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US 8,940,932 B2
6,143,930 A
6,458,996 B1
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(86)
PCT/JP2011/072059
PCT No.:
EP
JP
JP
JP
JP
JP
JP
JP
2 653 458
61-267533
63-290835
4-266843
8-67650
2001-300203
2007-224040
2010-106045
A1
A
A
A
A
A
A
A
10/2013
11/1986
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9/1992
3/1996
10/2001
9/2007
5/2010
OTHER PUBLICATIONS
371 (0X1)
(2), (4) Date:
(87)
US 2013/0303800 A1
(30)
Int. Cl.
co 70 51/12
co 70 51/44
(52)
ability and Written Opinion issued May 16, 2013, in PCT Interna
tional Application No. PCT/JP2011/072059.
Nov. 14,2013
(51)
(2006.01)
(2006.01)
US. Cl.
CPC ............... .. C07C 51/12 (2013.01); C07C 51/44
(2013.01)
USPC
(58)
........................................................ ..
562/519
Birch, LLP
(57)
ABSTRACT
A process for stably producing high purity acetic acid com
prising a condensation step for condensing and temporarily
holding the lower boiling component in a decanter and dis
charging from the decanter; and a step for separating the
lower boiling component discharged from the decanter into
acetaldehyde and a liquid residue and recycling the liquid
residue to the reaction system. In the condensation step, the
amount of the lower boiling component to be held is con
trolled based on the ?uctuating ?ow rate of the lower boiling
component to be fed to the decanter.
US. Patent
US 8,940,932 B2
Sheet 1 0f 2
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(NM:2/N
ow/
EE?F
mm?
m?
pm?
US. Patent
Sheet 2 0f2
US 8,940,932 B2
2
Fag
12b
CO
met-hanol>
US 8,940,932 B2
1
TECHNICAL FIELD
methyl iodide.
BACKGROUND ART
20
obtained.
In addition, this patent document discloses, relating to a
25
Patent Documents
50
55
removed ef?ciently.
Meanwhile, in a continuous reaction process, removal of a
removing acetaldehyde.
60
US 8,940,932 B2
3
20
25
30
45
50
decanter.
ings.
That is, the present invention includes a process (a closed
60
65
US 8,940,932 B2
5
decanter, and the upper layer and/ or the lower layer may be
For the method (b), the retention time of the lower boiling
nent (3A) in the decanter and the retention time of the lower
method (b)).
20
25
35
example, 95 to 105)).
For the method (a), in the condensation step, the amount (or
?ow rate) of the lower boiling point component (3A) to be fed
to the separation and recycling step may be adjusted by cir
culating part of the lower boiling point component (3A) dis
ration and recycling step. In the method (a), not less than 10%,
preferably not less than 20% (for example, about 20 to 90%),
of the average ?ow rate of the lower boiling point component
(3A) to be fed to the decanter may be circulated (or recycled),
in particular, not less than 40% (for example, about 40 to
90%) of the average ?ow rate may be circulated. Moreover, in
the method (a), the lower boiling point component (3A) may
be separated into an upper layer and a lower layer in the
60
65
US 8,940,932 B2
7
in more detail.
DESCRIPTION OF EMBODIMENTS
20
35
40
45
perature.
50
ing (or retaining) the lower boiling point component (3A) [or
55
rity having a boiling point higher than that of acetic acid [e.g.,
60
65
US 8,940,932 B2
9
10
liquid phase and others. For example, assuming that the aver
is 100, the ?ow rate (or ?ow velocity, hereinafter, the same
applies in the ?ow rate) of the reaction mixture to be fed to the
?asher 2 is about 98 to 102 in the process operation. As
described later, for a closed process, the ?uctuation of the
feed amount affects the succeeding step(s) and is a factor that
20
large ?uctuation.
The lower boiling point component (3A) separated through
the line 14 is condensed by cooling, continuously fed to the
30
35
40
ment of FIG. 1, the storage (or the liquid level) of the lower
boiling point component (condensate) (3A) to be held in the
decanter 4 is signi?cantly restrained from ?uctuating by cir
55
60
65
US 8,940,932 B2
11
12
umn 6.
10
20
(3A) to be circulated to the line 1711 and/or the line 18a. As far
as large ?uctuation of the ?ow rate to be fed to the line 19 is
the upper layer and the lower layer in the decanter 4 through
the line 17 and the line 18, respectively. The ?ow rate of the
not caused, the ?ow rate of the lower boiling point component
kept constant (in other words, the ?ow rate of the lower
boiling point component (3A) to be fed to the line 17b or the
line 18b may ?uctuate).
Moreover, in the embodiment of FIG. 1, the lower boiling
liquid levels of the upper layer and the lower layer may be
25
the line 18. The ?ow rate of the lower boiling point compo
nent (3A) to be fed to the line 19 may be regulated by dis
30
ence to the upper layer and the lower layer, the lower boiling
point component (3A) may be fed or discharged through a
35
40
decanter 4 (the liquid level of the upper layer and that of the
lower layer) is kept constant or almost constant by adjusting
(controlling) the ?ow rate in the process operation [for
instance, with respect to each of the upper layer and the lower
layer, assuming that the average liquid level is 100, the liquid
reduced).
