n tt nghip

Reforming xc tc.

Thit k phn xng

M u

Cng nghip du kh l mt ngnh cng nghip c

nhng bc thay i v pht trin khng ngng, c bit l
vo nhng nm cui th k XX. Cng nghip du kh v
ang tr thnh ngnh cng nghip mi nhn, bn cnh l
s pht trin khng ngng ca mt s qu trnh ch bin
du th ra cc nhin liu trong ngnh cng nghip ho du,
song khng th khng nhc n qu trnh qu trnh
reforming xc tc sn xut ra xng cht lng cao.
Ngy nay, qu trnh reforming xc tc c s dng rt
ph bin cho ngnh tng hp ho du v cc ngnh cng
nghip khc. Mc ch chnh ca qu trnh l bin i cc
hydrocacbon c trong phn on xng thnh nhng
hydrocacbon thm l h c tr s octan cao nht. Qu trnh
ny cho php sn xut ra cc cu t cao octan cho xng t
ti 98 100. Tuy nhin, ngoi vic sn xut ra xng c tr s
octan cao th qu trnh reforming xc tc cn sn xut ra
ngun nguyn liu BTX rt quan trng cho cng nghip ho
du. Bn cnh cn sn xut ra nhiu kh hydro (hm lng
> 85%). y l ngun kh hydro c s dng lm nguyn
liu sch v r tin phc v cho cc qu trnh ch bin du
m v tng hp hu c nh: lm sch nguyn liu, x l hydro
cc phn on sn phm trong khu lin hp lc ho du, sn
xut phn m. Do khng th ph nhn vai tr ca qu
trnh reforming xc tc trong cng nghip ch bin du nu
khng mun ni rng qu trnh reforming xc tc l mt qu
trnh ch bin th cp quan trng nht.
Cc phn ng xy ra trong qu trnh reforming xc tc
l izome ho,

dehydro ho, dehydro ho to vng cho sn

phm chnh l cc hydrocacbon thm c tr s octan cao.

Qu trnh reforming thng dng nguyn liu l phn on

-1-

 n tt nghip
Thit k phn xng
Reforming xc tc.
xng c tr s octan thp, khng tiu chun ca nhin liu
xng cho ng c xng. l phn on xng ca qu trnh
chng ct trc tip du th hay t phn on xng ca qu
trnh cracking nhit, cc ho.
Reforming xc tc do c tm quan trng nn qu trnh
ny ngy cng c nghin cu mt cch su rng v c p
dng mt cch rng ri trn th gii. Hin nay, lng xng sn
xut t qu trnh reforming chim mt phn ng k lng
xng tiu th trn th gii. Qu trnh reforming xc tc v
ang c ng dng rng ri trong nhiu lnh vc cng
nghip khc nhau v l qu trnh khng th thiu ca nh
my ch bin du m, nh my in, cng nghip cht do,
xng c tr s octan cao, BTX.
qu trnh reforming xc tc thc s bc vo vn hi
mi v cng ngnh du kh Vit Nam hi nhp vi cc ngnh
cng nghp khc trong khu vc th gii, th vn nghin
cu, trin khai cng ngh sn xut ra cc nhin liu khc t
nguyn liu du th sn c trong nc l rt cn thit. T
c th to ra nhng dy chuyn cng ngh v thit b hp
l sn xut ra nhin liu i t du m c th p ng c nhng yu cu cht lng sn phm cng nh ch tiu k
thut vi nhng nguyn liu sn c Vit Nam nhm phc
v nhu cu lu di trong nc v hng ti xut sang cc nc
trong khu vc v trn th gii.
Xng l mt trong nhng sn phm ch o ca nh
my lc du. c c cc chng loi xng c cht lng cao
phc v cho nhu cu quc dn th phi pht trin qu trnh
reforming xc tc. Nhu cu cp bch v cc sn phm ca lc
ho du ngy cng tng khi nn cng nghip ngy cng ln
mnh. Bi v cc sn phm lc ho du khng ch l ngun
nguyn liu chnh cho cc thit b my mc m cn l ngun

-2-

 n tt nghip
Thit k phn xng
Reforming xc tc.
nguyn liu quan trng cho nhiu ngnh cng nghip khc.
T gp phn vo cng vic cng nghip ho, hin i
ho ca t nc nhm a nn kinh t cng nh nn cng
nghip nc ta tin ln mt k nguyn mi, k nguyn ca s
hi nhp v pht trin.

Chng I
Tng quan l thuyt
I. Mc ch v ngha ca qu trnh reforming xc
tc [2]
Reforming xc tc l mt qu trnh quan trng trong cc
nh my ch bin du m trn th gii. Vai tr ca qu trnh
ny khng ngng c tng ln do nhu cu v xng c cht lng cao v nguyn liu cho ho du ngy mt nhiu. Qu
trnh reforming xc tc nhm sn xut ra xng c tr s
octan cao (98 100) v sn xut ra cc loi hydrocacbon
thm nh benzen, toluen, xilen (BTX) lm nguyn liu cho
ngnh cng nghip tng hp hu c ho du. Ngoi ra, qu
trnh cn cho php nhn c kh hydro k thut (hm lng

-3-

 n tt nghip
Thit k phn xng
Reforming xc tc.
hydro ti 85%) vi gi r nht so vi cc qu trnh sn xut khc
(r hn 10 15 ln so vi hydro thu c t cc qu trnh iu
ch khc). Sn phm hydro thu c t qu trnh cung
cp cho qu trnh lm sch nguyn liu, x l hydro cc
phn on sn phm trong khu lin hp lc ho du.
Hin nay, nh ci tin cng ngh v xc tc, qu trnh
reforming xc tc nhn c xng c tr s octan cao, khng
cn pha nc ch, trnh nhim mi trng v c hi cho ngi s dng.
Qu trnh reforming xc tc thng dng nguyn liu l
phn on xng c tr s octan thp, khng tiu chun
lm nhin liu xng cho ng c xng l phn on
xng ca qu trnh chng ct trc tip du th, phn on
xng ca qu trnh cracking nhit, cc ho ...
Qu trnh reforming xc tc dng xc tc a chc nng:
chc hydro-dehydro ho do kim loi m nhim (ch yu l
platin), c mang trn cht mang axit (thng dng l gama
oxit nhm tng tc cc phn ng theo c ch ion
cacboni nh izome ho, vng ho v hydrocracking).
II. C s ho hc [1,2]
II.1. C s chung ca qu trnh reforming
Reforming xc tc l mt qu trnh bin i cc thnh
phn hydrocacbon ca nguyn liu (ch yu l naphten v
parafin thnh hydrocacbon thm c tr s octan cao) m ch
o l xng chng ct trc tip v gn y nh s pht trin
ca qu trnh lm sch bng hydro do c th s dng c
xng ca cc qu trnh lc du khc nh xng ca qu trnh
cc ho, xng cracking nhit.
Nhng phn ng chnh xy ra trong qu trnh
reforming xc tc:

-4-

 n tt nghip
Thit k phn xng
Reforming xc tc.
- Dehydro ho cc hydrocacbon naphten.
- Dehydro vng ho cc hydrocacbon parafin.
- ng phn ho.
- Hydro cracking.
Dehydro vng ho

Dehydro ho

n_parafin

Alkyl cyclo

Hydrocacbon thm
Hydro

hexan

cracking
ng phn
ho
Sn phm
cracking
Hydrocracking
izo_parafin

Alkyl

Cyclopentan
Dehydro vng ho
Hnh 1: S cc phn ng chnh trong qu trnh
reforming xc tc.

Trong iu kin tin hnh qu trnh reforming cn xy

ra cc phn ng ph, tuy khng lm nh hng nhiu n
cn bng ca cc phn ng chnh nhng li c nh hng ln
n hot ng v bn ca xc tc. l cc phn
ng:
- Phn ng phn hu v kh cc hp cht cha oxi, nit, lu hunh thnh H2S, NH3, H2O.
- Phn ng phn hu cc hp cht cha kim loi v
halogen.

-5-

 n tt nghip
Thit k phn xng
Reforming xc tc.
- Phn ng ngng t ca cc hp cht trung gian khng bn
nh olefin, diolefin vi hydrocacbon thm dn n to
thnh cc cht nha v cc bm trn b mt xc tc.
V th pht trin qu trnh reforming xc tc, ngi
ta cn phi khc phc c qu trnh to cc trn xc tc, hay
t nht phi hn ch ti mc ti a qu trnh to cc. Trong
thc t sn xut, ngi ta p dng cc bin php khc nhau
nh dng p sut v nng hydro cao hoc tin hnh ti
sinh lin tc xc tc (qu trnh CCR).
II.2. Cc phn ng chnh ca qu trnh reforming xc
tc
II.2.1. Dehydro ho cc hydrocacbon naphten v to
thnh hydrocacbon thm:
1. Phn ng chuyn ho alkyl xyclohexan thnh
hydrocacbon thm
r

r
+

3h 2 + q

y l phn ng chnh ca qu trnh reforming. Khi R

l hydro th 500oC, nng lng to benzen l 51,6
kcal/mol.
y l phn ng thu nhit mnh. Khi tng nhit v
gim p sut, hiu sut hydrocacbon thm s tng ln. Vic
tng t s H2/RH nguyn liu c nh hng khng nhiu n
cn bng ca phn ng dehydro ho naphten v s nh hng
ny c th b li bng vic tng nhit ca qu trnh. Khi
hm lng ca hydrocacbon naphten trong nguyn liu cao,
qu trnh reforming s lm tng r rng hm lng ca
hydrocacbon thm. Do vy c th cho php ta la chn v
x l nguyn liu c th t mc ch mong mun:

-6-

 n tt nghip
Thit k phn xng
Reforming xc tc.
hoc tng hydrocacbon thm c tr s octan cao cho xng,
hoc nhn hydrocacbon thm ring bit (B, T, X). S
tng tr s octan cn ph thuc vo hm lng n-parafin cha b
bin i cha trong sn phm v chng c tr s octan kh
thp (tr s octan ca n-heptan bng 0). V vy, ngoi phn
ng dehydro ho naphten cng cn phi tin hnh cc phn
ng khc sao cho m bo c hiu qu ca qu trnh
reforming.
Phn ng dehydro ho naphten, trong c trng nht
l phn ng dehydro ho xyclohexan v dn xut ca n, c
tc kh ln khi ta dng xc tc c cha Pt. Nng lng hot
ho ca phn ng ny nh, ch vo khong 20 kcal/mol.
2. Phn ng chuyn ho alkyl xyclopentan thnh
hydrocacbon thm
Phn ng ng phn ho naphten vng 5 cnh thnh
vng 6 cnh l phn ng c hiu ng nhit thp (5 kcal/mol),
nn khi tng nhit th cn bng chuyn dch v pha
to vng naphten 5 cnh. V d phn ng ng phn ho ca
metyl xyclopentan thnh xyclohexan:
ch 3

+ 3h 2

Ti nhit 500oC, nng cn bng ca metyl

xyclopentan l 95%, cn ca xyclohexan ch l 5%. Nhng do
tc phn ng dehydro ho xy ra nhanh m cn bng
ca phn ng ng phn ho c iu kin chuyn ho
thnh xyclohexan v trong phn ng, nng ca naphten
cha b chuyn ho ch cn 5%. Nh vy, nh phn ng
dehydro ho naphten c tc cao m trong qu trnh
reforming ta s nhn c nhiu hydrocacbon thm v hydro.
Do phn ng thu nhit mnh, ngi ta phi tin hnh phn ng

-7-

 n tt nghip
Thit k phn xng
Reforming xc tc.
ni tip trong nhiu reactor nhn c chuyn ho
cao cn thit.
II.2.2. Phn ng dehydro vng ho n-parafin
Phng trnh tng qut:
r
r -c-c-c-c-c-c

+ 4h 2 +

Phn ng dehydro vng ho n-parafin xy ra kh hn so

vi phn ng ca naphten. Ch nhit cao mi c th
nhn c hiu sut hydrocacbon thm ng k. Khi tng
chiu di mch cacbon trong parafin, hng s cn bng to
hydrocacbon thm cng c tng ln, iu th hin s
liu trong bng sau:

Bng 1.1: nh hng ca nhit v chiu di mch

cacbon ti hng s
cn bng ca phn ng dehydro vng ho
parafin.

Phn ng

400oK

600oK

800oK

n_c 6h 14

c 6h 6 + 4h 2

3,82.10-12

0,67

3,68.105

n_c 7h 16

c 7h 8 + 4h 2

6,54.10-10

31,77

9,03.106

n_c 8h 18

-10
c 6h 5c 2h 5 + 4h 2 7,18.10

39,54

1,17.107

n_c 9h 20

c 6h 5c 3h 7 + 4h 2

65,02

1,81.107

1,42.10-9

Khi tng nhit , hng s cn bng ca phn ng

dehydro vng ho parafin tng ln rt nhanh, nhanh hn so
vi c phn ng dehydro ho naphten. Nhng tc ca phn
ng dehydro vng ho li rt nhy vi s thay i p sut
hoc t s H2/RH nguyn liu. Nng lng hot ng ca phn

-8-

 n tt nghip
Thit k phn xng
Reforming xc tc.
ng thay i t 25 n 40 kcal/mol khi dng xc tc
Cr2O3/Al2O3, cn khi dng xc tc Pt/Al2O3 l t 20 30
kcal/mol. Tc phn ng tng khi tng s nguyn t cacbon
trong phn t parafin, iu dn ti hm lng hydrocacbon
thm trong sn phm phn ng cng tng ln.
Bng 1.2: Dehydro vng ho parafin.

Nguyn liu

Hydrocacbon thm, chuyn ho,%V

%
Khi lng/nguyn
liu

n-C7H16

39,8

57,0

n-C12H26

60,2

67,0

Dehydro vng ho parafin to hydrocacbon thm l

mt trong nhng phn ng quan trng nht ca qu trnh
reforming xc tc. Nh phn ng ny m cho php bin i
mt lng ln cc hp cht c tr s octan thp ca nguyn liu
thnh cc hydrocacbon thm l cc cu t c tr s octan
cao. Phn ng ny xy ra u tin to thnh cc dn xut ca
bezen vi s lng cc i nhm metyl nh xung quanh, nu
nh nguyn liu cho php. Chng hn 465 oC, nu nguyn
liu l 2,3-dimetyl hexan th cho hiu sut ca o-xylen l ln
nht. Ngc li, nu nguyn liu l 2,2-dimetyl hexan th phn
ng xy ra kh hn v nu nguyn liu l 2,2,4-trimetyl
pentan th phn ng vng ho xy ra cn kh hn na. Nhng nu ta tng nhit ln trn 510 oC th hiu sut
hydrocacbon thm t cc hp cht trn li tng ln nh phn
ng ng phn ho lm thay i cu trc ca mch akyl.
II.2.3. Phn ng hydroizome ho
1. Phn ng izome ho n-parafin

-9-

 n tt nghip
Reforming xc tc.
n-parafin

Thit k phn xng

izo-parafin +

Q = 2 kcal/mol

Phn ng t cn bng trong vng lm vic ca reactor

iu kin 500oC vi xc tc Pt/Al2O3 nh sau:
Vi n-C6 l 30%, vi n-C5 l 40%, vi n-C4 l 60%.
Cc phn ng ny c vai tr quan trng trong qu trnh
reforming xc tc v:
- Vi cc n-parafin nh, s izome ho lm ci thin tr s
octan. V d ON ca n-C5 l 62, trong khi ON ca izoC5 l trn 80.
- Vi cc n-parafin cao hn C 5, phn ng izome ho d xy
ra, nhng n ch lm tng khng nhiu tr s octan v
cn c mt cc n-parafin cha bin i trong sn phm
phn ng. V d, n-C7 c ON = 0, cn trimetyl butan c
ON = 110 v hn hp C7 iu kin cn bng ca phn
ng izome ho ch c ON = 55. Do m phn ng
izome ho tt nht nn tin hnh vi n-parafin nh (C 5
hay C6). V khi sn phm c tr s octan hn so vi
khi tin hnh izome ho n-parafin cao hn.
2. Phn ng dehydroizome ho cc alkyl xyclopentan
r

r1

+ q =
r1
+ 3h 2 + q

= - 50 kcal/mol

II.2.4. Phn ng hydrocracking parafin v naphten

y l nhm phn ng khng mong mun ca qu trnh
reforming, cc hydrocacbon c trong phn on b gy mch

-10-

 n tt nghip
Thit k phn xng
Reforming xc tc.
v to thnh cc hydrocacbon no c s cacbon nh hn v
olefin.
C9H20

+ H2

C5H12

+ C4H10

C9H20

+ H2

CH4

CnH2n+2 + H2

C8H18

CmH2m+2 + CpH2p+2

cc iu kin nht nh c th xy ra cracking su

to kh v sn phm nh.
- i vi parafin, thng xy ra cc phn ng hydrocracking
v hydrogenolyse:
r -c-c-r 1 + h 2

r -ch 3 (izo) + r 1-ch 3 (izo) + q =11 (kcal/mol)

r -c-c-r 1 + h 2

r 2-ch 3 + ch 4 (phn ng hydrogenolyse)

- i vi naphten:
r1

+ h2

r 3h

+h 2

r 4h + r 3h + q =20 kcal/mol

r2

- Ngoi ra cn c phn ng hydrodealkyl ho cc

hydrocacbon thm:
r

+ h2

c 6h 6 + r h + Q

Sn phm ca qu trnh l cc hp cht izo-parafin

chim phn ch yu v v phn ng cng xy ra theo c
ch ion cacboni nn sn phm kh thng cha nhiu C3, C4 v
C5, rt t C1 v C2. Nhng nu tng nhit cao hn na th
s tng hm lng C1 v C2 v lc ny tc phn ng

-11-

 n tt nghip
Thit k phn xng
Reforming xc tc.
hydrogenolyse s cnh tranh vi tc phn ng cracking xc
tc. Khi metan s c to ra vi s lng ng k. Tc dng
ca cc phn ng ny trong qu trnh reforming l gp
phn lm tng tr s ON cho sn phm v to ra nhiu
izo-parafin. Nhng cn lu l cc phn ng ny lm gim th
tch sn phm lng v ng thi cng lm gim hiu sut
hydro (v tiu tn hydro cho phn ng).
II.2.5. Nhm cc phn ng tch cc nguyn t d th
Nu trong nguyn liu c cc cht cha S, N, O, s xy ra
phn ng tch cc nguyn t d th ra khi phn on.
- Hydrodenit ho:
+ 5h 2

c 5h 12 + nh 3

n
pyridin
- Hydrodesunfua ho (tch lu hunh):
+ 4h 2
s

c 5h 12 + h 2s

ch 3

- Tch oxy:
r oh

+ h2

r h + h 2o

y l nhng phn ng lm gim hm lng lu hunh,

nit, oxy trong xng, do l cc phn ng ph c li. Chnh
v vy m xc tc cho reforming phi m bo thc y
nhng qu trnh va nu trn.
II.2.6. Phn ng hydro ho
Phn ng ny xy ra vi olefin trong nguyn liu to
thnh parafin. Phn ng thc hin d dng trong iu kin
ca qu trnh reforming. Thnh phn olefin cng c th
chuyn ho trc tip thnh hydrocacbon thm, nhng khng

-12-

 n tt nghip
Thit k phn xng
Reforming xc tc.
ng k. y cng l mt phn ng quan trng v n
chuyn ho cc hydrocacbon cha no thnh cc hydrocacbon
no, trnh c s to cc gy nn s kh hoc lm gim hot
tnh cc xc tc.
II.2.7. Phn ng to cc
S to cc trong qu trnh reforming l khng mong
mun, nhng do s tng tc ca olefin, diolefin v cc hp cht
thm a vng m to thnh cc.

-h 2

-2h 2

Cc s kh to ra nu ta thao tc iu kin nhit

thp, p sut cao v t l H2/RH cao. Phn ng to cc l mt
loi phn ng phc tp, cc nghin cu v thc t sn xut
u cho thy, s to cc ph thuc vo nhiu yu t:
- Nhit phn ng.
- p sut ca hydro.
- nng ca nguyn liu v chnh l cc hp cht phi
hydrocacbon, olefin v cc hp cht thm a vng l cc
hp cht gp phn thc y nhanh qu trnh to cc.
hn ch s to cc, ngi ta phi s dng p sut
hydro va sao cho cc ch to ra khong 3 n 4% so vi
trng lng xc tc trong khong thi gian t 6 thng n 1
nm. Nhng nu tng p sut hydro s lm cn tr qu trnh
to thnh hydrocacbon thm do cn tr phn ng dehydro
ho. Do phi ch iu khin cc chc hot tnh ca xc

-13-

 n tt nghip
Thit k phn xng
Reforming xc tc.
tc gp phn iu khin c qu trnh to cc ca qu
trnh reforming.
III. C ch v ng hc ca phn ng reforming [1,4]
III.1. C ch phn ng reforming
III.1.1.

ch

phn

ng

reforming

hydrocacbon

parafin
Nhiu nh nghin cu cho rng, phn ng reforming
hydrocacbon parafin xy ra theo 3 giai on:
Loi hydro.
ng vng.
Loi hydro t hydrocacbon vng no thnh hydrocacbon
thm.
Giai on u v giai on cui xy ra trn tm xc tc
kim loi cn giai on gia xy ra trn tm xc tc axt. 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
xy ra. Nh c s tn ti ca nhng tm xc tc axit bn
cnh nhng tm xc tc kim loi m cc giai on c th xy
ra ni tip, trc tip hoc gn nh ng thi xy ra. Hay ni
cch khc l cc giai on xy ra ngay khi sn phm ca
giai on trc cha kp c cu trc hon chnh ang trng
thi nh hnh c kh nng phn ng cao.
Mt phn t n-heptan (n-C7H16) chuyn ha thnh toluen
theo nhng cch sau:

-14-

 n tt nghip
Reforming xc tc.

Thit k phn xng

-h 2

-h2
+h

+h

+h

-h

-h 2

-h 2

-h

-h

-h 2

-h 2

-h 2

Hnh 2: S tng qut reforming n-C7H16.

C ch ng vng ca cacboncation 3 cho thy khi

reforming n-C6 th khng phi vng 6 c to ra u tin m
chnh l cc hp cht vng 5 sinh ra metyl cyclopentan,
metyl cyclopenten. Cui cng chnh metyl cyclopentadien
mt hydro v ng phn ha thnh benzen. C th minh
ha r hn vi qu trnh chuyn ha n-hexan thnh benzen:

(-h 2)

(-a- )

m
+h 2

m
a
ng vng

c1 - c5

m
(-h 2)

to ion cacboni

+h 2
+
-h

-3h 2

Hnh 3: S qu trnh chuyn ho n-hexan thnh

benzen.

Tc giai on ng vng nh hn nhiu so vi tc

giai on dehydro ho. Bi vy khi reforming naphten d
hn nhiu so vi parafin. Ngi ta tnh c rng hng s tc

-15-

 n tt nghip
Thit k phn xng
Reforming xc tc.
phn ng khi reforming cc naphten th ln hn gp trm
ln so vi cc parafin, quan h bin i ph thuc vo
cht xc tc.
III.1.2. C ch reforming hydrocacbon naphten
Xt qu trnh chuyn ha cyclohexan thnh benzen:

Hnh 4: S biu din s chuyn ho cyclohexan

thnh benzen.
Trong :Chiu thng ng: Phn ng trn tm kim
loi
Chiu nm ngang: Phn ng trn tm
axit.

* Phn ng trn tm axit:

Trong cc iu kin reforming th trn cht mang c
th xy ra cc phn ng ng phn ha, ph v hoc ng
vng, m vng hoc thu nh vng hydrocacbon (Hnh 4).
Tt c cc phn ng trn u xy ra theo c ch ioncacboni.
Giai on quan trng nht l giai on to ioncacboni trn
tm axit. Tc to thnh ion cacboni v s chuyn ha

-16-

 n tt nghip
Thit k phn xng
Reforming xc tc.
tip theo ca n theo nhng hng khc nhau c quyt nh
trc ht bi cu trc hydrocacbon tham gia phn ng v bn
cht tm axit trn b mt cht mang.
* Cc phn ng trn tm kim loi:
Theo thuyt a v Baladin th hai phn ng dehydro
ha cyclohexan v dehydro ho benzen u xy ra theo c
ch hp ph lin tc trn b mt mt s kim loi nh: Pt, Ni,
Co, Pd, Rh... Phn t cyclohexan b hp ph ti tm hot
ng gm c 6 im. Phn ng dehydro ha s xy ra khi c
6 nguyn t hydro b tch loi khi nguyn t cyclohexan mt
cch ng thi.
Sau ny cng vi s pht trin ca l thuyt phc v nhng
phng php nghin cu hin i ng thi cng ph bin
mt quan nim khc v c ch dehydro ho cyclohexan.
Theo c ch ny, phn t cyclohexan ln lt b tch loi 6
nguyn t hydro v lin tip to phc trung gian.
III.2

Nhit

ng

hc

iu

kin

phn

ng

[3,4,11,12]
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 1.3: Cc thng s nhit ng hc ca cc phn
ng reforming
hydrocacbon C6.

