BI TP LN CNHD - Ch bin phn on C4 cracking

BI TP LN CNG NGH HA DU

ti:
TM HIU CNG NGH CH BIN PHN
ON C4 THU T SN PHM CRACING HI
V CRACKING XC TC
Bi tiu lun gm
Gii Thiu
1. Lm giu phn on C4
2. Phng php sn xut sn phm
3. Cng ngh
4. Kt lun
Ti liu tham kho
Gio vin hng dn : Ths.Nguyn Th Linh
Nhm sinh vin thc hin : Nhm 10
Lp Lc Ha Du K52

H Ni 10-2011
Nhm 10, Lp Lc Ha Du K52 1

BI TP LN CNHD - Ch bin phn on C4 cracking

Gii thiu
Cc sn phm c sn xut t phn on C4 ca qu trnh cracking
hi v cracking xc tc t hn c tng hp t etylen v propylene. Tuy
nhin sn phm olefin C4 v diolefin C4 m u cho mt s hp cht c
nhiu ng dng nh metyl butyl ete, adiponitril, 1,4-butenol v
polybutadien.
Butadien khng ch l monome quan trng nht tng hp cao su, m
cn l hp cht trung gian vi kh nng phn ng cao sn xut nhng hp
cht c ch nh sulfolan bng phn ng vi SO2, 1-4 butandiol bng
acetoxyl ha- hydro ha, cloropren bng clo ha v hydroclo ha.
Cc hp cht nh n-buten, 1-buten, cis-2-buten v trans-2-buten thu
c t phn on olefin C4 ca qu trnh cracking xc tc v cracking hi
nc sau khi loi iso-buten. Hn hp ng phn ny c th s dng trc
tip cho phn ng chung ca 3 ng phn sn xut nhng sn phm trung
gian v nhng sn phm ging nhau. Ngoi ra hn hp ny c th tch thnh
2 dng, mt dng cha 1-buten, dng cn li cha hn hp cis v trans-2
-buten. Mi dng c s dng sn sut hp cht ha hc ring bit. Gn
70% 1-buten c s dng lm monome cng vi etylen sn xut
polyetylen mch thng c nht thp. Ngoi ra 1-buten cn s dng
tng hp buten oxit. Cc hng cng ngh s dng 2-buten sn xut hp
cht ha hc khc. N-buten c th ng phn ha thnh iso buten.
Tng quan v cc qu trnh cng ngh c s dng trong cng nghip
x l v ch bin cc sn phm t phn on C4 cracking c trnh by
sau y s gip chng ta c ci nhn khi qut v c tnh v gi tr ca cc
sn phm sau khi ch bin.

Nhm 10, Lp Lc Ha Du K52 2

BI TP LN CNHD - Ch bin phn on C4 cracking

1. Lm giu phn on C4
Bng 1.1. Lm giu buten t phn on C4 cracking hi v cracking xc tc

Nh trnh by bng 1.1, thnh phn phn on C4 thu c t qu

trnh cracking hi nc, cracking xc tc, c bit l olefin, m ra nhiu
kh nng phn tch v lm giu cc cht. Butadien c ng dng trong
cng nghip sn xut cc vt liu c tnh n hi trong nhiu thp k. Ty
thuc vo yu cu cng ngh sau m ngun nguyn liu phn on C4
c s dng dng th hay c butan ha, hoc hn hp ca nButen v Butan, hay l sn phm isome ha Kh nng c th m rng
qu trnh x l phn on C4 l rt cn thit nhm phn tch cc
hydrocacbon khc nhau v chuyn ha ha hc thnh cc hp cht khc.
Phng php ny ch trng ti tnh cht vt l ca thnh phn C4, c bit
l im si (im si rt gn nhau) v c a ra trong bng 1.2.
Nhm 10, Lp Lc Ha Du K52 3

BI TP LN CNHD - Ch bin phn on C4 cracking

Thnh phn
Propylen
Propan
Propadien
Propyn
Isobutan
Isobuten
1-buten
1,3-butadien
n-butan
Trans-2-buten
Cis-2-buten
Vinylacetylen
1butyn
1,2-butadien
2-butyn

im si oC

bay hi tng

Nhit kt

1.013 MPA
- 47.7
-42.1
-34.5
-23.2
-11.7
-6.9
-6.3
-4.4
-0.5
+0.9
+3.7
+5.6
+8.1
+10.9
+27.0

i 40 oC
3.15
2.65
2.95
2.0
1.2
1.02
1.00
0.99
0.87
0.85
0.79
0.82
0.70
0.6
0.35

tinh oC
-185.3
-187.7
-136.0
-102.7
-159.6
-140.4
-185.4
-108.9
-138.4
-105.6
-138.9
-125.7
-136.2
-32.2

d204
0.514
0.501
0.557
0.594
0.595
0.621
0.579
0.604
0.621
0.650
0.652
0.691

Bng 3.1 : Tnh cht vt l c bn ca thnh phn phn on C4 t

cracking hi v cracking xc tc
Do chng ct n gin khng thch hp tch cc hydrocacbon
nh 1-buten, isobuten hay butadien do cc cht ny c bay hi rt gn
nhau. Cng c th p dng phng php kt tinh, trong ton b thnh
phn khc nhau c im kt tinh gn nhau, phi s dng nhit rt thp
nn khng m bo v hiu sut ca qu trnh. Cc nh sn xut bt buc
phi thm phng n s dng hn hp cc phng php nh: chng ct hp ph v chng chit hn ch nhng vn trn do li dng c kh
nng phn ng ha hc khc nhau. S phc tp ca cng ngh ph thuc s
c mt ca thnh phn cn acetylene v diolefin trong phn ng polyme ha
ban u. To thnh hp cht keo, hot tnh v phn cc ca xc tc anh
hng n lng dung mi s dng. Chnh v vy nhng thnh phn cn
phi loi b u tin.

2. Phng php ch bin phn on C4

Nhm 10, Lp Lc Ha Du K52 4

BI TP LN CNHD - Ch bin phn on C4 cracking

Hnh 1.1 biu th s khi ca qu trnh cng ngh ph hp vi yu
cu sn phm khi s dng phng php tch. Trong khi , cht lng sn
phm ban u c quyt nh bi cng ngh.

Hnh 1.1: S khi qu trnh cng ngh ch bin phn on C4

Do vy, butadien c thu hi u tin t phn on C4 ca cracking
hi nc bng dung mi chit. thun li, ngi ta hydro ha s b c
chn lc thnh phn acetylen. Trong mt s ng dng, dung dch tinh ch
(raffinate) phi c x l tng t loi b diolefin. Khi loi butadien
bng hydro ha, c th p ng c yu cu, nu hm lm butadien thp
c th c hydro ha li s dng.
Sau khi loi b diolefin. Qu trnh tip theo l tch 1- buten v isobuten
ca phn on C4. Hai phng php c bn c s dng ph thuc vo
Nhm 10, Lp Lc Ha Du K52 5

BI TP LN CNHD - Ch bin phn on C4 cracking

mc tiu sn xut hoc p ng nhng yu cu v c tnh k thut.
Trong sn phm cn li c nhng tp cht phi x l b xung lm giu.

3. Cc cng ngh ch bin phn on C4

3.1.

Qu trnh tch isobutene

p ng nhu cu th trng, vic u tin phi lm l thu hi

isobuten tinh khit. t c mc ch ny, hin nay c 2 phng php

tin hnh.
a. Chit bng dung mi axit. y l phng php c, n c nhiu cch.
S phn tch gm 2 bc: thy phn isobuten trong phn on C4 thnh tbutanol vi s c mt ca ion H+, bc 2 l tch nc.
b. Ete ha. Cng ngh ny ngy nay c s dng nhiu hn. Cch
tin hnh cng ging nh trn. Isobuten u tin s b loi b khi phn
on C4 bng ete ha to ra metyl t- butyl ete bng methanol, sau ti sinh
bng cracking hp cht thu c.
C 2 trng hp trn, ancohol hoc ete c th c to ra t sn phm
trung gian. Trong mt s trng hp nhm loi b hay lm giu isobuten
thun li hn vic thu hi n. Vi mc ch , phng php th 3 xut
hin, thc hin oligome ha c chn lc, phn ng ny c ng dng ln
trong xng vi tr s octan cao.
Trong gii hn no , tt c iso-buten c chuyn ha, iu kin thay
th bao gm 2 thp tch isobuten trn nh ca thp th 1, trong 1buten c tch nh ca thp th 2, 2-buten v cn n-butan s ly y,
hoc chng chit mi phn on sau khi thu hi.

