q4 = 0.0162.113,022 . 103 +23,85. 209,3 . 103

Q4 = 4993635,96 (kj/h)
Tnh Q3:
Chn nhit lng mt mt ra khi mi trng bng 5% nhit lng ca sn phm

mang ra:
Q5 = 0,05 . Q3
Vy tng lng nhit ca u ra l = Q3 + 0,05 . Q3 = 1,05 .Q3

1,05 . Q3 = Q1 + Q2 + Q4 (v phn ng ta nhit)

M ta c cc phn ng l to nhit do :
1,05 . Q3 = 2326673,25+46208465,25+4993635,96
= 53528774,46 (kj/h)

Q3 = 50979785,20

SVTH: Lng Ngc Thi

(kj/h)
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Q5 = 2548989,26

(kj/h).

Bng 3.13. Cn bng nhit lng ca thit b phn ng 1

Dng

Nhit lng (kJ/h)

Dng vo

Q1

8686805

Q2

180899678

Q4

4993635,96

194580119
Dng ra

Q3

46812813,49

Q5

2548989,26

53528774,46

3.2.2. Tnh ton cho l phn ng th 2

l ny thc hin nhit cao hn l 1 v s xy ra cc phn ng isome ho v
phn ng cracking. Nhit phn ng trong l l 400 oC (673K). tt p gia cc l
thng l: 0,15-0,35 at.
3.2.2.1. Tnh ton cn bng vt cht
Bng 3.14. Thnh phn nguyn liu vo l 2
Cu t

ni (kmol/h)

yi

Mi

Gi=Mi.ni (kg/h)

P5

467,72

0,0632

72

33665,76

P6

740,5

0,1043

86

58721,66

319,8

0,0387

84

26863,71

H2

5636,57

0,7938

11273,13

SVTH: Lng Ngc Thi

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1817,85

1,0000

130524,26

Ta chn tt p l th 2 l: 0,3 at.

Khi p chung ca hn hp kh nguyn liu vo l th 2 l:
P2= 20 - 0,3 = 19,7 (at) = 19,7 . 105 (Pa)
Bng 3.15. Thnh phn p sut nguyn liu v kh tun hon vo l 2
Cu

Gi=Mi.ni

ni (kmol/h)

yi

Mi

Pi=19,7.105.yi (Pa)

319,8

0,0387

84

76239

26863,71

1208.22

0,1675

80,58

329975

92387,426

H2

5636,57

0,7938

1563,786

11273,13

1817,85

1,0000

19,7.105

130524,26

Hng s tc ca phn ng hydrocracking naphten

T Tv = 673K 1000/Tv = 1,486 theo th (3.3) ta c :
k5 = 0,002647 (kmol/h.kgxtc).
S gim hm lng naphten tng i do phn ng (5) l:

dN N
P
k5 N
dVR
P

Mt khc, VR = mxt

= 0,002647.

SVTH: Lng Ngc Thi

86842,34
7164,6

76239
19,7.10 5

= 1,024.10-4

= 12,12 (kg/kmol.h)

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Suy ra - NN = 12,12. 1,04.10-4 = 12,6. 10-4

Vy hm lng naphten tham gia phn ng cracking l:

n N (5) = 12,6. 10-4 . 1479,2 = 1,86 (kmol/h).

Do hm lng naphten cn li sau phn ng (5) l:
nN = nN tng - nN(5) = 270,36 - 1,86 = 268,5 (kmol/h).
Lng H2 tham gia phn ng (5) :
H2(5) =

6
3

. nN(5) = 2.1,86= 3,72 (kmol/h).

Hng s tc ca phn ng hydrocracking parafin.

Theo th (3.3) ta c k6 = 0,002647 (kmol/h.kg).
- S gim tng i parafin phn ng (6) l:

dN P
P
k6 P
dVR
P
=0,002647. 0,1675 = 4,43. 10-4

Suy ra: -NP(6) = VR. 4,43.10-4 = 1,218. 4,43. 10-4

= 5,40.10-4
Vy lng parafin b hydrocracking l
nP(6) = NP(6).nc =5,40.10-4. 1479,2 = 0.8 (kmol/h).

Lng H2 tham gia phn ng (6) :

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 n c nhn

H2(6) = nP(6)

n 3
3

GVHD: PGS.TS. Nguyn Hu Trnh

= 0,8.

