Title: Process for producing epsilon-caprolactone
Abstract: A process produces ε-caprolactone by the oxidation of cyclohexanone by feeding a crude reaction mixture to a first distillation column; distilling off a first distillate containing low boiling components including unreacted cyclohexanone from the top of the first distillation column; recovering a first side-cut fraction containing unreacted cyclohexanone in a higher concentration than in the first distillate from an intermediate tray; recovering a first bottom liquid containing high boiling components including ε-caprolactone from the bottom; introducing the first side-cut fraction to a second distillation column; recovering a second bottom liquid containing unreacted cyclohexanone from the bottom of the second distillation column; recycling the second bottom liquid into the raw material cyclohexanone; introducing the first bottom liquid to a third distillation column to thereby yield a third distillate containing ε-caprolactone from the third distillation column.
Patent Number: 6,936,724 Issued on 08/30/2005 to Ohara, et al.
| Inventors:
|
Ohara; Eiji (Otake, JP);
Kawazumi; Ken-ichiro (Himeji, JP)
|
| Assignee:
|
Daicel Chemical Industries, LTD (Osaka, JP)
|
| Appl. No.:
|
688926 |
| Filed:
|
October 21, 2003 |
Foreign Application Priority Data
| Oct 22, 2002[JP] | 2002-306710 |
| Current U.S. Class: |
549/272; 203/77; 203/81; 203/82; 203/86 |
| Intern'l Class: |
C07D 313/04 |
| Field of Search: |
549/272,78
203/77,81,82,86
|
References Cited [Referenced By]
U.S. Patent Documents
| 4341709 | Jul., 1982 | Hofen et al.
| |
| Foreign Patent Documents |
| 0 972 771 | Jan., 2000 | EP.
| |
| 53-34789 | Mar., 1978 | JP.
| |
| 2002/-179667 | Jun., 2002 | JP.
| |
Other References
Perry, Chemical Engineers' Handbook, 5th. Ed., McGraw-Hill, New York,
p. Chapter 13, p.48 and 49 (1973).
|
Primary Examiner: Dentz; Bernard
Attorney, Agent or Firm: Birch, Stewart, Kolasch & Birch, LLP
Parent Case Text
This Nonprovisional application claims priority under 35 U.S.C. §119(a)
on patent application Ser. No(s). 2002-306710 filed in Japan on Oct. 22, 2002,
the entire contents of which are hereby incorporated by reference.
Claims
1. A process for producing ε-caprolactone by the oxidation of cyclohexanone,
comprising the steps of:
feeding a crude reaction mixture to a first distillation column having a column
bottom temperature from about 100° C. to about 200° C. and a column top
pressure of about 100 mmHg or less;
distilling off a first distillate from the top of the first distillation column,
the first distillate containing low boiling components including unreacted cyclohexanone;
recovering a first side-cut fraction from an intermediate tray of the first distillation
column, the first side-cut fraction containing unreacted cyclohexanone in a higher
concentration than in the first distillate;
recovering a first bottom liquid from the bottom of the first distillation column,
the first bottom liquid containing high boiling components including ε-caprolactone;
introducing the first side-cut fraction to a second distillation column;
recovering a second bottom liquid containing unreacted cyclohexanone from the
bottom of the second distillation column;
recycling the second bottom liquid into the raw material cyclohexanone;
introducing the first bottom liquid to a third distillation column to thereby
yield a third distillate containing ε-caprolactone from the third distillation
column.
2. The process according to claim 1, further comprising oxidizing cyclohexanone
with a peracid.
3. The process according to claim 2, wherein the peracid is an organic peracid.
4. The process according to claim 3, wherein the organic peracid is peracetic acid.
5. The process according to claim 2, wherein the crude reaction mixture mainly
comprises the peracid, an acid derived from the peracid, a solvent for the peracid,
cyclohexanone, ε-caprolactone, adipic acid, and a polymerized product of ε-caprolactone.