3.2. Qu trnh tch 1-buten

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BI TP LN CNHD - Ch bin phn on C4 cracking

Tip theo l qu trnh chit hoc loi b 1-buten.
a. Thu hi. Thu hi bng hp ph gi li cc phn t.
b. Chuyn ha. Trong qu trnh ny 1-buten c isome ha hoc hydroisomer ha thnh 2-buten.
Trong c 2 trng hp, hot ng bao gm chng ct tch phn on
giu iso-buten v 2-buten tng ng nh v y. Th hai l hydro-isome
ha thnh phn cha iso-buten tinh khit. Cng ngh ny cng c th p
dng cho cn ca phn on C4 bng cch chit vi dung mi axit hay ete
ha, thu c dng giu 2-buten.

3.3. Chit butadiene t sn phm cracking hi (phn on C4)

Hin nay ngun cung cp butadiene ch yu trn th gii l x l phn
on sn phm C4 t qu trnh cracking hi nc naphtha hoc gas oil. Ring
M ngi ta dng qu trnh dehydro ha butan hoc buten l ch yu, mc
d phng php ang t s dng dn. Nm 1980 n chim gn mt na
ngun cp ca th gii, so vi nm 1970 l 80% v sang nm 1990 th gim
thm 5% na.
Khu vc Bc M s dng nhng cng ngh u tin sn xut etylen,
etan, propan v n-butan. H qu ca vic la chn cng ngh ny l cc
ng sn phm ca butadiene khng p ng yu cu, do cn phi s
dng cng ngh sn xut khc. V sau, vic la chn cng ngh ny sn
xut v sn phm kh ha lng ca cc quc gia c xu hng gim dn. iu
chng t khng th p ng nhu cu khi s dng ngun nguyn liu
ethylene, dn n vic s dng cc sn phm naphtha v GO, sn phm t
qu trnh cracking hi, cung cp khong 4% trng lng nguyn liu
ca butadien, theo cch ny, lng butadien thu hi c nh mt ng sn
phm thu t phn on C4 do t tn km hn so vi sn xut bng cch
kh n-butan hoc n- butenes.

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BI TP LN CNHD - Ch bin phn on C4 cracking

3.3.1. Tnh cht ha l ca butadien c tch t phn on
C4 thu t sn phm cracking hi
Nh trnh by trong bng 2.1, cc c im k thut c tnh thng
mi cho butadien hon ton khc bit vi cc thnh phn cn li, c bit
lin quan n dn xut ca axetylen, s c mt ca n trong phn on ban
u t 0.5 n 0.7 % khi lng b loi b trc .
Bng 2.1

Phng php tch phc tp c s dng nhm t mc tinh khit

cao trong cng nghip, bao gm:
a) Chit bng dung dch mui ng amoni.
b) Chng- trch ly.
Qu trnh chit li dng tnh nng ca ng amoni acetat to thnh
mt phc cht c tnh chn lc vi butadien, c u tin gi li trong dung
dch mui ng, s hp th buten t hn t 10 n 50 ln. Mt khc, hp
cht axetylen l cc hp cht to phc u tin v n xy ra thun li hn.
Hiu qu ca phng php ny ph thuc rt nhiu vo nng ca
acetylen trong nguyn liu, trong thc t khng c vt qu 500 ppm.
Tuy nhin, C4 (cracking hi) khng p ng trc tip c im k thut
ny, v s hydro ha trc khi la chn l khng th thiu. Yu cu ny gii
thch ti sao, ngay t u k thut hydro ha khng hiu qu. Lng
butadiene thu hi c ch pht trin gn vi cc thit b cho qu trnh
hydo ha n-butan v n-buten.
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BI TP LN CNHD - Ch bin phn on C4 cracking

a)
b)
c)
d)
e)

Cc dung mi c s dng trong chng - trch ly phi kt hp mt s c

tnh tng t nh nhng yu cu ca qu trnh tch cc hydrocacbon thm.
Do , cc cht phi th hin tt c cc thuc tnh sau :
c tnh chn lc cc diolefin: tri ngc i vi cc hp cht acetylen v
olefin; l kh nng tt tng s khc bit trong bay hi tng i gia
cc thnh phn trong phn on c x l.
Dung mi c nng lng cao: cng sut ny gim trong hu ht cc tc nhn
chit, i vi cc hydrocarbon c cha cng s nguyn t carbon, khi i t
dn xut acetyn-dien, v sau l olefin.
Tng i d thc hin: nht thp, im si khc bit vi butadien,
khng c s hnh thnh hn hp ng ph hoc phn ng ha hc vi cc
thnh phn ca hn hp.
S dng n nh trong cc iu kin: dung mi phi th hin kh nng chu
nhit, n mn thp, kh chy v phi hon ton c th trn ln vi nc.
Gi c khng t qu.
Kt qu la chn mt dung mi trong cng nghip t mi lin quan gia cc
tnh cht khc nhau v ti u ha kinh t ca cng ngh c s dng cho
qu trnh.

Bng 2.2 Lit k mt s tnh cht vt l ca butadien s dng ch yu trong

cng nghip.
3.3.2. Qu trnh tch butadien t phn on C4 ca cracking hi
trong cng nghip
A. Hydro ha c chn lc cc hp cht acetylen trong nguyn liu.

Nhm 10, Lp Lc Ha Du K52 9

BI TP LN CNHD - Ch bin phn on C4 cracking

Hot ng ny cn thit tch butadien c trong phn on
C4 cracking hi bi tnh nng ca ng amoni, v khng cn
thit trong trng hp chng-trch ly.
Trong trng hp ny, s hydro ha trc khi ch bin s ci thin ng
k iu kin hot ng ca qu trnh tch sau , v nng cao t l hon
thin ca phn ng trng hp butadien.iu ny dn n s gim ng k
nng cc hp cht ny trong dung dch sau khi chit, ng thi chi ph
nng lng cng gim theo.
S cng ngh u tin bao gm qu trnh loi b nc t do t phn
on C4 trong mt b kt t, v b sung dng kh giu hydro, dng kt
hp c dn ti l phn ng, hot ng trong pha cht lng, di p sut
0.5 1 MPa, trong khong 10 60 oC. Thit b ny s dng cht xc tc
Platin kim loi trn nn xc tc c nh. Nhit ca phn ng c ly
ra bng cch bay hi mt phn kh trong phn ng hoc s dng mt
cun ng lm mt bng dng propylen tun hon. Sau khi lm mt thit b,
dng propylen c ha hi, nhm thu hi mt phn hydro cha chuyn
ha, sau c nn ti p sut l phn ng.
Nu qu trnh ny p dng cho c dng phn on C4 mi v dng tho
ra giu hydrocarbon acetylen tun hon li t qu trnh sn xut bi cc qu
trnh tch sau , h s thu hi butadien t cc ngun nguyn liu ban u
vt trn 99%. Bn quyn cng ngh bi BASF (Basdische Anilin v Soda
Fabrik). Bayer, Dow, Engelhard v IFP (Institut Francais du Perrole). Cng
ngh Dow c iu kin hot ng (phn ng trong pha hi, 200 oC, xc tc
palladium/ng). Chu k ngn khong 24 gi, v thu sn lng butadien
cao.
B. Chit bng mui ng amoni
K thut ny c xy dng ti Hoa K trong Chin tranh th gii th
hai, c s dng ch yu bi hng Esso Research and Engineering, ch
yu thu sn phm butadien bng s kh n-buten hoc n-butan hoc c hai.
Qu trnh trong cng nghip c tin hnh theo cc giai on sau y:
a) Hp th s b acetylen bng dung dch ng ammoni acetate 20% khi
lng, qu trnh gii hp bng cch un nng dng butadien dn vo 65
o
C, sau c tun hon li, tip theo l qu trnh gii hp cc hp cht
acetylen bng cch tng nhit ln 90 oC.
Nhm 10, Lp Lc Ha Du K52 10

