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MC LC

MC LC ........................................................................................................................... 1
M U ............................................................................................................................. 3
Chng 1. TNG QUAN V ISOBUTENE ...................................................................... 4
2.1. Tnh cht vt l .......................................................................................................... 4
2.2. Tnh cht ho hc ..................................................................................................... 5
2.2.1. Phn ng hydrat ho .......................................................................................... 5
2.2.2. Phn ng ete ho................................................................................................ 6
2.2.3. Tham gia phn ng cng hp ............................................................................ 6
2.2.4. Phn ng hydrofomyl ho: ................................................................................ 6
2.2.5. Phn ng Polyme ho v oligomer ho: ............................................................ 6
2.2.6. Phn ng vi (CO + H2O) ................................................................................. 7
2.2.7. Phn ng oxi ho: ............................................................................................. 7
2.2.8. Phn ng vi fomandehit: ................................................................................. 7
2.3. ng dng ca isobutylen .......................................................................................... 7
Chng 2. TNG QUAN V QU TRNH CRACKING HI ........................................ 8
2.1. Sn phm qu trnh cracking hi nc phn on C4.............................................. 8
2.2. Cc cng on ch bin phn on C4 ................................................................... 10
2.2.1. Qu trnh tch isobutene .................................................................................. 10
2.2.2. Qu trnh tch 1-buten ..................................................................................... 11
2.2.3. Chit butadiene t sn phm cracking hi (phn on C4) ............................. 11
Chng 3. PHNG PHP SN XUT ISO-BUTEN THEO PHNG PHP THY
PHN ................................................................................................................................ 13
3.1. Ngun nguyn liu.................................................................................................. 13

3.2. Cng ngh tch iso-buten t sn phm ca qu trnh cracking hi nc phn on


C4................................................................................................................................... 13
3.2.1. Hydrat ha ....................................................................................................... 14
3.2.2. S Ete ha ........................................................................................................ 16
3.3. Sn xut isobutene t cc thnh phn kh C4 khc ................................................ 21
3.3.1. Qu trnh hydro ha cc thnh phn kh C4 khc ........................................... 21
3.3.2. ng phn ha n-butane thnh isobutane ....................................................... 22
3.3.3. Dehydro ha isobutane v tch tinh ch isobutene t qu trnh dehydro ha
isobutane. ................................................................................................................... 25
KT LUN ....................................................................................................................... 27

M U
Metyl tert Butyl Ete (MTBE) l mt hp cht c s dng nhiu hin nay lm
ph gia cho xng. MTBE l hp cht c cha oxi c nhiu tnh cht ni bt nh: tr s
octan cao, bay hi thp, bn oxi ha, c nhng tnh cht tng thch tt vi xng,
khng gy nhim mi trng. Cc quc gia pht trin hin nay u s dng xng c
pha ph gia MTBE nh: M, Anh, c, Nht, Canada,
Isobutene l hp cht quan trng sn xut MTBE, Isobutene c nhiu trong
thnh phn kh C4 ca cc qu trnh cracking nhit v cracking hi nc. C nhiu
phng php tch isobutene t thnh phn kh C4 nh: Phng php thy phn,
oligomer ha, phng php hp th
Phng php tch isobutene bng qu trnh thy phn c s dng nhiu trong
cng nghip. Do , nhm nghin cu xut phng n: sn xut isobutene theo
phng php thy phn t sn phm ca qu trnh hydro ha chn lc phn on
C4 qu qu trnh cracking hi nc.

Nhm gm cc thnh vin:


1. Bi Vn Vng
2. Nguyn Thng Ti
3. Trng ng Thnh
4. Nguyn Vn Hong

Chng 1. TNG QUAN V ISOBUTENE


Isobutylen c cng thc phn t l C4H8
Khi lng phn t M =56.1080
Cng thc cu to ca isobutene :
CH3 C

CH2

CH3

Isobutene ( 2- metyl propene)


2.1. Tnh cht vt l
Isobutylen l cht kh khng mu, c th chy nhit phng .
Isobutylen tan hon ton trong ru, ete v hydrocabon, nhng t tan trong nc.
Bng 2.1. Cc tnh cht vt l ca Isobutene
Tnh cht

n v

Gi tr

Nhit nng chy(101,3 KPa)

