T hp sn xut hydrocacbon thm ca UOP

Mc lc
Phn 1. M u
Phn 2. Ni dung
2.1. Tnh cht k thut ch yu ca hydrocacbon thm
2.2. Mt s ngun sn xut chnh hydrocacbon thm
2.2.1.T qu trnh reforming xc tc
2.2.2. T xng nhit phn
2.2.3. T qu trnh cc ha than
2.3. T hp sn xut hydrocacbon thm ca UOP
2.3.1. X l nguyn liu Naphta
2.3.2. Qu trnh reforming xc tc
a. B phn phn ng
b. B phn ti sinh xc tc
c. B phn n nh
c. Xc tc cho CCR Platforming
2.3.3. Cc phn xng
a. Phn xng Tatoray
b. Phn xng THDA
c. Phn xng Isomar
d. Phn xng Parex
Phn 3. Kt lun
Ti liu tham kho

T hp sn xut hydrocacbon thm ca UOP

Phn 1: LI M U
Benzen, toluen, cc xylem (BTX), etylbenzen , cumen l cc hydrocacbon thm
c ng dng rng ri nht trong cng nghip tng hp hu c ha du.
Chng l cc cht u quan trng cho nhiu qu trnh sn xut ha cht v
polymer thng mi nh phenol, trinitroluen (TNT), nylon v cht do.
Cc hp cht hydrocacbon thm c c trng bi cu trc vng bn vng nh
s xen ph ca cc obital . Do , chng khng d dng tham gia phn ng cng cc tc
nhn dng halogen v axit nh l cc anken. Tuy nhin cc hydrocacbon thm rt nhy
vi phn ng th electrophil vi s c mt ca xc tc.
Mc d c rt nhiu ng dng quan trng, c sn xut vi quy m ln trn
phm vi rng ln trn th gii, nhng ti Vit Nam vic ng dng cc quy trnh sn xut
tin tin hin i cn rt hn ch. Hu ht lng hydrocacbon dung trong nc u phi
c nhp khu.
Trc tnh hnh , ti y T hp lc ha du Nghi Sn (Thanh Ha) s thit k
p dng cng ngh sn xut hydrocacbon thm ca hng UOP. l t hp sn xut
hydrocacbon thm ca UOP. y cng l ti ng quan tm m nhm tiu lun s
trnh by trong bi tiu lun ny. Mc ch nhm tm hiu k hn v thit k, cng nh
hot ng ca T hp sn xut hydrocacbon thm UOP.

T hp sn xut hydrocacbon thm ca UOP

Phn 2: NI DUNG
2.1. Tnh cht k thut ch yu ca hydrocacbon thm.
Bng 1: Mt s c trng k thut ca BTX v cumen [1]
Thng s

n v

Khi
lng
vC
phn t
T trng
200C
0
C
Nhit
nng chy
0
C
Nhit
si
Gii hn
n trong
% th
khng kh tch
Trn
Di
Nhit
chp chy 0C
cc kn
T trng
hi(khng
kh=1)
Gii hn
tip xc
(ppm; gi)

Benzen

Toluen

o-xylen

p-xylen

etylbenzen

106,16

mxylen
106,16

78,11

92,13

106,16

106,17

0,879

0,867

0.876

0.86

0.857

0.867

5,33

-94,99

-25,2

-48

13,3

-94,9

80,1

110,6

144,4

139

138,4

136,2

1,4
7,1
-11,1

1,3
6,8
4,4

1,1
6,4
17,2

1,1
6,4
25

1,1
6,6
25

0,99
6,7
15

3,14

3,7

3,7

3,7

3,7

3,7

5;8

50;8

100;8

100;8

100;8

100;8

2.2. Mt s ngun sn xut hydrocacbon ch yu

2.2.1.T qu trnh reforming xc tc
Hydrocacbon ni chung ch yu c tch t sn phm ca qu trnh reforming
xc tc, vi nguyn liu u l thng l phn on napthta. Trc khi i vo qu trnh
th nguyn liu cn phi c x l tp cht c bit l lu hunh, v lu hunh rt nhy
cm ti h xc tc Pt Re ca qu trnh reforming. Thnh phn cng ca sn phm