BI TP LN CNHD - Ch bin phn on C4 cracking

b) S dng cc my trn v b lng, hot ng trong dng i lu, khong
20 - 50 oC, t 0,3 - 0.4 MPa, butadien c hp th v lm giu bng amoni
bng phng php tip xc lng lng.
c) Gii hp butadien bng cch nung nng khong 80oC, 0.12 MPa.
d) Thu hi amoni b cun theo nc ra butadien v tinh ch trc khi n c
tun hon bng cch chng ct dung dch thu c.
e) Tinh ch bng cch chng ct vi s c mt ca cht ci to butadien (tbutylpyro-catechol).
C. Chng trch ly
Theo nguyn tc, quy trnh cng ngh trong cng nghip s dng c
phng php ny tch butadien da trn c s c trnh by trong s
cng ngh, bao gm cc bc ch yu sau y :
a) Chng trch ly mt hoc hai giai on, trong tt c cc hp cht
acetylen v butadien c chit ra: nu qu trnh c thc hin qua hai
giai on, buten c tch ra u tin, trong khi cc hp cht acetylen
c loi b giai on hai.
b) Thu hi dung mi s dng trong cc hot ng ny bng cch ha hi.
c) Chng ct phn on hn hp sau khi trch ly, loi b tp cht acetylen
v buten, p ng cc thng s k thut cn thit.
d) Nc lm sch ngho butadiene s dng thu hi dung mi b loi b.
Nhng hng u tin s dng cng ngh ny l:
a. Shell
Hng Shell u tin s dng aceton lm dung mi trch ly, sau
thay th n bng acetonitrile (1956).
b. Phillips
Phillips l hng u tin tin hnh chng trch ly trn quy m cng
nghip vo khong nm 1940, bng cch s dng furfural lm dung mi,
mt s ci tin c thc hin trong nhng nm 1960. Qu trnh ny c mt
giai on chit xut - ti sinh dung mi v mt giai on tinh ch.
c. Nippon Zeon

Nhm 10, Lp Lc Ha Du K52 11

BI TP LN CNHD - Ch bin phn on C4 cracking

Trong cng ngh tch butadiene ca Nippon Zeon, hng s dng
dimethylformamide lm dung mi, cc phn xng cng ngh u tin i
vo hot ng vo nm 1965.

Hnh 2.2: Tch butadiene t phn on C4 cracking. Cng ngh s

dng dymetylfocman ca Nippon Zeon.
Nhn chung, s cng ngh (hnh 2.2) gm hai giai on chit xut
ti sinh ni tip nhau, vi giai on trung gian nn dng kh thot ra. Trc
khi vo nh thp chng trch ly, phn on C4 c gia nhit v bay hi
khong 500oC bng cch trao i nhit vi dng dung mi nng tun hon.
Thp hot ng vi khong 200 a, gia 45 - 1150 oC t 0,5 - 0.7 MPa,
dng dung mi i vo thp t trn xung. Phn hi nh ch yu bao gm:
C3, butan v buten, sau khi lm lnh ngng t - hi lu, phn ch yu c
chuyn ti phn xng tinh ch C4. Dng trch ly giu butadien chuyn n
thp u tin hot ng ti sinh vi khong 15 a, gia 45 160 oC, p sut
0,11 0.14 Mpa. Sn phm ngng t mt phn, pha hi gm ch yu
butadien c nn li 0.5 MPa v c chuyn ti thp chng trch ly th
Nhm 10, Lp Lc Ha Du K52 12

BI TP LN CNHD - Ch bin phn on C4 cracking

hai, thp chng trch ly ny c khong 60 a v hot ng gia 45 180 oC.
Cc hp cht acetylen c chit bi dung mi, sau c ti sinh trong
iu kin tng t. Butadien thu hi pha trn vn cn cha
methylacetylen v cc tp cht nng. N c tinh ch bng cch chng ct
n gin trong hai thp. Thp chng phn nh (30 a) v thp th hai chng
phn nng (90 a), trong s c mt ca t-butylpyrocatechol (100 ppm) lm
cht c ch qu trnh oxy ha. Dimethyfomaide loi b di y hai thp
ti sinh c lm lnh v tun hon li. Dung mi ny c tinh ch mt
phn chng ct nc v polybutadien.
d. BASF / Lurgi
Cng ngh BASF Lurgi c a vo cng nghip t nm 1968 v s
dng N-methylpyrrolidone lm dung mi, y cng l mt trong nhng cng
ngh ph bin nht hin nay. N tng t nh trong nguyn l ca hnh 2.3,
qu trnh u tin l giai on trch ly ti sinh c chia thnh tng khu
vc :
Khu vc hp th, trong cc hp cht acetylen, butadien v mt
hm lng nht nh buten c chit t nguyn liu trong dng i lu
lng kh c x l bng N-methpyrrolidone, c cha khong 8% khi
lng nc. Qu trnh c thc hin trong iu kin thp cha 80 a hot
ng gia 45 55 oC, t 0.4 0.6 MPa. u tin dng nguyn liu c ha
hi bng cch trao i nhit vi dng dung mi hi lu nng v c a
vo y thp. N-methylpyrrolidone c a vo pha nh, ni cc cht
kh khng b hp thu, ch yu l butan v buten, ri khi cc thp. Cc
buten, c cha butadien, c tr li thp hp th.
Qu trnh tinh ct: khu vc tinh ct sn phm, phn buten ha tan
c chuyn t dung mi trong dng i lu cng vi hi butadien, thu
c bng cch ngng
t
dng
chit
ra. Dng
buten
c
cha butadien, c quay li khu vc hp th. Dng ph c xy dng
mc m hm lng olefin trn thc t bng khng, hm lng axetylen
thp v hm lng 1,3 butadien l ti a. Qu trnh tch din ra trong mt
thp khong 45a hot ng khong 75oC v 0.7 MPa.

Nhm 10, Lp Lc Ha Du K52 13

BI TP LN CNHD - Ch bin phn on C4 cracking

Hnh 2.3: Cng ngh BASF tch butadien t phn on C4 cracking s

dng dung mi hp th N-metylpirollidone.
Khu vc ti sinh, trong dng lng chit c a ra t khu tinh ct,
trc tin loi b buten cn li bng cch gia nhit, gim p v chi bay hi.
Sau c tch ra lin tip trong qu trnh hot ng sau:
(a) pha y, dung mi c tun hon li khu vc hp th, sau khi
tinh ch mt phn.
(b) Dng ph thot ra giu acetylen, 1,2- butadien v hydrocarbon C5.
(c) nh thp, dng 1,3-butadien dng kh quay li thp tinh ct sau khi
qua my nn.
Qu trnh ch bin c thc hin vi ba tng cht hp ph trong thp
hot ng 45oC pha trn nh v 150oC y, v di p sut thp ( 0,2
MPa). Quy trnh ny gip trnh s hnh thnh polyme do tng nhit qu
mc, nhng i hi dng kh thot ra phi c nn li khi tun hon.
Qu trnh b sung bao gm cc hot ng sau:

Nhm 10, Lp Lc Ha Du K52 14

BI TP LN CNHD - Ch bin phn on C4 cracking

(a) S hp th - tinh ch dng thot khi khu vc tinh ct. u tin hot ng
ny u tin ha tan cc cc hp cht acetylen. Sau chng trch ly trong
s c mt ca N-methylpirrolidone, c thc hin trong mt thp vi
khong 70 a, hot ng mc 45 oC v 0.5 MPa. Lng chit ra sau khi
thu hi c chuyn ti khu vc tinh ct, butadien thu c trn nh
khng b hp thu. Sau khi loi b cc tp cht, sn phm chng ct ny vn
cn cha methylacetylene, 1,2-butadien v hydrocacbon nng s c x l
phn nh bng chng n gin trong hai thp (70 a) v (80 a).
(b) Dung mi thu hi t dng thi giu acetylen s ri khi khu vc ti sinh sau
khi ra bng nc, tch kh thu hi dung dch N-methylpyrrolidone.
e. Union Carbide
Nh my bt u hot ng nm 1965. Qu trnh s dng
dimethylacetamide c cha (10% khi lng nc) lm dung mi. Trong
phin bn mi nht ca hng, cng ngh ch c duy nht mt giai on hp
th - ti sinh.
u tin nguyn liu phn on C4 c x l trong dng chy ngc
ca dung mi trong mt thp chng trch ly vi khong 90 a, hot ng
gia 45 70oC, 0,5 - 0,6 MPa. Buten v butan khng b hp th ra nh.
Dng chit sau khi ha hi gii phng olefin ha tan v sau khi nn li
c tr li thp chng - trch ly. Phn lng giu butadien v aetylen c
gia nhit v chuyn ti thp ti sinh c 20 a hot ng vo khong 0,2
MPa, 90 oC nh v 150 oC y. Dung mi c tun hon sau khi
tinh ch nu cn thit, sn phm chng ct c ngng t mt phn, mt
phn lng c hi lu, pha kh c nn v mt phn quay tr li thp hp
th. Butadien th cn li c loi b methylacetylene v cc hp cht nng
hn trong hai thp chng ct n gin, vi khong 40 v 100 a tng ng
vi s c mt ca t-butylpyrocatechol.