5,863
3

= 0,76 (kmol/h)

Bng 3.16. Thnh phn cc cu t trong nguyn liu vo l phn ng th 2

Cu t

ni (kmol/h)

yi

Mi

319,8

0,1831

84

n-C5

298,21

0,2016

72

i- C5

169,51

0,1146

72

i-C6

302,07

0,2042

86

n- C6

438,43

0,2965

86

1528,02

1,0000

Tnh lng n-C5 chuyn ha trong phn ng (1)

Theo th (3.4), ta c nng % mol trng thi cn bng nhit 643K.
% n-C5 = 18%.
% i-C5 = 82%.
Vi tng lu lng C5 bng 119,74 kmol/h, v th, sau phn ng, lng cc cht l:
Nn-C5 = 0,18. 298,21

= 53,68 (kmol/h)

Ni-C5 = 467,72 53,68 = 414,04 (kmol/h)

Lng n-C5 chuyn ha thnh i-C5:

nC5= 298,21 53,68 = 244,53 (kmol/h).

chuyn ha: C1=

54,79
76,34

.100% = 82 %

Tnh lng n-C6 chuyn ho trong phn ng (2)

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Theo th (3.15), nng phn mol ca cc cu t C 6 trng thi cn bng ti nhit

643K l :
%n-C6 = 20 %
%i-C6 = 80 %.
Vi tng lu lng C 6 bng 189,59 kmol/h, suy ra lng cc cu t C 6 sau l phn
ng th 2 l:
Nn-C6 = 0,2. 740,5 = 148,1 (kmol/h)
Ni-C6 = 740,5-148,1 = 592,4 (kmol/h).
Lng n-C6 chuyn ha thnh i-C6 l:
n = 438,43- 148,1 = 290,33 (kmol/h).
C6
290,33
chuyn ha: C2 = 438,43

.100% = 66,22 %

Tnh lng H2 tun hon

H2(th) = H2(nguyn liu) - H2(5) - H2(6).
Thay s ta c:

H2(th) = 5916,92- 3,72 -0,76 = 5912,44 (kmol/h).

Lng C1 C5 sinh ra trong qu trnh phn ng.

Theo phng trnh phn ng (5) v (6) ta c th tnh c tng i lng C 1 C5
sinh ra:
P*= nC1

C5

6
15 . nN(5) +

5,86
15

. nP(6) =

6
15

. 1,86 +

5,86
15

. 0,8= 1,06

(kmol/h).
Bng 3.17. Cn bng vt cht ca thit b phn ng th 2
Cu t

nC-i (kmol/h)

yi

Mi

Gi=Mi.ni (kg/h)

84

26863,71

u vo
N

319,8

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0,0387
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1208.22

0,1675

80,58

92387,426

H2

5636,57

0,7938

11273,13

1817,85

1,0000

130524,26

u ra
A

0,0000

319,8

0,00

0,0380

84

26863,2

n-C5

53,68

0,0118

72

3864,96

n-C6

148,1

0,0208

86

12736,6

i -C5

414,04

0,0539

72

29810,88

i -C6

592,4

0,0833

86

50946,4

P*

1,06

0,0001

44

46,64

H2

5912,44

0,7921

11824,88

7441,52

1,00000

136093,56

Bng 3.18. Lng sn phm v tun hon li

Sn Phm
Cu t

Tun hon

Lu lng (kmol/h)

i-C5

244,53

i-C6

592,4

319,8

P*

1,06

1157,79

SVTH: Lng Ngc Thi

Cu t

Lu lng (kmol/h)

H2

5912,44

n- C5

53,68

n- C6

148,1

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3.2.2.2. Tnh ton cn bng nhit lng

Ta c phng trnh cn bng nhit:
Q 1 + Q 2 = Q3 + Q4 + Q5
Q1 : Nhit lng mang vo bi sn phm v kh tun hon sau l 1.
Q2 : Nhit lng ca thit b trao i nhit thu c tng nhit ca sn
phm v kh tun hon sau l phn ng 1 t 370oC n 400oC.
Q3 : Nhit lng mang ra khi l phn ng do cc sn phm phn ng v kh tun
hon.
Q4 : Nhit phn ng.
Q5 : Nhit lng mt mt ra mi trng xung quanh.
Lng nhit c tnh theo cng thc:
Qi= nC-i.Ci.ti (KJ/h)
Trong :
nC-I : Lu lng ca tng cu t i (kmol/h).
Ci : Nhit dung ring ca cu t i (J/mol.).
ti

: Nhit cu t i (C).

Cc= nci. Ci (kJ/h.)

Trong ni: l cc thnh phn phn khi ca cu t th i.
Nhit dung ring ca mt cht c tnh theo:
Cp = a0+a1.T+a2.T2+ a-2.T-2
Trong cc gi tr a0 ;a1 ;a2 ;a-2 : l cc hng s thc nghim.
T : Nhit tuyt i 0k.
Bng 3.19. Nhit dung ring ca hn hp nguyn liu v hydro tun hon vo l 2.