T hp sn xut hydrocacbon thm ca UOP

reformate cng nh hm lng ca hydrocacbon ph thuc rt nhiu vo cch tin hnh
qu trnh reforming cng nh l loi nguyn liu naphta c s dng. Thnh phn ca
phn on naphtha c bit l hm lng naphthen hay cc hydrocacbon thm c nh
hng ln nht n n cht lng ca sn phm reformate thu c.
Trn thc t naphtha thu c t qu trnh chng du naphtenic th s ph hp
nht cho qu trnh reforming sn xut hp cht thm. Tuy nhin phn on naphtha c
sn xut t qu trnh hydrocracking thng cng thu c giu hm lng naphthen nn
rt ph hp lm nguyn liu u cho qu trnh reforming sn xut cc hydrocacbon.
Bn cnh thnh phn, khong nhit si ca naptha nguyn liu cng nh hng n
hiu xut thu c BTX.
Bng 3: S ph thuc ca thnh phn reformate vo nhit si ca nguyn liu
u vo [2]
Khong nhit si ca
Naphtha, 0C
60-160
107-160
90-160
Thnh phn ca nguyn liu, % khi
lng
Paraffin
69,6
62,2
64,2
Naphten
19,5
21,2
22,2
Hydrocacbon thm
10,9
16,6
13,6
Thnh phn hydrocacbon thm trong
Reformat, % khi lng
Benzen
9,3
1,6
5,2
Toluen
21,7
19,0
25,1
Hydrocacbon thm C8
20,8
34,3
26,2
Hydrocacbon thm C9+
8,8
15,2
11,2
Nh s liu trong bng, khong nhit si thch hp nht ca Naphtha lm nguyn
liu Reforming sn xut BTX l t 140 n 180 0C.
2.2.2. T xng nhit phn
Xng nhit phn c thnh phn t C5 tr ln l sn phm ca qu trnh cracking
hi nc cc phn on lng. Thnh phn ca xng nhit phn c cha hm lng ln
cc hydrocacbon thm, c bit l benzen. Chnh v vy y cng l mt ngun ng gp
sn phm c gi tr co cho c cng ngh sn xut xng cng nh cng ngh tng hp
hu c ha du. Sn lng xng nhit phn cng nh hm lng cc hydrocacbon trong
c quyt nh bi nguyn liu s dng v iu kin tin hnh sn xut. Sn phm
BTX t xng nhit phn l sn phm ph ca qu trnh sn xut etylen v propen, tuy
nhin trong mt s trng hp vic tch cc ng phn xylen li mang li hiu qu v
mt kinh t.
Vic iu chnh iu kin sn xut tuy khng ti a ha sn lng ca
hydrocacbon nhng cng c nh hng ng k, c th l nu tng nhit phn ng,

T hp sn xut hydrocacbon thm ca UOP

gim thi gian lu, gim thi gian lu bng cch tng lng hi vo th s lm gim ng
k lng xng nhit phn thu c, tuy nhin hm lng ca cc hydrocacbon trong
li tng ln.
2.2.3. T qu trnh cc ha than
Du nh, c hnh thnh nh l sn phm ca qu trnh cacbon ha than (cc
ha) nhit cao, c cha khong 60% benzen v 12-20 % toluen. Trong iu kin cc
ha 10000C, khng c khng kh, s xy ra cc qu trnh chuyn ha su (phn hy
nhit v thm ha) phn hu c ca than to thnh cc, cc sn phm lng v kh. Do
thanh ngho hydro hn so vi du m nn hiu sut sn phm cc to thnh (70-80%)
ln hn rt nhiu so vi sn phm lng (4-5%). Tuy nhin, v qu trnh cc ha din ra
nhit cao nn sn phm lng c thm ha hon ton (95-97%), v vy lng
hydrocacbon thm l rt ng k. Cc sn phm hydrocacbon thm hnh thnh t qu
trnh phn hy nhit v thm ha phn hydrocacbon ca than l benzen, toluen, xylen,
thiophen, pyridin
Cc hydrocacbon thm c th c tch ra nh qu trnh hp th ngc dng
bng phn on du m c nhit si cao, khong 300-400 0C. Hn hp c chng
tch trong thp chng ct li cun hi nc lin tc. Cc hydrocacbon nh c tch ra
nh qu trnh chng ct v sn phm th c ra bng dung dch axit sunfuric c
loi b hon ton cc hp cht lu hunh, cc hydrocacbon c tip tc chuyn v b
cha, trung ha ht phn axit d v ra li bng nc. Qu trnh hydro ha loi b cc
cht lu hunh, nit v cc hp cht khng no cn li. Benzen c tch ra t phn on
hydrocacbon thm nh qu trnh chng trch ly vi dung mi sunfolan. Cc ng phn
xylen c tch ra tng t so vi i t qu trnh Reforming xc tc.
Cng ngh sn xut hydrocacbon thm i t sn phm lng ca qu trnh cc ha
than trn thc t ch ph bin khi du m cha c bit n v khai thc. Ngy nay cng
ngh ny ch cn c s dng trng mt s nh my Nam Phi v Niudilan.
2.3. T hp sn xut hydrocacbon thm ca UOP
2.3.1. X l nguyn liu Naphta
Trong nguyn liu u hydrocacbon c cha cc hp cht lu hunh c th gy
ng c cho xc tc ca qu trnh chuyn ha, v vy cc hp cht cha lu hunh cn
phi c lm sch khi nguyn liu u. Cc hp cht lu hunh c chuyn sang
dng H2S bng qu trnh Hydrodesulfua ha (HDS) vi xc tc Co-Mo/Al2O3.
Sau H2S c hp ph bng ZnO (b mt ring 25 m2/g)
H2S + ZnO = ZnS + H2O
Hm lng lu hunh c gim xung mc nh hn 0,01 ppm. Cc hp cht clo
gy n mn cc thit b trao i nhit v gy ng c xc tc kh ha nhit cng c
lm gim xung mc di 5ppb s dng cht hp ph Al2O3 c x l vi kim.
2.3.2. Qu trnh Reforming xc tc

