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Asetaldehid (Recovered)
Asetaldehid (Recovered)
Asetaldehid (Recovered)
[11]
Patent Number:
Tustin et al.
[45]
Date of Patent:
[54]
[75]
6,121,498
Sep. 19, 2000
502/326; 502/339
[58]
[57]
ABSTRACT
[56]
References Cited
203/28
568/426
568/449
4/1993
11/1996
WO 96/18458
6/1996
OTHER PUBLICATIONS
Water.
OFFGAS
FEED
18
@ HAc
PRODUCT 19
23 TO HOAC
30
6,121,498
Page 2
OTHER PUBLICATIONS
pp. 142152.
U.S. Patent
99
(3x3\
E2
5
2%
PRODUCT
O)
(I
00%
QI A
Sep. 19,2000
HAc
[K
co
$9
Lkl
El
Sheet 1 of2
H23TOOAc
RECOV Y
1::
q-w
;; 07 :0 h?
E
my,
FE D
30
6,121,498
El CV1]
U.S. Patent
.UE
N
Sheet 2 012
6,121,498
6,121,498
1
route existed.
25
30
35
45
50
aO
6,121,498
3
selected from Cr, Mo, Co, Ni, Zn, Cd and Cu for the
hydrogenation of aromatic and aliphatic carboxylic acids
containing not more than one ot-hydrogen at 325425 C. at 15
1 bar in the presence of a large excess of hydrogen.
25
Yokoyama et al. stress that the reason for the high purity
requirement in the chromium oxide is to prevent the ketone
30
mixtures.
It is another object of the present invention to provide a
40
aldehydes.
50
55
60
6,121,498
6
AR, acetic acid is recovered from stream 33. This acetic acid
may be mixed With hydrogen and fed to reactor RX via
stream 3.
15
25
35
PU.
has a very loW boiling point, even loWer than the aZeotrope.
Thus, a Waste acetone stream 51 is produced after acetone
The liquid coming off of absorber A as stream 8 is sent to
column condenser WC. From the bottom of the Waste
distillation column D to recover acetaldehyde. The overhead
from distillation column D is cooled via condenser C to 45 acetone column W, a near ethyl acetate-Water aZeotrope
stream 50 is recycled after acetone column reboiler WR.
condense same. A portion of the condensed liquid is sent
back to the distillation column D as a re?ux. Offgas 18 is not
The tWo aZeotrope recycle streams 50 and 43 are not
acetate forms an aZeotrope With Water. The aZeotrope has a 65 highly dependent on this conversion of byproduct ethanol to
6,121,498
7
10
15
20
45
50
55
6,121,498
9
10
10
15
preferred.
30
40
50
60
6,121,498
11
12
tion. When the reactor Was idle betWeen acetic acid hydro
10
15
20
30
long 1A-inch O.D. kovar metal tubing sealed to the end of the
35
quartZ Wool plug from the top of the reactor into the top part
reactant mixture Was fed through the side arm, and the
50
6,121,498
14
13
% acetic acid accountability=100(mmoles acetic acid
recovered+mmoles acetate equivalents in products)/
Example 1
This example illustrates the effect of changing the Weight
Catalysts
10
20
Example 2
This example compares the performance of catalysts
ing dish. The mixture Was dried on the steam bath and
containing 2.5 and 5 Wt % Pd under conditions of compa
calcined in a muffle furnace for 5 hours at 400 C.
25
rable acetic acid conversion. The same feed conditions used
Catalyst No. 4: 10% Pd on Fe2O3. A solution Was pre
in Example 2 Were used as in Example 1, and the data Were
35
Example 3
This example compares the performance of catalysts
40
45
50
presented in Table 3.
Example 4
55
40% Pd.
Catalyst No. 7: 80% Pd on Fe2O3. A solution Was pre
60
65
Example 5
This example illustrates the performance of the 10 Wt. %
Pd on Fe2O3 at 250 psig pressure and at a 5/1 hydrogen/
6,121,498
15
16
TABLE 1
5 Wt % Pd
1O
2O
4O
80
100
1
19
280
80
4
96
499
56
5
98
157
38
6
99
79
35
7
81
45
15
8
26
1
4
Example 6
0.6
7
% cH4 Sel.
% C2 H. C. sel.
3.1
38
2.7
50
1.1
55
0.2
22
0.3
0.4
10.5
2.7
8.5
8.6
62.9
95.4
3.1
0.1
0.7
0.3
100
100
10g
107
0.1
105
100
on stream_
2.5
% HOAc Conv.
G/(l-hr) HAc
% HAc sel.*
%
%
%
%
%
acetone sel.
EtOH sel.