Phn ng

Kp [500oC]

H [Kcal/mol]

Cyclohexan C6H6 + 3H2

6.105

52,8

Metyl cyclopentan

0,086

- 3,8

0,78.105

63,8

Cyclohexan

-17-

 n tt nghip
Reforming xc tc.

Thit k phn xng

n-hexan C6H6 + 4H2

n-hexan Hexen-1 + H2

1,1

- 1,4

0,037

31,0

n-hexan 2-metyl pentan

Hng s cn bng K c xc nh theo p sut ring
phn atm ca tc nhn phn ng v sn phm sau phn ng.
Cc s liu nhit ng hc cho thy, ti cn bng
cyclohexan 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 1 v 4). Phn ng isomeho 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
xyclohexan trong nguyn liu v n hp th nhit mnh nht
do nhit ca phn ng c ly t hn hp nguyn liu v khi
nn nhit ca hn hp ny gim. Tc l phi cung cp
nhit cho hn hp phn ng.
Phn ng dehydro to vng ca parafin v phn ng
dehydro ha ca naphten l nhng phn ng chnh lm tng
tr s octan. Cn bng nhit ng ca nhng phn ng ny
dch chuyn v pha sn phm phn ng khi p sut ring
phn ca hydro thp v nhit phn ng cao (500 oC).
Tuy nhin, iu kin ny thch hp to thnh cc v
s to cc ch c th ngn chn bng cch tin hnh phn
ng trong mi trng hydro; 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 nhiu phn ng hydro ha to ra
aromatic.
Do vy, qu trnh reforming xc tc c thc hin di p sut
cao v hydro sn phm c hon li vng phn ng. Ngi ta

-18-

 n tt nghip
Thit k phn xng
Reforming xc tc.
nghin cu nh hng ca p sut, nhit , lng hydro
tun hon n cn bng. Kt qu cho thy khi p sut v lng hydro tun hon tng, cn bng cng khng n nh,
do vy hiu sut ring phn ca xng cng khng n nh.
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 kh, lm gim hiu sut pha lng. Hnh 5
minh ho s ph thuc ca hiu sut phn ng vo 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.

100
90

RON85
80

RON95
RON102

70

Hiu sut phn ng, %

RON104

60
0

p sut thit b, at
Hnh 5: Hiu sut phn ng v p sut ti nhng tr
s octan khc nhau.

Trong thc t, qu trnh c th c tin hnh trong

khong nhit 455 510oC v p sut 6,5 50 atm. iu

-19-

 n tt nghip
Thit k phn xng
Reforming xc tc.
kin ch chuyn ho v to c mt phn aromatic cn nu
thc hin nhit cao hn v p sut khong 10 atm th
c th chuyn ho 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
1.4), 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.
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 520oC v
thng l gia 482 500oC, nhng qu trnh hot ng p
sut thp v nhit kh cao to ra sn phm c tr s
octan cao 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 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 hydrocracking 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 izome ho 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.
Bng 1.4: c trng vn tc v hiu ng nhit ca
nhng phn ng
reforming quan trng.

-20-

 n tt nghip
Reforming xc tc.
Loi phn

Vn tc

ng

tng i

Hydrocracki
ng
Dehydro ha
to vng
Izome ha

Thp nht

Thit k phn xng

nh hng ca s
tng p sut tng
cng
Vn tc tng

Hiu ng
nhit
Ta nhit
va phi

Khng nh hng ti
Thp

s gim nh trong

Thu nhit

vn tc
Nhanh

Gim vn tc

Ta nhit t

Nhanh

Gim vn tc

Ta nhit t

Dehydro ha

Kh

Gim chuyn

parafin

nhanh

ha

ca parafin
Izome ha
naphten

Dehydro ha
naphten

Rt nhanh

Thu nhit

Gim chuyn

Rt thu

ha

nhit

T l mol gia hydro v hydrocacbon nguyn liu thay

i t 3 10, nhng ph bin nht l t 5 8. T l ny nh
hng bt li n phn ng thm ha, lm tng phn ng
hydrocracking. Gi tr la chn thng gii hn thp phn
ng hydrocracking xy ra t yu cu v s kh hot tnh xc
tc l thp. Nhng naphten 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 l cht
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 hydrodesunfua
ha trc khi phn ng. Cc hp cht nit hu c b chuyn

-21-

 n tt nghip
Thit k phn xng
Reforming xc tc.
thnh amoniac lm ng c chc nng axit ca xc tc nn
nng ca n phi nh hn 2 ppm. Nit thng c loi ra
khi nguyn liu bng cch 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 lm
thay i axit ca cht mang v lm o ln cn bng
ca nhng phn ng ang xy ra. Hm lng ca chng cn
phi iu khin cn thn duy tr axit ca xc tc.
Nhng kim loi nh Si, Pb, Cu phi c loi b n nng
thp nht v chng to hp kim vi ch lm kh hot tnh ca
xc tc.
IV. Xc tc ca qu trnh reforming [1,2,3,8,9]
Xc tc c s dng cho qu trnh reforming xc tc l
loi xc tc a chc nng, gm chc nng oxi ho kh v chc
nng axit. Chc nng oxi ho kh c tc dng lm tng tc
cc phn ng hydro ho, kh hydro cn chc nng axit c tc
dng thc y cc phn ng xy ra theo c ch ion cacboni
nh phn ng ng phn ho, phn ng hydrocracking.
IV.1. Lch s pht trin ca xc tc reforming
Theo lch s pht trin ca reforming xc tc, nm 1940
ngi ta p dng qu trnh u tin vi xc tc l axit
molipden mang trn oxit nhm MoO 2/Al2O3, loi xc tc ny r
tin, d ch to, bn vi lu hunh. Khi c mt ca lu hunh
trong nguyn liu th MoO2 c th chuyn mt phn thnh
MoS2, dng ny cng c hot tnh ging nh oxit molipden, cho
nn trong nguyn liu khng cn loi b lu hunh mt cch
trit . Song, loi xc tc ny c nhc im l hot tnh
khng cao nn qu trnh reforming phi thc hin ch
cng (vn tc th tch thp, vo khong 0,5 h -1, nhit
cao, vo khong 340oC). iu kin ny cc phn ng
hydrocracking xy ra mnh. tng chn lc ca qu

-22-

 n tt nghip
Thit k phn xng
Reforming xc tc.
trnh phi duy tr p sut thp (14 20 at). Nhng s gim p
sut li thc y qu trnh to cc do vy khng ko di c
thi gian lm vic ca xc tc. V cc l do trn nn hin nay
khng cn s dng loi xc tc ny.
Sau ny, loi xc tc Pt/Al2O3 ra i c nhiu u vit hn
v c s dng rng ri trong cng nghip. Hm lng Pt trong
xc tc t 0,3 0,8% trng lng, nhit phn ng l 500 oC,
p sut t 30 35 at, vn tc th tch 1,5 4h-1. Xc tc ny
c hot tnh v n nh cao, lm vic lu hn, cho
sn phm c tr s octan cao v lng cc to ra t. Sau mt
thi gian lm vic, hot tnh ca xc tc gim do axit ca
Al2O3 gim, v vy phi tin hnh clo ho tng axit.
Ngy nay, ngi ta ci tin xc tc reforming bng
cch bin tnh xc tc khi cho thm mt kim loi (bimetal)
hoc thay i cht mang, v d: Pt/SiO 2; Pt/SiO2-Al2O3; PtRe/SiO2-Al2O3; Pt-Sn/SiO2; Pt-Ir/axit rn.
Mc ch cho thm kim loi vo l lm tng hot
tnh xc tc hoc gim gi thnh xc tc. V d, cho thm Sn
(1/2 lng), hot tnh xc tc khng tng, nhng gi thnh li
gim i; khi cho Re th hot tnh tng v Re c vai tr lm
phn tn u cc nguyn t Pt trn b mt axit rn.
Vic cho thm nguyn t him nh Re cn c ngha
c bit nh km hm s thiu kt ca cc vi tinh th Pt v
to vi Pt hp kim c n nh cao hn so vi Pt nguyn
cht.
Xc tc s dng cho qu trnh reforming hin nay l
0,3%Pt + 0,3%Re mang trn -Al2O3, vi din tch b mt
khong 250 m2/g, c b sung cc hp cht halogen hu c.
Hm lng clo hoc flo khng ch khong 0,5 1% trng lng.
IV.2. Thnh phn xc tc reforming

-23-

 n tt nghip
Thit k phn xng
Reforming xc tc.
Nhn chung xc tc reforming bao gm 2 thnh phn
chnh:
1. Platin
Platin c a vo xc tc cc dng khc nhau, ph
bin l dng dung dch ca axit platin clohydric H 2(PtCl6).
y Pt mang chc nng oxy ho kh, xc tin cho phn ng
hydro ho, dehydro ho to hydrocacbon vng no v vng
thm. Trong qu trnh reforming, Pt lm tng tc ca
phn ng kh hydro cc hydrocacbon naphten, kh hydro
vng ho cc hydrocacbon parafin to thnh hydrocacbon
thm. Ngoi ra n cn thc y qu trnh no ho cc hp
cht trung gian l olefin, diolefin, lm gim tc to thnh
cc bm trn xc tc m l nguyn nhn chnh lm gim
hot tnh ca xc tc. Hm lng Pt trn xc tc chim vo
khong 0,3 0,7% khi lng v chim khong 1% din tch
b mt ca cht mang. Yu cu Pt phi phn tn u trn
b mt cc axit rn. phn tn cng cao th hot tnh
ca xc tc s cng cao, hiu sut xng thu c cao v cht lng xng thu c tt hn.
2. Cht mang c tnh axit
Cht mang trong xc tc reforming c th l Al 2O3 hoc
l hn hp ca Al2O3-SiO2. axit ca n c quyt nh bi
qu trnh x l c bit tch nc b mt nhm to ra
b mt ring ln (400 m2/g) v to ra cc tm axit.
Cht mang c th l -Al2O3 hay -Al2O3 vi din tch b
mt dao ng trong khong 200 300 m2/g. Al2O3 l cht
mang c tnh axit, ng vai tr chc nng axit-baz, thc
y phn ng izome ho, hydrocracking. Cht mang Al 2O3
cn phi tinh khit (hm lng Fe v Na khng qu 0,02%
trng lng). Al2O3 ho nc nn lun mang mt t nc hp th,

-24-

 n tt nghip
Thit k phn xng
Reforming xc tc.
k c 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 axt Brosted v n mang H+:

Al-O
Al-O

Al-O
Al

Al- OH -

Al-O

Al-O

H+

Al-O
B mt

B mt
Khi cht mang axt nhm hoc hn hp Al 2O3 -SiO2,
axt ca n c quyt nh bi qu trnh x l c bit
tch nc b mt nhm to ra b mt ring ln ( 400 m 2/g)
v to ra cc tm axt. 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
+ Cl

OHAl-OH

Al-Cl

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

-25-

 n tt nghip
Thit k phn xng
Reforming xc tc.
phn ng hydrocracking ca cc parafin, phn ng ng
phn ho hydrocacbon naphten 5 cnh thnh 6 cnh, tip
theo l cc naphten 6 cnh b kh hydro to thnh hydro
cacbon thm.
Yu cu t ra vi cht mang cng rt cao. i vi cht
mang Al2O3 cn phi tinh khit: hm lng Fe v Na khng qu
0,02% khi lng.
Vic tng axt thng l bng cch thm vo cc
halogen hu c nh C2H4Cl2, CH3Cl. Ngoi vic tng axt,
n cn c tc dng lm n nh phn tn ca Pt trn
cht mang nh n to phc hp Pt v Al 2O3. Mt trong nhng u
im ca cht xc tc cha clo l n t thc y cc phn
ng hydrocracking trong iu kin cng. Hm lng clo c
tng thm vo khong 0,5 1% khi lng.
a platin ln b mt cht mang trong cng nghip
ngi ta dng phng php ngm, tm. Tm Al2O3 bng dung
dch H2PtCl6 axit ho, nung v kh trong dng kh hydro.
S phn tn platin trn cht mang c th xy ra theo cch
sau:
Cl
2-

Al-OH

Al-O
+ [PtCl 6]2-

Cl

Pt

+ 2Cl- + 2H+
Al-OH

Al-O

Cl
Cl

Al-O

-26-

Cl

 n tt nghip
Reforming xc tc.

Thit k phn xng

O

Pt

+ 4ClAl-O

Cl

IV.3. Nhng yu cu c bn i vi xc tc cho qu

trnh
c mt xc tc reforming tt th xc tc cn phi
c hot tnh cao i vi cc phn ng to hydrocacbon thm,
c hot tnh i vi cc phn ng ng phn ho parafin
v c hot tnh thp i vi phn ng hydrocracking. Ngoi ra
cn th hin qua cc ch tiu sau:
- Xc tc phi c chn lc cao.
- Xc tc phi c bn nhit v kh nng ti sinh tt.
- Xc tc phi bn i vi cc cht gy ng c nh cc
hp cht ca S, N, O; nc, mui ca cc 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 h, d ch to.
Nh vy, mt xc tc reforming tt cn phi tng tc cc
phn ng c bn v cn phi hn ch cc phn ng ph, nht
l phn ng to cc. V th m tng quan gia phn ng to
cc vi tng cc phn ng c bn c ngha rt quan trng.
T s phn ng to cc trn tng s cc phn ng c bn
phi l cc tiu. tng tc cc phn ng c bn, ta c th
tng nhit hoc gim tc np liu. Nhng hot tnh
ca xc tc lm tng tc cc phn ng c bn l rt quan
trng v khi tng nhit hay thay i iu kin cng
ngh ch hn ch c mt phn rt nh cc phn ng ph.
Nhng phn ng to hydrocacbon thm (dehydro ho,

-27-

 n tt nghip
Thit k phn xng
Reforming xc tc.
dehydro vng ho) v cc phn ng izome ho hay
hydrocracking l cc phn ng chnh to ra cc cu t c tr
s octan cao v c p sut hi bo ho nh , thch hp cho
qu trnh pha trn to xng cht lng cao vi bt k cng thc
pha trn no. Hn na, khi gim tc to cc s lm cho
xc tc lm vic trong thi gian di hn v n nh hn.
c xc tc reforming tt, khi ch to, phi iu
chnh tng quan gia hai chc ca xc tc sao cho t
chn lc mong mun. chn lc ca xc tc c nh gi
thng qua biu thc sau:
dehydro vng ho
R =
hydrocracking + hydroizome ho + dehydro
vng ho
Gi tr ca R cng ln, chn lc ca xc tc cng cao.
Do vy, vic to nn s cn bng gia hai chc ca xc tc
gi vai tr ch o khi ch to xc tc reforming.
Thng thng, ngi ta nh gi cht lng xc tc
reforming thng qua cc ch tiu: hm lng Pt, b mt ring
ca cht mang, bn. Bng 1.3 cho bit mt s c trng
ca xc tc reforming.
Bng 1.3: Mt s c trng ca xc tc reforming.

Cc ch
s

Pt (%

Xc tc
A -64

8815

RY-302

RD-150

R-16

(Lin X

CHLB

France

M-c

c)

0,60,65

0,35

0,580,6

0,37

0,55

1,5

1,53,0

trng lng)
ng knh

2
1,8

2,2

-28-

 n tt nghip
Reforming xc tc.

Thit k phn xng

ht (m)
B mt

180

240280

160200

0,97

1,2

40120

40120

80100

0,750,8

ring
(m2/g)
Ch s
bn
(kg/mm)
ng knh
l ()
Th tch
l (ml/g)
Cht knh

8
clo

flo

clo

clo

clo

hot
Tt c cc xc tc trn u cha Re (0,5% trng lng)
trn cht mang Al2O3.
IV.4. Vai tr ca xc tc reforming
Qu trnh hin i ho cng ngh reforming cc nc
cng nghip du m pht trin, nhn chung gm cc giai
on: tm cch ch to xc tc mi c hiu qu cao gn lin
vi ci tin trang thit b v cng ngh. u im ni bt
nht ca xc tc a kim loi l tc tr ho xc tc ca n
nh hn nhiu so vi cc xc tc n kim loi. iu cho
php gim p sut qu trnh xung cn 1,4 1,5 MPa khi
lm vic vi dy chuyn xc tc c nh v vi dy chuyn
xc tc chuyn ng ch cn 0,5 1 MPa. Ngy nay, hng
UOP xy dng dy chuyn vi lp xc tc chuyn ng
CCR lm vic vi p sut cn thp hn na, ch khong 3,5
at (50 psi). Khi gim p sut, chn lc ca xc tc tng
cao, nht l khi ch bin nguyn liu c hm lng
hydrocacbon parafin ln. Khi lm tng vai tr ca phn

-29-

 n tt nghip
Thit k phn xng
Reforming xc tc.
ng dehydro vng ho parafin: 50 60% hydrocacbon thm
nhn c t chuyn ho parafin. Do tr s octan ca
sn phm xng rt cao (RON > 100).
Cc xc tc hai hay nhiu kim loi c tc to cc nh
hn, tc ca cc phn ng ph nh phn ng phn hu
cng nh hn v li lm tng thm vai tr ca phn ng
dehydro vng ho parafin, do vy m lm tng c hiu sut
v cht lng ca xng cng nh

tng hiu sut ca

hydrocacbon thm.
IV.5. Nguyn nhn lm gim hot tnh xc tc
Sau mt thi gian lm vic, hot tnh xc tc b gim
ng k. Mun nng cao hiu qu s dng ca xc tc
nhm gim gi thnh sn phm th xc tc phi c ti
sinh. c bin php khi phc li hot tnh ca xc tc mt
cch hu hiu, phi xut pht t nguyn nhn gy nn s
mt hot tnh ca xc tc.
IV.5.1. nh hng c hi ca cc hp cht cha lu
hunh
Cc hp cht ca lu hunh lm ng c trung tm kim
loi (Pt), lm nh hng khng tt n chc nng kh hydro
v vng ho. Trong cc cht cha lu hunh, mercaptan (RSH)
lm gim mnh nht hot tnh xc tc. Khi hot tnh xc tc
gim, khng nhng lm gim hiu sut xng, m c cht lng
xng cng gim theo. c bit lu hunh dng H2S cn gy
n mn thit b. Do vy cn phi lm sch lu hunh ngay t
khi a nguyn liu vo qu trnh reforming. Hm lng lu
hunh trong nguyn liu cho php t 0,01 n 0,07% trng
lng.
Khi xc tc tip xc vi nguyn liu cha lu hunh, khng
nhng ch kim loi trn xc tc b ng c m ngay c Al 2O3

-30-

 n tt nghip
Thit k phn xng
Reforming xc tc.
cng b bin i. N tc dng vi hp cht lu hunh to thnh
sunfat nhm Al2(SO4)3. Do vy lm cho qu trnh ti sinh xc
tc b phc tp hn v i hi mc ti sinh su hn.
Ngay c sau khi ti sinh chuyn Al2(SO4)3 v Al2O3, nhng
hot tnh ca xc tc vn b gim xung ng k so vi khi
nguyn liu khng cha lu hunh.
Bng 1.6: S nh hng ca hp cht lu hunh.

Ch tiu

Hm lng S trong nguyn

liu

Hiu sut xng ca qu trnh

0,002%S

0,009%S

90,9

87,5

47,0

44,0

81,5

80.6

95,5

93,5

(% trng lng)
Hm lng hydrocacbon thm
trong xng reforming (%)
Tr

octan

ca

xng

reforming
Theo phng php nghin cu
c thm 0,8 ml nc ch

IV.5.2. nh hng ca cc hp cht cha nit

Cc hp cht cha nit c trong nguyn liu cng nh hng xu n hot tnh ca xc tc. Khi tip xc vi cc hp
cht cha nit nh NH3, hot tnh ca xc tc gim nhanh,
c bit l chc axit. V NH3 mang tnh baz lm trung
ho cc tm axit ca xc tc. Nh vy s lm gim tc cc
phn ng ng phn ho, vng ho v hydrocracking. Hm lng ca nit cho php trong nguyn liu phi bng hoc nh
hn 1 ppm, nn a s cc qu trnh reforming u p dng
qu trnh hydro ho lm sch nguyn liu.

-31-

 n tt nghip
Reforming xc tc.

Thit k phn xng

Bng 1.7: nh hng gy c xc tc ca cc hp cht

nit.

Ch tiu

Hm lng cht nit trong nguyn

liu (mg/l)

Xc tc

Xc tc

cha b

sau khi

ng c

ng c

12

67

89

85

93

89,5

96,5

92,5

Hiu sut xng reforming (%)

Tr s octan:
Theo phng php mt (khng pha
ch)
Theo phng php nghin cu (c
pha 0,8 ml nc ch/1 lt)
IV.5.3. nh hng c hi ca cc kim loi
Cc hp cht ca ch (Pb), asen (As) gy ng c xc
tc rt mnh. S c mt ca ch trong nguyn liu c th do
nhiu nguyn nhn khc nhau. Cc hp cht ch tch ng
dn trn xc tc v lm thay i nhanh hot tnh xc tc.
Nu c 0,5% Pb th xc tc s khng c kh nng ti sinh. V
vy hm lng ca ch cho php c mt trong xc tc l 0,02
ppm v ca asen l 0,01 ppm. C th lm sch cc kim loi ra
khi nguyn liu bng phng php hydro ho trc khi a vo
qu trnh reforming xc tc.