-140

Nhit si

-6,9

Nhit ti hn

144,75

p sut ti hn

MPa

4,00

T trng ti hn

g/cm3

0,239

T trng( lng ,250C)

g/cm3

0,5879

T trng( hi ,00C)

g/cm3

2,582

p sut hi

KPa

00C

KPa

130,3

200C

KPa

257,0

400C

KPa

462,8

600C

KPa

774,3

800C

KPa

1219,0

1000C

KPa

1824,7

Nhit ho hi p sut bo ho ti

J/g

366,9

250C

J/g

394,2

J.kg-1.K-1

1589

J.kg-1.K-1

2336

KJ/mol

-16,9

KJ/mol

58,11

Ti im si
Nhit dung ring ng p 25oC khi
ktc
lng 101,3 KPa
Entanpy to thnh H0t
Entanpy t do G0t ( 25oC ; 101,3
KPa)

Nhit chy (DIN 51794)

Gii hn chy trong khng kh( 20o


C; 101,3KPa)

465

%V

1,8 - 8,8

khong nhit (82 - 120oC) p sut hi c th tnh theo cng thc:


log10P=A-B/(t+c).
trong :
-

P l p sut mmHg.

A=6,84134; C=140,00; B=923,20

t: nhit oC.

2.2. Tnh cht ho hc


Isobutene c y tnh cht ho hc ca mt olefin thng thng. Ngoi ra
isobutene hot ng mnh hn so vi cc butene ng phn khc.
2.2.1. Phn ng hydrat ho
Hydrat ho isobutene c ter-butyl alcohol (TBA), qu trnh phn ng c th
c thc hin trong pha hi hoc pha lng, xc tc cho phn ng l axit H2SO4nng
khong 45%( khi lng). Hoc xc tc nha trao i ion sunfonat styren-divinyl benren.

CH3 C
CH3

CH2

H2O

H+

CH3
CH3 C

OH

CH3

Tert-butyl alcohol
(TBA)

2.2.2. Phn ng ete ho


Phn ng ca isobutene vi metanol to thnh Metyltert butyl ether (hay MTBE),
qu trnh phn ng thc hin trong pha lng, xc tc cho phn ng l xc tc loi nha
trao i ion.
CH3

-CH3 C

CH2

xt

CH3OH

O CH3

CH3 C

+ H2 O

CH3

CH3

(MTBE)
2.2.3. Tham gia phn ng cng hp
Phn ng cng vi halogen, HX, Nc,
CH3 C

CH2

CH3 CCl

Cl2

CH3

CH3
CH3 C

CH2Cl

CH2

CH3 CX

HX

CH3

CH3

CH3
X : l halogen.

2.2.4. Phn ng hydrofomyl ho:


Isobutene tham gia phn ng hydrofomyl ho vi s c mt ca xc tc Co hoc
Rh, ch to ra 3-methylbutanol.
2.2.5. Phn ng Polyme ho v oligomer ho:
CH3
CH3 C

TH

CH2

- CH2

CH3

CH3

Poly isobutene
Phn ng ny thng c tin hnh trong dung mi tr, to= - 101000C
Phn ng oligome ho:
CH3
CH3 C
CH3

CH2

+ CH3

C
CH3

CH2

CH3 C
CH3

CH

C
CH3

CH3

2.2.6. Phn ng vi (CO + H2O)


CH3 C

CH2

H2O

CO

CH3
2.2.7. Phn ng oxi ho:

H+

(CH3)3CCOOH

Axit pivalic

S oxi ho isobutene trong khng kh trn hn hp xc tc oxit kim loi chuyn


tip cho methacrolein (nu tip tc oxi ho s to ra axit methacrylic), chn lc 7080%, chuyn ho t khong 80%