CH4 sel.
C2 H. C. sel.**
HOAc acct.***
54
597
78
0.8
15
4.6
1.0
91
50
621
79
52
656
77
50
698
80
45
527
73
0.8
15
4.1
0.9
107
0.9
17
4.4
0.9
103
0.8
14
3.8
0.8
103
1.6
18
6.1
1.6
101
59
748
82
51
694
84
48
674
84
45
662
84
0.7
0.7
0.6
0.6
12
10
9
9
5.2
5.7
5.9
5.9
0.7
0.7
0.6
0.6
97
101
102
105
Example 7
This example illustrates the integrated process of the 45
TABLE 3
2 3
Wt % Pd
'
10
% HOAC COW
G/(Hn) HAG
% HAG S614
% acetone 36L
% EtOH S61_
% CH4 S61_
% C2 H_(;_ 8614*
% HOAC any.
98
642
36
1_1
44
14
37
98
92
779
47
O_9
39
11
26
103
97
773
52
10
4O
5_4
10
98
91
994
68
10
27
3_4
06
103
6,121,498
TABLE 4
Effect of Changing the Mole Fraction of Acetic Acid in Hydrogen
on the Performance of 5 Wt. % Pd/Fe203
5350
90
73000
0.057
% HOAc conV.
G/(1-hr) HAc
% HAc sel.**
% Acetone sel.
% EtOH sel.
% CH4 sel.
% C2 H. C. sel.***
% HOAc acct.****
7033
30
24000
0.095
7141
90
73000
0.095
8134
90
73000
0.026
8886
90
73000
0.20
9291
90
73000
0.20
9328
25
20000
0.20
9396
25
20000
0.20
38
31
16
66
23
16
17
26
1003
87
1.1
8.0
3.2
0.6
86
283
87
1.1
6.8
4.8
0.8
82
497
89
0.9
5.3
3.9
0.5
91
740
79
0.9
15.8
3.7
0.7
92
523
87
2.5
7.5
2.7
0.2
81
899
90
1
5
1
0
95
338
89
3.9
4.6
1.9
0.3
96
407
89
3
5
2
0
89
8
8
8
4
0
4
2
6
TABLE 5
TABLE 6
25
TTOS, min"
TTOS, mm
1739
2089
22
1O
3350
970
512
HZ/HOAc
% HOAc Con
G/(l'hr) HAG
534
2318
30
GHSV, hr-1
3530
2600
2600
% HOAc Conv.
46
42
3s
2125
77.1
2175
77.0
77-9
1.5
62-7
4.6
% EtOH sel.
15.0
16.2
% acetone sel.
1.7
1.3
1.5
% EtOAC 36L
4_6
155
% EtOH sel.
9.6
15.9
15.2
% CH4 gel
07
O7
% c2 H.C. sel.***
0.2
0.1
35
40
G/(l-hr) HAC
% HAc sel.**
1530
86.4
% HAG 861-
% acetone sel.
% EtOAc Sel.
2.1
5.6
6.3
M
0
<01
<0.1
<01
<0.1
Conditions: 3000 C
"TIOS = total time on stream under hydrogen and acetic acid feed.
**Selectivities are normalized.
*TIOS : total time On Stream under hydrogen and acetic acid feed
45
TABLE 7
HOAc Hydrogenation Reaction Section Balance
Stream
Temperature C
Pressure BAR
Vapor Fraction
Mole Flow KGMOL/HR
Mass Flow KG/HR
Volume Flow M3/HR
Enthalpy MJ/HR
11
13
18
19
23
30
31
33
36
67.3
19.0
0.848
4982
63088
6348
37.8
6.9
1.000
22
510
84
2148
37.8
6.9
0.000
318
13455
18
61647
167.8
6.6
0.010
4466
183638
465
1624722
167.8
6.6
0.010
737
30312
77
268188
167.8
6.6
0.010
3729
153325
389
1356535
37.8
2.8
0.000
3729
153325
155
1397118
66.7
19.0
0.847
4982
63086
6333
388810
77.6
19.0
1.000
3845
18807
5914
57092
742.54
3742.14
33.21
358.78
2.59
0.23
15.63
3332.30
33.21
356.76
2.59
0.23
0.00
5.28
5.94
8.40
0.00
0.00
0.00
0.05
293.39
2.95
0.06
0.00
2265.66
0.00
0.30
0.00
26.65
6.11
373.98
0.00
0.05
0.00
4.40
1.01
1891.67
0.00
0.25
0.00
22.25
5.10
1891.67
0.00
0.25
0.00
22.25
5.10
748.43
3742.14
33.21
358.76
2.59
6.12
388610
6,121,498
19
20
TABLE 7-continued
HOAc Hydrogenation Reaction Section Balance
Stream