60
through the line 1711 and/or the line 18a in response to the
(3A) to be circulated through the line 1711 and/or the line 18a.
That is, in the embodiment of FIG. 1, as described above, the
?ow rate to be fed to the decanter is small, the ?ow rate of the
single line.
line 1711 may be fed to a line 30 through a line 17111 and
circulated to the splitter column 3, may be fed to a line 40
US 8,940,932 B2
13
14
the line 40 while keeping the ?ow rate of the higher boiling
point component (4B) to be fed to the line 23 constant (or
almost constant). Therefore, the ?ow rate ?uctuation of the
fed to the line 4011 may partly or wholly be fed to the distil
lation column 6 through a line 40111 as far as stable operation
of the distillation column 6 can be ensured.
20
25
30
35
45
6 minutes).
55
60
the upper layer and the lower layer, the lower boiling point
component (3A) may be fed through a single line.
the line 17 (and the line 18) is changed. When the ?ow rate is
101.5, that is, the ?uctuation of the ?ow rate can be adjusted
to at most about 1.5%) in the process operation.
Speci?cally, in the embodiment of FIG. 2, the ?ow rate of
(Reaction Step)
In the reaction step (carbonylation reaction system),
65
US 8,940,932 B2
15
16
30
50
atmospheres.
60
US 8,940,932 B2
17
18
weight), preferably not more than 10% by weight (e. g., about
in industrial application.
20
ppm) and preferably not more than 400 ppm (e.g., 5 to 300
ppm) in the liquid phase in the reactor in the process opera
tion.
25
1,000 kPa (e.g., about 100 to 1,000 kPa), preferably about 100
30
50
55
30% by weight).
(Acetic Acid Collection Step)
60
(component).
As described above, the feed amount of the reaction mix
ture to the ?asher ?uctuates. With respect to the degree of the
65
US 8,940,932 B2
19
20
(acetic acid stream) fed from the ?asher; and the liquid stream
(3B) (side cut stream, side stream) containing acetic acid is
withdrawn by side cut. Incidentally, in the distillation col
umn, a higher boiling point component (3C) containing acetic
acid, water, propionic acid, an entrained metal catalyst com
ponent, the halide salt, and others may be separated. The
(2A).
(Condensation and Discharge Step)
In the condensation and discharge step (which may simply
25
30
40
45
to the decanter is 100, the ?ow rate of the lower boiling point
component (or condensate) (3A) to be fed to the decanter is
about 80 to 120 (e.g., about 85 to 115), preferably about 90 to
110 (e.g., about 93 to 107), and more preferably about 95 to
105, in the process operation. According to the present inven
50
55
60
65
US 8,940,932 B2
21
22
upper layer or the lower layer or both upper and lower layers.
In the lower boiling point component (3A) to be fed to the
decanter, the volume ratio of the upper layer relative to the
lower layer may be selected from the range of about 0.2/1 to
5/1 (e.g., about 0.3/1 to 3/1) as a ratio ofthe former/the latter,
that the average interface level is 100, the interface level of the
ratio of the former/the latter. In the upper layer and the lower
20
25
35
40
45
50
FIG. 1), (b) a method for feeding the separation and recycling
55
ited to a speci?c one, and may for example be not less than 5
60
65
recycling step, and thus the amount of the lower boiling point
component (3A) to be fed to the separation and recycling step
US 8,940,932 B2
23
24
boiling point component (3A) of the lower layer may be, for
volume).
20
For the method (b), before the lower boiling point compo
nent (3A) discharged from the decanter is fed to the separa
40
the reactor and the acetic acid collection step (or distillation
0.5 minutes [for example, not less than 1 minute (e.g., about
1.5 minutes to 3 hours)], preferably not less than 2 minutes
[for example, not less than 3 minutes (e.g., about 4 to 60
minutes)], more preferably not less than 6 minutes (e.g.,
about 8 to 50 minutes), and particularly not less than 12
minutes (e.g., about 15 to 40 minutes).
When the ?ow rate ?uctuation of the lower boiling point
component (3A) can be eased in the decanter in some degree,
the retention time of the lower boiling point component (3A)
limited to a speci?c one, and may for example be not less than
45
50
60
65
vessel may ne not less than 1 minute [for example, not less
US 8,940,932 B2
25
26
separation column.
For the method (c), the amount of the lower boiling point
component (3A) to be discharged from the decanter is kept
stably.
20
25
30
into an upper layer and a lower layer inside the decanter, the
acetaldehyde separation.
The discharged lower boiling point component (3A) may
further contain a vapor component withdrawn from the top of
plates.