IV.5.4. nh hng ca nc
Nc c mt trong nguyn liu s pha long cc trung tm
axit, lm gim axit ca cht mang, ng thi gy n

-32-

 n tt nghip
Thit k phn xng
Reforming xc tc.
mn thit b. Hm lng nc cho php khng c vt qu (10
20).10-4% trng lng.
trnh n mn thit b, cn tch nc ra khi nguyn
liu bng cch dng qu trnh lm kh nh ry phn t hoc
phun kh clo vo nguyn liu cha nc.
IV.5.5. nh hng ca hm lng olefin n qu trnh to
cc
Cc hp cht olefin thc y nhanh qu trnh to cc.
Hm lng ca chng trong nguyn liu cn phi nh hn 2%.
nh hng n qu trnh to cc cn do trong nguyn liu c
nhiu cc hp cht a vng hay chnh l olefin v diolefin c to ra trong qu trnh reforming. Cc to ra s bm dnh
trn b mt xc tc, lm bt i cc trung tm hot tnh,
ngn cch s tip xc ca tc nhn phn ng vi xc tc lm
gim dn hot tnh ca n.
IV.5.6. nh hng ca halogen
Halogen hot ho cho xc tc Pt/Al 2O3. Nu hm lng
halogen trong xc tc qu thp, hot tnh axit v nhng phn
ng xy ra trn tm axit gim nhanh, tr s octan do vy
cng gim. Ngc li, nng halogen qu ln th axit ca
xc tc tng lm tng phn ng hydrocracking v gim tr s
octan. Nng halogen trong xc tc c th thay i trong
sut qu trnh tu thuc nhng nhn t nh hm lng
halogen v nc trong nguyn liu, nhit v p sut qu
trnh. Nng halogen trong xc tc tng khi hm lng
halogen trong nguyn liu tng v hm lng nc gim. Mc
halogen trong nguyn liu cao nht l 5 ppm, nu cao hn
phi x l nguyn liu bng hydro.
IV.6. Ti sinh xc tc
IV.6.1. Qu trnh thay i tnh cht ca xc tc

-33-

 n tt nghip
Thit k phn xng
Reforming xc tc.
Trong qu trnh lm vic, xc tc b thay i cc tnh
cht vt l khi tip xc vi nhit cao v thng xuyn phi
tip xc vi cc c t. S thay i cc tnh cht ca xc tc
reforming khi lm vic c th phn chia thnh cc loi sau:
Nhng thay i c tnh cht tm thi, ngha l c th
khi phc li cc tnh cht ban u ca n bng qu trnh ti
sinh xc tc. l cc thay i do s to cc hay s ng c
thun nghch bi cc hp cht ca oxy, nit, lu hunh.
Nhng thay i vnh vin, l nhng thay i
khng c kh nng ti sinh. V d do s thiu kt nhit
cao m b mt ring ca xc tc v cu trc ca Al 2O3 cng
nh phn tn ca kim loi Pt gim i. S thay i ny
cn d xy ra hn nu xc tc l n kim loi hay khi ti
sinh xc tc khng khng ch c nhit cht ch.
Nhng thay i trn s lm gi ho nhanh xc tc v
n mt thi gian no , phn xc tc gi ho ny phi
c thay th bng xc tc mi c hot tnh cao hn nhm
gi cho hot tnh chung ca xc tc khng thay i
hiu sut v cht lng ca xng c n nh trong sut qu
trnh.
IV.6.2. Cc phng php ti sinh xc tc
tng hiu qu kinh t ca vic s dng cht xc tc,
ngi ta phi ti sinh khi phc cc tnh cht ca xc tc.
Yu cu ti sinh xc tc ph thuc vo tnh khc nghit
ca qu trnh. Mi qu trnh reforming cn mt iu kin
ti sinh ring.
Da vo cc nguyn nhn gy mt hot tnh xc tc,
trong cng nghip p dng cc bin php sau ti sinh xc
tc.
IV.6.2.1. Phng php oxi ho

-34-

 n tt nghip
Thit k phn xng
Reforming xc tc.
y l phng php ti sinh xc tc bng cch t chy
cc bm trn b mt xc tc bng oxi ca khng kh nhit
300 500oC. Dng dng kh nng cha t 2 15% oxy
(O2) t cc v gi khong nhit trn khng
lm tn hi n tm kim loi platin. i vi cc xc tc b
mt hot tnh, sau khi ti sinh, s t c hot tnh xp x
ban u v cha t hn 0,2% cc. Nhng sau nhiu ln ti
sinh, hot tnh s gim.
Qu trnh t chy cc c biu din theo phng
trnh sau:
CxHy + O2

CO2 + H2O + Q

Ta thy rng qu trnh ny to nhit, s to nhit ny

c nh hng rt ln ti bn ca cht xc tc:
- Khi nhit qu cao th Al2O3 s b thay i cu trc.
- Khi nhit cao dn ti s gim phn tn ca platin
do cc phn t ny b t chy.
Chnh v vy ngi ta tm cch gim nhit xung
mc cho php trnh gy nh hng ti cht xc tc.
IV.6.2.2. Phng php kh
Khi trn b mt xc tc tch t nhiu lu hunh, c th
s khng loi b c bng cch t, th s tip tc loi b
bng phng php kh, (bng hydro di p sut 20 at, 10% H2)
lc y lu hunh s b kh thnh H2S v do hm lng ca n
gim xung ch cn 0,03 0,05% trng lng.
IV.6.2.3. Phng php oxyclo ho
Trong qu trnh lm vic, hm lng clo trn cht mang
gim dn. khc phc, ngi ta thng b sung thm cc hp
cht hu c cha clo vo sau khi ti sinh oxy ho - kh,
ngha l sau khi t cc.

-35-

 n tt nghip
Thit k phn xng
Reforming xc tc.
Ngoi ra, ngi ta cn tin hnh clo ho trong khi ti sinh cht
xc tc. Vi phng php ny cn thc hin nhit khong
500oC, p sut kh quyn vi nng clo trong khng kh
khong 0,4 0,5% th tch sao cho kh clo c bo ho trong
xc tc. Ngoi tc dng lm tng axit ca cht xc tc,
vic clo ho cn c tc dng lm gim hm lng mt s kim
loi nh: Bi, Pb, Fe...c bit cc nguyn t clo c tc dng
phn tn li cc phn t platin mt cch tt hn.
325o
2Fe2O3 + 6Cl2

4FeCl3 + 3O2

Qu trnh ti sinh bng clo khng nhng c tc dng

nng cao hot tnh axit m cn c tc dng tch cc hp
cht kim loi lng ng trn xc tc. Hm lng st, ch v
bimut gim r rt.
Hm lng clo trong xc tc khng nn cao qu,v d, nu
clo chim 1,4% trng lng th kh nng phn hu tng ln
mnh dn n tng hiu sut kh, iu ny khng mong
mun i vi qu trnh reforming. Hm lng clo trn xc tc
c khng ch sao cho mc 1% khi lng, l nng
ti u cho chc axit ca xc tc Pt/Al 2O3. Qua thc nghim thy
rng, ch ti sinh xc tc bng clo nh sau:
- Tc th tch np khng kh (h-1)

1000
500

- Nhit (oC)

- Thi gian ti sinh (h)

- Nng clo trong khng kh (%

0,4 0,5

trng lng)
V. Nguyn liu v sn phm ca qu trnh reforming
xc tc [1,2,3,4,12,13,15]
V.1. Nguyn liu

-36-

 n tt nghip
Thit k phn xng
Reforming xc tc.
Nguyn liu ca qu trnh reforming l cc phn on
xng chng ct trc tip, c gii hn si t 60 210oC, xng ca
qu trnh cracking nhit hoc c th s dng phn on
xng ca qu trnh th cp.
Tu thuc vo mc ch ca qu trnh reforming xc
tc nhn xng c tr s octan cao hay nhn cc
hydrocacbon thm ring r m chn gii hn si ca phn
on xng lm nguyn liu khc nhau.
sn xut xng c tr s octan cao, ngi ta dng phn
on xng c gii hn si t 85 180oC, phn on ny cho
php sn xut xng c tr s octan cao v hn ch to cc.
sn xut cc hydrocacbon thm ring r, ngi ta s
dng cc phn on xng hp:
- sn xut bezen s dng xng c gii hn si 62 85oC.
- sn xut toluen s dng xng c gii hn si 85
120oC.
- sn xut xylen s dng xng c gii hn si 120
140oC.
Thnh phn ct ca nguyn liu c nh hng nhiu
n hiu sut v cht lng ca sn phm. Nu thnh phn
ct c nhit si qu rng, c cha nhiu phn nh s lm
cho hiu sut v cht lng xng gim xung.
Nguyn liu thun li nht cho qu trnh sn xut cc
cu t c tr s octan cao (ON = 100) l phn on si t
105 140oC hay phn on 105 180oC.
Nu ta s dng nguyn liu c nhit si nh hn
60oC l khng thch hp v n khng cha cycloankan v
hon ton khng c kh nng chuyn ho thnh aren m ch

-37-

 n tt nghip
Thit k phn xng
Reforming xc tc.
cha cc hydrocacbon c s nguyn t nh hn 6, c kh
nng chuyn ho thnh cc hydrocacbon kh.
Phn on c nhit si cao hn 180 oC th gy ra
nhiu cc lng ng trn xc tc, lm gim thi gian sng
ca xc tc trong iu kin phn ng.
nh hng n qu trnh reforming xc tc khng ch l
thnh phn ct m quan trng hn l thnh phn ho
hc ca phn on nguyn liu. Trong nguyn liu c cha
cc hp cht khc nhau ca parafin, ca naphten, ca
hydrocacbon thm v cc hp cht phi hydrocacbon khc nh
hp cht ca oxy, nit, lu hunh. Nu hm lng ca naphten
trong nguyn liu cng cao, nht l xyclohexan v dn xut
ca n cng nhiu, th phn ng dehydro ho xy ra cng
trit v hm lng hydrocacbon thm s cng nhiu. Hay
ni cch khc l qu trnh reforming xc tc cng d xy ra
v ch cn tin hnh qu trnh iu kin mm, khe
kht nh m vn cho hiu sut v cht lng xng cao. Nu
nguyn liu cha nhiu hp cht parafin th cc phn ng
ca parafin ch gp phn nh to ra cc hydrocacbon
thm bng phn ng dehydro vng ho (khi m xc tc cha
c ci tin), cn i b phn parafin s tham gia phn ng
izome ho v hydrocracking. Phn ng hydrocracking cn lm
gim hiu sut H2 do tiu hao H2 cho phn ng ny. Do vy,
thnh phn ho hc ca nguyn liu trong iu kin
reforming xc tc s xc nh c hiu sut H 2 to ra trong qu
trnh. Nu hm lng parafin trong nguyn liu cng thp th
hiu sut H2 s cng cao (ch dng vi xc tc th h c).
Cc hydrocacbon thm c trong nguyn liu thng nh,
c bit khi nguyn liu l phn on xng chng ct trc
tip. Hydrocacbon thm c nh hng n tc cc phn
ng dehydro ho hay dehydro vng ho theo hng ngn cn

-38-

 n tt nghip
Thit k phn xng
Reforming xc tc.
cc phn ng ny. V vy, nu mc ch ca qu trnh l
sn xut hydrocacbon thm ring bit th nn tch trc
hydrocacbon thm khi nguyn liu.
Nh vy, naphten l thnh phn mong mun cn
aromatic v olefin l thnh phn khng mong mun trong
nguyn liu.
nh gi cht lng nguyn liu reforming xc tc
thng qua thnh phn ho hc ca nguyn liu, hng UOP
a ra mt chun s tng quan KUOP c xc nh theo biu
thc:
KUOP = 12,6 - (N + 2Ar)/100
N : hm lng % ca naphten.
Ar : hm lng % ca hydrocacbon thm.
Trong nguyn liu reforming xc tc, KUOP v c bit l
tng s N + 2Ar thay i trong mt khong rng (tng N +
2Ar c th t 30 80). Nu KUOP = 10 th nguyn liu cha
nhiu hydrocacbon thm hn. Nu KUOP = 11 th nguyn
liu cha nhiu naphten v hydrocacbon thm mt vng.
Cn nu KUOP = 12 l nguyn liu cha mt hn hp bng
nhau gia hydrocacbon vng v hydrocacbon parafin v nu
KUOP = 13 th nguyn liu ch yu l hydrocacbon thm. Nh
vy, nu KUOP thp hay tng s N + 2Ar trong nguyn liu
cng cao th nguyn liu cng cha nhiu naphten v
nguyn liu cng thun li nhn reformat c tr s
octan cao. Ngoi ra, thnh phn phn on cng c nh hng ln n cc ch tiu ca qu trnh reforming xc tc.
Hiu sut reformat v H2 cng nh hot ng ca xc tc
s

tng

khi

tng

hm

lng

hydrocacbon

hydrocacbon thm trong nguyn liu.

-39-

naphten

 n tt nghip
Thit k phn xng
Reforming xc tc.
Cc hp cht phi hydrocacbon, c bit l cc hp cht
ca lu hunh v ca nit trong nguyn liu phi gim ti mc
ti thiu v nh hn gii hn cho php. V cc hp cht ny
ch lm tng tc cc phn ng ngng t to nha v cc, gy
c cho xc tc, lm gim nhanh hot tnh ca xc tc. V
th nguyn liu trc khi a vo reforming xc tc u phi
c a qua cng on x l bng hydro ho lm sch loi
b cc hp cht phi hydrocacbon, cc hp cht olefin, diolefin
v c kim loi do nhim bn vo nguyn liu reforming trong
qu trnh ch bin. Cc hp cht phi hydrocacbon s c loi
ra dng kh nh H2S, NH3 v H2O nh qu trnh hydro ho
lm sch. Tu thuc vo ch cng ngh v nht l xc tc
m qu trnh hydro ho lm sch s t c cc ch tiu v
cht lng cho nguyn liu reforming.
Bng 1.8: Hm lng cho php cc hp cht phi
hydrocacbon c mt
trong nguyn liu reformat xc tc.

Hm lng lu hunh

Max

0,5 ppm

Hm lng nit

Max

0,5 ppm

Hm lng oxy

Max

2 ppm

Hm lng clo

Max

0,5 ppm

Hm lng asenic

Max

1 ppb

Hm lng ch

Max

20 ppb

Hm lng ng

Max

5 ppb

Hm lng cc kim loi

V.1.1. Qu trnh hydro ho lm sch nguyn liu

Tt c qu trnh reforming xc tc thng p dng mt
trong hai loi s cng ngh, l ti sinh xc tc gin
on v ti sinh xc tc lin tc. Nhng d p dng s no,

-40-

 n tt nghip
Thit k phn xng
Reforming xc tc.
nguyn liu trc khi a vo qu trnh reforming xc tc cng
cn phi c qua cng on lm sch vi tn gi l hydro ho
lm sch hay x l bng hydro (nht l khi qu trnh s dng
xc tc a kim loi).
Nguyn liu naphta, xng, (c th dng c kerosen,
gasoil khi x l cc nguyn liu ny) c trn vi hydro
tin hnh phn ng nhit v p sut cao. Cc phn ng
ho hc s xy ra cng vi qu trnh hydrodesunfua ho l no
ho olefin v thm, demetal ho v hydrocracking. Khi mc
ch ca qu trnh ny l x l nguyn liu cho reforming
xc tc, th hydrodesunfua ho v demetal ho l nhim v
chnh ca cng on ny. Nhng hydrocacbon cha lu
hunh v cc tp cht khc cha trong nguyn liu s c
phn ng vi hydro trn xc tc Co hoc xc tc Ni/Mo trn
cht mang cc tp cht ny c tch ra mt cch chn lc
v nh cc c tnh ca nguyn liu c ci thin.
Cc tp cht khc nh hp cht cha nit, oxy v kim loi,
khi phn ng vi hydro s to ra cc hp cht amoniac, nc v
hydrogenat kim loi. Cc hp cht olefin c no ho, nh vy
ci thin c n nh ca sn phm.
Cc phn ng chnh c th xy ra:
- Tch lu hunh:
Mercaptan:
r -s-h + h 2

r h + h 2s

Sunfit:
r -s-r

+ 3h 2

2r h + h 2s

Disunfit:
r -s-s-r

+ 3h 2

2r h + 2h 2s

-41-

 n tt nghip
Reforming xc tc.
Sunfit vng:
s

+ 2h 2

Thit k phn xng

c-c-c-c + h 2s

Thiophen:
s

c 4h 6 + h 2s

+ 4h 2

- Tch nit: nit c loi b di dng NH3.

Pyridin:

+ 5h 2

c-c-c-c-c + nh 3

Quinolin:
c-c-c-c
+ nh 3

+ 4h 2
n

Pyrol:
n

+ 4h 2

c-c-c-c + nh 3

- Tch oxy:
Phenol:
oh

+ h 2o

+ h2

- Phn ng vi olefin:
olefin + h 2

parafin

Olefin thng:

-42-

 n tt nghip
Reforming xc tc.
c-c=c-c-c-c + h 2

Thit k phn xng

c-c-c-c-c-c

Olefin vng:
+ h2

(naphten)

- Tch kim loi:

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

V.1.2. Dy chuyn x l nguyn liu lm sch bng

hydro
Cc bc x l nguyn liu lm sch bng hydro c tin
hnh nh sau:
- Nguyn liu naphta c trn vi kh hydro (tun hon)
v c gia nhit ban u bng nhit tn dng ca sn
phm lng, sau tip tc gia nhit n nhit cn
thit.
- Dng ra khi thit b c h thp nhit nh b phn
lm lnh.

-43-

 n tt nghip
Thit k phn xng
Reforming xc tc.
- Tip theo hn hp c a vo thit b tch, hi c nn
li v kt hp vi kh hydro mi quay tr li trn ln vi
nguyn liu.
- Phn lng tch ra t thp c a n mt thp chng.
y, H2S v NH3 c tch ra khi nguyn liu.
V.2. Sn phm
Sn phm thu ca qu trnh reforming bao gm xng c
tr s octan cao, cc hydrocacbon thm v kh H 2, trong
xng c tr s octan cao l sn phm quan trng nht.
1. Xng c tr s octan cao
Cht lng ca xng nhn c ph thuc vo cht lng ca
nguyn liu , xc tc v ch cng ngh ca qu trnh.
T bng 1.9 ta thy, nu xng c cng tr s octan th
xng nhn c t nguyn liu c hm lng parafin thp c
thnh phn phn on nng hn so vi xng nhn c t
nguyn liu c hm lng parafin cao.
Tu thuc vo nguyn liu ban u v ch cng
ngh ca qu trnh, c th nhn c xng c tr s octan
cao, c th t t 100 n 105.
Thnh phn ca xng reforming xc tc nh sau: olefin
khng qu 3%, naphten khng qu 10%, cn li l izo_parafin
v aromat.
Nh vy, xng reforming xc tc c cht lng rt cao, c
bit hm lng olefin thp (< 3%) cho php s dng lm xng
my bay. Tuy nhin nhc im ca xng ny l tr s octan
phn b khng ng u trong khp khong nhit si
ca xng, do cc hydrocacbon thm ch yu tp trung
phn on xng c nhit cao nn ng c kh khi
ng nhit thp v lm vic ch khng n

-44-

 n tt nghip
Thit k phn xng
Reforming xc tc.
nh, v vy thng phi pha trn thm cc thnh phn nh
c tr s octan cao vo xng nng cao ch tiu ny.
Trong qu trnh bo qun, vn chuyn v s dng, xng
u d b oxy ho bi oxy trong khng kh v to thnh cc
sn phm cha oxy rt a dng, mc oxy ho ph thuc
vo cht lng ca xng v c th l thnh phn ho hc ca
xng. Cc hp cht olefin c hai ni i i xng v
hydrocacbon dng mono hoc diolefin ni vi phn thm l
km bn nht. sn phm c bo qun lu v gi c
n nh cao, ta cn phi cho thm cht chng oxy ho
vo vi lng nht nh.
Bng 1.9: Tnh cht ca xng reforming.

Cc thng s

Hm lng parafin trong

nguyn liu (%)
65%

Trng lng ring 20oC (g/cm3)

< 4%

0,785 0,783 0,796

0,77
2

Thnh phn phn on (oC)

- Nhit si u

49

42

58

- Nhit si 10%

82

76

97

58

- Nht si 50%

135

137

141

110

- Nhit si 90%

172

170

171

141

- Nhit si cui

202

214

199

168
205

Thnh phn ho hc (% trng

lng)

2,2

0,9

1,0

0,5

- Hydrocacbon khng no

59,0

65,4

62

68,5

- Hydrocacbon thm

38,8

33,7

37

31

-45-

 n tt nghip
Reforming xc tc.

Thit k phn xng

- Parafin + naphten
Tr s octan
- Phng php mt theo
MON

80

85

80

85

89

95

89

95

- Phng php nghin cu

theo RON
2. Sn phm hydrocacbon thm
Hydrocacbon thm nhn c t qu trnh reforming xc
tc l benzen, toluen, xylen (gi tt l B, T, X), c dng lm
nguyn liu cho tng hp hu c ho du v ho hc. Sn
phm hydrocacbon thm ph thuc vo thnh phn ca
nguyn liu. Nguyn liu tt nht l naphten v parafin.
Nhng sn phm thm c nhit cao nh 1,2,4 v 1,3,5
trimetylbenzen; 1,2,4,5 v 1,2,3,5 trimetylbenzen c sn
xut t qu trnh c thu hi v tinh ch bng cc qu trnh
hp ph (cht hp ph l silicagen), chng trch ly, chng
ng ph hoc trch ly bng dung mi dietylenglycol, nhng
tinh khit khng cao v kh tch ra t pha lng v chng
c nhit si

gn vi

parafin v naphten, khong 90%

hiu sut thm p sut cao (200 400 psi).

ch nhit va phi v vn tc th tch thp,
sn phm thng l hn hp toluen-xylen, benzen-toluen hoc
hn hp c 3 thnh phn .
- Benzen: Trong qu trnh reforming xc tc, benzen thng c to ra di dng hn hp vi cc hydrocacbon khc v c tch ra bng phng php trch ly dung mi hoc chng ct
ng ph v n to hn hp ng ph vi cc hydrocacbon
thm khc. i vi nguyn liu c nhit si l 62 85oC
th chuyn ho benzen l 80%. Benzen thu c c

-46-

 n tt nghip
Thit k phn xng
Reforming xc tc.
tinh khit cao, thng s dng trn vi xng chng ct lm xng
thng phm v n c kh nng chng kch n cao, c xu hng lm gim qu trnh kh khi ng my. Ngoi ra, benzen
cn iu ch phenol, lm ngun nguyn liu sn
xut si polyamit, capron, cc hp cht ha hc khc v dung
mi cho ngnh cng nghip.
- Toluen: Thng thu c ng thi vi benzen trong qu
trnh reforming. Tuy nhin s dehydro ho ca naphten d
dng hn benzen, lng toluen thu c t reforming l rt ln,
c ng dng ch yu pha trn vo xng, lm dung mi
cho nhiu qu trnh khc.
- Xylen: Xylen thu c t qu trnh vi hiu sut nh
hn benzen v toluen. Nh c qu trnh trch ly dung mi
chn lc cao, c ng dng nhiu trong cng nghip nh:
+/ T m-xylen iu ch c p-xylen dng lm nguyn
liu sn xut si nilon polyeste.
+/ T m-xylen iu ch c o-xylen dng lm nguyn
liu tng hp anhydric phtalic.
3. Sn phm kh hydro
Trong kh reforming xc tc cha 70 90% th tch
hydro, kh ny c s dng mt phn tun hon li thit
b phn ng, mt phn a ra khi h thng lm sch, ri s
dng cho mt s qu trnh nh hydrocracking sn xut
du nhn.y l ngun thu hydro r tin nht trong tt c cc
qu trnh sn xut hydro, khi qu trnh reforming xc tc
pht trin th thc y cc qu trnh s dng hydro pht
trin theo. Thng thng, hm lng hydro thu c t 81 93%
(th tch).
4. Kh ho lng:

-47-

 n tt nghip
Thit k phn xng
Reforming xc tc.
Qu trnh reforming xc tc thu c ngoi kh cha
hydro cn thu c kh ho lng khi n nh thnh phn ca
xng, ta thu kh propan v butan.
Hiu sut pzo pan
v bu tan % thtch

25
20
3

15
2

10
1

5
0
60

65

70

75

80

85

90

95

Hiu sut xng kh butan %V

S ph thuc gia hiu sut xng
kh butan v i hiu sut propan v butan lng
1. Hiu sut min butan lng
2. Hiu sut max butan lng
3. Hiu sut propan lng

Hnh 6:

S ph thuc gia hiu sut xng kh

butan vi hiu sut

propan v butan lng

Chng II
Cng ngh reforming xc tc
I. Ch cng ngh ca qu trnh [1,2,3]
C 4 thng s cng ngh quan trng nht cn quan
tm trong qu trnh reforming xc tc, l nhit , tc
np liu ring LHSV, p sut v t l mol H 2/RH ca
nguyn liu.
I.1. p sut
Cc phn ng chnh ca qu trnh reforming xc tc
u l cc phn ng tng th tch, in hnh nht l phn
ng dehydro ho naphten thnh hydrocacbon thm, c 1 mol
naphten s to ra 3 mol H2, nh vy th tch hydrocacbon tng
cng tng ln 4 ln. Cn phn ng dehydro vng ho parafin
th 1 mol nguyn liu s to ra mol H2 v nh vy th tch

-48-

 n tt nghip
Thit k phn xng
Reforming xc tc.
hydrocacbon tng cng s tng ln 5 ln so vi th tch ban
u.
Do , theo quan im nhit ng hc, khi tng p
sut s cn tr qu trnh tng th tch, c ngha l cn tr
cc phn ng chnh to hydrocacbon thm ca qu trnh
reforming xc tc.
Cn khi tng khe kht ca qu trnh, ngha l lm
vic p sut ca hydro thp s cho php tng tr s octan
ca xng v tng c hiu sut xng, gim lng kh v tng
nng hydro trong kh, nhng tc to cc li tng ln,
iu ny lm gim thi gian lm vic ca xc tc v tn s
ti sinh xc tc s tng ln. S to cc trong iu kin sn
xut c th gim bng cch h thp nhit si cui ca
nguyn liu, v trong phn nng ny c cha cc thnh
phn a vng, chng d ngng t, d to cc. Do , nhit
si cui ca nguyn liu nn h xung 160oC.
Ta thy p sut trong h thng nh hng ln n hiu
sut to hydrocacbon thm v tr s octan cho xng sn
phm, cng nh nh hng n hiu sut to hydro v thi
gian lm vic ca xc tc. Nu cc iu kin lm vic khc
nhau ca qu trnh l khng i, khi ta tng p sut duy tr
trong h thng th vn tc cc phn ng hydrocracking v
kh alkan s tng, trong trng hp ny, cn bng s chuyn
dch v pha to thnh parafin.
Khi gim p sut lm vic trong h thng, s gim p
sut ring phn hydro v lm tng mc thm ho cc
hydrocacbon parafin v naphten, ng thi gim tc
phn ng hydrocracking v kh alkyl. iu lm tng hiu
sut hydro v tng n nh ca xng.
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

-49-

 n tt nghip
Thit k phn xng
Reforming xc tc.
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 at th c th loi b cc hu nh hon ton.
Nhng nu tng hn na th hn ch vn tc phn ng
dehydro ho, p sut ring phn cng nh hng n phn
ng izome ho v dehydroizome ho.
p sut quyt nh bi hot tnh v chn lc ca
xc tc. Trc y, ngi ta s dng xc tc Mo/Al2O3, P = 15
20 atm. Ngy nay, ngi ta s dng xc tc mi l Pt/Al 2O3 duy
tr P = 20 40 atm trong h thng m hot tnh to
hydrocacbon thm vn m bo.
Cng vi qu trnh ci tin xc tc, cng ngh cng c
ci tin theo v ngi ta p dng p sut ca qu trnh ngy
mt thp. Nhng ci tin cho php tng tr s octan ca
xng, tng c hiu sut xng v lng hydro. Do p dng qu
trnh p sut thp, tc to cc tng ln, dn n cc
cng ngh c s ln ti sinh xc tc tng ln.
Nh vy, p sut trong h thng nh hng n hiu sut
to hydrocacbon thm v tr s octan ca xng, ngoi ra cn
nh hng n vic to ra hydro v thi gian lm vic ca
xc tc.
Bng 2.1: nh hng ca p sut ti cc ch tiu ca
xng.

