Beruflich Dokumente
Kultur Dokumente
Keyworth et a1.
[54]
AssigneeZ
[21] Appl No
22
F} d:
[51] I I eCl4
.:
Tex.
Houston, Tex.
.
4,570,026
Feb. 11, 1986
22
5 ,60
A
585/639
. 12 1983
ug
[57]
ABSTRACT
[58]
56
[ 1
4,232,177 11/1980
4,320,232
/
C4
37
u SYNTHESIS
MTBE
ME THANOL
OTHER LIGHTS
ISOBUTENE
D/SSOC/AT/ON
REACTOR
MTBE PRODUCT
MTBE
ME THANOL
'
ISOBUTENE
ME THA NOL
C4 FEED
METHA/VOL
I
37
4,570,026
OTHER L/GHTS
M TBE
_ SYNTHES/S
_ ;\55
MTBE PRODUCT
N6
M TBE
ME THA NOL
Sheet 1 of3
ISOBUTENE
/5
5b H2O
D/SSOC/A T/ON
/SOBUTE/\/E
REACTOR
,0
/9
lSOBU TEA/E
ME THANOL
/4
4 ,6
/
MTBE
4,570,026
'
groups are lost from the resin. This effect becomes more
pronounced and accelerated with the increases in tem
2. Related Art
3,121,124;
3,170,000;
3,634,534;
tion.
Nos.
3,634,535;
4,570,026
cess.
bottoms may contain some isobutene. The bottoms are
FIG. 2 is a cross sectional elevation of a reactor for
recycled to MTBE synthesis in the ?rst or second reac
tor in a multiple reactor system. As an additional step, 0 carrying out the dissociation process of the present
invention.
the isobutene which contains some methanol (azeo
FIG. 3 is a cross sectional view of the reactor of FIG.
trope) may be taken to a wash column where the metha
2 taken along line 33.
nol is removed by washing with Water. By this means
selectivity.
25
4,570,026
the LHSV within the speci?ed ranges the oligomeriza - 5 unreacted sulfur trioxide after the reaction. The result
ing products preferably contain an average of 1.3 to 1.8
tion is reduced. The increased temperature also favors
sulfonic acid groups per aromatic nucleus. Particularly,
the conversion. Hence at high through puts (high
suitable polymers which contain sulfonic acid groups
LHSV), high conversions and high selectivity are ob
and are copolymers of aromatic monovinyl compounds
tained with a favorable unit productivity.
with aromatic polyvinyl compounds, particularly divi
The optization of the operation of the dissociation
nyl compounds, in which the polyvinyl benzene content
reactor within the ranges provided and the guidelines
catalyst.
which contain sulfonic acid groups, and which have 55 preferred size and substantially free of ?nes are not
4,570,026
(not shown).
" generally conducted at 90~120 C. A reactor or series 35 tography of the hydrogenated ole?ns. In the examples
of reactors as described below for the dissociation is a
the term yield means conversion X selectivity. In the
the fact a ?xed bed resin system is used for the liquid
ery systems (not shown) and the like, which (other than
invention and are indicated as 3.
4,570,026
10
TABLE I
LHSV
MTBE
Preheater
Inlet "C.
Bath In
RUN NO.