Bng d liu qu trnh hydro ha chn lc phn on C4 v trch ly

butadiene (theo iu kin ca Php, 1986).
Nhm 10, Lp Lc Ha Du K52 15

BI TP LN CNHD - Ch bin phn on C4 cracking

Cng ngh

Dung mi s dng

Nng sut sn phm (t

/ nm

hydro
ha
chn lc
acetylen

BASF/

Phillips
( ci
tin)

Unlon
Carbide

Nippon
Zeon

Shell

lurgi

acetonitrile

N-methylPirrolidone

furfural

Dimethylacetimide

Dimethylfomamide

100,000

50.000

50.000

50.000

50.000

50.000

11,4

11,6

15,5

12,1

Gi tr u t (triu
USD)

0,5

u t ban u (triu
USD)

0,05

12,5

0,1
_
1
_
_
0,5

2,5
250
235
0,2
1,200
0,9

5,4
3,5
240
0,25
1,700
0,9

2,5
120
255
0,25
1,400
0,9

1,7
280
220
0,20
2,800
0,9

2,2
260
150
0,20
1,700
0,9

S ngi vn hnh

Lng butadiene thu

hi (%)

97.5

97

98

98

97

Lng tiu th /mi

tn nguyn liu hoc
butadien
Hi nc
in nng (kwh)
Nc lm lnh (m3)
Dung mi (kg)
n gi (USD)
Ha cht (USD)

3.4. Tch olefin t phn on C4 cracking hi v cracking xc

tc
Qu trnh chit tch v chuyn ha iso-buten v 1-buten nhm cung cp
cc sn phm p ng yu cu th trng, yu cu ngy cng cao tinh
khit ph hp i hi cng ngh, to iu kin thun li cho qu trnh
phn tch cc thnh phn sau .
3.4.1.

Chun b nguyn liu

Phn on C4 t qu trnh cracking xc tc c cha rt t butadien v

acetylen. Do c th s dng trc tip lm nguyn liu cho qu trnh tch
Nhm 10, Lp Lc Ha Du K52 16

BI TP LN CNHD - Ch bin phn on C4 cracking

iso-buten, nhng yu cu hydro ha trc thu c 1-butene. Ngc li,
dng C4 t cracking hi phi tri qua h thng x l trc khi hydro ha.
iu ny l cn thit loi b cc hp cht gy ra s ta nhit cao dn ti
s polime ha, v c ch hot ng ca h thng xc tc, dung mi v cc
cht hp ph c s dng trong cc cng ngh sn xut C4 olefin khc
nhau.
Hai qu trnh hidrotreating c th c s dng hoc khng s dng nhm
ph hp vi nguyn liu t cracking hi hay dng loi butandien :
a) i vi dng loi butadien, thc hin qu trnh hydro ha chn lc i
khi cn thit trc khi tin hnh hot ng. Nhit v p sut s
chuyn ha to iu kin cho isome ha 1-butene thnh 2-butene. Tuy
nhin, nu -olefin to thnh mt trong nhng sn phm , n cn thit
hn ch phn ng ph. iu ny t c bng cch iu chnh cc thng
s vn hnh v bng cch thay i thit k ca phn xng trong thc t,
s cng ngh bao gm qu trnh loi nc t do t nguyn liu bng
cch cho qua mt b kt t, hn hp sau c gia nhit v a vo l
phn ng hot ng khong 40 - 60 oC, p sut 0,5 - 1 MPa, trong s c
mt ca mt thm xc tc palatin c nh. Sau khi lm lnh, cc kh cn li
c phn tch thit b bay hi. Nu sn phm chnh cui cng l 1butene, cc cht xc tc palladium c b sung cc kim loi khc, nhm
hn ch to thnh ng phn 2-buten. Bi s chuyn ha din ra nhanh
chng vi cc h thng palladium thng thng. Bn quyn cng ngh ca
hng Huis (c k thut c cp php bi UOP) v IFP.
b) Trong trng hp th hai, trn c s l thuyt, butadien c hm lng
ng k, hot ng c th c tin hnh trong pha hn hp v c pha
long vi dng sn phm tun hon, khong 60 - 80oC, p sut 0,5-1,1
MPa, trong s c mt ca thm xc tc Palatin c nh. Nu cn thit, mt
l phn ng kt thc c th c s dng loi b cc vt butadien v
acetylen.
Bng 3.6 ch ra cc mc hiu sut thu c vi qu trnh hydro ha trc
khi ch bin.

Nhm 10, Lp Lc Ha Du K52 17

BI TP LN CNHD - Ch bin phn on C4 cracking

3.4.2. Tch iso-buten

Theo th t, u tin tin hnh chit hay chuyn ha iso-buten cha
trong nguyn liu phn on C4, c hai phng php s dng trong cng
nghip :
(a) Hydrat ha
(b) Ete ha
Cc phng php tch khc cng c pht trin. Do , Hng Hoechst
xut este ha thng qua t-butylacetat, v hng Union Carbide
xut hp ph trn ry phn t. Isome ha butene, hydro ha isobutane, v
hydrat ha t-butyl ancohol (ARCO) cung cp b sung cho phng php
tng hp isobutene.

A.

Hydrat ha

Cng ngh s dng 1-butanol thc hin hydrat ha iso-buten trong mi

trng axit theo phn ng ta nhit sau y :
Tip theo l hydrat alcohol hnh thnh, thu sn phm i tinh ch.
Trn c s s n nh ca cc ion carboni bc ba so vi cc ion bc hai
v bc mt, thc hin chuyn ha c chn lc cc isobuten trong hn hp
phn on C4. S chn lc ny ph thuc nhiu vo nng axit v nhit
, gim khi iu kin hot ng khc nghit hn. Phn ng polime ha thu
c hnh thnh dime trong mt s cc sn phm khc. Trong mt s trng
hp, sn phm ph c khai thc nhm ng dng trong dung mi v xng.
Tuy nhin, hp cht dime c duy tr mc di 5% khi lng. Hn
na, ng hc ca phn ng chuyn ha isobuten ph thuc vo tnh tan ca
Nhm 10, Lp Lc Ha Du K52 18