T hp sn xut hydrocacbon thm ca UOP

Hnh 1: S cng ngh CCR Platforming ca UOP [3]

Cng ngh CCR Platforming ca UOP vi cc thit b phn ng chng ln nhau
thnh mt khi. Xc tc chuyn ng t thit b phn ng trn xung thit b phn ng
di cng, sau xc tc lm vic c chuyn sang thit b ti sinh khi phc li
hot tnh ri np li thit b phn ng th nht to thnh mt chu k khp kn.
a. B phn phn ng
Nguyn liu trn vi kh H2 tun hon c t nng n nhit phn ng trong
thit b trao i nhit v b phn th nht ca l ri c np vo thit b phn ng th
nht ( trn cng). Sau khi tip xc vi xc tc, nguyn liu b bin i ty thuc vo
kht khe, cc iu kin cng ngh ca qu trnh, to nn sn phm c tr s octane cao
hn hay hydrocarbon thm nhiu hn.
Khi thit b phn ng gm c 3 4 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 k ring v ng dn xc tc, b phn phn phi, b phn cch ly v cc

T hp sn xut hydrocacbon thm ca UOP

thit b khc sao cho ph hp vi qu trnh chuyn ng ca xc tc v cc phn ng ha
hc xy ra.
Lng xc tc trong thit b phn ng rt khc nhau, trong khi thit b phn ng
th nht ch cha 10 20% lng xc tc th thit b phn ng cui cng cha n 45%
xc tc. T l phn b xc tc trong cc thit b phn ng vi s 4 thit b phn ng
thng theo t l 1 : 1,5 : 3 : 4,5. Xc tc lm vic chuyn sang l ti sinh xc tc, hn
hp hi-kh phn ng i ra khi thit b phn ng th nht c qua l t nng li nhit
n nhit phn ng ri c np ngay vo thit b phn ng th hai. C nh vy
cho n thit b phn ng th 4. Sau , hi-kh sn phm c lm lnh do trao i
nhit vi nguyn liu ri ngng t v lm lnh tip trc khi chuyn sang b phn phn
tch sn phm. thit b tch, sn phm c chia thnh hydrocarbon lng ngng t v
kh giu H2. Mt phn kh ny c quay li thit b phn ng nh my nn kh tun
hon, phn cn li c trn vi b ti tip xc ri i vo ct n nh sn phm.
b. B phn ti sinh xc tc
Xc tc lm vic chy t y ca thit b phn ng cui cng xung b phn
thu xc tc bunke cha sau n chy xung ng nng. Ngi ta dng kh H 2 tun
hon t my nn y xc tc v vn chuyn n ln nh vo b phn phn tch bi pha
trn l ti sinh. b phn tch ny, ngi ta b sung thm mt lng kh H 2 tun hon
tch cc ht bi mn ca xc tc v mang chng ra ngoi vi kh vo ng tp trung bi,
cn xc tc ri xung y b phn tch bi ri chy xung l ti sinh.
Ti sinh xc tc gm 5 bc: ui hydrocarbon ra khi xc tc bng kh tr, thi
khng kh nng vo t cc, tin hnh clo ho xc tc nhm tng hot tnh xc tc, sy
cht xc tc, ui ht O2 ra khi xc tc bng lung kh tr N2 sau tin hnh hydro ho
chuyn t mi trng oxy ho sang mi trng kh.
c. B phn n nh
Thp n nh s tch hydrocarbon nh v thu c reformate n nh. Sn
phm reformate n nh c cho qua thit b trao i nhit vi nguyn liu ri cho
vo b cha.
d. Xc tc cho CCR Platforming