9
10
11
12
13
14
15
16
17
18
19
7
110
7
118
7
122
7
123
7
135
10
132
10
130
11.8
130
14.3
130
14.3
130
18.4
133
18.4
125
20.0
114
20.0
140
20.0
128
20.0
142
20.4
122
20.0
145
20.0
121
110
118
122
123
130
123
130
130
130
131
137
137
130
130
130
139
141
148
150
80
77
97
71.2
80
82
113
79.1
93
72
101
81 0
85
75
104
83.7
85
77
95
69
94
73.0
100
73
100
79.3
101
73
95
75 3
101
73
93
67 6
105
75
96
68.3
106
78
100
73.8
107
75
92
62.8
107
73
90
53.0
111
72
87
54.9
109
72
87
56.1
116
72
91
58.9
110
72
92
61.3
120
73
94
67.2
115
74
97
68.1
(Reactor)
Reactor
Pro?le
(Catalyst)
w
0
14
30 (bottom)
%C
(MTBE)
TABLE II
1
Methyl Ether, Wt. %
Isobutylene, Wt. %
MTBE, Wt. %
Methanol, Wt. %
TBA, Wt. %
Octenes, Wt. %
Dodecenes, Wt. %
Data Consistency
Conversion (isobutene)
Conversion (MeOH)
EXAMPLE
6
10
.059
45.03
28.78
23.13
.065
2.179
.757
.846
.724
.689
.117
45.37
20.87
27.97
.045
4.798
.832
.965
.793
.788
.102
45.43
18.94
31.35
.053
3.786
.356
1.111
.805
.821
.317
50.99
8.98
26.08
.049
10.93
2.659
.719
.919
.890
.040
44.15
27.05
27.31
.039
1.376
.063
1.050
.726
.736
.056
45.51
20.73
31.33
.033
2.079
.297
1.148
784
.807
.038
45.60
24.73
28.30
.040
1.250
.054
1.057
.749
.759
.021
41.68
32.41
25.10
.043
.742
.035
1.036
.673
.681
.938
.889
.916
.789
.968
.950
.972
.981
.746
.967
.001
.001
.001
--
.006
.001
.005
.001
.001
.001
.045
.094
.076
.169
.030
.043
.027
.017
.031
.016
.016
.007
.041
.001
.006
.001
.001
.001
Selectivity to
.003
.006
.005
.012
.002
.003
.002
.001
.002
Selectivity to
.843
.960
1.106
.707
1.048
1.144
1.056
1.034
1.068
.002
Selectivity to
Isobutene
Selectivity to
TBA
Selectivity to
.038
44.32
26.20
27.95
.040
1.441
.043
1.07
.733
Octenes
Selectivity to
Dodecenes
Dirnethylether
Methanol
Selectivity to Water
STY = LHSV X S X C X 100
.001
.002
.005
507
.000
703
.001
.000
744
855
.000
941
.000
475
494
516
1010
11
12
13
14
15
16
17
18
19
.023
41.85
31.67
25.50
.060
.854
.048
1.044
.680
.690
.978
.015
38.54
37.22
23.62
.050
.536
.032
1.057
.623
.636
.984
.009
31.93
47.04
20.68
.060
.277
.000
1.123
.519
.547
.990
.009
34.11
45.12
20.44
.060
.277
.000
1.04
.545
.555
.991
.010
39.57
43.88
16.25
.055
.242
.000
.714
.588
.505
.993
.013
37.44
41.09
21.01
.051
.418
.000
.972
.592
.585
.988
.014
38.19
38.69
22.58
.049
.487
.000
1.022
.611
.675
.986
.019
41.82
32.80
24.71
.051
.602
.002
1.020
.670
.675
.985
.023
43.24
31.92
2409
.034
.702
.000
.961
.684
.675
.983
EXAMPLE
Methyl Ether, Wt. %
Isobutylene, Wt. %
MTBE, Wt. %
Methanol, Wt. %
TBA, Wt. %
Octenes, Wt. %
Dodecenes, Wt. %
Data Consistency
Conversion (isobutene)
Conversion (MeOI-I)
Selectivity to
lsobutene
4,570,026
11
12
TABLE II-continued
Selectivity to
TBA
Selectivity to
Octenes
Selectivity to
.001
.001
.001
.001
.001
.001
.001
.001
.001
.020
.013
.009
.008
.006
.011
.0126
.014
.016
.001
.001
.000
.000
.000
.000
.000
.000
.001
.001
.001
.001
.001
.001
.001
.001
.001
1.043
1.057
1.122
1.039
.714
.971
.959
1.019
.959
.001
Dodecenes
Selectivity to
Dimethylether
Selectivity to
Methanol
Selectivity to Water
.000
.000
947
.000
1129
.000
1027
1080
.000
.000
1168
.000
1169
1206
.000
1320
.000
1345
TABLE III
2
10
11
12
13
14
2
121
97
2
120
107
12.0
129
133
12.0
134
140
12.0
131
133
12.0
142
139
12.0
139
140
14.0
118
142
14.0
122
137
14.0
139
136
14.0
130
143
20.8
146
142
20.0
142
144
20.0
142
142
0.05/0
0.05/0
57/40
75/73
38/21
17/0
18/0
104/99
19/0 22/0
22/0
90
73
92
67.3
97
8O
103
80.9
116
85
105
59.3
122
94
111
59.9
115
77
103
65.0
119
81
112
75.6
116
72
99
79.2
128
98
100
38.1
113
73
95
65 9
124
73
94
62 9
LHSV
Preheater Inlet C. (Vapor)
Bath In (Reactor) C.
Inlet/Exit Pressure
RUN NO.
6
7
(PSIG)
Reactor Pro?le
112%
0
14
30(Bottom)
% C MTBE
TABLE IV
RUN NO.