BI TP LN CNHD - Ch bin phn on C4 cracking

n trong pha nc, v tan ca cc olefin khc nhau tng ng vi hm
lng t-butanol. Tuy nhin, phn ng phn hy th ngc li, phi hn ch
ti a nng ancohol. trnh phn ng trng hp xy ra, hm lng
acetylen v butadien trong nguyn liu khng c vt qu 1% khi lng.
Trong quy m cng nghip, hai phng php chnh c phn bit theo loi
axit s dng (qu trnh hydrat ha din ra trong mi trng axit sulfutic hoc
hydrochloric).
Trong cng ngh hydrat ha mi trng axit sulfuric, hot ng c
thc hin trong s c mt ca axit sulfuric m c. iu ny lm gim hiu
sut, bi hnh thnh sunfat v polyme. V sau, nng axit gim t 60 65% khi lng ( cng ngh ca hng Esso, Petrotex vv ...), nhng nng
sut vn thp v tinh khit ca sn phm khng qu 96 % khi lng.
Cng ngh c pht trin bng cch s dng t 40 - 45% khi
lng dung dch v hot ng nhit thp (CFR, BASF ...), vi hiu sut
90 - 95% v sn phm tinh khit ti 99%. Trong thc t, n c chng
minh rng, 30oC, v vi dung dch 45%khi lng axit sulfuric, hydrat ha
isobutene xy ra nhanh hn 1500 ln so vi n-buten, v nhanh hn 300 ln
so vi 1,3-butadien.
Cng ngh CFR (hnh 3.4) in hnh cho qu trnh ny c xy dng
Grangemouth ( Hoa K) vo nm 1963 gm ba giai on:
a) Khu vc hp th: c thc hin trong ba thp hp th v bnh tch.
Nguyn liu chy ngc vi dung dch 50% khi lng axit sulfuric,
nhit khong 50 oC, t 0,4 - 0,5 Mpa. Pha hydrocarbon (cht lng
tinh ch) c ra bng nc v c chuyn ti phn xng tip theo.
b) Khu vc Ti Sinh: pha nc sau khi trch ly u tin c ha hi di
p sut chn khng loi b cc hydrocacbon. Pha ny di dng
sunfat thy phn mt phn vi t-butyl ancohol. N c chuyn n mt
thp ti sinh thc hin ba chc nng, pha long axit, phc hi isobuten v
lm giu axit khong 120 oC.
c) Khu vc tinh ch sn phm: dng kh thi t thp ti sinh c cha
isobuten to thnh, khng th chuyn ha Ancohol, polyme v nc.
N c ra bng dung dch kim ngng t polyme, mt phn ca tbutanol cn li v isobuten thu hi sau khi lm lnh, v sau tch ra
bng cch chng ct. t-butyl ancohol c chng ct ng ph trong hn
hp vi nc v tun hon li ti sinh. Bng cch ny, t 87 - 93%
dng nguyn liu isobuten b thu hi vi tinh khit t 99 99.8%, v
5% sn phm ph polyme c th s dng trong GO.
Nhm 10, Lp Lc Ha Du K52 19

BI TP LN CNHD - Ch bin phn on C4 cracking

B. S Ete ha
Metyl tert Butyl Ete ( MTBE ) c iu ch bi s cng metanol vo
Isobutan trong phn on C4, y l hp cht quan trng bi tnh chng
kch n ca n, MTBE cho php ci thin cht lng ca xng thng mi,
c th a gin tip metanol vo trong . y cng l mt khu trung gian
rt quan trng trong cng nghip ha du. Cho n nay qu trnh bt u
dn n s ti sinh ca Olefin vi tinh khit mc cao .Bi v qu
trnh chuyn ha iso-buten c m bo gn nh hon ton, S Ete ha to
iu kin cho vic phn tch phn on C4 cn li sau . Do qu trnh
c thc hin qua 2 giai on :
a ) Tng hp v tinh ch MTBE
b) Cracking MTBE v tinh ch Isobuten

a. iu ch MTBE

Nhm 10, Lp Lc Ha Du K52 20

BI TP LN CNHD - Ch bin phn on C4 cracking

S Ete ha isobuten trong phn on C4 c thc hin theo phng trnh
cn bng di y :

Phn ng c thc hin trong pha lng gia 50 - 80 C, ti 0.7 - 1.5

MPa, ty thuc vo tng qu trnh ring bit. Xc tc s dng l nha trao
i ion DOWEX 50 W, Amberlite IR 1 or IR 100, Nalcite MX poly axit
c hot ha bng kim loi. u l phn ng, t l phn mol gia
metanol vi Isobuten khong 1.15/1 n 1.1/1. V WHSV (tc np liu)
khong chng 10 n 15 h-1. Hnh thnh nn cc sn phm chnh l
diisobuten v t-butyl ancohol. Cc sn phm c gii hn bng vic
iu chnh nhit giai on u tin, v lng dung mi nc ca phn
ng ti giai on 2. Vng i ca cht xc tc l 1 nm.
Nguyn liu cung cp cho nh my sn xut MTBE bao gm phn on
C4 tho ra t cracking xc tc, cracking hi, hoc hn hp. chuyn ha 1
ln ca iso-buten cao, tuy nhin n ph thuc vo thnh phn ca nguyn
liu s dng. Trong trng hp phn on C4 c ly t cracking xc tc,
lng isobuten khng vt qu 17-18 % khi lng, chuyn ha
tng i cao 93-94 %. Vi crack hi, nng Isobuten sau khi butadien
l 43-45 % khi lng, chuyn ha thp nht l 96 %, thm ch ti 98%.
Nu mc ch iu ch 1-Buten, c th loi b gn nh hon ton
isobuten bng cch tng chuyn ha ln 99,9% s dng qu trnh Ete ha
hai ln. Bn quyn cng ngh sn xut MTBE bi cc hng: ANJC, ARCO,
UOP, IFP, Shell, Sohio, Suntech, Texaco V nguyn tc hot ng, mi
hng ging nhau v thit k cn bn. Bao gm 3 bc : Tng hp ete, phn
tch n, x l phn on C4 d ( sn phm tinh ch ). Chng c s khc
nhau trong thit k ca khu vc phn ng :

Tng hp MTBE : Nguyn liu phn on C4, dng b sung v tun hon
metanol c a cng mt lc vo trong vng phn ng. Hn hp ny
c lm nng s b bng cch trao i nhit vi dng Ete ra. Qu trnh i
hi mt hay nhiu thit phn ng, cht xc tc phn tn trong h nhiu ng
( ALCO ), hay dng nn c nh (ANIC, Suntech ), hay ( IFP ). Dng tun

Nhm 10, Lp Lc Ha Du K52 21

BI TP LN CNHD - Ch bin phn on C4 cracking

hon pha ngoi l cht lng trao i nhit vi cc ng loi b nhit gii
phng bi phn ng s s dng sn xut hi nc. Nguyn liu c lm
lnh v sau chuyn n l phn ng. Hu ht cc qu trnh hot ng vi
mt dng chy xung, nhng s dng c nn xc tc m rng (IFP)
yu cu phi c mt dng chy ln. Bng cch li dng s bay hi mt phn
ca dung mi, ngn chn s gia tng s nhim nn cht xc tc bi cn v
bi. S kt hp mt s l phn ng trong cng ngh, nhm thu c
chuyn ha cui cng ca Isobuten, c th t c bng cc h thng khc
nhau. Bao gm c loi nhiu ng v l phn ng nn xc tc c nh
(HULS), xc tc m rng v l phn ng nn c nh ( IFP ).
S tch MTBE: Trong thc tin, phn on ny ch c mt thp chng ct,
hot ng di p sut kh quyn v s dng nc ngng lm lnh, n tch
MTBE y, v Metanol v phn khng chuyn ha ca C4 ra nh. Bi
v hnh thnh hn hp ng ph cc hydrocacbon vi ancohol c im si
thp hn s hnh thnh hn hp ng ph Metanol v Ete. Sau c im
si 51,6C ti 0.1 MPa thnh phn khi lng tng thnh phn ca n l 14
v 86 % ( 30 70 C ti 0.8 MPa ).
X l sn phm tinh ch: phn on ny bao gm hai giai on: ra sn
phm tinh ch bi nc loi b cc metanol, tip theo l phn on trn
Nc/Metanol. Ancohol thu hi bng cch cho tun hon li l phn ng.
Hnh 3.5 minh ha s cng ngh chng ct s dng xc tc m rng IFP.

Nhm 10, Lp Lc Ha Du K52 22

BI TP LN CNHD - Ch bin phn on C4 cracking

b.Cracking MTBE
Nh my cng nghip c thit k cho hot ng ny vn cha c
xy dng. Cc hot ng c thc hin ng vai tr lm ni bt cc c
im chnh ca cng ngh ny da trn cc phn ng cracking di y :

l qu trnh thu nhit, phn ng xy ra trong pha kh khong 150

300 C ( Tt nht l 275C ), p sut thp nht c th. Nhng thu
hi li Isobuten trong pha lng sau qu trnh lm lnh bng nc, l khong
0.6 MPa. trnh phn ng hydro ha, hot ng c tin hnh vi s
c mt ca hi nc, vi mt t l phn mol c trng ca H20/MTBE ti
u vo l phn ng l 5/1. Nh trong qu trnh cracking hi nc ca cc
HC, qu trnh ny nhm mc ch lm gim mt phn p sut ca cc thnh
phn, to iu kin thun li cho vic iu ch ca Isobuten v Metanol.