Ch tiu

35

49

63 at

at

at

92,6

92,9

93,2

95,5

95,7

96

1. Hiu sut sn phm tnh theo nguyn

liu:
- Xng kh propan
- Xng vi p sut hi bo ho, %V

-50-

 n tt nghip
Reforming xc tc.

Thit k phn xng

(520 mmHg)
2. Hydro m3/m3 (%TL)

1,4

1,0

0,6

84,1

84,8

47,9

45,4

3. c tnh ca xng vi p sut hi bo

ho (520 mmHg)
4. Tr s octan theo phng php nghin 85,1
cu RON
5. Hm lng hydrocacbon thm (%V)

53,9

Trong iu kin lm vic ca qu trnh khng i, khi

tng p sut th vn tc cc phn ng hydrocracking v kh
alkyl s tng ln, trong trng hp ny cn bng s chuyn dch
v pha to parafin.
Khi gim p sut trong h thng, dn n gim p sut ring
phn ca hydro, lm tng mc thm ho cc hydrocacbon
parafin v naphten.
I.2. Tc np liu ring th tch hay thi gian tip
xc (thi gian phn ng)
Khi tng lu lng ca nguyn liu hay gim lng xc tc
trong reactor s lm tng tc np liu ring th tch v
nh vy s lm gim thi gian tip xc ca nguyn liu vi xc
tc, tc l gim thi gian phn ng. T d dng thy rng,
khi tng tc np liu ring, hiu sut xng tng ln v tng
hm lng hydro trong kh tun hon, gim hiu sut
hydrocacbon nh do gim tc phn ng hydrocracking v
hydrogenolyse. Cht lng ca xng s chuyn qua cc i khi
tng tip tc tc np liu ring (v thi gian tip xc nh,
hydrocacbon thm to ra cng t do ch c phn ng
dehydro ho cc naphten xy ra hon ton iu kin ny).
Nh vy, nhn chung khi tng tc np liu qu gi tr ti u
s lm tng hiu sut xng ng thi li gim tr s octan v
lm gim p sut hi bo ho ca xng.

-51-

 n tt nghip
Thit k phn xng
Reforming xc tc.
Tc np liu ring th tch thng duy tr trong
khong 1,2 2 h-1. Nu gim tc np liu th tch s dn
n lm gim chn lc ca qu trnh, gim hiu sut
xng v hydro, tng hiu sut hydrocacbon kh, gim nng
hydro trong kh tun hon, lm tng lng cc bm trn xc
tc.
Nu mc ch ca qu trnh reforming xc tc l nhn
BTX, qu trnh phi tin hnh iu kin thi gian lu ca
nguyn liu trong vng phn ng ngn, c ngha l tc
th tch khi s dng nguyn liu phi ln, nhit trung
bnh, p sut thp (10 20 atm).
Bng 2.2: nh hng tc th tch n qu trnh
reforming.

Tc th tch h-1

Ch tiu
Hiu sut xng kh propan, %V
Hm lng phn on c nhit

91,8

93,9

95,1

32

25

17

625

520

360

85

81

76

43,0

40,5

38,0

si n 100 C
p sut hi bo ho ca xng mmHg
Tr

s octan theo

phng php

nghin cu (khng pha ch)

Hm lng hydrocacbon thm trong
xng,%V
I.3. Nhit

Qu trnh reforming xc tc tin hnh trong iu kin

nhit nm trong gii hn t 470 525oC. Khi iu kin p
sut v tc th tch khng i, nu gim nhit s
dn n tng hiu sut xng, gim hiu sut kh, gim vic
to cc, ng thi li gim lng hydrocacbon thm.

-52-

 n tt nghip
Thit k phn xng
Reforming xc tc.
Ngc li, nu tng nhit , dn n tng s to thnh
hydrocacbon thm, gim hiu sut xng, gim nng
hydro trong kh tun hon (v khi nhit cao, thun li cho
cc phn ng hydro ho v kh hydro vng ho) to
hydrocacbon thm. Song bn cnh cng tng cng cc
phn ng hydrocracking lm cho hiu sut kh tng ln, do
vy mc ho cc cng tng.
Nh vy, khi nhit tng th lng hydrocacbon thm
to thnh cng tng lm cho tr s octan ca xng tng. Nhng
nhit cng ch tng n gii hn cho php, nu tng qu
cao th vic to cc tng, dn n gim hot tnh v thi
gian lm vic ca xc tc.

Bng 2.3: S ph thuc hiu sut v cht lng ca sn

phm
reforming xc tc vo nhit .

Nhit ,oC

Ch tiu
435

450

465

480

Hiu sut xng kh propan

98

96,8

95

91,6

Hm lng phn on c tos

34

36

41

46

310

350

430

590

67,5

74

80,5

89

19

27

35

45

n 100oC, %V
p sut hi bo ho ca xng
(mmHg)
Tr s octan theo phng php
nghin cu (khng pha nc
ch)
Hm lng hydrocacbon thm

-53-

 n tt nghip
Reforming xc tc.

Thit k phn xng

trong xng, %V
T phn tch trn, vic la chn nhit trong qu
trnh reforming xc tc cn kt hp vi cc thng s cng
ngh khc ca qu trnh. Ngoi ra cng cn phi tnh n
cht lng ca nguyn liu v xc tc. Thng thng, ch gi
nhit sao cho m bo yu cu v tr s octan ch
khng yu cu cao hn nhit ny.
I.4. T l hydro trn nguyn liu (H2/RH)
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 ty 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 H2 s dng n nh do np kh cha hydro
cho tun hon li t qu trnh phn ng.
Khi tng bi s tun hon kh cha hydro, s tng ch
tiu nng lng cho my nn kh tun hon v tng ch tiu
nng lng trong l ng t nng kh ny, c ngha l chi
ph kinh t tng.
Chn t s tun hon kh cha hydro c quyt nh
bi cc yu t: thnh phn phn on ca nguyn liu,
kht khe ca qu trnh v tr s octan ca sn phm xng.
V d, khi reforming xc tc c nh vi nguyn liu l phn
on 85 180oC c hm lng hydrocacbon parafin cao, p
sut 25 35 at. T l H2/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 mol H 2/RH 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.

-54-

 n tt nghip
Thit k phn xng
Reforming xc tc.
T s mol H2 (N) c tnh chuyn qua i lng bi s
tun hon kh cha hydro (W, m 3/m3 nguyn liu) theo biu
thc:
-3

W = 2,24.10 . .

N
M.[H2]

Trong :

: mt ca nguyn liu.

[H2] : nng hydro trong kh tun hon.

M

: khi lng trrung bnh mol ca nguyn liu.

Khi thi gian lm vic lin tc ca xc tc ln hn 6

thng, xng thu c c ch s RON = 95 th bi s tun
hon kh cha hydro c chn l 1500 1800 m3/m3 ( H2/RH
= 8 n 9). Cn nu khi nhn xng thu c c RON = 85 th
bi s tun hon kh cha hydro thp hn, trong khong
1200 1500 m3/m3 ( H2/RH = 5 n 7).
Trong trng hp nu nguyn liu cha nhiu naphten,
bi s tun hon kh cha hydro s chn thp v nu tng
bi s ny s c nh hng xu, lm gim mc chuyn ho
cc hydrocacbon thnh hydrocacbon thm. Nn dy
chuyn lp xc tc chuyn ng, nhn xng vi RON = 100
102 th H2/RH 3.
I.5. khe kht ca qu trnh reforming xc tc
Trong qu trnh reforming xc tc, khe kht ca qu
trnh chnh l iu kin kh khn hn i vi xc tc.
khe kht cng cao, xc tc s gim nhanh hot tnh, gim
thi gian lm vic v tn s tin hnh ti sinh s cao hn. Nhng iu ny c b li bi tr s octan ca xng cao hn,

-55-

 n tt nghip
Thit k phn xng
Reforming xc tc.
hm lng hydrocacbon thm nhiu hn. kht khe khng
phi l mt i lng c s o c th m thng qua cc thng
s cng ngh ca qu trnh s dn ti cc nh hng trn,
thm ch ngay cng mt iu kin lm vic nh: nhit , p
sut, tc np liu, t l H 2/RH, vn c th dn n bin
thin tr s octan, nng sut v lm gim hot tnh ca xc
tc tu theo bn cht nguyn liu a vo reforming. Do vy,
i vi mi loi nguyn liu v mi loi xc tc, khe kht
hon ton khc nhau.
Khi tng nhit , tr s octan tng nhng ng thi li
lm gim hiu sut xng n nh (phn on C 5+) v
H2. Xc tc lm vic trong iu kin d to cc v nhanh
chng gi ho, do vy khe kht l cao.
Nu ta gim tc np liu, NO tng v ng thi lm gim
C5+ v H2, lm tng hydrocacbon nh v cng tng qu trnh
to cc. iu lm cho xc tc chng b gi ho v lm
tng tn s ti sinh, do khe kht trong trng hp ny
cng ln.
Nu ta gim p sut, NO tng v cng tng c hiu sut
phn on C5+ v H2 nhng xc tc lm vic trong iu kin
to cc rt nhanh, do vy khe kht cng l cao
nh hng ca t l H2/RH cng ging nh nh hng p
sut chung ca h thng. Khi ni ti mt xc tc no , cn
phi tin hnh qu trnh reforming iu kin khe kht
hn so vi xc tc khc, ngha l cng nhn sn phm
xng c tr s octan nh nhau, phi tin hnh thao tc iu
kin hoc l tng nhit hoc gim tc np liu hoc
l gim p sut, gim t l H 2/RH. Nh vy lun dn ti s to
cc nhanh v gi ho nhanh xc tc.
Trong thc t, ngi ta khng ch ch n cht lng m cn
ch n s lng xng nhn c tc l hiu sut xng. Do

-56-

 n tt nghip
Thit k phn xng
Reforming xc tc.
vy tng khe kht thng ch p dng bng cch gim p
sut ca h thng v gim t l H2/RH, t khi gim tc
np liu hay tng nhit qu trnh cao hn so vi thit k.
II. Cng ngh ca qu trnh reforming xc tc
T khi ra i n nay qu trnh reforming xc tc lun
c nghin cu, ci tin v i mi v cng ngh v xc tc.
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. Nhiu nghin cu ci tin
c thc hin theo hai hng: ci tin c v xc tc v cng
ngh. Bng 2.4 cho ta thy tin trnh ci tin v xc tc v
cng ngh trong cng nghip du kh.
Bng 2.4: S ci tin xc tc v cng ngh reforming
xc tc trn th
gii.

1940

Reforming xc tc u tin s dng xc tc

1949

molipden

1950 1960

Pht trin xc tc Pt
Rt nhiu qu trnh reforming xc tc c pht
trin t xc tc Pt

1960
1970
1980
1990

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 xut
hydrocacbon thm

-57-

 n tt nghip
Reforming xc tc.

Thit k phn xng

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 xut

xng c tr s

octan cao cng vi qu trnh cracking vi lp xc tc si (FCC).

Qu trnh reforming xc tc khi s dng thit b phn ng vi
lp xc tc c nh nn phi nh k dng lm vic ti
sinh xc tc b cc ho. Mt s qu trnh s dng thit b
phn ng c ng van song song d ti sinh xc tc
tng thit b phn ng ring m khng cn dng lm vic
ton b h thng (qu trnh Power former).
Vo thp nin 1960, xc tc hai v nhiu kim loi c
pht trin. Xc tc hai v nhiu 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
ho c tho ra lin tc khi thit b phn ng v c a
quay tr li thit b 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 ho, qu trnh CCR cho php dng p sut thp v
thao tc lin tc, hng nm cha phi thay xc tc mi. Cng
nh gim p sut m hiu sut hydrocacbon thm v H 2 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.

-58-

 n tt nghip
Thit k phn xng
Reforming xc tc.
Cc hng i u trong qu trnh ci tin reforming xc tc
c dn ra bng 2.5.
Bng 2.5: Cc hng i u trong qu trnh

ci tin

reforming xc tc.

Tn qu

Hng

Loi thit b

trnh

thit k

phn ng

Platformer

UOP

Xc tc c

Exxon

er

Loi l
ti sinh

R11-R12

Ti sinh

Pt=0,3750,

gin

75

on

Xc tc c

KX, RO, BO

Ti sinh

nh

(Pt, Re)

gin

nh

Powerform

Loi xc tc

on
IFP

IFP

Reforming

Xc tc c

RG 400

Ti sinh

nh

Pt (0,2-0,6)

gin
on

Maona

Engelha

Xc tc c

RD.150

Ti sinh

Former

rd

nh

(Pt=0,6);

gin

Reni

CRC

Former

Xc tc c

E.500

on

F (Pt, Re)

Ti sinh

nh

gin
on

CCR
Platformer

UOP

Xc tc

R 16; 20

Ti sinh

chuyn

Pt, Re

lin tc

ng, thit
b
phn ng
chng
ln nhau

-59-

 n tt nghip
Thit k phn xng
Reforming xc tc.
II.1. Cng ngh reforming xc tc 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 1 nm). Qu trnh
ti sinh xc tc c tin hnh ng thi trong tt c cc thit
b phn ng. Thi gian tng cng ti sinh v bo dng
thit b l 20 n 40 ngy/nm. S cng ngh ca qu
trnh reforming vi lp xc tc c nh c trnh by hnh
7:

H2

L gia
nhit

Thit b phn
ng

Ngng
t h
lu

Thit
b
phn
tch
Thit b t
nng

Sn
phm

Nguyn
liu

-60-

 n tt nghip
Reforming xc tc.

Thit k phn xng

Hnh 7: Cng ngh reforming vi lp xc tc c nh

UOP Platforming.

Hot ng ca n nh sau:
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, c np
ni tip vo l t nng v cc thit b phn ng theo th t
t 1 n 3 (ngy nay thng hay dng 4 l). Sn phm ra khi
l sau khi qua cc thit b trao i nhit, c np tip vo
thit b t nng v thit b lm sch. Sau qua thit b
ngng t, sn phm s gi nhit 380C, kh khng ngng s
c tch ra thit b tch kh. Phn ln kh ny c my nn
nn v tip tc tun hon li l reforming. Phn cn li c
dn sang b phn tch kh v s dng H 2, v d cho qu
trnh hydro ho lm sch. Sn phm y ca thit b tch
c a qua thit b t nng bi sn phm nng ca y
ct. Sn phm nh ca ct c dn sang thit b ngng t.
Cc hp cht hi s tch khi dy chuyn, sn phm lng c
hi lu bng bm. Xng reforming n nh y c cho
qua thit b trao i nhit ri qua thit b lm sch, sau
vo b cha.
Cc dy chuyn reforming vi xc tc Pt lp xc tc c
nh thng dng p sut cao (t 20 45 at). Sau ny thng
dng qu trnh p sut thp hn (t 10 16 at). Gim p
sut lm cho qu trnh dehydro ho v dehydro vng ho c
tng cng. Nh vy m cho php nhn c sn phm c ON
cao hn, tuy nhin s ln ti sinh xc tc cng tng ln nh s
cng ngh ca Magnaforming (hnh 8).

-61-

 n tt nghip
Thit k phn xng
Reforming xc tc.
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. Trong thit b u tin, do
nhng phn ng to 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.
L
ph
n
ng

L
gia
nhi
t

Lm lnh

Hi
Hi

Trao
i
nhi
t

Nguyn
liu

Thp
n
nh

Thit
b
phn
tch
Bm

My
nn

-62-

 n tt nghip
Reforming xc tc.
Hnh

8:

Thit k phn xng

cng

ngh

xc

tc

nh

Magnaforming.

II.2. Cng ngh reforming vi lp xc tc chuyn ng

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) v do vy, xc tc
va mi ti sinh c lin tc chuyn vo thit b phn ng.
iu lm cho xc tc c hot tnh cao hn v n nh
hn, lm vic iu kin kht khe hn m vn cho hiu
qu cao hn.
Sau y s cp mt cch chi tit qu trnh
reforming xc tc chuyn ng ca hng UOP.
S reforming ti sinh xc tc lin tc ca hng UOP
c trnh by hnh 9.
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 di cng
thnh mt khi. 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. 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 nm 1971. 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 th nht xung
thit b phn ng th 2 ri t thit b th 2 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 tr 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

-63-

 n tt nghip
Thit k phn xng
Reforming xc tc.
nn c th duy tr mc hot tnh trung bnh ca cht
xc tc cao hn v n nh 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 tng ng t 3,5 n 12
at v t 400 n 500m3/m3. Vic gim c p sut c nh tt
n qu trnh, tng c hiu sut, tng c nng hydro
trong kh cha hydro.
Kh thin
nhin

Kh

Thu hi
phn
nh

Cc thit b phn
ng
Xc tc ti
sinh

Thi
t b
ph
n
tch

Hnh 9: S cng ngh reforming xc tc chuyn

ng ti sinh lin tc.

S reforming nhn chung gm cc b phn sau:

1. B phn thit b phn ng
Nguyn liu trn vi kh hydro tun hon c t nng
n nhit phn ng (526 5300C) trong cc thit b trao
i nhit v b phn th nht ca l ng ri c np vo
thit b phn ng th nht trn cng. Sau khi tip xc vi

-64-

 n tt nghip
Thit k phn xng
Reforming xc tc.
xc tc, nguyn liu b bin i tu thuc vo cc iu
kin cng ngh ca qu trnh. Khi thit b phn ng gm
bn thit b chng ln nhau theo trc thng ng, kch thc
tng dn t trn xung di v u l kiu xuyn tm. Trong
mi thit b phn ng c thit b ring v ng dn xc tc,
b phn phn phi, b phn cch ly v cc thit b khc sao
cho ph hp vi qu trnh chuyn ng ca xc tc v cc
phn ng ho hc xy ra. Lng xc tc cha trong thit b
phn ng rt khc nhau, thit b phn ng th nht ch cha
10 20% lng xc tc v thit b phn ng cui cha khong
50% khi lng xc tc. Xc tc lm vic c chuyn sang
l ti sinh xc tc, hn hp kh phn ng i ra khi thit b
phn ng th nht c qua l t nng li n nhit
phn ng ri c np ngay vo thit b phn ng th 2, c
nh vy cho n thit b phn ng th 4. Sau thit b phn
ng th 4, hi kh sn phm c ngng t v lm lnh tip trc
khi chuyn sang b phn phn tch sn phm. thit b
tch, sn phm c chia thnh hydrocacbon lng ngng t v
hi kh giu hydro. Phn ln kh ny c quay li thit b
phn ng nh kh tun hon, phn kh cn li c trn vi b
phn ti tip xc ri i vo ct n nh sn phm.
2. B phn l ti sinh xc tc
Xc tc lm vic chy t y 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 xung y b phn tch bi ri chy
xung l ti sinh.

-65-

 n tt nghip
Thit k phn xng
Reforming xc tc.
Ti sinh xc tc gm 4 bc, ba bc u l t chy cc,
clo ho v lm kh. Ba bc ny 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
pha di gia mng chn hnh tr t thng ng, khng
kh nng c thi theo hng bn knh i t ngoi vo trong
qua lp xc tc. Kh chy nng c thi nh bm sau lm
lnh v tun hon qua cc ng trong vng chy.
t chy cc xy ra trong khi xc tc vn chuyn ng
xung pha di 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. Cn b phn t nng ti sinh s lm vic khi cn phi
t nng kh m bo nhit pha trong vng thch
hp.
Qu trnh oxy ho, phn tn kim loi trn xc tc v b
sung thm clo c thc hin trong vng clo ho ca l ti sinh
b tr pha di vng chy. Xc tc ri xung theo cc lp
hnh tr. Kh clo ho nng c thi qua lp xc tc v i ra
vng chy, t vng sy kh thi qua cc ng vng trn i vo
vng clo ho. Hp cht clo hu c c phun vo khng kh
dn vo vng clo ho v cng c t nng b phn gia
nhit ring m bo nhit vo.
Sy kh xc tc thc hin vng sy. Vng sy nm pha
di vng clo ho, kh kh nng c thi qua lp xc tc v tch
m. Vic t nng kh kh c thc hin bi l t khng
kh.
Qu trnh kh kim loi trn xc tc xy ra vng kh.
Vng kh t pha di v tch bit vi ba vng trn. Kh kh
nng c thi qua lp xc tc. H thng tinh ch s tch cc

-66-

 n tt nghip
Thit k phn xng
Reforming xc tc.
hydrocacbon nh t kh ny v lm tng tinh khit ca
hydro. Kh kh c t nng nh l t ring m bo
nhit vo vng kh.
Cui cng, xc tc c a theo ng dn xc tc vo
ng nng. Tc chy c khng ch m bo chu
trnh ti sinh v kh xy ra . Tip theo xc tc c kh
hydro vn chuyn v nng ln bunke cha t pha trn
nh ca thit b phn ng

th nht, tip tc chuyn

ng vo cc thit b phn ng lm vic. Chuyn ng ca

xc tc t thit b phn ng ny xung thit b phn ng kia
c khng ch v phn phi qua 8 ng dn hay nhiu hn
tu theo thit k m bo iu ho, phn phi u,
trnh chy tho xc tc hay t qung lp xc tc.
3. B phn n nh
Reformat t b phn tch c np vo ct n nh
iu chnh p sut hi ca n. Reformat s c tch
hydrocacbon nh v thu reformat n nh. iu
chnh nhit ca ct n nh ta dng thit b t nng
khi cn nhit b sung.
Snxc
phm y c bm qua vng i
Thp cha
tc
lu ca b phn t
nng cho thit b phn ng, sau mi

cho qua thit b trao i nhit tn dng nhit. Ct n

nh lm vic L
p ti
sut
sinh cao c th phn hi lu
v ch tch sn phm kh kh (hydro, metan). Sn phm
reformat n nh c cho qua thit b trao i nhit
vi nguyn liu ri vo b cha.

Kh
chy

My
nn

L
phn
ng
Kh
nit

Sn
phm

-67Nguy
H2
n liu

L
phn
ng

Thng
phn
L tphi

 n tt nghip
Reforming xc tc.

Thit k phn xng

Hnh 10: Cng ngh reforming xc tc ca FIN.