T hp sn xut hydrocacbon thm ca UOP

Xc tc th h mi nht ca cng ngh CCR Platforming ca UOP l R-254 v R284, vi cc u im ni tri nh: sn lng cao, hot tnh tt, lng cc to thnh thp
v n nh cao.
Xc tc ngy nay l xc tc lng chc nng. Thnh phn ca xc tc l Pt- Re/
Al2O3 vi 0.3% Pt + 0.3% Re mang trn - Al 2O3, vi din tch b mt khong 250m2/g,
c b sung thm cc hp cht halogen hu c. Hm lng Clo thm vo khong 0.5
n 1% trng lng.

Yu cu i vi xc tc
Xc tc phi c chn lc cao
Phi c bn nhit v kh nng ti sinh tt
Xc tc phi b vi cc cht gy ng c
C n nh cao
C gi thnh hp l, d ch to.

2.3.3. Cc phn xng

a. Phn xng Tatoray

Trong cng nghip ha du, do toluen c t gi tr ng dng, ngi ta thng
chuyn ha toluen tng sn lng benzen v hn hp xylene thng qua vic phn tch

T hp sn xut hydrocacbon thm ca UOP

p-xylene theo phng php kt tinh hoc hp ph. Cng ngh ny thng c s dng
sn xut mt lng ln o-xylene v p-xylene m khng cn tng lng reformate cn
x l.
Phn ng chnh xy ra:
2C6H5CH3 C6H6 + C6H4(CH3)2
Hoc phn ng chuyn nhm alkyl nu c trimetyl benzen trong thnh phn nguyn liu
u:
C6H5CH3 + C6H3(CH3)3 2C6H4(CH3)2
Phn ng ny c s dng iu chnh t l benzen/C8 bng cch a vo hn hp
nguyn liu cc hydrocacbon thm C9 c tch trong qu trnh x l phn on C8.
S cng ngh

Hnh 3: S cng ngh Tatoray ca UOP [3]

Cng ngh Tatoray bao gm 1 thit b phn ng loi tng c xc tc c nh v 1
thp tch sn phm. Nguyn liu u vo gm Toluene v C9 c kt hp vi ngun kh
tun hon giu hydro c gia nhit trc bi thit b trao i nhit. V mt l thuyt,
qu trnh c th tin hnh m khng cn s c mt ca hydro, nhng s c mt ca n
hn ch s to cc. Sau , hn hp s c nng ln n nhit phn ng thit b t
nng. Sau , hn hp hi c a vo thit b phn ng chnh loi tng c lp xc tc
c nh. Dng ra sau c lm lnh qua thit b trao i nhit vi ngun lnh chnh l

T hp sn xut hydrocacbon thm ca UOP

hn hp vo. Dng sn phm trc khi vo thp tch cn c cho qua thit b ngng t.
Kh giu hydro c ly ra pha trn nh thp, mt phn nh ca n c lc tch
loi cu t nh v quay tr li i v trn vi nguyn liu u. Dng lng pha di
ca thp tch c chuyn qua thp tch kh lng. Sn phm nh ca thit b c lm
lnh sau c tch ra mt phn l kh, 1 phn l lng. Phn kh bao gm cc cu t
nh c chuyn qua h thng kh nhin liu. Sn phm lng nh th c chuyn qua
phn xng Platforming thp debutan. Dng Benzen trong dng ny th c tch ra
v chuyn sang b phn tch benzene toluene. Benzen v cc ng phn xylene, cng
vi toluene cha phn ng v hydrocacbon thm C9, c ly t y thp tch Stripper
s tun hon chuyn n b phn tch benzene-toluen.
iu kin cng ngh
T l mol H2/hydrocacbon = 5-20
Nng hydro trong dng kh tun hon >70%
p sut: 3-4 MPa
Nhit tng t 410 n 470OC
Xc tc
Xc tc th h mi nht ca qu trnh Tatoray l T-20 l xc tc zeolite c cha
1,25% Cr v 0.5% Mo. Vic ci tin to nn rt nhiu u im cho xc tc ny:

Tnh n nh cao hn
Hot tnh cao hn
Khng thay i cc iu kin m h thng yu cu
chuyn ha v sn lng tng
Khng cha kim loi qu
Cht lng benzene cao, tinh khit
C th ti sinh

b. Phn xng THDA

Qu trnh hyro alkyl ca cc cht thm, thng l toluen (Mc d, c s dng cho
cc hp cht thm nng hn l tt. )
Hydrodealkyl ha l phn ng cracking hydrocacbon thm c mch nhnh trong
dng hydro. Ging nh hydrocracking, phn ng ny tiu th hydro v thun li iu
kin p sut ring phn hydro cao. Qu trnh ny c thit k hydrodealkyl ha cc
metylbenzen, etylbenzen C9+ thnh benzen. N xut pht t nhu cu benzen trong cng
ngh tng hp ha du ln hn nhiu so vi cc hp cht ny cng nh vi toloen v cc
xylen (sn phm BTX). Sau khi phn tch benzen khi sn phm reforming, cc
hydrocacbon thm cao hn s c n phn xng hydrodealkyl ha. Thit b phn ng

10

T hp sn xut hydrocacbon thm ca UOP

c dng tng t hydrocracking. Ti y, phn nhnh alkyl s c b gy v ng thi
c hydro ha. Dealkyl ha cc hp cht dng vng benzen th nhiu s lm tng lng
hydro tiu th v ng thi to ra nhiu sn phm kh hn. Di y l 1 s v d:

Phn ng benzen nhiu nhm alkyl l:

Trong qu trnh hydrodealkyl ha, phn ng c bn l tch cc nhm alkyl gn

vi nhn benzen ra di dng alkan. Nu qu trnh vn hnh ng, v chuyn ha c
hon ton nh tun hon phn hydrocacbon thm cha phn ng, cc sn phm thu c
l benzen v rt nhiu cc hydrocacbon nh, ch yu l metan. Bt k loi no khng
phi hydrocacbon thm c trong nguyn liu, v d trong phn x l trc tip phn on
xng C5+ khng qua giai on chit dung mi, s b phn hy thnh cc parafin nh
(metan). iu ny nhm mc ch thu sn phm benzen c tinh khit cao, nh ng cng
ko theo lng hydro tiu th rt ln. Cc hp cht lu hunh chuyn ha 1 phn thnh
H2S.
Phn ng chnh :

Cc phn ng ph:
Hnh thnh hydrocacbon thm phn t lng ln (diphenyl). Chng chim phn
ln trong cc phn ng ph:

11

T hp sn xut hydrocacbon thm ca UOP

Hydro ha vng benzen v phn hy chng to thnh metan:

Phn hy cc parafin v naphten thnh metan, hnh thnh cacbon:

CnH2n+2 + H2 CH4
iu kin lm vic:
- Nhit dng vo thit b phn ng 620oC, nhit ti a 730 750oC.
- p sut 4,3 MPa.
- Thi gian lu trung bnh 25 30 giy.
- T l mol H2/hydrocacbon trong dng vo thit b l 4.
- chuyn ha 75%.
- tinh khit ti thiu ca dng hydro l 50 60% TT.
Sn phm benzen c tinh khit rt cao, v hiu sut qu trnh t 97 99% mol ty
thuc chu trnh tun hon phn sn phm nng (diphenyl, dibenzyl).
Trong qu trnh ny, iu kin ( nhit , p sut) thng kht khe hn trong
phng php hydrodealkyl c s dng xc tc. iu ny li t ra yu cu vi cc thit b
trong qu trnh sn xut. C th:
+ Cc thit b phi phi c sc chu ng bn b vi nhit , dn n vt liu ch
to tn km hn.
+ Do phn ng hydrodealkyl l phn ng ta nhit (vi hn khong 10 kcal / mol
cho mi nhm methyl khi nhm alkyl l methyl), trong qu trnh thit k, phi c thm
cc thit b ngn chn s gia tng nhit trong l.
S cng ngh THDA ca UOP:

12

T hp sn xut hydrocacbon thm ca UOP

Nguyn liu Toluen tinh khit c trn vi dng toluen ti sinh, dng ti sinh v
kh Hydro tinh khit c gia nhit trong thit b trao i nhit v sau chuyn n
thit b phn ng. Hp cht thm ankyl c hydro deankyl ha thnh benzene v hp
cht khng thm, cc paraffin v naphten c hydro cracking. Dng ra t thit b phn
ng c lm mt v chuyn n thit b phn tch sn phm thnh pha lng v pha kh.
Pha kh giu hydro c ti sinh n thit b phn ng. Dng cht lng ra khi thit b
phn tch c chuyn n ct loi b nhng cht nh cui cng. Dng sn phm y
ct ct c a qua mt thit b x l bng t st ct phn on. Ti y benzen c
tinh khit cao thu c t pha trn ca ct ct phn on. Phn toluene khng phn
ng c ti sinh n thit b phn ng t on thp hn trn ct ct phn on. Nhng
sn phm l cacs hp cht thm nng c ly ra t cui ct lu tr. C 70-85%
chuyn ha ca toluen thnh benzen qua qu trnh ny.
c. Phn xng Isomar
Phn xng UOP Isomar c s dng thu ti a mt ng phn xylen no
trong hn hp ng phn hydrocacbon thm C8. Thng thng Isomar ch yu c s
dng tn thu ti a p-xylen nhng n cng c th s dng thu hi c o-, m-xylen.
Trong trng hp thu hi p-xylen th nguyn liu ca qu trnh ny l phn raffinat ca
phn xng Parex, ni m p-xylen c thu hi ti 97% v c tinh khit ln ti
99% khi lng. Phn Raffinat cn li ch yu gm m-xylen v etylbenzen mt lng
nh cn li l p- v o-xylen. y hiu sut ca p-xylen c tng cng nh qu trnh
isome ha cc ng phn m-,o-xylen v c etylbenzen.
Isome ha to ra s chuyn ha lin tc v dn n cn bng gia 4 loi
hydrocacbon thm C8 theo s sau:

13

T hp sn xut hydrocacbon thm ca UOP

Cc phn ng chnh
Phn ng Isome ha xylen

Phn ng Isome ha Etylbenzen

Xc tc ca qu trnh
Xc tc dng cho qu trnh ny l xc tc lng chc, chc axit (zeolit) v chc
kim loi. Chc nng ca chc axit l isome ha cc ng phn xylen to thnh mt
hn hp cn bng ng. Chc kim loi ch yu thc y cc phn ng hydro ha v
hydro ha, gp phn chuyn ha etylbenzen thnh cc ng phn xylen.
Theo dy chuyn ca UOP ti a ha lng p-xylen thu c h a ra mt
lot cc mu xc tc nh I-9, I-210, I-400
Dy chuyn cng ngh

Hnh 5: S cng ngh UOP Isomar [2]

14

T hp sn xut hydrocacbon thm ca UOP

Mt phn xng Isomar thng thng s lun i cng vi mt phn xng thu
hi mt hay nhiu ng xylen. V hu ht cc phn xng Isomar thng i cng vi
phn xng Parex thu hi p-xylen. Hn hp xylen nguyn liu vo phn xng Parex
c a ti thp chng ct xylen, y l b phn thit k khng nhng thu c o-xylen
y thp m cn n gin loi b c cc hydrocacbon thm C9+ p ng c cc
ch tiu nguyn liu ca phn xng Parex. Cn sn phm nh ca thp chng xylen s
c a thng vo qu trnh Parex ni m c th thu hi 97% lng p-xylen v sn xut
c p-xylen vi tinh khit 99,9%. Cn sau sn phm Raffinat ca qu trnh Parex,
cha hm lng p-xylen di 1% c a sang qu trnh Isomar.
Dng nguyn liu ca qu trnh Isomar u tin phi trn vi dng kh giu Hydro
tun hon v lun c b vo lng Hydro mt i do phn ng ca qu trnh Isomar.
Sau dng nguyn liu c gia nhit bi dng sn phm ra t thit b phn ng, tip
theo chng c bc hi trong thit b nung nng, nhit c nng ti nhit phn
ng. Dng kh nng c a vo thit b phn ng ri i qua cc lp xc tc c nh,
thit b thng dng hng trc. Dng sn phm ra khi thit b phn ng c lm lnh
khi trao i nhit vi hn hp nguyn liu u sau c a vo thit b tch sn
phm. Dng kh giu hydro s c ly ra nh ca thp tch v tun hon li thit b
phn ng. Mt phn ca dng kh c lm sch loi b phn nh ln vo trong dng
kh tun hon. Phn lng y thp tch c a n thp chng loi b cc hp
cht C7. Phn C7 nh thp ny c cng c lm lnh v a vo mt b phn tch
kh lng, phn kh c s dng lm nhin liu cn phn lng th c tun hon li qu
trnh UOP Platforming. Phn hydrocacbon C8 di y ca thp deheptan ha c x
l bng vt liu t st loi b vt tp cht, cc loi nha v polime to thnh, sau
tip tc tun hon v thp tch xylen.
Cc ch tiu nguyn liu ca qu trnh Isomar
Bng 5: Ch tiu nguyn liu ca qu trnh Isomar
Tp cht
Tc hi
Gii hn
Nc
Tng n mn, gim hot 200 ppm, max
tnh xc tc, khng ti sinh
c
Tng clo
Tng cng chc axit, tng 2 ppm, max
phn ng cracking, c th
ti sinh
Tng nit
Trung ha vng axit, gim 1 ppm, max
hot tnh xc tc, khng ti
sinh c
Tng lu hunh
Gim hot tnh chc kim 1 ppm, max
loi, tng phn ng
cracking, c th ti sinh
Ch
Lm ng c chc axit v 20 ppb, max