ETHENE
H2O
CO2
ETOAC
Mass Fraction
HOAC
H2
HAC
METHANE
ACETONE
ETHANOL
ETHENE
H2O
CO2
ETOAC
11
13
18
19
28.43
28.98
39.37
5.89
28.43
28.98
39.37
5.89
1.28
0.11
1.49
0.00
2.18
16.85
2.61
0.00
0.7070
0.1200
0.0230
0.0910
0.0020
0.0002
0.0130
0.0080
0.0270
0.0080
0.0500
0.3610
0.0790
0.3090
0.0080
0.0008
0.0430
0.0280
0.0930
0.0280
0.0000
0.0210
0.5130
0.2840
0.0000
0.0000
0.0700
0.0040
0.1280
0.0000
23
30
0.00
2071.76
0.00
95.49
0.0000
0.0000
0.9610
0.0040
0.0003
0.0000
0.0050
0.0230
0.0090
0.0000
31
0.00
341.98
0.00
15.76
0.7410
0.0000
0.0001
0.0000
0.0080
0.0020
0.0000
0.2030
0.0000
0.0460
33
0.00
1729.78
0.00
79.73
0.7410
0.0000
0.0001
0.0000
0.0080
0.0020
0.0000
0.2030
0.0000
0.0460
36
0.00
1729.78
0.00
79.73
0.7410
0.0000
0.0001
0.0000
0.0080
0.0020
0.0000
0.2030
0.0000
0.0460
0.7410
0.0000
0.0001
0.0000
0.0080
0.0020
0.0000
0.2030
0.0000
0.0460
28.43
23.09
39.37
0.00
0.7120
0.1200
0.0230
0.0910
0.0020
0.0040
0.0130
0.0070
0.0270
0.0000
TABLE 8
HOAc Hvdrogwtion Recovery Section Balance
Stream
12
Temperature C
Pressure BAR
Vapor Fraction
Mole Flow KGMOL/HR
Mass Flow KG/HR
Volume Flow M3/HR
Enthalpy MJ/HR
Mole Flow KGMOL/HR
167.8
8.8
0.006
737.5
30323
61.4
268378
96.8
2.1
1.000
1490.7
87620
22170.6
515645
141.5
2.1
0.000
382.8
22466
24.8
169455
43.3
2.1
0.000
1136.1
79762
89.5
473168
43.3
2.1
0.000
1198.6
84156
94.4
499232
43.3
2.1
0.000
353.3
7270
7.6
102244
43.3
2.1
0.000
62.6
4394
4.9
26065
102.2
2.1
0.000
16.9
1445
1.8
7813
HOAC
ACETONE
ETHANOL
H2O
ETOAC
HAC
Mass Fraction
374.10
4.40
1.01
342.15
15.77
0.05
25.00
82.96
9.91
238.03
779.28
0.87
26.38
87.53
10.46
251.14
822.21
0.92
2.41
4.96
1.60
336.28
7.98
0.05
1.38
4.57
0.55
13.11
42.93
0.05
1.36
0.09
0.01
0.01
15.41
0.00
HOAC
ACETONE
ETHANOL
H2O
ETOAC
HAC
0.7410
0.0080
0.0020
0.2030
0.0460
0.0001
28.74
87.36
10.92
587.71
795.05
0.92
0.0200
0.0580
0.0060
0.1170
0.7990
0.0005
370.36
0.00
0.00
12.47
0.00
0.00
0.9900
0.0000
0.0000
0.0100
0.0000
0.0000
0.0190
0.0600
0.0060
0.0540
0.8610
0.0005
0.0190
0.0600
0.0060
0.0540
0.8610
0.0005
oxide is Fe2O3.
8. The method according to claim 1, wherein the hydro
9. The method according to claim 1, wherein the hydro
0.0570
0.0040
0.0004
0.0001
0.9390
0.0000
0.0190
0.0600
0.0060
0.0540
0.8610
0.0005
0.0200
0.0400
0.0100
0.8330
0.0970
0.0003
65
6,121,498
21
22
dehyde.
26. Aprocess for the preparation and recovery of acetal
15
comprising the step of (d) recovering the acetic acid from the
mixture of ethyl acetate, Water, acetic acid and acetone using
an aZeotropic distillation.
20. The method according to claim 19, Wherein a hetero
geneous Water aZeotrope is used for the aZeotropic distilla
tion.
21. The method according to claim 19, Wherein an aZeo
25
reactor Zone.
30
solvent;
(d) recovering unconverted acetic acid by aZeotropic
distillation;
35