Cng ngh ca FIN (hnh 10). s c bn thit b

phn ng, sp xp theo mt dy. trong thit b phn ng
c h thng nhiu li tun hon u xc tc.
Trn ng dn cha xc tc phi b tr van t ng. S
ny lm vic vi diu kin p sut tt c 1,4 at; xc tc
cha 0,35 v 0,5% khi lng Pt. V s ny nhn c
xng c tr s octan 100 105. Khi dng xc tc RG-451 v
dng nguyn liu phn on 70 1540C, t trng 736 th
thu c sn phm c thnh phn hydro cacbon: parafin 51%;
naphten 43% v thm 6% th tch, t l mol hydro/nguyn
liu l 6/1; tc khng gian np nguyn liu l 2,5/gi.
II.3. So snh cc qu trnh cng ngh khc nhau ca
reforming xc tc
Khi thc hin 2 cng ngh reforming xc tc chuyn
ng (CCR) v reforming xc tc c nh ta thy im khc
bit trong ch lm vic l :
p sut ca qu trnh cng ngh reforming xc tc
chuyn ng l thp hn nhiu so vi qu trnh reforming

-68-

 n tt nghip
Thit k phn xng
Reforming xc tc.
xc tc c nh. iu dn n cc u th sau: Ti iu
kin p sut thp cho php nhn c nhiu hydrocacbon
thm , nng cao tr s octan v nng cao hiu sut xng,
nhng n i hi rt ngn chu k ti sinh xc tc.
Khi p sut thp, chn lc xc tc tng nht l khi
ch bin c hm lng hydrocacbon parafin ln. Khi lm
tng vai tr ca phn ng dehydro vng ha parafin 50 60%
aren nhn c t chuyn ho parafin. Do tr s octan ca
sn phm rt cao.
Nh kh nng ti sinh lin tc xc tc b cc ho, qu
trnh CCR cho php dng p sut thp, thao tc lin tc hng
nm cha phi thay th xc tc mi, hiu sut aren v H 2 tng
ln ng k.
Nh ti sinh lin tc m khng phi dng qu trnh
ti sinh xc tc nh dy chuyn reforming xc tc c nh do
vy xc tc mi lin tc c chuyn vo reactor dn n xc
tc c hot tnh cao hn v n nh hn, lm vic
iu kin kht khe hn m vn cho hiu qu cao hn.
Tuy vy, qu trnh dng lp xc tc c nh th c kt
cu n gin, iu kin vn hnh khng qu kht khe, d
iu chnh. Gi c u t ban u va phi. Cn dy
chuyn xc tc chuyn ng th li c chiu cao ln, gi ban
u t cao v qu trnh ti sinh xc tc i hi rt cn thn,
nguyn liu phi lm sch bng hydro ho mc su.
Trong thi im hin nay th vi mc ch tng tr s
octan, hiu qu nht vn l qu trnh reforming xc tc ti
sinh lin tc.
III. La chn s cng ngh v thuyt minh
p ng cc yu cu v ch cng ngh cng nh
ph hp vi nguyn liu, ta phi chn dy chuyn cng

-69-

 n tt nghip
Thit k phn xng
Reforming xc tc.
ngh ph hp cho qu trnh reforming xc tc vi nng sut
1,7 triu tn/ nm.
Cn c vo cc dy chuyn cng ngh gii thiu trn ti
chn dy chuyn cng ngh thit k da trn s
reforming vi lp xc tc chuyn ng v ti sinh lin tc.
iu kin lm vic ca qu trnh nh sau:
B phn reactor v ct n nh:
Nng sut theo nguyn liu:

1,7 triu

tn/nm
520 540oC

Nhit vo reactor:
LHSV, h-1:

H2/RH, mol:

2,5

p sut trong thit b phn ng:

3,5 kg/cm 2

(50 psi)
2,5 kg/cm 2

p sut trong thit b tch:

p sut trong cc thit b ti tip xc:
S 1:

6,6 kg/cm 2

S 2:

15,6 kg/cm 2
34,8 kg/cm 2

S 3:

11,3 12

p sut trong ct n nh:

kg/cm2

227 oC

Nhit y ct n nh:
Nhit nh ct n nh:

85 oC

B phn ti sinh:
Tc dng xc tc:

3000 Ib/h

Nng oxy trong vng chy:

-70-

0,5% mol

 n tt nghip
Reforming xc tc.
p sut ct ti sinh:

Thit k phn xng

2,5 kg/cm 2

Tc dng kh ti sinh:

1229

m3/ngy
38.000 m 3/

Tc khng kh kh:
ngy

36.000 m 3/

Tc dng kh kh
ngy
Nhit trong cc vng ca l ti sinh:

497 oC

Vng chy trung bnh:

Vng clo ho:

519 oC

Vng sy kh:

573 oC

Vng kh:

567 oC

Tc dng kh nng N0.1/N0.2:

680/12200

m3/ngy
160.000 m 3/

Tc dng kh y:
ngy
Thuyt minh dy chuyn:

Nguyn liu c lm sch bng hydro b phn lm sch

ri trn vi hydro tun hon t b cha trung gian (12) qua
thit b trao i nhit (3), ri c gia nhit b phn gia
nhit th nht ca l ng (4) n nhit 520 oC 540oC ri
np vo reactor th nht trn cng. Lng xc tc c phn
b cc reactor khc nhau, thng theo t l 1/1,5/2,5/5. Hn
hp kh sau khi phn ng thit b th nht b gim nhit
nn c a ra khi reactor th nht, cho qua l t
gia nhit n nhit phn ng, sau np ngay vo
reactor th hai. C tip tc cho n khi hn hp hi kh c
np vo reactor th t. Sn phm hi sau khi ra khi nh ca
reactor th t c lm lnh qua thit b trao i nhit vi

-71-

 n tt nghip
Thit k phn xng
Reforming xc tc.
nguyn liu tn dng nhit v tip tc ngng t lm lnh
trc khi chuyn sang b phn tch sn phm. Sn phm
y bao gm hydrocacbon lng v kh giu hydro. Phn ln
hydro c tun hon tr li b cha trung gian (12) trn
vi nguyn liu ban u nh my nn (14), phn hydro cn li
c trn vi sn phm lng ly ra y thp ti tip xc (8)
qua b phn ti tip xc (7). Ti thp (7) sn phm kh C 1,
C2...C5 giu hydro tip tc qua my nn v ngng t lm lnh,
sau trn vi sn phm lng c tch ra t y ca thp (9)
i vo thp (8) ri tip tc qua my nn, thit b ngng t
lm lnh v trn vi sn phm lng ly ra t y thp tch (6)
a vo thp ti tip xc (9). Ti thp (9) sn phm kh ch
yu l hydro c ly ra t nh. Sn phm lng c ly ra
y thp (9) c tun hon tr li thp (8), sn phm lng ly
ra y thp (8) c tun hon tr li thp (7). Sn phm
lng y thp (7) c a sang thp n nh (10) qua
thit b trao i nhit. Ti thp (10) sn phm kh c tch
ra nh gm C1, C2 v LPG a vo thit b lng tch (16)
qua thit b lm lnh (19). Kh C 1, C2 c ly ra trn cn
LPG c ly ra y mt phn cho tun hon tr li thp
(10), phn ln a v b cha sn phm (17). y thp (10)
sn phm lng reforming c tch ra mt phn qua thit b
gia nhit ri tun hon tr li, phn ln a v b cha sn
phm (18).
Xc tc chuyn ng t reactor th nht n rector th
t. Xc tc sau phn ng c ly ra t y reactor th t a
vo bunke (13) c kh tun hon nng ln nh l ti sinh
(2) ln lt qua b phn t cc, b phn clo ho sau qua
b phn kh bng hydro. Xc tc sau khi ti sinh c kh tun
hon y ln nh reactor th nht v tip tc tham gia
phn ng.

-72-

 n tt nghip
Reforming xc tc.

Thit k phn xng

Chng III
tnh ton cng ngh
I. Cc s liu u
Nng sut: 1.700.000 tn/ nm.
Nhit : 830oC.
Tc th tch: 1.5 h-1.
p sut : 3,5 at.
T l H2/RH: 2,5 mol.
Phn b xc tc trong l phn ng ln lt l: 1:1,5:2,5:5.
Bng 3.1: Thnh phn ca nguyn liu.

Khi l-

Thnh phn phn on

% khi lng

ng
ring

0,728

T0s

T0s10

T0s50

T0s90

T0scu

3330K

3480K

3850K

4280K

4530K

-73-

50

38

12

 n tt nghip
Reforming xc tc.
II. Tnh ton

Thit k phn xng

Cc phn ng chnh xy ra trong qu trnh

reforming xc tc:
Phn

ng

chuyn

ho

hydrocacbon

naphten

thnh

hydrocacbon thm:
CnH2n

CnH2n-6 + 3H2

(1)

Phn ng chuyn ho hydrocacbon naphten thnh parafin:

CnH2n

CnH2n+2

(2)

Phn ng hydrocracking parafin:

CnH2n+2 + (n-3)/3.H2
C5H12)

n/15(CH4 + C2H6 + C3H8 + C4H10 +

(3)

S gim hm lng hydrocacbon do chuyn ho ho hc

c th hin bng phng trnh vi phn sau:

dNN
k
= k1.PN 1 .PA .PH3
dVR
k P1

(4)

dNN
k
= k2 .PN .PH 2 .PP
dVR
k P2

(5)

dNP
P
= k3 . P
dVR
P

(6)

Trong :
NN, NP: ln lt l phn mol ca hydrocacbon naphten v
parafin trong nguyn liu b chuyn ho (kmol/kmol).
VR: i lng nghch o ca tc np liu theo mol [kg xc
tc/(kmol/h) nguyn liu].
k1: hng s tc ca phn ng (1) c xc nh bng
th ph lc (1) (kmol/h.Pa.kg.xc tc).
k2: hng s tc ca phn ng (2) c xc nh bng
th ph lc (2) (kmol/h.Pa.kg.xc tc).

-74-

 n tt nghip
Thit k phn xng
Reforming xc tc.
k3: hng s tc ca phn ng (3) c xc nh bng
th ph lc (3) (kmol/h.Pa.kg.xc tc).
kp1,kp2: hng s cn bng ca phn ng (1) v (2) c xc
nh theo cng thc sau:
46,15

k P1 = 9,81.10 .e
3

12

25600
T

4450
7,12
T

k P 2 = 98,1 .10 .e
1

(Pa3)
(Pa-1)

T: nhit phn ng (K).

PA, PN, PP, PH , P: p sut ca hp cht thm, naphten, parafin,
2

hydro v p sut chung ca h (Pa).

Thnh phn ca kh tun hon cho bng sau:

Bng 3.2: Thnh phn ca kh tun hon.

Cu t

H2

CH4

C2H6

C3H8

C4H10

C5H12

% mol

86

tnh thnh phn ca hn hp dng cng thc sau:

MC.yi = Mi.yi
Trong :
MC: khi lng phn t trung bnh ca nguyn liu.
Mi: khi lng phn t trung bnh ca cc hydrocacbon trong
nguyn liu.
yi, yi: phn khi lng v phn mol ca cu t i trong nguyn
liu.
Mt khc: MC = 0,4.T50 - 45
Trong T50: nhit si ti 50% th tch nguyn liu.

-75-

 n tt nghip
Thit k phn xng
Reforming xc tc.
Vy ta tnh c MC = 0,4.385 - 45 = 109
Khi lng ca cc hydrocacbon trong nguyn liu c tnh
theo bng sau:
Bng 3.3: Khi lng ca cc hydrocacbon trong nguyn
liu.

Hydrocacbon

Cng thc ho hc

Cng thc khi lng

Parafin

CnH2n+2

MP = 14.n + 2

Naphten

CnH2n

MN = 14.n

Aromat

CnH2n-6

MA = 14.n - 6

Ngoi ra MC cn c tnh theo cng thc:

1
MC= Y A + Y N + Y P
MA MN MP

Trong :
YA, YN, YP: phn khi lng ca aromatic, naphten v parafin
trong nguyn liu.
MA, MN, MP: khi lng phn t trung bnh ca cc
hydrocacbon aromatic, naphten, parafin.
Vy ta c:
1
Y
YP
MC = Y A
+ N +
14n 6 14n 14n + 2

Bin i phng trnh ny ta c:

n3 -

[ (

1
( M C + 4) n2 1 6 + yA 2yN 3yP .M C n + 3 .yN .M C = 0
14
98
686

Vi yA = 0,12.MC, yN = 0,38.MC, yP = 0,50.MC, MC = 109

Gii phng trnh trn ta c: n = 7,77.
Khi ta c:

-76-

 n tt nghip
Thit k phn xng
Reforming xc tc.
MA = 14n - 6 = 14.7,77 - 6 = 102,78
MN = 14n

= 14.7,77

= 108,78

MP = 14n + 2 = 14.7,77 + 2 = 110,78

Ta c cc s liu v thnh phn nguyn liu nh sau:
Bng 3.4: Thnh phn ca nguyn liu.

Cu t

Mi

Hm lng hydrocacbon cc loi

Khi lng

yi

Yi = yi.MC/Mi

phn t
CnH2n-6

102,78

0,12

0,127

CnH2n

108,78

0,38

0,381

CnH2n+2

110,78

0,50

0,492

1,00

1,000

Tng
Tnh nng sut thit b

Gi thit s ngy lm vic trong mt nm ca nh my

l 340 ngy, c 25 ngy ngh dng bo dng v sa cha
thit b.
Vy nng sut thit b l:
GC =

L
(kg.h)
24.340

L: nng sut trong mt nm ca thit b.

GC=

1,7.106.103
= 208333
,333
24.340

Nng sut thit b tnh theo kmol/h:

G

C
C
NC = M = 109=
C

208333
,333
= 1911
,3149
109

Vy ta c bng sau:
Bng 3.5: Thnh phn cc cu t trong nguyn liu.

-77-

 n tt nghip
Reforming xc tc.

Thit k phn xng

Cu t

yi

NCi = NC.yi

CnH2n-6

0,127

242,7370

CnH2n

0,381

728,2110

CnH2n+2

0,492

940,3669

Tng

1,000

1911,3149

Tnh lng kh tun hon cn thit

Ta c H2/RH = 2,5 mol.
Nng sut H2 l: nH = 2,5.NC = 2,5.1911,3149 = 4778,2873
2

(kmol/h).
Vy lng kh tun hon l:
nkth = nH .100/86 = 5556,1480 (kmol/h).
2

Vy thnh phn ca kh tun hon c cho nh sau:

Bng 3.6: Thnh phn ca cc cu t trong kh tun

hon.

Cu t

Mi

yi

Mi.yi

ni = nkth.yi
(kmol/h)

H2

0,86

1,72

4778,2873

CH4

16

0,04

0,64

222,2459

C2H6

30

0,05

1,50

277,8074

C3H8

44

0,03

1,32

166,6844

C4H10

58

0,01

0,58

55,5615

C5H12

72

0,01

0,72

555,5615

1,00

6,48

5556,1480

Tng

-78-

 n tt nghip
Thit k phn xng
Reforming xc tc.
Lng hydrocacbon trong kh tun hon
5556,1480 - 4778,2873 = 777,8607 (kmol/h).
Tnh lng xc tc cho ton b qu trnh
Vxt =

GC
C V0

GC: nng sut thit b (kg/h).

C: khi lng ring ca nguyn liu th lng.
C : 728,8 (kg/m3).
Vo = 1,5 h-1: tc th tch.
Vxt =

208333
,333
=190
,572 (m3)
728
,8.1,5

Lng xc tc c tnh theo cng thc sau:

mxt = Vxt.xt (kg).
Trong : xt l khi lng ring ca xc tc, xt = 550 650
(kg/m3).
Chn xt = 600 (kg/m3)
mxt = 190,572.600 = 114343,2 (kg).
S phn b xc tc trong cc l phn ng nh sau: 1:1,5:2,5:5.
Nn ta c bng sau:
Bng 3.7: S phn b xc tc trong cc l phn ng.

L phn ng

Vxt(m3)

mxt(kg) =
Vxt.600(kg)

19,0572

11434,32

28,5850

17151,48

47,6430

28585,80

95,2860

57171,60

-79-

 n tt nghip
Reforming xc tc.

Thit k phn xng

Tng

190,5720

114343,20

Tnh s phn b p sut ca cc cu t trong hn hp

nguyn liu v kh tun hon
Pi = P.yi
Trong :
Pi: p sut ring phn ca cu t i (Pa).
P: p sut chung ca l phn ng (Pa).
yi: nng phn mol ca cu t trong hn hp.
P = 3,5 kg/cm3 = 343234,5 (Pa).
Bng 3.8: Phn b p sut theo cu t.

Cu t

ni (kmol/h)

yi = ni/ni

Pi = 343238.21.yi
(Pa)

CnH2n-6

242,7370

0,0325

11155,1213

CnH2n

728,2110

0,0975

33465,3638

CnH2n+2

940,3669

0,1259

43213,2236

H2

4778,2873

0,6399

219635,7566

P*

777,8607

0,1042

35765,0349

Tng

7467,4629

1,0000

343234,5

Trong P* l lng hydrocacbon trong kh tun hon.

II.1. Tnh ton cho l phn ng th nht
II.1.1. Tnh cn bng vt cht
Hng s tc ca phn ng chuyn ho naphten thnh
aromatic:
T = 8030K

1000/T = 1000/803 = 1,245

Tra th ph lc (1) ta c k1 = 3,145.10-7 (kmol/h.Pa.kg

xc tc).

-80-

 n tt nghip
Thit k phn xng
Reforming xc tc.
Phng trnh tnh cn hng s cn bng phn ng:
25600
46,15
803

k P1 = 9,813.1012.e

= 14,866.10

20

(Pa3)

gim tng i hm lng naphten do phn ng thm ho:

dNN11
k
= k1.PN 1 .PA .PH3
dVR1
kp1

dNN11
3,145.107
)3
= 3,145.107.33465
,3638
.11155
,1213
.( 219635
,7566
20
dVR1
14,866.10

dNN11
= 0,011
dVR1

Suy ra: NN11 = -0,011.VR1

m1

M VR1 = N
C1
Trong : m1 = 11434,32 kg.
NC1: lng nguyn liu vo l th nht (kmol/h).
VR1 =

11434
,32
= 5,9824(kg/kmol)
1911
,3149

Vy NN11 = - 0,011.5,9824 = -0,066 (kg xc tc/kmol).

Lng naphten cn li sau phn ng (1) l:
nN11 = (yN1 - NN11).NC1 = (0,381 - 0,066).1911,3149 =
602,0642 (kmol/h).
Lng naphten tham gia phn ng (1) l:
728,2110 - 602,0642 = 126,1468 (kmol/h).
Hng s tc phn ng chuyn ho naphten to thnh
prarafin:
T = 8030K

1000/T = 1000/803 = 1,245

Tra th ph lc (2) ta c k1 = 2,55.10-15 (kmol/h.Pa.kg

xc tc).
Phng trnh tnh hng s cn bng phn ng:

-81-

 n tt nghip
Reforming xc tc.
4450
7,12
803

k P2 = 98,1 .10 .e
1

Thit k phn xng

= 0,0021.10-3 (Pa-1)

Do kP2 << 1, chng t u th thuc v phn ng nghch tc l

phn ng chuyn ho parafin thnh naphten.
S tng hm lng naphten trong l phn ng th (1) l:

dNN

12

dVR1

= k2 .PN .PH
2

k2
.PP
k p2

dNN12
2,55.1015
= 2,55.1015.33465
,3638
.219635
,7566
.43213
,2236
dVR1
0,0021
.103

dNN12
= 0,337.10-4
dVR1

Suy ra: NN12 = 0,337.10-4.VR1 = 0,337.10-4.5,9824 = 2,02.10-4

Lng naphten sau phn ng (1) v(2) l:
nN12 = (yN1 - NN11 + NN12).NC1 = (0,381- 0,066 + 2,02.104

).1911,3149
= 602,4503 (kmol/h).

Lng naphten to thnh do phn ng (2) l:

nN12 - nN11 = 602,4503 - 602,0642 = 0,3861 (kmol/h)
Hng s tc phn ng hydrocracking parafin:
T = 803ok

1000/T = 1000/803 = 1,245.

Tra th ph lc (3) ta c k3 = 0,075 (kmol/h.Pa.kg xc

tc).

dNP13
P
= k3 P
dVR1
P

dNP13
43213
,2236
= 0,075
= 9,4425.10-3
dVR1
343234
,5

Suy ra: NP13 = - 9,4425.10-3.VR1 = - 9,4425.10-3.5,9824 = 0,056

-82-

 n tt nghip
Thit k phn xng
Reforming xc tc.
Lng parafin cn li sau phn ng (2) v (3) l:
nP1 = (yP1- NP13).NC1 = (0,492 - 0,056).1911,3149 =
833,3333 (kmol/h).
Vy lng parafin tham gia phn ng hydrocracking l:
NP1 - nP1 = 940,3669 - 833,3333 = 107,0336
Vy ta c cn bng vt cht cc phn ng ho hc nh sau:
Bng 3.9: Cn bng ho hc ca l phn ng th
nht .

Lng cc cht tham gia phn ng Lng cc sn phm (kmol/h)

(kmol)
126,1468 CnH2n

126,1468 CnH2n-6 +
26,1468.3 H2

0,3861 CnH2n+2

0,3861CnH2n + 0,3861

107,0336 CnH2n+2 + [107,0336(n- 107,0336. n/15 (CH4 + C2H6

3)/3] H2

+ C3H8 + C4H10 + C5H12)

Vi gi tr n = 7,0336 ta tnh c lng kh hydrocacbon c

sinh ra trong l phn ng th nht l:
107,0336.(7,0336/15)(CH4+C2H6+C3H8+C4H10+C5H12)

55,4434(kmol/h).
Bng 3.10: Lng cht dng vo v dng ra ca l
phn ng th nht.

Cu t

Lng vo

Lng ra (kmol/h)

(kmol/h)
A

242,7370

242,7370 + 126,1468 = 368,8838

728,2110

728,2110 - 126,1468 + 0,3861 =

602,4503

940,3669

940,3669 - 0,3861 - 107,0336 =

832,9472

-83-

 n tt nghip
Reforming xc tc.
Tng

Thit k phn xng

1911,3149

1804,2813

Bn 3.11: Lng kh tun hon.

Cu t

Lng vo

Lng ra

H2

4778,2873

4778,2875 + 126,1468.3 + 0,3861

- 107,0336(4,77/3) = 4986,9304

CH4

222,2459

222,2459 + 55,4434 = 277,6893

C2H6

277,8074

277,8074 + 55,4434 = 333,2508

C3H8

166,6844

166,6844 + 55,4434 = 222,1278

C4H10

55,5615

55,5615 + 55,4434 = 111,0049

C5H12

55,5615

55,5615 + 55,4434 = 111,0049

Tng

5556,1480

6042,0081

Bng 3.12: Lng kh tun hon ra khi l phn ng th

nht.

Cu t

Mi

ni (kmol/h)

yi = ni/ni

Mi.yi

H2

02

4986,9304

0,8178

1,6356

CH4

16

277,6893

0,0479

0,7664

C2H6

30

333,2508

0,0575

1,7250

C3H8

44

222,1278

0,0384

1,6896

C4H10

58

111,0049

0,0192

1,1136

C5H12

72

111,0049

0,0192

1,3824

6042,0081

1,0000

8,3126

Tng

Vy ta tnh c lng kh tun hon:

6042,0081.8,3126 = 50224,7965 (kg/h).
Lng sn phm kh ra khi l th nht l:
244340,9857 - 50224,7965 = 194116,1892
Vy ta c phng trnh l:

-84-

 n tt nghip
Thit k phn xng
Reforming xc tc.
368,8838.(14n - 6) + 602,4503.14n + 832,9472.(14n + 2) =
194116,1892
Suy ra: n = 7,7064
MA = 14n - 6 = 101,8896
MN = 14n

= 107,8896

MP = 14n + 2 = 109,8896
Bng 3.13: Tng kt cn bng vt cht ca l phn
ng th nht.

Cu t

ni (kmol/h)

yi

Mi

Gi = Mi.ni

u vo
A

242,7370

0,0325

102,78

24948,5089

728,2110

0,0975

108,78

79214,7926

940,3669

0,1259

110,78

104173,845
2

H2

4778,2873

0,6399

P*

777,8607

0,1042

Tng

7467,4629

1,0000

6,48

36003,8390
244340,98
57

u ra
A

368,8838

0,0470

101,8896

37585,4228

602,4503

0,0768

107,8896

64998,1219

832,9472

0,1062

109,8896

91532,2346

H2

4986,9304

0,6355

8,3126

50224,7965

P*

1055,0777

0,1345

Tng

7846,2894

1,000

244340,57
58

II.1.2. Tnh cn bng nhit lng ca l phn ng th

nht

-85-

 n tt nghip
Thit k phn xng
Reforming xc tc.
Ta c cn bng nhit lng:Q11 + Q21 = Q31 + Q41 + Q51 + Q61
Trong :
Q11: nhit do hn hp kh nguyn liu v kh tun hon mang
vo l (kJ/h).
Q21: nhit do lng xc tc mang vo l (kJ/h).
Q31: nhit do hn hp kh sn phm v kh tun hon mang
ra l (kJ/h).
Q41: nhit do lng xc tc mang ra l (kJ/h).
Q51: nhit tn tht do phn ng reforming (kJ/h).
Q61: nhit mt mt (kJ/h).
Tnh Q11: Ta cn xc nh Entanpi ca dng hi nguyn
liu ca vo ca l th nht. S liu Entanpi ca H 2, CH4,
C2H6, C3H8, C4H10, C5H12 tra s tay ho l. xc nh c
Entanpi ca aromatic, naphten, parafin ta da theo trng lng
phn t trung bnh c t trng ri tra bng [5] c
Entanpi.
Bng 3.14: T trng ca cc cu t.