Nhm 10, Lp Lc Ha Du K52 23

BI TP LN CNHD - Ch bin phn on C4 cracking

Phn ng c din ra vi s c mt ca cht xc tc axit. Xc tc
c xut bao gm nha DOW 50X 12, axit polyphotphoric, c cht rn
hay cht khong kt ta Kieselguhr, oxit metallic hay Nhm oxit vi din
tch b mt ring l 200 m2/g. Cc h thng ny hot ng vi VHSV gn
bng. chuyn ha qua 1 ln cao t 95 n 98% v chn lc trn 99.9
% vi n-butane v t ti 94 % vi methanol. Chng hn nh x l MTBE
hi lu, nhng hn hp sn phm ng ph c th so snh nhit si vi
methanol v nc. Tuy nhin s chuyn ha khng vt qu 65%, hot ng
ny tr nn khng cn thit. Trong trng hp ny nhit cng c th thp
hn (=150oC).
Nhng sn phm nh chnh ca qu trnh Cracking MTBE l cc
dimethyl khng mu, c th thu c chng t qu trnh dehydro ha
methanol, cn cc dimer v trimer ca i-butence v ru t-butyl l kt qu
ca qu trnh polyme ha v hydrat hoa cc olefin.

Nhm 10, Lp Lc Ha Du K52 24

BI TP LN CNHD - Ch bin phn on C4 cracking

S cng ngh (hnh 3.6) ca mt phn xng Cracking MTBE bao gm 3
cng on chnh.
(a) Qu trnh chuyn ha, c a sang mt l phn ng kiu trao i nhit, n
c mt dng cht lng trao i nhit pha ngoi lp v. Trong khi
nguyn liu c th l mt dng hi lu v dng hi c a vo tubin sau
khi c gia nhit. Sau khi c lm lnh, dng tho ra s c c c v
c tch thnh 2 pha lng.
(b) Qu trnh tinh ch isobuten, c th t c bng cch ra dng HC bng
nc ly ra cc thnh phn c th tan nh t-butanol, methanol sau
chng ct chui 2 thp chng ct, ti cc dimethyl khng mu, nc v
cc sn phm nng nh dime ca iso butene v ca MTBE s c tch loi
mt cch d dng.
(c) Hi lu methanol c mt ca pha nc v nc ra gii bng qu trnh c
c dn tng nng ca chng trong mt thp chng ct.
C.QU TRNH OLIGOME HA.
Mt phm vi ln ca qu trnh oligome ha c th p dng cho olefin
C4. Tuy nhin mt im u vit cn c rt ra gia cc qu trnh dng
sn xut cc olefin cao hn, c tc dng pha ng nht hoc trong mt pha
khng ng nht, trong phn 2.3.3.2 v chng ch thun li cho qu trnh gia
nhit sau .
C hai phng php c hiu qu la chon qu trnh oligome ha isobutene. Chng c thc hin mt cch ring bit bi 2 hng UOP v IFP v
c p dng trong nhng trng hp sau.
(a) Qu trnh chuyn ha mt lng ln iso-butene chng hn nh chng bao
gm c phn on C4 thu c t qu trnh Cracking xc tc hoc Cracking
hi.
(b) Qu trnh tch cc cht kt ta cha isobutene c trong nc thi ca qu
trnh Hydrat ha hoc qu trnh c ch bng methyl.
Cc cng ngh ny c vn hnh theo nguyn l ging nhau. Nguyn
liu c gia nhit, thng thng th n c c gia nhit bng cch
trao i nhit vi dng nc thi ca l phn ng. N c a vo l phn
ng pha di. Qu trnh chuyn ha din ra khi c mt ca cht xc tc
Nhm 10, Lp Lc Ha Du K52 25

BI TP LN CNHD - Ch bin phn on C4 cracking

axit v d nh axit photphoric c tm trn cht mang l silica-aluminat.
S sp xp ny c iu khin bng nhit v c tng bi chnh nhit
lng ca phn ng ta ra. Bng cch a vo gia hai dng cht lng c
thnh phn khng thay i C4. Cc iu kin thc hin: trung bnh l 120 0C
trong gii hn 50 n 2000C v p sut t 1 - 4 MPa.

Dng tho ra t l phn ng c lm lnh hi lu dng cht lng

ngui. Sau n c chng ct tch ra mt dng giu buten i ra nh
v sn phm oligome ha hnh thnh y l phn ng.
A.

Mt s phng php khc thu c iso-butene t qu trnh

phn tch C4 t nhiu ngun khc nhau.
Hng Union Carbide xut thc hin trn hp cht ry phn t tch
isobutene t cc dng phn on C4. y l qu trnh Olefin-siv, chnh l
ng qu trnh sn xut 1-butene v c a ra trc .

Nhm 10, Lp Lc Ha Du K52 26

BI TP LN CNHD - Ch bin phn on C4 cracking

Trong qu trnh lin kt vi giai on gia nhit cho dng C4, n rt
quan trng sn xut isobutene bng phng php isome ha n-butene c
trong dng tho ra. y l qu trnh hon i vi tr ca mch phn t xut
hin mt H, lng nhit ta ra ny khng ng k ( 0298= -6 kJ/mol)
trong qu trnh hnh thnh isobutene, v xy ra rt chm nhit va phi.
Do thng thng n c khng ch pha kh nhit khong 500 oC
v p sut thp (0.1 n 0.2 MPa). hn ch ti a cc phn ng ph xy
ra nhit cao v ch c qu trnh oligome ha isobutene l c th xy ra,
tuy nhin phn ng ny xy ra va phi v b pha long bi hi nc, thm
vo s thun li trong vic cung cp lng nhit u vo v nhit
trong phn ng lun c kim sot. ng thi cng phi hn ch phn ng
Cracking v s cc ha bm ln b mt cht xc tc. Qu trnh ny xy ra
khi c mt ca hn hp silicagen-alumina. chuyn ha 1 ln tng i
cao khong 30%, chn lc t 75 n 80% v thi gian lu khong 2.5
giy.
Nguyn l n gin ca qu trnh ny thuc bn quyn ca hng IFP,
SNAM, vi iu kin dng nguyn liu c x l nhit s b v un
nng hn hp nguyn liu - nc bng thit b trao i nhit. Sau hn
hp c a xung di vng phn ng c mt cht xc tc. u ra, sn
phm c lm lnh thit b lm lnh nhiu tng. Condensat c hi lu
tr li l phn ng, v vi phn on kh c nn ln th nht p sut
khong 0.6 MPa. Lng kh cn d c lm sch v pha lng ( c
nn) th c bm 1.8 MPa. tch cc hp phn nh (C3) v hp phn
nng (C5-C8) c chng ct chui hai thp chng ct. Dng C4 giu
isobutene c a n thp chit.
Gia cc phng php sn xut olefin tho lun phn 2 cc qu
trnh nh dehydro ha parafin v qu trnh tch nc ca ru th u c
tnh u vit ring u c p dng sn xut isobutene. Sau y l mt
trong nhng xut phi hp 2 phng php trn.
(a) Qu trnh dehydro isobutane c th c tng cng bi qu trnh isome ha
n-butane. Qu trnh sn xut olefin c phn tch k lng. Cn v bc
isome ha n c thc hin trong cng nghip nhit khong 150 n
Nhm 10, Lp Lc Ha Du K52 27