15

T hp sn xut hydrocacbon thm ca UOP

ng

Asen

chc kim loi, khng th

ti sinh
Lm ng c chc axit v 20 ppb, max
chc kim loi, khng th
ti sinh
Lm ng c chc axit v 2 ppb, max
chc kim loi, khng th
ti sinh

d. Phn xng Parex

UOP Parex l qu trnh s dng phng php tch vi h hp ph zeolit sng phn
t thu hi p-X t hn cc ng phn xylen. Hu ht cc qu trnh Parex ngy nay c
thit k sn xut p-X c tinh khit l 99,9 % khi lng v thu hi c trn 97 %
lng a vo.
Khng ging nh cc phng php sc k thng thng, qu trnh Parex m
phng s chuyn ng ngc chiu nhau ca lng lng nguyn liu so vi lp cht hp
ph tc c nh. Nguyn liu v sn phm vo v ra khi lp cht hp ph mt cch lin
tc vi thnh phn gn nh khng thay i. K thut ny cn i khi gi l simulated
moving-bed (MBA) lp hp ph gi chuyn ng.
Trong mt t hp sn xut hp cht thm hin i (Hnh 2), Phn xng Parex
thng nm di thp tch xylen v thng i cng vi phn xng Isomar. Nguyn liu
ca thp tch xylen cha sn phm hydrocacbon thm C8+ t qu trnh CCR*
Platforming cng vi sn phm t phn xng Tatoray. Phn C8 t nh ca thp tch
xylen c a thng ti phn xng Parex, ni m p-xylen c tinh khit cao c
thu hi. Phn Raffinat ca qu trnh Parex sau c a sang phn xng Isomar, ni
m cc ng phn C8 c chuyn ha thm thnh p-xylen v li tun hon v thp
chng tch xylen.
Trc khi qu trnh Parex c bin n, p-xylen ch yu ch c sn xut bng
phng php kt tinh phn on. Trong phng php kt tinh, hn hp xylen c lm
lnh xung khong -750C (-1000F) ti im m p-xylen bt u kt tinh. Cc tinh th
c tch ra khi nc ci bng my lc ly tm hay tch lc thng thng. Sau sn
phm s c ra bi Toluen hay chnh mt phn sn phm p-xylen. Nhng khong
khng lu sau , nm 1971 cng ngh UOP Parex nhanh chng tr thnh cng ngh
c la chn nht sn xut p-xylen. V t thi im hu nh tt c cc dy
chuyn sn xut p-xylen da trn cng ngh UOP Parex. Li th chnh ca qu trnh
Parex so vi phng php kt tinh l kh nng thu hi trn 97% lng p-xylen a vo.
Cn cc phng php kt tinh cha cc hn hp -tec-tc nn lng p-xylen thu hi c
ch t khong 65%.
nh gi nguyn liu

16

T hp sn xut hydrocacbon thm ca UOP

Hu ht hn hp xylen c s dng sn xut xylen c sn xut t naphta
du m bi qu trnh reforming xc tc. Cng ngh UOP CCR Platforming hot ng
iu kin cc k kht khe nn trong thnh phn C8+ ca phn Reformat hu nh khng
cha cc tp cht khng thm. Nh cc ng phn hydrocacbon thm C8 c th a
trc tip vo t hp thu hi xylen. Nhng c trn mt na tn lng hn hp xylen c
sn xut t qu trnh chuyn ha ca toluen v hydrocacbon thm C9 trong qu trnh
Tatoray.
Cc tp cht khng thm trong nguyn liu ca qu trnh Parex ch lm tng nng
lng tiu th v chim nhiu khng gian ch khng nh hng n tinh khit ca pxylen sn phm. Nhng nguyn liu phi c tin hnh phn on trc tch hn
hp hydrocacbon thm C8 v x l bng t st bo v cht hp ph.
Bng 6: Ch tiu thnh phn nguyn liu ca qu trnh Parex [3]
Thnh phn