Cu t

298
288

u vo

u ra

0,718

0,722

0,731

0,733

0,733

0,737

Bng 3.15: Entanpi ca cc cht vo l phn ng th

nht.

Cu

Mi

t
H2

ni

yi

Mi.yi

(kmol/h)
2

4778,28 0,639

1,279

-86-

0,039

Entanpi
qti

qyi.yi

770

301,070

 n tt nghip
Reforming xc tc.
73
CH4

16
30
44

C4H1

58

0,476

0,014

161

1,116

0,034

143

0,981

0,029

140

0,429

0,013

140

0,532

0,016

139

3,340

0,102

171

174,897

10,61

0,324

170

552,948

69

13,94

0,426

170

725,988

72

32,72

1,000

166,684 0,022
4

277,807 0,037
4

C3H8

222,245 0,029
9

C2H6

Thit k phn xng

55,5615 0,007
4

C5H1

72

55,5615 0,007
4

102,7 242,737 0,032

8

108,7 728,211 0,097

8

110,7 940,366 0,125

8

Tn
g

7467,46 1,000
29

23,6228
48,8994
42,0095
18,3400
22,6896

1910,46

03

55

Nhit do hn hp nguyn liu v kh tun hon mang vo l

th nht:
Q11 = 244340,9857.1910,4655 = 466805023,4158
Tnh Q21:
Ta c: Q21 = mxt1.q21 = mxt1.Cpxt.T
Trong :
Q21 = Cpxt.T: hm nhit xc tc (kJ/kg).
Cpxt: nhit dung ring ca cht xc tc nhit d T ( 0K).
Cpxt = a0 + a1 - a2.T-2 (kJ/h).
Tra s tay ho l [9]: Cpxt (Al2O3)

-87-

 n tt nghip
Thit k phn xng
Reforming xc tc.
Cpxt = 22,08 + 8,971.10-3.T - 5,225.105.T-2
Ti T = 803K ta c:
Cpxt = 22,08 + 8,971.10-3.803 - 5,225.105.803-2 = 28,47
(kcal/kmol.K)
Hay:
CpXT =

28,47.4,186
= 1,17 (kJ/kg.K)
102

MAl2O3 = 102 kg/kmol.

q21 = Cpxt.T = 1,17.803 = 939,51
Vy Q21 = mxt1.q21 = 11434,32.939,51 = 10742657,9832 (kJ/h)
Tnh Q41:
Gi thit nhit l th nht gim: T = 70K
Ta c: Q41 = mxt1. Cpxt.T
Trong : Cpxt l nhit dung ring xc tc T = 803 - 70 =
733K
Vy Cpxt = 22,08 + 8,971.10-3.733 - 5,225.105.733-2 = 27,68
(kcal/kmol.K)
CpXT =

27,68.4,186
= 1,14
102

(kJ/kg.K)

Vy Q41 = mxt1.Cpxt.T = 11434,32.1,14.733 = 9554746,4784

(kJ/h)
Tnh Q51:
tnh hiu ng nhit ca phn ng ta dng cng thc sau:
qP = -355.b [5]
Trong :
b: hiu sut to hydro tnh theo khi lng nguyn liu ban
u (%kl)

-88-

 n tt nghip
Thit k phn xng
Reforming xc tc.
GH = 4986,9304 - 4778,2873 = 208,6431 (kmol/h)
2

GH = 208,6431. M H = 208,6431.2 = 417,2862 (kg/h)

2

b=

GH

GC

100% =

417,2862
100% = 0,20029
%
108333
,333

Vy qP = -335.0,20029 = - 67,097 (kJ/kg)

Nhit tiu tn cho phn ng reforming:
Q51 = GC.QP = 208333,333.(- 67,097) = - 13978541,6443
Tnh Q61: Nhit mt mt:
Q61 = 0,01(Q11 + Q12)
= 0,01(466805023,4 + 10742657,98) =
4775476,8140
Tnh Q31: Nhit do sn phm v kh tun hon mang ra:
Q31 = Q11 + Q21 - Q41 - Q51 - Q61
=

466805023,4158

10742657,9832

9554746,4784 +
+ 13978541,6443 4775476,8140
= 477195999,7510 (kJ/h)
Q31 = 244340,5758.qtr1
Suy ra: qtr1 = 1952,9953 (kJ/h)
qtr1: hm nhit ca sn phm v kh tun hon mang ra
Bng 3.16: Cn bng nhit lng ca l phn ng th
nht.

Dng

Nhit

Lng (kg/h)

Entanpi

Nhit lng
(kJ/h)

u vo

-89-

 n tt nghip
Reforming xc tc.
Q11

803

Thit k phn xng

244340,98

1910,4655

57
Q21

803

11434,32

466805023,4
58

939,51

10742657,98
32

Tng

477547681,
3990
u ra

Q31

733

Q41

244340,57

733

1952,9953

477195999,7

58

510

11434,32

9554746,478
4

Q51

208333,33

13978541,64
43

Q61

4775476,814
0

Tng

477547681,
3990

II.1.3 Tnh ton kch thc chnh ca l phn ng th

nht
Chiu cao lp xc tc chuyn ng trong l phn ng th
nht c tnh:
H xt1 =

Vxt1
(m)
F

Trong :
Vxt1: th tch lp xc tc trong l phn ng th nht (m3).
F: tit din vng gia cc ng lc (m2).
Gi tr F c tnh theo cng thc:

2
F = [(Dt1 2.)2 D1 ]
4

(m2)

-90-

 n tt nghip
Reforming xc tc.
Trong

Thit k phn xng

Dt1: ng knh trong ca l phn ng th nht, chn Dt1 =

2,4 m.
: khong cch gia thn l v v l, chn = 0,05 m.
D1 : ng knh ca ng trung tm, chn D1 = 0,5 m.
F=

3,14
[(2,4 2.0,05)2 0,52 ] = 3,9564(m2)
4

Chiu cao lp xc tc: H xt1 =

Vxt1 19,0572
=
= 4,82 (m)
F
3,9564

Chn chiu cao lp xc tc quy chun l Hxt1 = 5 (m)

Chiu cao ni gia cc l l 2 m.
Chiu cao ca l th nht l: H1 = Hxt1 + 2 = 7 (m).
II.2. Tnh ton cho l phn ng th hai
II.2.1.Tnh cn bng vt cht
Bng 3.17: Thnh phn cc cu t ca l phn ng th
hai.

Cu t

nCi2 (kmol/h)

yCi2 = nCi2/nCi2

CnH2n-6

368,8838

0,2044

CnH2n

602,4503

0,3339

CnH2+2

832,9472

0,4617

Tng

1804,2813

1,0000

tt p sut gia cc l phn ng thng t 0,15 n 0,35

(kg/cm2)
Chn tt p sut l th 2 l 0,2 kg/cm2.
Khi p sut chung ca hn hp kh nguyn liu vo l th
hai l:

-91-

 n tt nghip
Thit k phn xng
Reforming xc tc.
P2 = 3,5 - 0,2 = 3,3 (kg/cm 2) = 3,3.98067 = 323621,1
(Pa)
Bng 3.18: Thnh phn p sut nguyn liu v kh
tun hon vo l
phn ng th hai.

Cu t

yi

Pi = 323621,1.yi
(Pa)

CnH2n-6

0,0470

15210,1917

CnH2n

0,0768

24854,1005

CnH2n+2

0,1062

34368,5608

H2

0,6355

205661,2091

P*

0,1345

43527,0379

Tng

1,000

323621,1000

Hng s tc ca phn ng chuyn ho naphten thnh

aromatic:
T = 803oK

1000/T = 1000/803 = 1,245

Tra th ph lc (1) ta c k1 = 3,145.10-7 (kmol/h.Pa.kg

xc tc).
Phng trnh tnh hng s cn bng phn ng:
46,15

kP1 = 9,813.1012.e

25600
803

= 14,866.10

20

(Pa3)

gim tng i hm lng naphten do phn ng thm ho:

dNN 21
k
= k1.PN 1 .PA .PH3
dVR 2
kp1

dNN 21
3,145.107
= 3,145.107.24854
,1005
.15210
,1917
.(205661
,2091
)3
dVR 2
14,866.1020

dNN 21
= 7,817.10-3
dVR 2

-92-

 n tt nghip
Reforming xc tc.

Thit k phn xng

m2

M: VR2 = N
C2
Trong : m2 = 17151,48 (kg)
NC2: lng nguyn liu vo l phn ng th 2 (kg xc tc/ kmol)
VR 2 =

17151
,48
= 9,506 [kg/(kmol/h)]
1804
,2813

Vy NN21 = - 7,817.10-3.9,506 = - 0,0743 (kg xc tc/kmol).

Lng naphten cn li sau phn ng (1) l:
nN21 = (yN2 - NN21).NC2 = (0,3339 - 0,0743).1804,2813 =
468,3914 (kmol/h).
Lng naphten tham gia phn ng (1) l:
602,4503 - 468,391 = 134,0589 (kmol/h).
Hng s tc phn ng chuyn ho naphten to thnh
prarafin:
T = 8030K

1000/T = 1000/803 = 1,245

Tra th ph lc (2) ta c k1 = 2,55.10-15 (kmol/h.Pa.kg

xc tc).
Phng trnh tnh hng s cn bng phn ng:
4450
7,12

k P2 = 98,11.103.e 803

= 0,0021.10-3 (Pa-1)

Do kP2 << 1, chng t u th thuc v phn ng nghch tc l

phn ng chuyn ho parafin thnh naphten.
S tng hm lng naphten trong l phn ng th (1) l:

dNN 22
k
= k2 .PN .PH 2 .PP
dVR 2
k p2

dNN 22
2,55.1015
= 2,55.1015.24854
,1005
.205661
,2091
.34368
,5608
dVR 2
0,0021
.103

dNN 22
= 0,287.10-4
dVR 2

-93-

 n tt nghip
Thit k phn xng
Reforming xc tc.
Suy ra: NN22 = 0,287.10-4.VR2 = 0,287.10-4.9,506 = 2,728.10-4
Lng naphten sau phn ng (1) v (2) l:
nN22 = (yN2 - NN21 + NN22).NC2
= (0,3339 - 0,0743 + 2,728.10-4).1804,2813
= 468,8836 (kmol/h).
Lng naphten to thnh do phn ng (2) l:
nN22 - nN21 = 468,8836 - 468,3914 = 0,4922 (kmol/h)
Hng s tc phn ng hydrocracking parafin:
T = 8030k

1000/T = 1000/803 = 1,245.

Tra th ph lc (3) ta c k3 = 0,075 (kmol/h.Pa.kg xc

tc).

dNP 23
P
= k3 P
dVR 2
P

dNP23
34368
,5608
= 0,075
= 7,96.10-3
dVR 2
323621
,1

Suy ra: NP23 = - 7,96.10-3.VR2 = - 7,96.10-3.9,506 = - 0,0757

Lng parafin cn li sau phn ng (2) v (3) l:
nP2 = (yP2 - NP23).NC2 = (0,4617 - 0,0757).1804,2813 =
696,4526 (kmol/h).
Vy lng parafin tham gia phn ng hydrocracking l:
NP2 - nP2 = 832,9472 - 696,4526 = 136,4946 (kmol/h)
Vy ta c cn bng vt cht cc phn ng ho hc nh sau:
Bng 3.19: Cn bng ho hc ca l phn ng th hai.

Lng cc cht tham gia phn ng

Lng cc sn phm

(kmol)

(kmol/h)

134,0589 CnH2n

134,0589 CnH2n-6 +

-94-

 n tt nghip
Reforming xc tc.

Thit k phn xng

134,0589.3 H2

0,4922 CnH2n+2

0,4922 CnH2n + 0,4922

136,4946 CnH2n+2 + [107,0336(n-

136,4946 n/15 (CH4 +

3)/3] H2

C2H6 + C3H8 + C4H10 +

C5H12)

Vi gi tr n = 7,7064 ta tnh c lng kh hydrocacbon c

sinh ra trong l phn ng th nht l:
136,4946.(7,7064/15)(CH4+C2H6+C3H8+C4H10+C5H12)

70,1255 (kmol/h).
Bng 3.20: Lng cht dng vo v dng ra ca l
phn ng th hai.

Cu t

Lng vo

Lng ra (kmol/h)

(kmol/h)
A

368,8838

368,8838 + 134,0589 = 502,9427

602,4503

602,4503 - 134,0589 + 0,4922 =

468,8836

832,9472

832,9472 - 0,4922 - 136,4946 =

695,9604

Tng

1804,2813

1667,7867

Bng3.21: Lng kh tun hon.

Cu t

Lng vo

Lng ra

H2

4986,9304

4986,9304 + 134,0589.3 + 0,4922

136,4946 (4,7064/3) = 5175,4666

CH4

277,6893

277,6893 + 70,1255 = 347,8148

C2H6

333,2508

333,2508 + 70,1255 = 403,3763

C3H8

222,1278

222,1278 + 70,1255 = 292,2533

C4H10

111,0049

111,0049 + 70,1255 = 181,1304

-95-

 n tt nghip
Reforming xc tc.

Thit k phn xng

C5H,

111,0049

111,0049 + 70,1255 = 181,1304

Tng

6042,0081

6581,1718

Bng 3.22: Kh tun hon ra khi l phn ng th hai.

Cu t

Mi

ni (kmol/h)

yi = ni/ni

Mi.yi

H2

02

5175,4666

0,7864

1,5728

CH4

16

347,8148

0,0529

0,8464

C2H6

30

403,3763

0,0613

1,8390

C3H8

44

292,2533

0,0444

1,9536

C4H10

58

181,1304

0,0275

1,5950

C5H12

72

181,1304

0,0275

1,9800

6581,1718

1,0000

9,7868

Tng

Vy ta tnh c lng kh tun hon:

6581,1718.9,7868 = 64408,6122 (kg/h).

Lng sn phm kh ra khi l th nht l:

244340,5758 - 64408,6122 = 179931,9636
Vy ta c phng trnh l:
502,9427.(14n - 6) + 468,8836.14n + 695,9604.(14n + 2) =
179931,9636
Suy ra: n = 7,7758
MA = 14n - 6 = 102,8612
MN = 14n

= 108,8612

MP = 14n + 2 = 110,8612
Bng 3.23: Tng kt cn bng vt cht ca l phn
ng th hai.

Cu t

ni (kmol/h)

yi

-96-

Mi

Gi = Mi.ni

 n tt nghip
Reforming xc tc.

Thit k phn xng

u vo

368,8838

0,0470

101,8896

37585,4228

602,4503

0,0768

107,8896

64998,1219

832,9472

0,1061

109,8896

91532,2346

H2

4986,9304

0,6356

8,3126

50224,7965

P*

1055,0777

0,1345

Tng

7846,2894

1,0000

244340,57
58

u ra
A

502,9427

0,0610

102,8612

51733,2897

468,8836

0,0568

108,8612

51043,2314

695,9604

0,0844

110,8612

77155,0051

H2

5175,4666

0,6274

9,7868

64408,6122

P*

1405,7052

0,1704

Tng

8248,9585

1,0000

244340,13
84

II.1.2. Tnh cn bng nhit lng ca l phn ng th

hai
Ta c cn bng nhit lng:Q12 + Q22 = Q32 + Q42 + Q52 + Q62
Trong :
Q12: nhit do hn hp kh nguyn liu v kh tun hon mang
vo l (kJ/h).
Q22: nhit do lng xc tc mang vo l (kJ/h).
Q32: nhit do hn hp kh sn phm v kh tun hon mang
ra l (kJ/h).
Q42: nhit do lng xc tc mang ra l (kJ/h).
Q52: nhit tn tht do phn ng reforming (kJ/h).

-97-

 n tt nghip
Reforming xc tc.
Q62: nhit mt mt (kJ/h).

Thit k phn xng

Tnh Q12: Ta cn xc nh Entanpi ca dng hi nguyn

liu ca vo ca l th nht.
Bng 3.24: Entanpi ca cc cht vo l phn ng th
hai.

Cu

Mi

ni

yi

Mi.yi

(kmol/h)

H2

Entanpi
qti

qyi.yi

4986,93

0,63

1,271

0,04

770

316,470

04

56

11

277,689

0,03

0,566

0,01

161

29,6094

54

83

333,250

0,04

1,275

0,04

143

25

12

222,127

0,02

1,245

0,04

140

83

03

111,004

0,01

0,817

0,02

140

41

65

111,004

0,01

1,015

0,03

139

41

28

0,04

4,788

0,15

171

265,172

70

48

0,07

8,285

0,26

170

456,331

68

78

0,10

11,67

0,37

170

642,371

62

03

72

Tn

7846,28

1,00

30,93

1,00

1908,41

94

00

58

00

45

CH4

16

C2H6

30

C3H8

44

C4H1

58

C5H1

72

101,88 368,883
96

107,88 602,450
96

8
3

109,88 832,947
96

59,0808
56,6215
37,1000
45,6576

Nhit do hn hp nguyn liu v kh tun hon mang vo l

th (2):

-98-

 n tt nghip
Thit k phn xng
Reforming xc tc.
Q12 = 244340,5758.1908,4145 = 466303097,7951
Tnh Q22:
Ta c: Q22 = mxt2.q22 = mxt2.Cpxt.T
Trong :
Q22 = Cpxt.T: hm nhit xc tc (kJ/kg).
Cpxt: nhit dung ring ca cht xc tc nhit d T ( 0K).
Cpxt = a0 + a1 - a2.T-2 (kJ/h).
Tra s tay ho l [9]: Cpxt (Al2O3)
Cpxt = 22,08 + 8,971.10-3.T - 5,225.105.T-2
Ti T = 803K ta c:
Cpxt = 22,08 + 8,971.10-3.803 - 5,225.105.803-2 = 28,47
(kcal/kmol.K)
Hay:
CpXT =

28,47.4,186
= 1,17 (kJ/kg.K)
102

MAl2O3 = 102 kg/kmol.

q22 = Cpxt.T = 1,17.803 = 939,51
Vy Q22 = mxt2.q22 = 17151,48.939,51 = 16113986,9748 (kJ/h)
Tnh Q42:
Gi thit nhit l th nht gim: T = 70K
Ta c: Q42 =mxt2.Cpxt.T
Trong : Cpxt l nhit dung ring xc tc T = 803 - 70 =
733K
Vy Cpxt = 22,08 + 8,971.10-3.733 - 5,225.105.733-2 = 27,68
(kcal/kmol.K)
CpXT =

27,68.4,186
= 1,14
102

(kJ/kg.K)

-99-

 n tt nghip
Thit k phn xng
Reforming xc tc.
Vy Q42 = mxt2.Cpxt.T = 17151,48.1,14.743 = 14527646,5896
(kJ/h)
Tnh Q52:
tnh hiu ng nhit ca phn ng ta dng cng thc sau:
qP = -355.b [5]
Trong :
b: hiu sut to hydro tnh theo khi lng nguyn liu ban
u (%kl)
GH = 5175,4666 - 4986,9304 = 188,5362 (kmol/h)
2

GH = 188,5362. M H = 188,5362.2 = 377,0724 (kg/h)

2

b=

GH

GC

100% =

377,0724
100% = 0,194%%
194115
,7793

Vy qP = -335.0,194 = - 64,99 (kJ/kg)

Nhit tiu tn cho phn ng reforming:
Q52 = GC.QP = 194115,7793.(- 64,99) = - 12615584,4967
Tnh Q62:
Nhit mt mt:
Q62 = 0,01(Q12 + Q22)
= 0,01(466303097,7951 + 16113986,9748)
= 4824170,8477
Tnh Q32:
Nhit do sn phm v kh tun hon mang ra:
Q32 = Q12 + Q22 - Q42 - Q52 - Q62
=

466303097,7951

16113986,9748

14527646,5896
+12615584,4967 - 4824170,8477

-100-

 n tt nghip
Reforming xc tc.
= 475680851,8293 (kJ/h)

Thit k phn xng

Q32 = 244340,1384.qtr1
Suy ra: qtr2 = 1946,7978 (kJ/h)
qtr2: hm nhit ca sn phm v kh tun hon mang ra

Bng 3.25: Cn bng nhit lng ca l phn ng th

hai.

Dng

Nhit

Lng (kg/h)

Entanpi

Nhit lng (kJ/h)

1908,4145

466303097,79

u vo
Q12

803

244340,57
58

Q22

803

51

17151,48

939,51

16113986,974
8

Tng

482417084,7
699
u ra

Q32
Q42

733
733

244340,13

1946,7978

475680851,82

84

93

17151,48

14527646,589
6

Q52

208333,33
3

- 64,99

12615584,496
7

Q62

4824170,8477

Tng

482417084,7
699

-101-

 n tt nghip
Thit k phn xng
Reforming xc tc.
II.1.3 Tnh ton kch thc chnh ca l phn ng th
hai
Chiu cao lp xc tc chuyn ng trong l phn ng th
nht c tnh:
H xt2 =

Vxt2
(m)
F

Trong :
Vxt2: th tch lp xc tc trong l phn ng th 2 (m3).
F: tit din vng gia cc ng lc (m2).
Gi tr F c tnh theo cng thc:

2
F = [(Dt2 2.)2 D2 ]
4

(m2)

Trong
Dt2: ng knh trong ca l phn ng th 2, chn Dt 2 = 2,6
m.
: khong cch gia thn l v v l, chn = 0,05 m.
D2 : ng knh ca ng trung tm, chn D2 = 0,5 m.
F=

3,14
[(2,6 2.0,05)2 0,52 ] = 4,71 (m2)
4

Chiu cao lp xc tc: H xt2 =

Vxt2 28,5850
=
= 6,07 (m)
F
4,71

Chn chiu cao lp xc tc quy chun l Hxt2 = 6 (m)

Chiu cao ni gia cc l l 2 m.
Chiu cao ca l th 2 l: H1 = Hxt2 + 2 = 8 (m).
II.2. Tnh ton cho l phn ng th ba
II.2.1.Tnh cn bng vt cht
Bng 3.26: Thnh phn cc cu t ca l phn ng th
ba.

-102-

 n tt nghip
Reforming xc tc.

Thit k phn xng

Cu t

nCi3 (kmol/h)

yCi3 = nCi3/nCi3

CnH2n-6

502,9427

0,3016

CnH2n

468,8836

0,2811

CnH2+2

695,9604

0,4173

Tng

1667,7867

1,0000

tt p sut gia cc l phn ng thng t 0,15 n 0,35

(kg/cm2)
Chn tt p sut l th 2 l 0,2 kg/cm2.
Khi p sut chung ca hn hp kh nguyn liu vo l th
hai l:
P2 = 3,3 - 0,2 = 3,1 (kg/cm 2) = 3,1.98067 = 304007,7
(Pa)
Bng 3.27: Thnh phn p sut nguyn liu v kh
tun hon vo l
phn ng th ba.

Cu t

yi

Pi = 304007,7.yi
(Pa)

CnH2n-6

0,0610

18544,4697

CnH2n

0,00568

17267,6374

CnH2n+2

0,0844

25658,2499

H2

0,6274

190734,4310

P*

0,1704

51802,9121

Tng

1,0000

304007,7

Hng s tc ca phn ng chuyn ho naphten thnh

aromatic:
T = 8030K

1000/T = 1000/803 = 1,245

Tra th ph lc (1) ta c k1 = 3,145.10-7 (kmol/h.Pa.kg

xc tc).

-103-

 n tt nghip
Thit k phn xng
Reforming xc tc.
Phng trnh tnh hng s cn bng phn ng:
46,15

kP1 = 9,81.10 .e
3

12

25600
803

= 14,866.10

20

(Pa3)

gim tng i hm lng naphten do phn ng thm ho:

dNN 31
k
= k1.PN 1 .PA .PH3
dVR 3
k p1

dNN 31
3,145.107
= 3,145.107.17267
,6374
.18544
,4697
.(190734
,4310
)3
20
dVR 3
14,866.10

dNN 31
= 5,431.10-3
dVR 3
m3

M: VR3 = N
C3
Trong : m3 = 28585,8 (kg)
NC3: lng nguyn liu vo l phn ng th 3 (kg xc tc/ kmol)
VR 3 =

28585
,8
= 17,1399[kg/(kmol/h)]
1667
,7867

Vy NN31 = - 5,431.10-3.17,1399 = - 0,093 (kg xc tc/kmol).