Cu t

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nci,(kmol/h)

Page 53

Ci 4000C

Ci.nci 4000C

j/mol.

kj/h.

 n c nhn

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P

Iso-pentan

169,51

235,51

39921,3

n- pentan

298,21

228,73

68209,6

2,2-dimetylbutan

10,95

283,54

3104,76

2,3-imetylbutan

23,96

280,09

6710,96

Metylpentan

267,14

278,00

74264,92

438,43

264,35

115898,97

Metylxyclopentan
Xyclohexan

91,86

252,15

23162,5

85,94

239,81

20609,3

H2

5916,92

26,69

157922,6

7303,92

n-hexan
N

609804,91

Q2 = ( ni.Ci ).t1 Q1 = 609804,91. 400 - 50979785,20

Q2 = 192942178,8 (kj/h).
Tnh nhit phn ng Q4
Lng nhit sinh ra do qu trnh phn ng. thit b phn ng 2 xy ra cc phn
ng (1), (2), (5) v phn ng (6).
n1 .Q1 n 2 .Q2 n5 .Q5 n6 .Q6

Vy: Q2 =

(kj/h)

Bng 3.20. Tnh ton nhit ca phn ng

Ph
n
ng
1
2
5
SVTH: Lng Ngc Thi

ni

Qi

ni .Qi

kmol/
h
54,79
74,34
0,050

kcal/m
ol
2
2
20

kcal/h

Page 54

109580
148680
1000

 n c nhn

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6

0,204

11

2250

5
-

261510

Q4 = 261510. 4,186 = 1094680,86 (kj/h)

Tnh Q3:
Chn nhit lng mt mt ra khi mi trng phn ng bng 5% nhit lng ca
sn phm mang ra:

Q5 = 0,05 . Q3

Vy tng lng nhit ca u ra l : Q3 + 0,05 . Q3 = 1,05 .Q3

1,05. Q3 = Q1 +Q2 +Q4 ( v phn ng to nhit)
Hay 1,05. Q3 = 50979785,20 + 192942178,8 + 1094680,86

Q3 = 233349185,6 (kj/h)

Q5 = 11667459,28 (kj/h)

Bng 3.21. Cn bng nhit lng ca thit b phn ng 2

Dng

Lng
Kmol/h

Nhit lng
Kj/h

u vo
Q1

50979785,20

Q2

192942178,8

Q4

1094680,86

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7303,92

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245016644,9

 n c nhn

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u ra
Q3

233349185,6

Q5

11667459,28

7441,52

245016644,9

Kt Lun
Qu trnh isome ha n-parafin c dng nng cao tr s octan ca phn on C5
v C6 ca xng si n 70 0C, ng thi cho php nhn cc iso-parafin ring bit nh isopentan v iso-butan t nguyn liu l n-pentan v butan tng ng, nhm p ng ngun
nguyn liu cho qu trnh tng hp isopren v isobutan l ngun nguyn liu tt cho qu
trnh alkyl ha hoc nhn isobuten cho qu trnh tng hp MTBE.
y l mt qu trnh rt quan trng v c trong hu ht cc nh my lc du hin i
v ang c nghin cu v pht trin rng ri vi nhiu hng ln trn th gii. Qu trnh
kt hp Penex va Molex ca UOP l mt trong nhng qu trnh isome c ng dng
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nhiu nht trn th gii, c chi ph vn hnh thp, gip cho ta thu c hiu sut v cht
lng (RON) isomerat cao.
Qua vic thc hin bn n ny, gip em hiu thm v qu trnh isome ha, t c
ch phn ng ti cc thng s hot ng ca cng ngh. Tuy nhin, do thi gian v kin
thc c hn, nn em khng th trnh khi nhng thiu st.
Em mong PGS.TS Nguyn Hu Trnh gp bn n ca em c hon thin
hn. Em xin chn thnh cm n thy.

Ti liu tham kho

1. inh Th Ng, Nguyn Khnh Diu Hng: Ha hc du m v kh, Nh xut bn
khoa hc v k thut, 2012.
2. L Vn Hiu, Cng ngh ch bin du, Nh xut bn khoa hc v k thut, 2000.
3. Handbook of Petroleum Refining Processes, Third Edition .
4. OPERATING MANUAL LIGHT NAPHTA ISOMERIZATION UNIT (DQR).
5. PERRY Chemiscal engineers handbook 8 edition, Secsion 2 Physical and
chemiscal data.
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6. S tay tm tt cc i lng ha l, b mn Ha l, trng HBK H Ni.

7. Tp th tc gi, S tay qu trnh v thit b trong cng ngh ha hc, tp 1,2, nh
xut bn khoa hc v k thut.

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