CH3 C

CH2

O2

Oxit kim

Methcrolein

Loi chuyn tip

CH3

2.2.8. Phn ng vi fomandehit:


Isobutene phn ng vi formandehit, xc tc axit, to sn phm l isoputene.
2.3. ng dng ca isobutylen
Isobutene c rt nhiu ng dng trong cng nghip cng nh trong i sng.
Isobutylen c dng lm nguyn liu chnh trong qu trnh sn xut ph gia MTBE cho
xng, ngoi ra Isobutylen cng c dng sn xut TBA, Isobutylen cng c dng
trong tng hp ho hc,

Chng 2. TNG QUAN V QU TRNH CRACKING HI


2.1. Sn phm qu trnh cracking hi nc phn on C4
Qu trnh hydro ha chn lc butadien trong phn on C4 ca qu trnh cracking
hi nc cho sn phm c thnh phn nh bng sau:
Bng 2.1. thnh phn sn phm ca qu trnh cracking hi nc
Thnh phn

Gi tr (% th tch)

Vinylaxetylen

0.7

Etylaxetylen

0.2

1,2-butadien

0.3

1,3-butadien

49.1

1-buten

14

2-buten

7.6

Iso-buten

22.5

n-butan

3.0

Iso-butan

2.6

Chng ta thy sn phm t qu trnh trn cha nhiu nht l 1,3-butadien (49.1%)
tip theo l Iso-buten (22.5%) v nhiu sn phm c gi tr khc. Ta thy thnh phn
phn on C4 thu c t qu trnh cracking hi nc m ra nhiu kh nng phn tch
v lm giu cc cht. V d qu trnh lm giu buten t phn on C4 cracking hi nc
v cracking xc tc.

Bng 2.2. Lm giu buten t phn on C4 cracking hi v cracking xc tc

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 n-Buten
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 1.3.
Bng 2.3. Tnh cht vt l c bn ca thnh phn phn on C4 t cracking hi v
cracking xc tc.
Thnh phn
Vinylacetylen
Etylacetylen
1,2-butadien
1,3-butadien

im si oC

1.013 MPA
+5.6

bay hi
tng i 40
o
C
0.82

+10.9
-4.4

0.6
0.99

Nhit kt
tinh oC

d204

-136.2
-108.9

0.652
0.621

1-buten
2-buten
Isobuten
n-butan
Isobutan

-6.3

1.00

-185.4

0.595

-6.9
-0.5
-11.7

1.02
0.87
1.2

-140.4
-138.4
-159.6

0.594
0.579
0.557

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.
2.2. Cc cng on ch bin phn on C4
2.2.1. 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 t- butanol 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 1-buten 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.
2.2.2. Qu trnh tch 1-buten
Tip theo l qu trnh chit hoc loi b 1-buten:
Thu hi. Thu hi bng hp ph gi li cc phn t.
Chuyn ha. Trong qu trnh ny 1-buten c isome ha hoc hydro- isomer ha
thnh 2-buten.
Trong c 2 trng hp, hot ng bao gm chng ct tch phn on giu isobuten 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.
2.2.3. 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 nbutenes.

Chng 3. PHNG PHP SN XUT ISO-BUTEN THEO


PHNG PHP THY PHN
3.1. Ngun nguyn liu
Nguyn liu cho qu trnh tch iso-butene t sn phm ca qu trnh cracking hi
nc phn on C4 nh trong bng 3.1:
Bng 3.1. hydro ha chn lc butadien trong phn on C4 cracking
Thnh phn

Nguyn liu

Sn phm

Nguyn liu

Sn phm

Vinylacetylen

0.7

<0.01

Etylacetylen

0.2

<0.01

1,2-butadien

0.3

<0.01

1,3-butadien

0.8

10 ppm

49.1

1.0

1-buten

41.0

40.6

14.0

41.8

2-buten

31.1

31.8

7.6

26.2

Isobuten

18.9

18.9

22.5

22.2

n-butan

5.8

6.3

3.0

5.9

Isobutan

2.4

2.4

2.6

2.9

100.0

100.0

100.0

100.0

3.2. Cng ngh tch iso-buten t sn phm ca qu trnh cracking hi nc phn


on C4
Qu trnh tch iso-butene t sn phm ca qu trnh cracking hi nc phn on
C4 bng phng php thy phn trong cng nghip c thc hin theo hai phng
php:
Hydrat ha
Ete ha
Cc phng php tch khc cng c pht trin. Do , Hng Hoechst xut
este ha thng qua tert-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.
3.2.1. 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
n trong pha nc, v tan ca cc olefin khc nhau tng ng vi hm lng tbutanol. 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 nbuten, v nhanh hn 300 ln so vi 1,3-butadien.
Cng ngh CFR (hnh 3.1) in hnh cho qu trnh ny c xy dng
Grangemouth (Hoa K) vo nm 1963 gm ba giai on:
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.
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.
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 t- butanol 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.