Lng naphten cn li sau phn ng (1) l:
nN31 = (yN3 - NN31).NC3= (0,2811 - 0,093).1667,7867 =
313,7107 (kmol/h).
Lng naphten tham gia phn ng (1) l:
468,8836 - 313,7107 = 155,1729 (kmol/h).
Hng s tc phn ng chuyn ho naphten to thnh
prarafin:
T = 8030K

1000/T = 1000/803 = 1,245

Tra th ph lc (2) ta c k1 = 2,55.10-15 (kmol/h.Pa.kg

xc tc).
Phng trnh tnh hng s cn bng phn ng:

-104-

 n tt nghip
Reforming xc tc.

Thit k phn xng

4450
7,12
803

k P 2 = 98,1 .10 .e
1

= 0,0021.10-3 (Pa-1)

Do kP2 << 1, chng t u th thuc v phn ng nghch tc l

phn ng chuyn ho parafin thnh naphten.
S tng hm lng naphten trong l phn ng th (1) l:

dNN 32
k
= k2 .PN .PH 2 .PP
dVR 3
k p2

dNN 32
2,55.1015
= 2,55.1015.17267
,6374
.190734
,4310
.25658
,2499
dVR 3
0,0021
.103

dNN 32
= 0,23.10-4
dVR 3

Suy ra: NN32 = 0,23.10-4.VR3 = 0,23.10-4.17,1399 = 0,39.10-3

Lng naphten sau phn ng (1) v(2) l:
nN32 = (yN3 - NN31 + NN32).NC3 = (0,2811 - 0,093 + 0,39.103

).1667,7867
= 314,3611 (kmol/h).

Lng naphten to thnh do phn ng (2) l:

nN32 - nN31 = 314,3611 - 313,7107 = 0,6504 (kmol/h)
Hng s tc phn ng hydrocracking parafin:
T = 8030k

1000/T = 1000/803 = 1,245.

Tra th ph lc (3) ta c k3 = 0,075 (kmol/h.Pa.kg xc

tc).

dNP33
P
= k3 P
dVR 3
P

dNP33
25658
,2499
= 0,075
= 6,33.10-3
dVR 3
304007
,7

Suy ra: NP33 = - 6,33.10-3.VR3= - 6,33.10-3.17,1399 = - 0,1085

Lng parafin cn li sau phn ng (2) v (3) l:

-105-

 n tt nghip
Thit k phn xng
Reforming xc tc.
nP3 = (yP3 - NP33).NC3 = (0,4173 - 0,1085).1667,7867 =
515,0125 (kmol/h).
Vy lng parafin tham gia phn ng hydrocracking l:
NP3 - nP3 = 695,9604 - 515,0125 = 180,9479 (kmol/h)
Vy ta c cn bng vt cht cc phn ng ho hc nh sau:
Bng 3.28: Cn bng ho hc ca l phn ng th ba .

Lng cc cht tham gia phn ng

Lng cc sn phm

(kmol)

(kmol/h)

155,1729 CnH2n

155,1729 CnH2n-6 +
155,1729.3 H2

0,6504 CnH2n+2

0,6504 CnH2n + 0,6504

180,9479 CnH2n+2 + [107,0336(n-

180,9479 n/15 (CH4

3)/3] H2

+ C2H6 + C3H8 + C4H10

+C5H12)

Vi gi tr n = 7,7758 ta tnh c lng kh hydrocacbon c

sinh ra trong l phn ng th nht l:
180,9479.(7,7758/15)(CH4+C2H6+C3H8+C4H10+C5H12)

93,8010 (kmol/h).
Bng 3.29: Lng cht dng vo v dng ra ca l
phn ng th ba.

Cu t

Lng vo

Lng ra (kmol/h)

(kmol/h)
A

502,9427

502,9427 + 155,1729 = 658,1156

468,8836

468,8836 - 155,1729 + 0,6504 =

314,3611

695,9604

695,9604 - 0,6504 - 180,9479 =

514,3621

-106-

 n tt nghip
Reforming xc tc.
Tng

Thit k phn xng

1804,2813

1486,8388

Bng3.30: Lng kh tun hon.

Cu t

Lng vo

Lng ra

H2

5175,4666

5175,4666 + 155,1729.3 + 0,6504

180,9479 (4,7758/3) = 5353,5787

CH4

347,8148

347,8148 + 93,8010 = 441,6158

C2H6

403,3763

403,3763 + 93,8010 = 497,1773

C3H8

292,2533

292,2533 + 93,8010 = 386,0543

C4H10

181,1304

181,1304 + 93,8010 = 274,9314

C5H12

181,1304

181,1304 + 93,8010 = 274,9314

Tng

6581,1718

7228,2889

Bng 3.31: Kh tun hon ra khi l phn ng th ba.

Cu t

Mi

ni (kmol/h)

yi = ni/ni

Mi.yi

H2

02

5353,5787

0,7407

1,4814

CH4

16

441,6158

0,0611

0,9776

C2H6

30

497,1773

0,0688

2,0640

C3H8

44

386,0543

0,0534

2,3496

C4H10

58

274,9314

0,0380

2,204

C5H12

72

274,9314

0,0380

2,736

7228,2889

1,0000

11,8126

Tng

Vy ta tnh c lng kh tun hon:

7228,2889. 11,8126 = 85384,8855 (kg/h).
Lng sn phm kh ra khi l th 3 l:
244340,1384 - 85384,8855 = 158955,2529
Vy ta c phng trnh l:

-107-

 n tt nghip
Thit k phn xng
Reforming xc tc.
658,1156.(14n - 6) + 314,3611.14n + 514,3621.(14n + 2) =
158955,2529
Suy ra: n = 7,7766
MA = 14n - 6 = 102,8724
MN = 14n

= 108,8724

MP = 14n + 2 = 110,8724
Bng 3.32: Tng kt cn bng vt cht ca l phn
ng th ba.

Cu t

ni (kmol/h)

yi

Mi

Gi = Mi.ni

u vo
A

502,9427

0,0610

102,8612

51733,2897

468,8836

0,0568

108,8612

51043,2314

695,9604

0,0844

110,8612

77155,0051

H2

5175,4666

0,6274

9,7868

64408,6122

P*

1405,7052

0,1704

Tng

8248,9585

1,0000

244340,13
84

u ra
A

658,1156

0,0755

102,8724

67701,9313

314,3611

0,0361

108,8724

34225,2474

514,3621

0,0590

110,8724

57028,5605

H2

5353,5787

0,6143

11,8126

85384,8855

P*

1874,7102

0,2151

Tng

8715,1277

1,0000

244340,62
47

II.1.2. Tnh cn bng nhit lng ca l phn ng th

ba
Ta c cn bng nhit lng:Q13 + Q23 = Q33 + Q43 + Q53 + Q63

-108-

 n tt nghip
Reforming xc tc.
Trong :

Thit k phn xng

Q13: nhit do hn hp kh nguyn liu v kh tun hon mang

vo l (kJ/h).
Q23: nhit do lng xc tc mang vo l (kJ/h).
Q33: nhit do hn hp kh sn phm v kh tun hon mang
ra l (kJ/h).
Q43: nhit do lng xc tc mang ra l (kJ/h).
Q53: nhit tn tht do phn ng reforming (kJ/h).
Q63: nhit mt mt (kJ/h).
Tnh Q13:
Bng 3.33: Entanpi ca cc cht vo l phn ng th
ba.

Cu

Mi

t
H2
CH4
C2H6
C3H8
C4H1

2
16
30
44
58
72

yi

Mi.yi

(kmol/h)

C5H1

ni

qti

qyi.yi

5175,46

0,62

1,254

0,04

770

326,480

66

74

24

347,814

0,04

0,675

0,02

161

36,8904

22

28

403,376

0,04

1,467

0,04

143

89

96

292,253

0,03

1,557

0,05

140

54

27

181,130

0,02

1,276

0,04

140

20

31

181,130

0,02

1,584

0,05

139

20

35

0,06

6,253

0,21

171

362,128

09

14

102,68 502,942
12

Entanpi

-109-

71,1264
74,0435
60,3400
74,4720

 n tt nghip
Reforming xc tc.
N

108,68 468,883

Thit k phn xng

0,05

6,173

0,20

170

355,624

68

87

0,08

9,341

0,31

170

537,807

44

58

Tn

8248,95

1,00

29,58

1,00

1898,91

85

00

25

00

27

12
P

110,68 695,960
12

Nhit do hn hp nguyn liu v kh tun hon mang vo l

th ba:
Q13 = 244340,1384.1898,9127 = 463980591,9275
Tnh Q23:
Ta c: Q23 = mxt2.q23 = mxt3.Cpxt.T
Trong :
q23: hm nhit xc tc (kJ/kg)
Q23 = Cpxt.T: hm nhit xc tc (kJ/kg).
Cpxt: nhit dung ring ca cht xc tc nhit T ( 0K).
Cpxt = ao + a1 - a2.T-2 (kJ/h).
Tra s tay ho l [9]: Cpxt (Al2O3)
Cpxt = 22,08 + 8,971.10-3.T - 5,225.105.T-2
Ti T = 803K ta c:
Cpxt = 22,08 + 8,971.10-3.803 - 5,225.105.803-2 = 28,47
(kcal/kmol.K)
Hay:
CpXT =

28,47.4,186
= 1,17 (kJ/kg.K)
102

MAl2O3 = 102 kg/kmol.

q23 = Cpxt.T = 1,17.803 = 939,51

-110-

 n tt nghip
Thit k phn xng
Reforming xc tc.
Vy Q23 = mxt3.q23 = 28585,8.939,51 = 26856644,9580 (kJ/h)
Tnh Q43:
Gi thit nhit l th nht gim: T = 50K
Ta c: Q43 = mxt3. Cpxt.T
Trong : Cpxt l nhit dung ring xc tc T = 803 - 50 =
753K
Vy Cpxt = 22,08 + 8,971.10-3.753 - 5,225.105.753-2 = 27,914
(kcal/kmol.K)
CpXT =

Vy

27,914.4,186
= 1,145 (kJ/kg.K)
102

Q43

mxt3.Cpxt.T

28585,8.1,14.753

24646247,9730(kJ/h)
Tnh Q53:
tnh hiu ng nhit ca phn ng ta dng cng thc sau:
qP = -355.b [5]
Trong :
b: hiu sut to hydro tnh theo khi lng nguyn liu ban
u (%kl)
GH = 5353,5787 - 5175,4666 = 178,1121 (kmol/h)
2

GH = 178,1121. M H = 178,1121.2 = 356,2242 (kg/h)

2

b=

GH

GC

100% =

356,2242
100% = 0,198%
179931
,5262

Vy qP = -335.0,198 = - 66,33 (kJ/kg)

Nhit tiu tn cho phn ng reforming:
Q53 = GC.QP = 179931,5262.(- 66,33) = - 11934858,1328
Tnh Q63: Nhit mt mt:

-111-

 n tt nghip
Thit k phn xng
Reforming xc tc.
Q63 = 0,01(Q13 + Q23) = 0,01(463980591,9275 +
26856644,9580)
= 4908372,3689
Tnh Q33:
Nhit do sn phm v kh tun hon mang ra:
Q33 = Q13 + Q23 - Q43 - Q53 - Q63
= 463980591,9 + 26856644,96 - 24646247,97 +
+11934858,13 4908372,369
= 473217474,6765 (kJ/h)
Q33 = 244340,6247.qtr3
Suy ra: qtr3 = 1936,7122 (kJ/h)
qtr3: hm nhit ca sn phm v kh tun hon mang ra
Bng 3.34: Cn bng nhit lng ca l phn ng th
ba.

Dng

Nhit

Lng

Entanpi

Nhit lng (kJ/h)

(kg/h)
u vo
Q13

803

463980591,92
75

Q23

803

26856644,958
0

Tng

490837236,8
855
u ra

Q33

753

473217474,67
65

-112-

 n tt nghip
Reforming xc tc.
Q43

Thit k phn xng

753

24646247,973
0

Q53

11934858,132
8

Q63

4908372,3689

Tng

490837236,8
855

II.1.3 Tnh ton kch thc chnh ca l phn ng th

ba
Chiu cao lp xc tc chuyn ng trong l phn ng th
nht c tnh:
H xt3 =

Vxt3
(m)
F

Trong :
Vxt3: th tch lp xc tc trong l phn ng th 3 (m3).
F: tit din vng gia cc ng lc (m2).
Gi tr F c tnh theo cng thc:

2
F = [(Dt3 2.)2 D3 ]
4

(m2)

Trong
Dt3: ng knh trong ca l phn ng th 3, chn Dt 3 = 2,8
m.
: khong cch gia thn l v v l, chn = 0,05 m.
D3 : ng knh ca ng trung tm, chn D3 = 0,5 m.
F=

3,14
[(2,8 2.0,05)2 0,52 ] = 5,526 (m2)
4

Chiu cao lp xc tc: H xt3 =

Vxt3 47,643
=
= 8,62 (m)
F
5,526

-113-

 n tt nghip
Thit k phn xng
Reforming xc tc.
Chn chiu cao lp xc tc quy chun l Hxt3 = 9 (m)
Chiu cao ni gia cc l l 2 m.
Chiu cao ca l th 3 l: H3 = Hxt3 + 2 = 11 (m).
II.2. Tnh ton cho l phn ng th t
II.2.1.Tnh cn bng vt cht
Bng 3.35: Thnh phn cc cu t ca l phn ng th
t.

Cu t

nCi4(kmol/h)

yCi4 = nCi4/nCi4

CnH2n-6

658,1156

0,4426

CnH2n

314,3611

0,2114

CnH2+2

514,3621

0,3460

Tng

1486,8388

1,0000

tt p sut gia cc l phn ng thng t 0,15 n 0,35

(kg/cm2)
Chn tt p sut l th 4 l 0,2 kg/cm2.
Khi p sut chung ca hn hp kh nguyn liu vo l th
4 l:
P2 = 3,1 - 0,2 = 2,9 (kg/cm 2) = 2,9.98067 = 284394,3
(Pa)
Bng 3.36: Thnh phn p sut nguyn liu v kh
tun hon vo l
phn ng th t.

Cu t

yi

Pi = 304007,7.yi
(Pa)

CnH2n-6

0,0755

21471,7697

CnH2n

0,0361

10266,6342

CnH2n+2

0,0590

16779,2637

-114-

 n tt nghip
Reforming xc tc.

Thit k phn xng

H2

0,6143

174703,4185

P*

0,2151

61173,2139

Tng

1,0000

284394,3

Hng s tc ca phn ng chuyn ho naphten thnh

aromatic:
T = 8030K

1000/T = 1000/803 = 1,245

Tra th ph lc (1) ta c k1 = 3,145.10-7 (kmol/h.Pa.kg

xc tc).
Phng trnh tnh hng s cn bng phn ng:
46,15

kP1 = 9,81.10 .e
3

12

25600
803

= 14,866.1020(Pa3 )

gim tng i hm lng naphten do phn ng thm ho:

dNN 41
k
= k1.PN 1 .PA .PH3
dVR 4
kp1

dNN 41
3,145.107
= 3,145.107.10266
,6342
.21471
,7697
.(174703
,4185
)3
20
dVR 4
14,866.10

dNN 41
= 3,229.10-3
dVR 4
m4

M: VR4 = N
C4
Trong :
m4 = 57171,6 (kg)
NC4: lng nguyn liu vo l phn ng th 4 (kg xc tc/ kmol)
VR 4 =

57171
,6
= 38,4518[kg/(kmol/h)]
1486
,8388

Vy NN41 = - 3,229.10-3.38,4518 = - 0,124 (kg xc tc/kmol).

Lng naphten cn li sau phn ng (1) l:
nN41 = (yN4 - NN41).NC4 = (0,2114 - 0,124).1486,8388 =
129,9497 (kmol/h).

-115-

 n tt nghip
Thit k phn xng
Reforming xc tc.
Lng naphten tham gia phn ng (1) l:
314,3611 - 129,9497 = 184,4114 (kmol/h).
Hng s tc phn ng chuyn ho naphten to thnh
prarafin:
T = 8030K

1000/T = 1000/803 = 1,245

Tra th ph lc (2) ta c k1 = 2,55.10-15 (kmol/h.Pa.kg

xc tc).
Phng trnh tnh hng s cn bng phn ng:
4450
7,12

k P 2 = 98,11.103.e 803

= 0,0021.10-3 (Pa-1)

Do kP2 << 1, chng t u th thuc v phn ng nghch tc l

phn ng chuyn ho parafin thnh naphten.
S tng hm lng naphten trong l phn ng th (1) l:

dNN

42

dVR 4

= k2 .PN .PH
2

k2
.PP
k p2

dNN 42
2,55.1015
= 2,55.1015.10266
,6342
.174703
,4185
.16779
,2637
dVR 4
0,0021
.103

dNN 42
= 0,158.10-4
dVR 4

Suy ra: NN42 = 0,158.10-4.VR4 = 0,158.10-4.38,4518 = 0,608.103

Lng naphten sau phn ng (1) v(2) l:

nN42 = (yN4 - NN41 + NN42).NC4
= (0,2114 - 0,124 + 0,608.10-3).1486,8388
= 130,8537 (kmol/h).
Lng naphten to thnh do phn ng (2) l:
nN42 - nN41 = 130,8537 - 129,9497 = 0,904 (kmol/h)
Hng s tc phn ng hydrocracking parafin:

-116-

 n tt nghip
Reforming xc tc.
T = 8030k

Thit k phn xng

1000/T = 1000/803 = 1,245.

Tra th ph lc (3) ta c k3 = 0,075 (kmol/h.Pa.kg xc

tc).

dNP

43

dVR

dNP

43

dVR

= k3

PP
P

16779
,2637
= 0,075
= 4,425.10-3
284394
,3

Suy ra: NP43 = - 4,425.10-3.VR4 = - 4,425.10-3.38,4518 = - 0,17

Lng parafin cn li sau phn ng (2) v (3) l:

nP4 = (yP4 - NP43).NC4
= (0,346 - 0,17).1486,8388
= 261,6836 (kmol/h).
Vy lng parafin tham gia phn ng hydrocracking l:
NP4 - nP4 = 514,3621 - 261,6836 = 252,6785 (kmol/h)
Vy ta c cn bng vt cht cc phn ng ho hc nh sau:
Bng 3.37: Cn bng ho hc ca l phn ng th t.

Lng cc cht tham gia phn ng

Lng cc sn phm

(kmol)

(kmol/h)

184,4114 CnH2n

184,4114 CnH2n-6 +
184,4114.3 H2

0,904 CnH2n+2

0,904 CnH2n + 0,904

252,6785 CnH2n+2 + [252,6785(n-

252,6785 n/15 (CH4 + C2H6

3)/3] H2

+ C3H8 + C4H10 + C5H12)

Vi gi tr n = 7,7766 ta tnh c lng kh hydrocacbon c

sinh ra trong l phn ng th t l:

-117-

 n tt nghip
Thit k phn xng
Reforming xc tc.
252,6785.(7,7766/15)(CH4 + C2H6 + C3H8 + C4H10 + C5H12) =
130,9986 (kmol/h).
Bng 3.38: Lng cht dng vo v dng ra ca l
phn ng th t.

Cu t

Lng vo

Lng ra (kmol/h)

(kmol/h)
A

658,1156

658,1156 + 184,4114 = 842,527

314,3611

314,3611 - 184,4114 + 0,904 =

130,8537

514,3621

514,3621 - 0,904 - 252,6785 =

260,7796

Tng

1486,8388

1234,1603

Bng 3.39: Lng kh tun hon.

Cu t

Lng vo

Lng ra

H2

5353,5787

5353,5787 + 184,4114.3 + 0,904 252,6785.(4,7766/3) = 5505,4022

CH4

441,6158

441,6158 + 130,9986 = 572,6144

C2H6

497,1773

497,1773 + 130,9986 = 628,1759

C3H8

386,0543

386,0543 + 130,9986 = 517,0529

C4H10

274,9314

274,9314 + 130,9986 = 405,9300

C5H12

274,9314

274,9314 + 130,9986 = 405,9300

Tng

7228,2889

8035,1054

Bng 3.40: Kh tun hon ra khi l phn ng th t.

Cu t

Mi

ni (kmol/h)

yi = ni/ni

Mi.yi

H2

02

5505,4022

0,6852

1,3704

CH4

16

572,6144

0,0713

1,1408

-118-

 n tt nghip
Reforming xc tc.

Thit k phn xng

C2H6

30

628,1759

0,0782

2,3460

C3H8

44

517,0529

0,0643

2,8292

C4H10

58

405,93

0,0505

2,9290

C5H12

72

405,93

0,0505

3,6360

8035,1054

1,0000

14,2514

Tng

Vy ta tnh c lng kh tun hon:

8035,1054. 14,2514 = 114511,5011 (kg/h).
Lng sn phm kh ra khi l th 4 l:
244340,6247 - 114511,5011 = 129829,1236
Vy ta c phng trnh l:
842,527.(14n - 6) + 130,8537.14n + 260,7796.(14n + 2)
= 129829,1236
Suy ra: n = 7,7764
MA = 14n - 6 = 102,8696
MN = 14n

= 108,8696

MP = 14n + 2 = 110,8696
Bng 3.41: Tng kt cn bng vt cht ca l phn
ng th t.

Cu t

ni (kmol/h)

yi

Mi

Gi = Mi.ni

u vo
A

658,1156

0,0755

102,8724

67701,9313

314,3611

0,0361

108,8724

34225,2474

514,3621

0,0590

110,8724

57028,5605

H2

5353,5787

0,6143

11,8126

85384,8855

P*

1874,7102

0,2151

Tng

8715,1277

1,0000

244340,62
47

-119-

 n tt nghip
Reforming xc tc.

Thit k phn xng

u ra

842,5270

0,0909

102,8696

86670,4155

130,8537

0,0141

108,8696

14245,9899

260,7796

0,0281

110,8696

28912,5299

H2

5505,4022

0,5940

14,2514

114511,501

P*

2529,7032

0,2729

Tng

9269.2657

1
244340,43
64

II.1.2. Tnh cn bng nhit lng ca l phn ng th t

Ta c cn bng nhit lng:Q14 + Q24 = Q34 + Q44 + Q54 + Q64
Trong :
Q14: nhit do hn hp kh nguyn liu v kh tun hon mang
vo l (kJ/h).
Q24: nhit do lng xc tc mang vo l (kJ/h).
Q34: nhit do hn hp kh sn phm v kh tun hon mang
ra l (kJ/h).
Q44: nhit do lng xc tc mang ra l (kJ/h).
Q54: nhit tn tht do phn ng reforming (kJ/h).
Q64: nhit mt mt (kJ/h).
Tnh Q14: Ta cn xc nh Entanpi ca dng hi nguyn
liu ca vo ca l th nht.
Bng 3.42: Entanpi ca cc cht vo l phn ng th t.

Cu

Mi

t
H2
CH4

ni

yi

Mi.yi

(kmol/h)
2
16

Entanpi
qti

qyi.yi

5353,57

0,61

1,228

0,04

770

337,260

87

43

38

441,615

0,05

0,811

0,02

161

46,7602

-120-

 n tt nghip
Reforming xc tc.

Thit k phn xng

07

89

497,177

0,05

1,710

0,06

143

07

10

386,054

0,04

1,949

0,06

140

43

95

274,931

0,03

1,827

0,06

140

15

52

274,931

0,03

2,268

0,08

139

112,612

15

09

0,07

7,766

0,27

171

474,672

55

71

0,03

3,930

0,14

170

238,900

61

02

0,05

6,541

0,23

170

397,480

90

34

Tn

8715,12

1,00

28,03

1,00

1884,08

77

00

27

00

78

C2H6

30

C3H8

44

C4H1

58

C5H1

72

102,87 658,115
24

108,87 314,361
24

110,87 514,362
24

87,4740
97,6475
91,2800

Nhit do hn hp nguyn liu v kh tun hon mang vo l

th nht:
Q14 = 244340,6247.1884,0878 = 460359190,0614
Tnh Q24:
Ta c: Q24 = mxt4.q24 = mxt4.Cpxt.T
Trong :
Q24 = Cpxt.T: hm nhit xc tc (kJ/kg).
Cpxt: nhit dung ring ca cht xc tc nhit T ( 0K).
Cpxt = a0 + a1 - a2.T-2 (kJ/h).
Tra s tay ho l [9]: Cpxt (Al2O3)
Cpxt = 22,08 + 8,971.10-3.T - 5,225.105.T-2

-121-

 n tt nghip
Reforming xc tc.
Ti T = 803K ta c:

Thit k phn xng

Cpxt = 22,08 + 8,971.10-3.803 - 5,225.105.803-2 = 28,47

(kcal/kmol.K)
Hay:
CpXT =

28,47.4,186
= 1,17 (kJ/kg.K)
102

MAl2O3 = 102 kg/kmol.

q24 = Cpxt.T = 1,17.803 = 939,51
Vy Q24 = mxt1.q24 = 57171,6.939,51 = 53713289,9160 (kJ/h)
Tnh Q44:
Gi thit nhit l th nht gim: T = 40K
Ta c:
Q44 = mxt4. Cpxt.T
Trong : Cpxt l nhit dung ring xc tc T = 803 - 40 =
763K
Vy Cpxt = 22,08 + 8,971.10-3.763 - 5,225.105.763-2 = 28,027
(kcal/kmol.K)
CpXT =

28,027.4,186
= 1,15 (kJ/kg.K)
102

Vy Q44 = mxt4.Cpxt.T = 57171,6.1,15.763 = 50165220,4200

(kJ/h)
Tnh Q54:
tnh hiu ng nhit ca phn ng ta dng cng thc sau:
qP = -355.b [5]
Trong :
b: hiu sut to hydro tnh theo khi lng nguyn liu ban
u (%kl)

-122-

 n tt nghip
Reforming xc tc.