I
. . Inlet/Exit Pressure,
pslg
LHSV
Bath In.(Reactor) C.
Methyl Ether, Wt. %
Isobutene, Wt. %
I MTBE, Wt. %
5 Methanol, Wt. %
0.05/0
0.05/0
57/40
75/73
38/21
17/0
18/0
2
121
2
120
12
129
12
134
12
131
12
142
12
139
.14
37.5
.39
38.8
.011
37.3
.06
99.7
.08
41.6
.04
44.5
.16
37.1
32.7
24.6
19.1
25.4
40.7
20.2
20.8
27.1
35.1
21.7
24.4
29.9
40.1
20.1
TBA, Wt. %
if. Octenes, Wt. %
.13
4.51
.14
12.6
.16
1.53
.04
2.28
.12
1.4-8
.40
3.62
, Doclecenes, Wt. %
.05
1.07
.22
2.37
.06
.17
.04
.04
.03
1.023
.671
.676
.882
.823
.819
.789
.704
.913
.601
.579
.956
.913
.798
.782
.953
.884
.659
.631
.963
1.121
.751
.772
.951
.899
.608
.582
.940
.002
.002
.003
.001
.002
.001
.004
.106
.229
.039
.043
.034
.048
.057
.009
.007
.002
.003
.001
.001
.000
.008
.017
.007
.003
.005
.002
.010
1.0145
.805
.906
.910
.879
.007
.007
.000
.001
.000
Data Consistency
Conversion (i C = /4)
Conversion (MeOH)
Selectivity to
Isobutene
Selectivity to
TBA
Selectivity to
Octenes
Selectivity to
Dodecenes
Selectivity to
Methyl Ether
Selectivity to
Methanol
Selectivity to
Water
STY - LHSV X S
X %C
Inlet/Exit Pressure,
P512
LHSV
Bath In. (Reactor) C.
Methyl Ether, Wt. %
Isobutene, Wt. %
MTBE, Wt. %
Methanol, Wt. %
TBA, Wt. %
Octenes, Wt. %
118
115
507
10
104/99
70/62
20/0
14
118
14
122
.109
23.4
61.9
11.7
.44
2.5
.09
34.4
42.5
21.7
.19
14
139
762
20/0
.03
47.7
23.6
27.6
.04
.59
1.030
Dodecenes, Wt. %
.02
02
Data Consistency
.791
1.07
1.061
I992
19/0
20.8
146
.393
38.8
19.1
25.4
.14
12.6
3 62
I383
.879
.006
856
RUN NO.
11
12
14
130
.21
43.7
28.8
26.8
.06
1.13
912
1.12
.001
684
13
14
22/0
22/0
20
142
20
142
.021
41.7
37.4
20.3
.05
.019
39.0
37.1
23.4
.05
. .58
.42
.070
.839
1.038
116
104
117
57.5
120
82
107
71.2
118
77
9076.4
125
73
94
62 7
4,570,026
13
14
TABLE IV-continued
Conversion (i C = /4)
Conversion (MeOH)
Selectivity to
.399
.344
.891
.569
.586
.964
.707
.720
.986
.764
.763
.978
.819
.789
.704
.641
.599
.984
.626
.635
.988
.012
.004
.001
.001
.002
.001
.009
.095
.032
.013
.021
.229
.014
.011
lsobutene
Selectivity to
TBA
Selectivity to
Octenes
Selectivity to
.000
.066
.002
.010
.001
.006
.001
.021
.017
.001
.001
.781
1.064
1.060
.000
.838
1.038
1.038
.000
.000
.000
.000
Dodecenes
Selectivity to
Methyl Ether
Selectivity to
Methanol
Selectivity to
wet
wet
wet
Water
feed
feed
feed
STY - LHSV X S
498
769
976
1046
1199
1261
1237
>< % C
4 atmospheres.
12. A process for producing high purity isobutene
from a C4 hydrocarbon stream containing isobutene
comprising contacting said C4 hydrocarbon stream and
produce MTBE,
CERTIFICATE OF CORRECTION
PATENT NO. : 4,570 ,026
DATED
Iv February 11., 1.986
INVENTOR) ; D. A. Keyworth and C. G; McFarland
It is certified that error appears in the above-identified patent and that said Letters Patent
are hereby corrected as shown below:
being
isobutane
--
read
'
---
'
Profile"
Reactor
Profile
but
should
should read -
Reactor Profile
conversion
(isobutene)
Attesting O?icer