Hnh 3.1. Tch isobutene bng phng php hydrat ha. Qu trnh CFR
3.2.2. 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 :
Tng hp v tinh ch MTBE
Cracking MTBE v tinh ch Isobuten
3.2.2.1. iu ch MTBE
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 isobutene 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 cracking hi nc, 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 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 3.2 Tch isobutene bng phng php ester ha. S IFP
3.2.2.2. 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.

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.

Hnh 3.3. Cracking MBTE thnh isobutene. Cng ngh IFP


S cng ngh (hnh 3.3) ca mt phn xng Cracking MTBE bao gm 3 cng
on chnh:

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.
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.
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.
3.3. Sn xut isobutene t cc thnh phn kh C4 khc
Sau khi tch isobutene theo phng php thy phn t sn phm ca qu trnh
hydro ha chn lc phn on C4 ca qu trnh cracking hi nc. Cc thnh phn kh
khc cn li nhm xut tin hnh hydro ha su thu c n-butane. Sau , ng
phn ha (isome ha) n-butane thnh isobutene. Ri t isobutane hydro ha thu
c isobutene.
3.3.1. Qu trnh hydro ha cc thnh phn kh C4 khc
Sau khi tch c isobutene thc hin qu trnh hydro ha hon ton thu c
n-butane v isobutane s dng xc tc Ni hoc Pt ngay iu kin thng. Thnh phn
cc kh C4 sau khi hydro ha hon ton nh trong bng 3.2:

Bng 3.2. Thnh phn cc kh C4 sau khi hydro ha hon ton


Thnh phn

Nguyn liu

Sn phm

Vinylacetylen

<0.01

<0.01

Etylacetylen

<0.01

<0.01

1,2-butadien

<0.01

<0.01

1,3-butadien

1.0

<0.01

1-buten

41.8

<0.01

2-buten

26.2

<0.01

Isobuten

0.01

<0.01

n-butan

5.9

74.9

Isobutan

2.9

2.9

77.8

77.8

Phng trnh phn ng:

Olefin (C4)

Ni, Pt
H2

n-butane, isobutane

3.3.2. ng phn ha n-butane thnh isobutane


Sau khi thu c n-butane, thc hin qu trnh isomer ha thu c isobutane.
Qu trnh isomer ha n-butane c thc hin trong pha lng hoc pha kh:
3.3.2.1. Isome ha n-butan trong pha lng
Cc qu trnh isome ha loi ny c t rt lu v ph bin isomer ha nbutane thnh isobutane. S nguyn l qu trnh isomate (Standard oil Co.Indiana)
c th hin trn hnh:

Hnh 3.4. Qu trnh isomate (Standard oil Co.Indiana)


Qu trnh ny c thc hin c hoc khng c tun hon n-parafin. Chng ch
khc nhau bi ct tch phn on C4. Qu trnh hot ng lin tc v khng cn ti sinh
xc tc.
Xc tc c dng l hn hp ca AlCl3 v HCl khan. Vng phn ng c duy
tr p sut H2 hn ch cc phn ng ph nh phn ng cracking v a t.
iu kin thao tc ca qu trnh nh sau:
ToC = 120; p = 50 60 at; H2/RH = 10 18 m3/m3 nguyn liu.
Nguyn liu c bo ha bng HCl khan v H2 trong thit b hp th, sau
c t nng n nhit cn thit v c np vo reator. Xc tc dng c tch
ra cng cn nha v phn ng izome ha xy ra trong pha lng.
Sn phm phn ng sau khi qua thit b tch xc tc v tch kh, c qua thp
tch vt axit, ri vo ct phn on tch ring n-parafin v cho tun hon tr li
nguyn liu