Thit k phn xng

GH = 5505,4022 - 5353,5787 = 151,8235 (kmol/h)

2

GH = 151,8235. M H = 151,8235.2 = 303,647 (kg/h)

2

b=

GH

GC

100% =

303,647
100% = 0,19%
158955
,7392

Vy qP = -335.0,19 = - 63,65 (kJ/kg)

Nhit tiu tn cho phn ng reforming:
Q54 = GC.QP = 158955,7392.(- 63,65) = - 10117532,8001
Tnh Q64: Nhit mt mt:
Q64 = 0,01(Q14 + Q24)
= 0,01(460359190,0416 + 53713289,9160) =
5140724,7996
Tnh Q34: Nhit do sn phm v kh tun hon mang ra:
Q34 = Q14 + Q24 - Q44 - Q54 - Q64
=

460359190,0416

53713289,9160

50165220,4200
+ 10117532,8001 5140724,7996
= 468884067,5382 (kJ/h)
Q34 = 244340,4364.qtr4
Suy ra: qtr4 = 1918,9786 (kJ/h)
qtr4: hm nhit ca sn phm v kh tun hon mang ra
Bng 3.43: Cn bng nhit lng ca l phn ng th t.

Dng

Nhit

Lng
(kg/h)
u vo

-123-

Entanpi

Nhit lng
(kJ/h)

 n tt nghip
Reforming xc tc.
Q14

Thit k phn xng

803

460359190,0
416

Q24

803

53713289,91
60

Tng

514072479,
9576
u ra

Q34

763

468884067,5
382

Q44

763

50165220,42
00

Q54

10117532,80
01

Q64

5140724,799
6

Tng

514072479,
9576

II.1.3 Tnh ton kch thc chnh ca l phn ng th t

Chiu cao lp xc tc chuyn ng trong l phn ng th
nht c tnh:
H xt4 =

Vxt4
(m)
F

Trong :
Vxt4: th tch lp xc tc trong l phn ng th 4 (m3).
F: tit din vng gia cc ng lc (m2).
Gi tr F c tnh theo cng thc:

2
F = [(Dt4 2.)2 D4 ]
4

(m2)

-124-

 n tt nghip
Reforming xc tc.
Trong

Thit k phn xng

Dt4: ng knh trong ca l phn ng th 4, chn Dt 4 = 3,2

m.
: khong cch gia thn l v v l, chn = 0,05 m.
D4 : ng knh ca ng trung tm, chn D4 = 0,5 m.
F=

3,14
[(3,2 2.0,05)2 0,52 ] = 7,348 (m2)
4

Chiu cao lp xc tc: H xt4 =

Vxt4 95,286
=
= 12,97 (m)
F
7,348

Chn chiu cao lp xc tc quy chun l Hxt4 = 13 (m)

Chiu cao ni gia cc l l 2 m.
Chiu cao ca l th 4 l: H4 = Hxt4 + 2 = 15 (m).
Bng 3.44: Tng kt kch thc ca khi l phn ng.

Kch thc

L
phn

L phn L phn L phn

ng 2

ng 3

ng 4

ng 1
ng knh trong (m)

2,4

2,6

2,8

3,2

Din tch (m2)

3,956

4,710

5,526

7,348

Chiu cao lp xc tc

13

11

15

chuyn ng trong l
(m)
Chiu cao l (m)

Tnh hiu sut ca qu trnh reformat xc tc:

Lng reformat ra khi l phn ng th t l:
Greformat = 86670,4155 + 14245,9899 + 28912,5299
= 129828,9353 (kg/h)
Hiu sut reformat:

-125-

 n tt nghip
Reforming xc tc.

Thit k phn xng

129828
,9353
reformat
.100% = 62,32%
HR = G 100%= 208333
,333
C

Tnh hiu sut hydro to thnh :

Lng hydro to thnh sau khi ra khi l phn ng th t l:
GH =

5505,4022.14,2514

4778,2875.6,48

47496,3859 (kg/h).
Hiu sut kh hydro l:
HH =
2

GH

GC

100% =

47496
,3859
100% = 22,8%
208333
,333

Tnh hiu sut sn phm kh hydrocacbon:

Lng kh hydrocacbon to thnh sau khi ra khi l phn ng
th t l:
2529,7032.14,2514 - 777,8607.6,48 = 31011,2749
Hiu sut sn phm kh thu c l:
HK =

31011
,2749
100%
208333
,333

= 14,88%.

-126-

 n tt nghip
Reforming xc tc.

Thit k phn xng

Chng III
Xy dng
I. La chn a im xy dng
I.1. Nhng c s la chn a im xy dng
Reforming xc tc l mt trong s cc qu trnh quan
trng ca cng ngh ch bin du v cng l mt phn
khng th thiu ca nh my lc du. V vy, vic la chn
a im xy dng nh my lc du ni chung v
phn xng reforming xc tc ni ring l bc u tin rt
quan trng ca vic thit k. la chn c a im
xy dng nh my lc du hp l cn phi tm hiu nhiu
yu t nh: iu kin a hnh, kh hu, ti nguyn khong
sn, t ai, dn s, h thng giao thng...v c bit l
ngun ti nguyn. ng thi, cn phi c s gn kt cht ch
ti chin lc pht trin kinh t - x hi ca vng, ca c nc. Do

-127-

 n tt nghip
Thit k phn xng
Reforming xc tc.
vy, vic la chn a im xy dng cn phi c xem
xt v cn nhc ht sc k lng.
I.2. Cc yu cu i vi a im xy dng
I.2.1. Cc yu cu chung
V mt quy hoch:
a im c chn phi ph hp vi quy hoch chung ca
c vng v c th ni rng hn l ca cc cm kinh t, cng
nghip chung ca c nc.
V iu kin t chc:
- Thun li cho vic cung cp nguyn liu v tiu th sn
phm.
- Gn ngun cung cp nng lng: in, nc, than, du
hn ch chi ph vn chuyn, h gi thnh sn phm gp
phn thc y s pht trin ca nh my.
V iu kin h tng k thut:
a im c chn cn c v tr ph hp c th
pht huy ti a nhng u th, nhng thun li ca h thng
giao thng quc gia v quc t nh: ng b, ng thu, ng st v k c hng khng. Ngoi ra phi tn dng ti a
h thng cp in, thng tin lin lc v cc mng li k thut
khc.
V iu kin xy lp v vn hnh:
- a im c chn phi tnh n kh nng cung cp
nguyn vt liu v vt t xy dng.
- C kh nng cung ng cng nhn trong qu trnh xy
dng nh my v vn hnh nh my sau ny.
V iu kin chnh tr - x hi:

-128-

 n tt nghip
Thit k phn xng
Reforming xc tc.
a im xy dng nh my phi thuc vng c iu
kin kinh t, chnh tr x hi n nh.
I.2.2. Cc yu t v k thut xy dng
V a hnh:
- Khu t phi cao ro, khng ngp lt, c mc nc
ngm thp to iu kin to iu kin thun li cho vic
thot nc thi.
- Khu t phi tng i bng phng, dc t nhin i
= 0,5 1%.
V a cht:
- Khu t c chn khng nm trn vng c khong sn
hoc a cht khng n nh.
- Cng khu t xy dng: 1,5 2,5 kg/cm2.
I.2.3. Cc yu cu v v sinh cng nghip
- m bo cc khong cch v sinh cng nghip thch
hp, nn trng cy xanh hn ch tc hi ca khu cng
nghip gy nn.
- V tr xy dng phi cui hng gi ch o.
I.3. c im ca a im xy dng
a im xy dng nh my trong phm vi n
ny l khu Dung Qut (Qung Ngi). Khu vc ny c nhng
c im sau:
V dn c v kinh t:
- Qung Ngi l mt tnh thuc min Trung nc ta. Nn
kinh t nhn chung cha pht trin.
- Trnh dn tr cha cao v khng ng u.
c im v kh hu:

-129-

 n tt nghip
Thit k phn xng
Reforming xc tc.
Mt nm thng c 2 ma l ma ma v ma kh. Kh hu
ni chung khng n ho. Quanh nm nng nng, nhit
kh cao, y l vng thng hay c bo.
c im v a hnh:
Qung Ngi c a hnh khng bng phng, pha ty
l dy Trng Sn, pha ng gip vi bin.
Qua nhng c im trn ta nhn thy a im c chn c nhng u nhc im sau:
- u im:
+/ Qung Ngi ni chung v Dung Qut ni ring nm
trong vng trng im ang c s u t ca chnh ph vi
nhiu d n pht trin kinh t ang c xy dng v trin
khai.
+/ Pha bc gip vi Nng l mt thnh ph cng
nghip c tc pht trin nhanh chng, nh vy s c
nhng thun li nht nh trong khi xy dng cng nh khi
vn hnh.
+/ C sn bay Chu Lai, cng nc su Dung Qut cng vi
h thng giao thng ng b xuyn quc gia i qua nn
thun li v giao thng.
- Nhc im:
+/ Xa ngun nguyn liu. Nguyn liu cho phn xng
reforming xc tc ch yu l xng chng ct trc tip t du
th. Tuy nhin ngun nguyn liu du th li kh xa (m du
ca Vit Nam tp trung ch yu khu vc pha nam). Do
vy, vic cung cp nguyn liu s gp kh khn.
+/ C s h tng cha pht trin do s gp phi rt
nhiu kh khn khi xy dng cng nh khi vn hnh nh my
sau ny.

-130-

 n tt nghip
Thit k phn xng
Reforming xc tc.
+/ Kh hu khc nghit, thng hay c bo l.
Kt lun: Khi la chn Dung Qut xy dng nh
my lc du ta thy c nhiu im cha ph hp. Tuy nhin
nu xt mt cch tng th th khu vc ny vn c tnh kh
thi khi xy dng phn xng reforming xc tc.
II. Cc nguyn tc khi thit k xy dng
Vic xy dng cn phi tun theo nhng nguyn tc
sau:
- Cn b tr cc hng mc trong dy chuyn mt cch
thch hp bo m cc hng mc hot ng thun
tin v hp l nht.
- Cc hng mc cn thit k gn gng, b tr hp l v
tit kim din tch t.
- Khi b tr cc cng trnh trn mt bng cn phi d
kin trc cc hng mc s xy dng giai on sau, to iu
kin thun li cho vic m rng sn xut. Trnh gy nh hng sn xut khi cn m rng.
- Cc cng trnh ph tr cn t gn cc cng trnh
chnh gim chi ph vn chuyn.
- Cc cng trnh gy nhim bn, c hi nn b tr
ring bit xa cc cng trnh chnh, cui hng gi v t ngi
qua li.
- Trm bin th in t ni s dng in nhiu
nht nh my bm, my nn v gn ng ni b.
- ng giao thng ni b cn phi b tr hp l, chiu
rng ln xe t c th ra vo thun tin.
III. B tr mt bng

-131-

 n tt nghip
Thit k phn xng
Reforming xc tc.
Trn khu t c chn xy dng tt c cc hng mc
cng trnh cn c b tr mt cch hp l, m bo cc
iu kin k thut v m quan cng trnh.
III.1. c im ca dy chuyn sn xut
- Qu trnh reforming xc tc l mt qu trnh lin tc.
- Trong khi vn hnh c th thi kh c v nc gy
nhim.
- Ton b dy chuyn u l thin.
- Reforming xc tc l mt phn quan trng ca nh my
lc du, qu trnh hot ng ca n c s kt hp cht ch
vi cc phn xng khc ca nh my lc du do qu trnh
hot ng khng th tch ri c.
III.2. Mt bng phn xng
Cc hng mc cng trnh trong phn xng reforming
xc tc c trnh by trong bng sau:
Bng 4.1: Cc hng mc cng trnh trong phn xng
reforming xc
tc.

TT

Tn cng trnh

S
lng

Kch thc

Din

Di

Rng

tch

(m)

(m)

(m2)

L ti sinh xc tc

12

12

144

Thit b phn ng

12

12

144

Thp tch

12

12

144

Thp n nh

12

12

144

Bm, my nn v lm lnh

24

12

288

Thit b trao i nhit

12

12

144

L gia nhit

12

12

144

-132-

 n tt nghip
Reforming xc tc.

Thit k phn xng

Thit b tip xc li

162

Nh iu hnh

12

12

144

B cha nc

162

Nh sn xut nc

12

108

Trm in

36

Nh cu ho

24

216

Phng ho nghim

12

108

Nh c kh

12

12

144

Nh xe

30

12

360

Nh hnh chnh

12

108

Nh n

24

12

28

Hi trng

24

12

28

B cha nguyn liu

12

12

864

B cha reforming

12

12

288

B cha LPG

12

12

288

B cha kh nh

12

12

144

Thng cha trung gian v 2

12

12

144

0
1
1
1
2
1
3
1
4
1
5
1
6
1
7
1
8
1
9
2
0
2
1
2
2
2
3
2

-133-

 n tt nghip
Reforming xc tc.

Thit k phn xng

cha H2

Nh bo v

144

Nh y t

12

108

Khu x l kh thi

12

108

Khu x l nc thi

12

108

5
2
6
2
7
2
8
Tng

5364

Tng din tch phn xng:

F = 5364.4 = 21456 (m2).
- Chiu di phn xng: 165 m
- Chiu rng phn xng: 130 m
Ch tiu kinh t k thut:
H s xy dng Kxd:
Kxd =

A+B
100%
F

Kxd =

5364
100%=25%
21456

H s s dng Ksd:
Ksd=

A + B+ C
100%
F

A: Din tch ca nh v cng trnh (m2).

B: Din tch kho bi l thin (m2).
C: Din tch ca t chim ng b, h thng thot nc, C
= 7900 (m2)
Ksd =

5364+ 7900
100%=
21456

62%

-134-

 n tt nghip
Reforming xc tc.

Thit k phn xng

Chng IV
An ton lao ng v bo v mi trng
I. An ton lao ng trong phn xng reforming xc tc
Trong qu trnh sn xut cc nh my lc du ni
chung v trong cc phn xng reforming ni ring th vn
an ton lao ng v bo v mi trng c vai tr ht sc
quan trng v cn thit nhm ci thin iu kin lm vic

-135-

 n tt nghip
Thit k phn xng
Reforming xc tc.
ca cng nhn, m bo sc kho, an ton cho cng nhn
trong nh my. m bo an ton lao ng ta cn phi
nm c cc nguyn nhn gy ra tai nn chy n. Cc
nguyn nhn gy ra tai nn chy n nh sau:
I.1. Nguyn nhn do k thut
Nguyn nhn ny ph thuc ch yu vo tnh trng
my mc, thit b, ng ng ni lm vic:
- My mc v cc thit b trong nh my b hng hc,
khng m bo an ton trong qu trnh sn xut.
- S r r cc ng ng.
- Kt cu thit b khng m bo an ton, h thng
thit b khng ng b d gy ra s c trong qu trnh lm
vic.
- Khng m bo khong cch an ton gia cc my
mc, gia my mc v ngi lao ng.
- Khng thc hin ng

v y cc yu cu v

kim tra nh k, bo dng, sa cha my mc thit b.

I.2. Nguyn nhn do t chc
- Vi phm cc quy tc, quy trnh k thut.
- T chc lao ng, ni lm vic khng ng yu cu.
- Gim st k thut khng cht ch.
- Vi phm ch lm vic.
- S dng lao ng khng ng ngnh ngh, chuyn
mn.
- Ngi lao ng cha nm vng cc quy tc an ton lao
ng.
I.3. Nguyn nhn do cng tc v sinh
- Mi trng lm vic b nhim.

-136-

 n tt nghip
Thit k phn xng
Reforming xc tc.
- iu kin kh hu khng thch hp.
- Vic m bo chiu sng v thng gi khng c tt.
- Ting n v chn ng vt qu quy nh cho php.
- Vi phm cc quy nh v v sinh c nhn.
II. Cng tc phng chng chy n
Nh chng ta bit nguyn liu cng nh sn phm
trong qu trnh reforming xc tc u rt d chy n. V
vy, vn gio dc an ton phng chy n cho cn b,
cng nhn vin trong nh my l ht sc quan trng v phi
c t ln hng u.
II.1. Nguyn nhn gy chy n
Do c ngn la h trong khu vc sn xut:
Do nhng ngi thiu kin thc phng chy, cha chy
s dng ngun nhit nh dim, bt la, n du vi phm
cc quy nh nn gy chy.
Vi phm quy trnh k thut:
Coi nh cng tc phng chy cha chy, khng thc
hin nghim ni quy, quy nh phng chy to nn nguy c
chy.
t ph:
- t phi tang do trm cp, tham .
- t do mu thun tr th.
- t vi mc ch ph hoi.
Do tnh in hoc st nh gy chy n.
II.2. Cc bin php phng chng chy n
- phng chng chy n cn thc hin nhng bin
php sau y:

-137-

 n tt nghip
Thit k phn xng
Reforming xc tc.
- Ngn nga kh nng to ra mi trng chy n.
- Ngn nga kh nng xut hin nhng ngun chy n
trong mi trng d chy n.
- Duy tr nhit mi trng thp hn nhit cho
php ln nht c th chy n c.
- Duy tr p sut ca mi trng thp hn p sut cho
php ln nht c th chy n c.
ngn nga kh nng xut hin nhng ngun chy n
phi tun th cht ch cc quy nh sau:
- Tun th cht ch cc quy nh v s dng, vn
hnh v bo v my mc thit b cng nh s dng vt liu
v cc sn phm khc c th l ngun chy.
- S dng cc loi thit b in ph hp.
- p dng quy trnh cng ngh v s dng thit b bo
m khng pht sinh tia la in.
- C bin php chng st cho nh xng, thit b.
- Quy nh nhit nung nng cho php ln nht ca
b mt thit b, sn phm v vt liu tip xc vi mi trng
chy.
- Loi tr nhng iu kin c th dn n t chy do
nhit , do cht xc tc, do tc dng ho hc...
II.3. Nhng bin php t chc m bo an ton
phng chy n
m bo an ton trong qu trnh xy dng cng
nh vn hnh sn xut cn phi thc thi nhng bin php sau
y:
- Trc khi giao vic phi t chc cho cng nhn v
nhng ngi lin quan hc tp v cng tc an ton chy n.

-138-

 n tt nghip
Thit k phn xng
Reforming xc tc.
i vi nhng mi trng lm vic c bit nguy him v
chy n th cn b v cng nhn vin cn c cp giy
chng nhn v nh k kim tra li.
- Mi phn xng, x nghip cn phi xy dng cc ni
quy, quy nh v an ton chy n v cc phng n cha
chy thch hp cho n v mnh.
- Trang b cc phng tin phng chy cha chy y
, ng b. Thng xuyn luyn tp cc phng n cha
chy nhm m bo x l tt khi c s c xy ra.
- Cn t chc thnh cc t, i cha chy chuyn
nghip trong mi phn xng thc hin tt cc yu cu
ra v m bo cng tc phng chng chy n trong
mi phn xng tt hn.
- Xy dng cc phng n cha chy, phn cng c th
trch nhim cho tng t, tng ngi.
Vi cc ngun gy chy phi thc hin cc bin php
sau y:
- C kh ho, t ng ho cc qu trnh cng ngh c
lin quan n s dng vn chuyn nhng cht d chy.
- S dng cc thit b sn xut, bao b kn cho nhng
cht d chy n.
- S dng nhng ngn, khoang, bung cch ly i vi
nhng qu trnh d chy n.
Bn cnh nhng tai nn c th xy ra do chy n th
cn mt vn cn c quan tm l c tnh ca cc
ho cht. Nh chng ta bit hu ht cc ho cht trong
nhng iu kin nht nh u c th gy tc hi i vi
con ngi. Do vy phng trnh nhng c t gy hi cho
sc khe ca con ngi cn thc hin nhng bin php sau:

-139-

 n tt nghip
Thit k phn xng
Reforming xc tc.
- Trong qu trnh sn xut phi ch m bo an ton
trong cc khu tho, np sn phm, lc, sy l nhng khu
m cng nhn thng phi tip xc trc tip.
- Duy tr chn khng trong sn xut.
- Thay nhng cht c dng trong qu trnh bng
nhng cht t c hi hn nu c th.
- T ng ho, bn t ng ho nhng qu trnh s
dng nhiu ho cht c hi.
- Ni lm vic ca cng nhn cn c thng thong
nhm lm gim ti a nng cht c c trong mi trng
lm vic.
- T chc cc bui hc tp v an ton ng thi nng
cao thc t gic thc hin cc bin php an ton trong ni
lm vic v sn xut.
III. Yu cu v bo v mi trng [12,13]
III.1.

Tnh

hi

ca

nguyn

liu,

sn

phm

reforming v cch x l
1. i vi cc sn phm kh
Cc hp cht olefin v parafin phn t lng thp l
nhng cht kh d ho tan trong khng kh v to thnh hn
hp d n rt nguy him. V vy, trong phn xng sn xut
v s dng th ta xp cc hydrocacbon ny thuc loi A.
Chng c kh nng lm m man khi ht th v c tc hi lu
di v sau. Nng cho php ca chng trong khu sn xut
nm ngoi gii hn n cho php (5,0% 7,6% th tch), cng
nhn phi eo khu trang, trang b y bo h lao
ng trong qu trnh lm vic.
Xy dng cc b cha phi xa ni dn c, khng c r
r.

-140-

 n tt nghip
Thit k phn xng
Reforming xc tc.
Trng cy xanh c kh nng hp th kh tt xung
quanh.
2. i vi sn phm LPG
LPG l sn phm kh ho lng nhit thp v p
sut cao (6 7 atm), c kh nng d n, do ta cn phi
cn thn trong khu bo qun v s dng. Ta cn phi duy
tr p sut v nhit trong gii hn cho php.
3. Nguyn liu v sn phm refomat
Nguyn liu v sn phm refomat trng thi lng, d
bay hi v c kh nng ho tan trong khng kh to thnh
hn hp d chy n, rt nguy him.
Ta cn xy dng khu cha sn phm v nguyn liu xa
khu dn c, gn nh cu ho v cui hng gi ca phn xng, trng cy xung quanh hp th kh khi b b r r.
B cha phi c van th trnh hin tng n khi
nguyn liu v sn phm gin n, tng p sut trong b v c
b phn thu hi kh trnh nhim mi trng.
Ta cn xy dng b cha ngm di t, s b bng
sn trng trnh hin tng hp th cc tia hng ngoi, t
ngoi.
4. Sn phm hydrocacbon thm (BTX)
BTX l sn phm lng c nhit bt chy thp nn
nguy him chy ca chng rt ln. S c hi ca chng
vt tri hn nhng hydrocacbon khc loi.
Nng c cho php ca chng ti khu sn xut i vi
benzen l 20 mg/m3.
Ta cn phi trng cy xanh xung quanh khu sn xut
cng nh khu cha sn phm BTX hp th kh b r r,

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 n tt nghip
Thit k phn xng
Reforming xc tc.
trnh nhim mi trng v c hi cho cng nhn v dn
c.
Cng nhn phi trang b y bo h lao ng
trong khi lm vic.
III.2. V tr mt bng phn xng
La chn mt bng nh my phi tng i bng
phng, c h thng thot nc thi tt. t nh my cch khu
dn c mt khong cch an ton cui hng gi v trng nhiu
cy xanh xung quanh nh my. Cng tc chiu sng v thng
gi tt m bo mi trng thong ng cho cng nhn
lm vic.

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