Ch tiu

Para Xylen min, % khi lng

18

Etyl Benzen max, % khi lng

20

Toluen max, % khi lng

0.5

Hydrocacbon C9+ max, % khi lng

1.5

Hydrocacbon khng thm max, % khi lng

0.3

Nit max, mg/kg

1.0

Lu hunh max, mg/kg

1.0

Axit

Khng c c

S dy chuyn cng ngh

17

T hp sn xut hydrocacbon thm ca UOP

Hnh 6: S cng ngh UOP Parex [3]

Cc qu trnh chia tch din ra trng cc thp hp ph. Mi thp hp ph c
chia thnh cc lp cha cht hp ph. Mi lp hp ph c gn bi mt b phn phi
c bit, mi b phn phi ny c ni chung vi mt van quay nh cc ng ni. B
phn phi gia cc lp hp ph dng a cht lng vo v rt cht lng ra khi thp,
cng nh thu hi cht lng a trn v phn phi cht lng cho a di.
Thng thng mt Phn xng Parex c 24 lp hp ph v 24 ng ni mi lp n
van quay chung. Nhng theo thc t kho st v ng gi mi Phn xng Parex c 2
thp hp ph mi thp c ch 12 lp cht hp ph. Qu trnh Parex thng c bn dng
chnh c phn phi vo trong thp hp ph bi van quay l:
Dng nguyn liu: Hn hp xylen vo
Dng trch ra: Gm c sn phm p-xylen cng vi cht nh hp ph
Dng raffinat ra: Gm c etylbenzen, m-xylen, o-xylen, v cht nh hp ph
Dng cht nh hp ph vo: Cht nh hp ph c tun hon t khu vc phn
tch.
Ti bt c thi im no cng ch c 4 ng dn hot ng a 4 dng ra v vo
thp hp ph. Van quay c s dng chuyn theo chu k v tr ca lng vo v ra
khi thp tng ng vi mi v tr c thnh phn xc nh dc theo thn thp. Mt bm
c s dng bm cht lng t y thp 1 ln nh ca thp 2 v mt bm c s
dng bm cht lng t y thp 2 nn nh thp 1. Nh vy 2 thp hp ph hot ng
nh mt thp c ln lt tun hon tng lp cht hp ph.
Dng trch t thp hp th c van quay a n thp chng tch sn phm ra
khi cht nh hp ph. Sn phm nh ca thp c a sang thp cui cng tch
loi bt c lng toluen no cn ln phi p-xylen tinh khit.

18

T hp sn xut hydrocacbon thm ca UOP

Dng raffinat tng t cng c van quay a sang thp chng tch cht nh
hp th. Sn phm nh ca thp l hn hp ng phn C8: etylbenzen; m-xylen; o-xylen
cng vi bt c hp cht thm no cn ln phi trong nguyn liu vo.
Sn phm raffinat li tip tc a sang qu trnh Isomar chuyn ha thnh p-xylen ri
li tun hon v qu trnh Parex.

Hnh 7: S cng ngh Parex kiu 1 thp hp ph [3]

Nh vy qua cc qu trnh:
La chn nguyn liu naphta
Tin hnh qu trnh reforming xc tc
Phn b li Toluen bng phn xng Tatoray
Isome ha xylen v etylbenzen trong phn xng Isomar
Tch p-xylen bng qu trnh Parex
Ta c th thu c benzene, p-xylen c tinh khit cao, c nhiu ng dng trong cng
nghip tng hp hu c ha du.

Phn 3: KT LUN

19

T hp sn xut hydrocacbon thm ca UOP

Cc ng dng quan trng v ph bin ca cc hydrocacbon thm ch yu lin
quan ti ba loi nguyn liu chnh l benzene, toluen v xylene. Tuy nhin nc ta th
vic t sn xut ra cc hydrocacbon thm, c bit l BTX cn rt hn ch. Ha hn
trong tng lai gn vi d n lc ha du Nghi Sn, Thanh Ha, chng ta s a cng
ngh sn xut ca UOP vo sn xut. V thnh cng trong vic sn xut ra cc
hydrocacbon thm thit yu phc v cho nn cng nghip ha cht nc nh.

TI LIU THAM KHO

20

T hp sn xut hydrocacbon thm ca UOP

[1] Phm Thanh Huyn, Nguyn Hng Lin. Cng ngh tng hp Hu c
Ha du
[2] Willey-VCH. ULLMANN'S Encyclopedia of Industrial Chemistry
[3] Robert Meyers. Handbook of Petroleum Refining Process
[4] http://www.uop.com/processing-solutions/refining/gasoline/#naphthareforming

21