40
45
reaction step (or reactor), the ?ash distillation step (or ?ash
distillation column), and the acetic acid collection step (or
40% by weight.
50
55
60
65
US 8,940,932 B2
27
28
operation.
EXAMPLES
Example 1
average ?ow rate of the liquid residue is 100, the ?ow rate of
the liquid residue to be recycled to the separation column may
35
was fed to the reactor 1, and the process was started. Through
out the process, the variation in the ?ow rate of the liquid
reaction medium fed from the reactor 1 to the ?asher 2 was in
the range of about 11.6% relative to the average ?ow rate. In
except that the lower boiling point component (3A) was fed to
a high level, the ?ow rate of the higher boiling point compo
nent (4B) to be recycled to the separation column may be
constant or almost constant [for example, assuming that the
point component (2A) (the variation in the ?ow rate was in the
range of 1 1 % relative to the average ?ow rate); the remaining
45
reactor 1.
50
side cut, and the higher boiling point component (3C) was
directly recycled to the reactor. In the splitter column 3, the
55
was fed to the decanter 4, the variation in the ?ow rate was in
the range of 15% relative to the average ?ow rate (48.5
65
weight).
In the decanter 4, the lowerboilingpoint component (3A)
was separated into an upper layer and a lower layer (the
US 8,940,932 B2
29
30
the line 18 such that the liquid level and the interface level of
by weight).
In the distillation column 6 (a distillation column having 80
plates, re?ux ratio: 170, feeding plate: the 70th plate from the
the line 17a and the line 18a and by adjusting the retention
decanter 4. In the decanter 4, the retention time of the upper
layer was 13 minutes and the retention time of the lower layer
was 6 minutes. That is, the amount of the lower boiling point
component (3A) to be fed to each of the line 17b and the line
30
35
Example 2
changing the ?ow rate of each of the line 17a and the line 1811
that the rest was fed to the distillation column 6 in the process
as described later.
55
component (3A) fed to the decanter 4 was fed to the line 19 (or
the distillation column 6), and 73% by volume of the total
lower boiling point component (3A) fed to the decanter 4 was
60
to the line 19 or the line 17b); with respect to the lower boiling
component (3A) fed to the line 19 (or the line 17b) was 0% by
volume in the total lower boiling point component (3A) fed to
the decanter 4 (that is, the lower boiling point component
(3A) of the upper layer is wholly recycled without being fed
65
US 8,940,932 B2
31
32
Example 3
Example 3 was conducted in the same manner as in
the line 20) such that the ?ow rate thereof was substantially
constant (the ?uctuation of the ?ow rate was about 12.5%
that the rest was fed to the distillation column 6 in the process
as described later.
20
25
the ?ow rate of the line 1811 so as to correspond to the ?ow rate
30
35
(0.001% by weight).
that the ?uctuation of the liquid level was about 11% relative
to the average liquid level and the ?uctuation of the interface
level (or the liquid level of the lower layer) was about 11%
relative to the average interface level). That is, the liquid level
and the interface level of the lower boiling point component
(3A) in the decanter 4 were maintained substantially constant
by changing the ?ow rate of the lower boiling point compo
nent (3A) to be discharged through the line 17 along with the
?ow rate ?uctuation of the lower boiling point component
(3A) to be fed to the decanter 4.
The ?ow rate to be fed to the line 19 was successfully
relatively reduced by changing the ?ow rate to be fed to the
line 1711 (about 11.5% relative to the average ?ow rate).
component (3A) fed to the line 19 (or the line 17b) was 27%
by volume (corresponding to 51% by volume of the whole
plates, re?ux ratio: 170, feeding plate: the 70th plate from the
45
50
by volume of the whole lower layer, that is, the lower boiling
point component (3A) of the lower layer was wholly recycled
without being fed to the line 19 or the line 18b).
55
60
tank 5, and the lower boiling point component (3A) was fed at
a constant ?ow rate to the distillation column 6.
US 8,940,932 B2
33
34
Comparative Example 1
5
6 was about 14%, the ?ow rate of the higher boiling point
component (4B) to be recycled through the line 23 was suc
Example 4
Comparative Example 2
20
25
level (or the liquid level of the lower layer) was about 11%
relative to the average interface level). That is, the liquid level
and the interface level of the lower boiling point component
(3A) in the decanter 4 were maintained substantially constant
by changing the ?ow rate of the lower boiling point compo
nent (3A) discharged through the line 18 along with the ?ow
rate ?uctuation of the lower boiling point component (3A) to
be fed to the decanter 4. Then, the discharged lower boiling
point component (3A) was fed to the buffer tank 5 and
30
35
Comparative Example 3
40
from the decanter 4. The variation in the ?ow rate of the lower
of the ?ow rate in the buffer tank 5, and the lower boiling point
lation column 6.
plates, re?ux ratio: 170, feeding plate: the 70th plate from the
50
(0.001% by weight).
Moreover, about 80% by volume of the higher boiling
point component (4B) separated in the distillation column 6
55
65