BI TP LN CNHD - Ch bin phn on C4 cracking

2000C v p sut 1.5 - 2.5 MPa, thc hin pha kh vi s c mt ca
Hydro v cht xc tc trn nn cht mang Alumina v Plantium.
(b) Qu trnh tch nc ca ru t-butyl, mt sn phm nh ca qu trnh sn
xut propylene oxit c thc hin bi cng ngh ca hng ARCO ng ch
bi qu trnh oxi ha hai ln isobutane v propylene.
3.4.3. Tch iso-buten
Hai phng php chnh s dng l trch ly hoc chuyn ha 1-butene. Chng
lin quan n cc hot ng sau y:
a. Hp ph trn ry phn t
b. Hydro-isome ha Olefin
A. S hp ph
Cht hp ph ry phn t c s dng l silico - alumina c cha cc
ion kim loi, vi ng knh l mao qun t 3 10 Ao, v c cu trc tng
t zeolit t nhin. Chui carbon mch thng b hp ph khi hn hp cc
hydrocarbon mch nhnh. Cc cng ngh c pht trin nh Exxon, BP
(British Petroleum), Texaco, UOP v Union Carbide, s hp ph chn lc
cc n-parafin t hn hp cc ng phn mch nhnh ca chng cng tng
t olefin mch thng t cc ng ng mch nhnh ca chng.
Cc phng php s dng trong nh my cng nghip nh qu trnh
Oefin-siv ca Union Carbide v cng ngh Sorbutene UOP.

a. Qu trnh olefin-SIV ca Union Carbide

Qu trnh ny hot ng theo chu k ngn, vi ba giai on chnh, qua
nhiu thp hp ph song song, bn trong c cha lp cht hp ph ry phn
t tng c nh, cc dng qu trnh c iu khin bi tp hp cc van t
ng.
Giai on u tin phn tch c chn lc n-buten t nguyn liu c
ha hi 100oC, 0.2 MPa, bng cch cho mt dng i qua thp hp ph.
Phn on C4 cn li giu iso-butene cng cha hydrocarbon nng hn nh
hexan, dung mi chit c s dng trong hot ng tip theo, l s di
chuyn t cc l mao qun ban u chng chim ch vo dung dch. Dng
lng chit ny c lm lnh n 40oC v c c mt phn. Cc phn chit
lng v kh c tch ra, sau c bm v nn tng ng ti 0.6 MPa,
qu trnh c thc hin bng cch chng ct n gin, dng iso-butene ra
nh v dung mi chit ra y.
Nhm 10, Lp Lc Ha Du K52 28

BI TP LN CNHD - Ch bin phn on C4 cracking

Giai on th hai gm trong cng dng chy lm sch, c gi l
dng dng, lp hp ph c np vi n-butenes, vi mt lng dung mi
chit li ko C4 t cc l m chng chim ch. Sau nhp cng vi
dng lng chit ra trc giai on mt.
Giai on cui cng tng hp ph c ra gii, s dng dng lng
chit gi li n-buten. Tng t nh trn, lng chit c lm lnh v c
c mt phn. Cc phn ct lng v kh c tch ra, v sau c bm v
nn tng ng ti 0.5 MPa, bng cch chng ct n gin, n-buten ra nh
40oC, v dung mi chit ra y.
m bo hot ng lin tc, mt lng ch ba lp cht hp ph
song song l cn thit. Trong thc t, cn b sung thit b ti sinh, bi v
phn ng ph xy ra trong qu trnh, bao gm c ng phn 1-butenes, 2butenes, dime- isobutene, v hn na, qu trnh trng hp hnh thnh cc
trn cht hp th. Do , qu trnh t chy c kim sot phi c thc
hin nh k, mi ln t 3-4 ngy, 400oC, s dng khng kh ngho oxy
(1% th tch).
Dn dn dung mi chit tch ly cc hp cht nng, phi c tinh ch
bng cch chng ct trc khi ti s dng.
Bng 3.7 cung cp cho cc thnh phn in hnh ca dng lng sau khi
chit.

Nhm 10, Lp Lc Ha Du K52 29

BI TP LN CNHD - Ch bin phn on C4 cracking

b. Cng ngh ca hng UOP

Cng ngh ny p dng x l phn on C4 v c th hn sn

xut 1-butene, l mt trong cc bin th ca nhiu cng ngh hp ph vo
cc ry phn t c gi l Sorbex v pht trin bi UOP, tch ring parafin
(Molex), olefin (Olex) v p-xylen (Palex). Qu trnh Sn xut 1-butene i
hi phi hydro ha chn lc cc hp cht butadien v acetylenic trong
nguyn liu.
K thut ny (Hnh 3.8), nghin cu chi tit hn trong kt ni vi vic
nng cp phn on C8 aromatic, c da trn vic s dng dng gi si
gia nguyn liu lng v lp hp ph. Chuyn dch ca cht rn trn thc t
do s tr gip bi h thng van, gy ra mt s thay i dn dn trong cc
vi phun v cc im thu gom ca cc dng cht lng trong li lc phn t
c t trong mt thp nhiu lp.
Nh trong trng hp ca Xylen, ti bt k thi im no v trong iu
kin trng thi n nh, mt gradient nng thit lp qua khi cht hp
ph, gia cc thnh phn nguyn liu khc nhau v dung mi chit s dng
di chuyn chng. Kh nng phn b C4 trong lp ry phn t vi chn
lc khc nhau. bng cch chng ct n gin, nhm sn xut olefin trong
Nhm 10, Lp Lc Ha Du K52 30

BI TP LN CNHD - Ch bin phn on C4 cracking

mc tinh khit (99,2%). Mt khu vc ti u cng tn ti ti sinh cc
hp cht khc trong hn hp vi cht chit tch bng cch chng ct cho
php vic ti sinh dung mi gii hp, thng thng l mt hydrocarbon vi
trng lng phn t cao hn ca cc hp cht C4 v vi mt im si khc
bit r rng.
t c s n nh tt trong cc iu kin mc hp ph ca cc
cht khc nhau, qu trnh vn hnh phi c thc hin nhit hon <
100oC) v di p lc (<2 MPa) gi tt c cc hydrocarbon trng thi
lng. Mt my bm hn hp y ca thp hp ph, tun hon n ln trn,
m bo dng chy ngc lin tc.
Qu trnh Sorbutene t c mt t l thu hi 1-butene 92%.

Hydroisomerization
Izome ha butene-1 thnh 2-butenes l c gi tr v hai nguyn nhn:
(a) i vi cc sn phm ha du, n phc v n gin ha cc phng
n phn tch tip theo ca cc thnh phn trong phn on C4.
(b) Trong lc du, sn xut cc alkylate vi ch-isobutene c tr s octane
cao hn so vi ankyl ha trc tip cc nguyn liu hydrocarbon ban u.
Th hin trong cc th trong hnh 3.9 cho thy s bin i ca thnh phn
trng thi cn bng nhit ng nh mt c trng ca nhit 0.1MPa:

B.

(a) Ch hn hp ca n-butenes.
(b) T hp ca n-butenes v isobutene.
Qu trnh khng thu nhit, thch hp nhit thp. Ngc li, s sp xp
Nhm 10, Lp Lc Ha Du K52 31

BI TP LN CNHD - Ch bin phn on C4 cracking

li cu trc theo hng hnh thnh olefin mch thng t ng phn nhnh
tng ng ca chng din ra nhit cao.
Hn na, phn on C4 c s dng c t l 1-butene khong 10 n 15%
trng lng, biu ny cng cho thy rng, t c chuyn i, cn
hot ng di 150oC. Trong thc t, hot ng c thc hin khong
100oC, trong duy tr hm lng 1-butene cn li khong 5% trng lng
trong dng thi. Tuy nhin, trong nhng iu kin ny, tc phn ng thp.
Cht xc tc c s dng tng vn tc phn ng, thng trn c s kim
loi qu (palladium, rhodium ...) trn nhm oxit, phn ng thun li hn
trong mi trng c cha Hydro. iu ny cng cho php hydro ha chn
lc cc butadien cn li, v gii thch l do ti sao vic chuyn i ny c
gi l hydro-isomerization.

Nhm 10, Lp Lc Ha Du K52 32

BI TP LN CNHD - Ch bin phn on C4 cracking

V nguyn tc, s cng ngh ca mt c s cng nghip tng t

cc qu trnh hydrotreating khc c phn tch. Nguyn liu phn on
C4 u tin phi loi nc sau nn n khong 1,5 - 2 MPa bng cch
trn vi kh giu hydro, sau lm nng trc bng cch trao i nhit vi
cc dng ra v bng hi nc. Trong mt dng downflow hoc upflow, sau
i vo cc l phn ng, hot ng trong pha trn vi mt hoc nhiu tng
xc tc. Sau khi lm mt, cc sn phm ng phn c tch kh hir d
tha.
sn xut mt phn on isobutene (90-95%), hai giai on
hydroisomerization l cn thit, c qu trnh tch trung gian hu ht 2butenes, nng cao hiu qu qu trnh chuyn ha gia on hai (Hnh 3,10).
Bng 3.9 cung cp mt tng v thnh phn ca nc thi thu c.
Ch s hu giy php chnh l Engelhard, IFP, UOP, vv, v Phillips, m
cng thc hin ng phn o ngc trong mt qu trnh hai bc, vi s
iu hnh th hai xung quanh 500oC.

