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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
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.
CH2
CH3
n v
Gi tr
-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
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)
465
%V
1,8 - 8,8
P l p sut mmHg.
t: nhit oC.
CH3 C
CH3
CH2
H2O
H+
CH3
CH3 C
OH
CH3
Tert-butyl alcohol
(TBA)
-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.
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
CH2
H2O
CO
CH3
2.2.7. Phn ng oxi ho:
H+
(CH3)3CCOOH
Axit pivalic
CH3 C
CH2
O2
Oxit kim
Methcrolein
CH3
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.
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
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
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
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 :
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
Olefin (C4)
Ni, Pt
H2
n-butane, isobutane
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
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.