3.3.2.2. Qu trnh izome ha pha hi


Qu trnh izome ha n-butan trn xc tc aluminoplatin c hot ha bng clo
thc hin pha hi di p sut hydro vi lp xc tc c nh nhit t 120 n
240oC. Khi nhn c hiu sut izo-butan ln hn 50% sau mt chu trnh. chn
lc cao ca xc tc hn ch cc phn ng ph. Hiu sut sn phm t trn 90% v
tiu hao H2 tng i thp, ng thi do t xy ra cc phn ng ph nn t l H2/RH
nguyn liu cn thp hn m khng lm nh hng n thi gian lm vic ca xc tc.
S cng ngh ca qu trnh c tun hon n-butan cha phn ng trnh by trn (hnh
3.5).

Hnh 3.5. S cng ngh butamer


1. Thp tch isobutane, 2. Thp n nh, 3. Thit b phn ng, 4. Bung t, 5. My nn
I. Nguyn liu, II. Hydro, III. Kh t, IV. Isobutane
Hn hp nguyn liu mi v sn phm ca phn ng n nh c a vo
thp tch isobutane, ti y sn phm tch ra c tinh khit cao. N-butan c trn vi

kh cha H2 tun hon, qua thit b t nng 4 n nhit phn ng ri c np vo l


phn ng 3 bn trong c cha xc tc. Sn phm phn ng c lm lnh ri c dn
vo thit b tch p sut cao 6. Kh H2 tch ra c b sng mt lng nh hydro ri qua
my nn quay li l phn ng. Sn phm lng sau khi tch c a vo ct n nh 2,
ti y s tch tip mt phn hydro v C1, C2 (cn gi l kh nguyn liu). Sn phm
chnh c cho qua thp tch izobutan 1. Ngi ta cn b sung vo nguyn liu izome
ha mt lng nh cc hp cht halogen hu c duy tr hot ng ca xc tc.
Qu trnh butamer rt ph bin v c cc hng nh: UOP, BP, HIIO pht
trin. ch cng ngh ca mt s qu trnh va c nu dn ra bng 3.3:
Bng 3.3.Ch cng ngh ca mt s qu trnh butamer
Qu trnh

UOP

BP

Xc tc

I4

Pt/Al2O3

Nhit , oC

150-200

180-220

n 3.8

n 3.8

1-3

1-3

1-2

>12 thng

24 thng

24 thng

p sut, Mpa
Tc np liu, h-1
Thi gian lm vic ca xc tc

HIIO

3.3.3. Dehydro ha isobutane v tch tinh ch isobutene t qu trnh dehydro ha


isobutane.
Isobutene to ra t qu trnh dehydro ha isobutane nht khong 540 650oC
v p sut thp, xc tc cho qu trnh l Cr/Al2O3 hoc Pt/Al2O3. Sn phm thu c l
75 - 85% isobutene v isobutane, cn li l cc sn phm ph khc nhau Propan,
Propylen, Etylen, Metan, Propan...

Hnh 3.6. S cng ngh dehydro ho iso-butan ca Oleflex.(UOP)


Qu trnh olefex s dng xc tc l Pt/Al2O3 (khong 2% Pt) trong qu trnh ny
song song vi vic thc hin dehydro ha (thit b tng si) vic thc hin ti sinh xc tc
l lin tc. Qu trnh dehydro ha cc Alkal t C1C4 v cng ngh ti sinh xc tc lin
tc CCR s dng trong s lin kt vi reforming xc tc ca Naphta.

KT LUN
Qua bi tp ny nhm thu c nhiu kin thc b ch v qu trnh tch
isobutene t sn phm kh ca qu trnh cracking hi nc.
Tm hiu v isobutene : tnh cht l, ha, ng dng, phng php sn xut.
Tm hiu v qu trnh cracking hi nuocs v cc sn phm kh ca chng
Tm hiu c cc cng ngh tch isobutene thng c s dng trong cng
nghip.
xut phng n tch iu ch isobutene t cc kh C4 khc.

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