Nhm 10, Lp Lc Ha Du K52 33

BI TP LN CNHD - Ch bin phn on C4 cracking

3.4.4. X l cc phn cn li ca phn on C4

Ph thuc vo phng php s dng tch isobutan hoc1- buten, v
ph hp vi nhu cu ng dng cho cc thnh phn ph ca phn on C4
ban u sn c. Cc phng php x l b sung c th a ra cc giai on
phc tp. Do c th xy ra hoc khng th, v c nguyn nhn cng ngh
v kinh t, kt hp chng trong cc trng hp chit thch hp l vn
c bn la chn cc phng php ti u.tt nhin trong thc t, mt
qu trnh tch u tin c kim tra c th s dng nh l cng c b tr
cho cc qu trnh cng ngh khc, do n c thit k phn u tin.
Nh trong hnh 3.10 qu trnh m phng chnh bao gm cc phn x l
nh sau:
(a) Tch phn on C4 sn phm thnh cc phn on ln. N bao gm
kt hp chng ct vi hp th hoc hydroisomer ha, y cc s liu kinh
t c a vo cng vi cc iu kin hot ng b sung.
(b) Cc cng ngh c bn ni tip nhau trong trng hp kt hp gia
hp th vi thy phn isobutene, v hydroisomer ha,n thu c nhiu nh
thnh phn b sung cho n hoc qua trnh thy phn v este ha. Chng ta
c th tham kho cc qu trnh x l trn v a ra cc s liu ph hp.
(c) Tip tc pht trin qu trnh tinh ch v qu trnh chng chit.
Phng n la chn u tin l ph bin nht. N bao gm 4 thp
chng ct dng ct ni tip nhau thnh tng cp, thp u c 65 a tch
Nhm 10, Lp Lc Ha Du K52 34

BI TP LN CNHD - Ch bin phn on C4 cracking

isobutan nh vi ch s hi lu l 140/1. Chng hot ng p sut 0.80.9.106 Pa. Nhit 60oC, trong trng hp ni tip th tng tn tht p sut
l nh nht do nhit ti un nh nht. thc hin iu ny, theo hng
pha hi phun t nh thp u tin vo y ca thp th 2, v s dng bm
a cht lng t thp ny tr li nh ca thp u tin. Cp thp th 2
hot ng p sut 0.7-0.8.106 Pa v nhit 60oC v mi thp c 70 a, t
s hi lu l 16/1. thu 1-buten nh vi tinh khit khong 99,5 %,
v 2-buten giu ra y, v ln tp cht chnh l n-butan.
Phng n la chn th 2 gm qu trnh chng ct n gin tch 2
phn on.
(a) nh : isobutan,1-buten, c th c isobutene cn d
(b) y : n-butan, 2-buten
bc th 2, cc olefin c tch ra t mi thp chng chit, v d s
dng dung mi furfural, aceton, acetonitril, hoc cc dung mi khc. Thp
chng chit c th chuyn ton b vo phn on ca isobutene tch
butan t buten.
y l cng ngh c bit ca Nippon Zeon sn xut polymer ha 1buten bng cng ngh GDP III, s dng dung mi dymetylformat.
Bng 3.10: X l phn on C4 bng hydro ha chn lc
Phn on ct C4 cha hm lng
butadien
Dung tch sn phm
Gii hn u t
Cht xc tc ban u
Phn trm nguyn liu tiu th
Kh hydro (kg)
Hi nc (tn)
Nng lng in (kwh)
Nc lnh (m3)
Xc tc (USD)
K thut

Nhm 10, Lp Lc Ha Du K52 35

Thp

cao

50000
0.35
0.05
0.4
0.02
1
0.5
0.3

150000
0.9
0.09
123
3
40
0.4

BI TP LN CNHD - Ch bin phn on C4 cracking

Bng 3.11: Qu trnh tch isobutan v sn phm

Bng 3.12:qu trnh tch n-butylene

Nhm 10, Lp Lc Ha Du K52 36

BI TP LN CNHD - Ch bin phn on C4 cracking

(a) thp chng chit u tin tch butan v isobutan nh.

(b) Stripping n-buten cha trong phn chit, bng ti sinh dung mi y thp
v tun hon n.
(c) Chng ct di p sut thu 2-buten nh v cc thnh phn 1-buten,
acetylene, v dienic ra y.
(d) Thp chng chit th 2, sn phm tinh lc cha 1-buten tnh khit(99.5%)
phn chit cha cc thnh phn dien,acetylene,v mt vi l 1-buten.
(e) thp stripping th 2 ti sinh v tun hon dung mi.
3.4.5. S liu kinh t
Bng 3.10, 3.1, v 3.12 cung cp cc s liu kinh t thun li cho
cng ngh la chn s hydro ha butadiene cha trong phn on C4, l
qu trnh tch v sn xut isobutene, v tp cht chnh l n-buten.
3.4.6. ng dng v sn xut
Bng 3.13 v 3.14 ch ra cch s dng, sn xut v tiu th ca butylen,
n-buten v isobutene pha Ty chu u, M v Nht Bn vo nm 1984 v
mt vi s liu vo nm 1986 cho 3 vng trn.

Nhm 10, Lp Lc Ha Du K52 37

BI TP LN CNHD - Ch bin phn on C4 cracking

Vng a l
S dng% sn phm
Nhu cu ha hc
n-buten
isobutene
Nhu cu nhin liu
akyl ha
LPG,kh poly
MTBE

Ty u
20

80

3
3
94

22
50
8
100

(% sn phm) Chng ct
Cracking xc tc
Cracking nhit
Cracking hi nc
Hn hp

Cung cp (106t/nm)
Nhu cu

Nht bn

10
10

Tng

Tng

29
12
17
71
4

86
67
100

100
82

57
2
39
2

9
7
2

100

100

4.6
4.5

13.7
13.6

Nhm 10, Lp Lc Ha Du K52 38

47
53
100
1.5
1.5

BI TP LN CNHD - Ch bin phn on C4 cracking

4. Kt lun
Cc sn phm thu c t cc qu trnh ch bin phn on C4 ch yu
nhm tn thu cc sn phm kh nh buatn, butadiene, cc ng phn ca
buten ng dng trong lnh vc ha du nhm tng hp cc ha cht c
tnh ng dng cao trong cng nghip. y l ngun nguyn liu qu cho
tng hp ha du, c pht trin bi cc cng ty hng u hot ng
trong lnh vc cng nghip du kh.
Nhn chung cc qu trnh cng ngh u hot ng trn nguyn tc kt
hp chng ct, trch ly, hp thu do da vo cc c tnh ca cc thnh
phn c trong phn on C4. Hu ht cc cng ngh u tn dng c u
im ca cc cht h tr cho cng ngh v tin hnh nhiu bc, nhiu giai
on thu cc sn phm c tinh khit cao p ng cc tiu chun k
thut v tiu chun thng mai.
Kt qu thu c sau c phn tch nh gi hiu qu ca cng
ngh, trn c s nng cp cng ngh nhm ph hp vi cc iu kin vn
hnh v dng nguyn liu s dng quy trnh hot ng n inh trong iu
kin nhit ng hc c th vi mc u t thit k cc thit b c tnh
ton cn thn. iu ny gip cc nh sn xut nh hng pht trin quy m
sn xut trong cng nghip.

TI LIU THAM KHO

1.
CHEMICAL
PROCESS
SYNTHESIS
DERIVATIVES AND MAJOR HYDROCARBON
Nhm 10, Lp Lc Ha Du K52 39

GAS

BI TP LN CNHD - Ch bin phn on C4 cracking

2.

CHEMISTRY OF PETROCHEMICAL PROCESS

Nhm 10, Lp Lc Ha Du K52 40