6. The process according to claim 2, wherein the first side-cut fraction mainly
comprises the peracid, an acid derived from the peracid, a solvent for the peracid,
and cyclohexanone.
7. The process according to claim 2, wherein the first distillate mainly comprises
the peracid, an acid derived from the peracid, a solvent for the peracid, and cyclohexanone.
8. The process according to claim 2, wherein the first bottom liquid mainly comprises
ε-caprolactone, adipic acid, and a polymerized product of ε-caprolactone.
9. The process according to claim 2, wherein the second bottom liquid mainly
comprises an acid derived from the peracid and unreacted cyclohexanone.
10. The process according to claim 2, wherein the third distillate mainly comprises ε-caprolactone.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for producing ε-caprolactone
by the oxidation of cyclohexanone.
2. Description of the Related Art
ε-Caprolactone is widely used as a raw material for polyester
polyols for the production of polyurethanes, and for other polymers as molding
materials. ε-Caprolactone is typically produced by the oxidation of cyclohexanone.
The oxidation of cyclohexanone is performed, for example, by a co-oxidation process
in which cyclohexanone is oxidized with air in the coexistence of acetaldehyde
or an oxidation process in which an organic peracid such as peracetic acid is used
as an oxidizing agent.
In the production of ε-caprolactone by the oxidation of cyclohexanone,
the
resulting crude reaction mixture generally comprises unreacted raw material cyclohexanone,
in addition to the target ε-caprolactone. In the oxidation using an oxidizing
agent such as a peracid, the crude reaction mixture further comprises, for example,
an unreacted oxidizing agent, by-products derived from the oxidizing agent (e.g.,
an acid derived from the peracid serving as the oxidizing agent), a solvent for
the oxidizing agent, by-products derived from cyclohexanone (e.g., adipic acid),
and a polymerized product of ε-caprolactone, in addition to the above components.
The crude reaction mixture comprising multiple components is separated and purified
by distillation to yield ε-caprolactone as a product and to recover and recycle
unreacted cyclohexanone.
Demands have been made to increase the yield of ε-caprolactone by increasing
the conversion from cyclohexanone as high as possible and to increase the productivity
by reducing the amount of recovered and recycled cyclohexanone in the production
of ε-caprolactone. As a possible solution to this, a process has been proposed
in which the reaction is performed under severe conditions such as an increased
amount of the oxidizing agent or an increased reaction temperature. However, this
process also facilitates side reactions and thereby increases the by-products derived
from cyclohexanone and by-products such as a polymerized product of ε-caprolactone.
The reaction mixture containing these components should be heated in a distillation
column for separation and purification, but the by-products further react with
ε-caprolactone to yield more complicated by-products. Thus, the final yield
of ε-caprolactone decreases, failing to achieve the initial object.
In contrast, a process in which steps relating to separation of ε-caprolactone
and recovery of cyclohexanone are improved without changing reaction conditions
has been proposed. For example, Japanese Unexamined Patent Application Publication
(JP-A) No. 2002-179667 (p. 3-5 and FIG. 1) describes a process, in which a crude
reaction mixture is fed to a first distillation column, a distillate containing
cyclohexanone and a bottom liquid containing ε-caprolactone are separated,
recovered and are then fed to second and third distillation columns for purification,
respectively. However, according to this process, the distillate recovered from
the first distillation column comprises cyclohexanone in a low concentration, and
the second distillation column for recovering cyclohexanone must treat a large
amount of the distillate. The size and treating capability of the second distillation
column therefore must be increased, inviting increased energy for operation. Thus,
the process is economically unadvantageous.
SUMMARY OF THE INVENTION
Accordingly, an object of the present invention is to provide an economically
advantageous process for producing ε-caprolactone which can efficiently separate
unreacted cyclohexanone from a crude reaction mixture and can efficiently yield
high-quality ε-caprolactone.
After intensive investigations to achieve the above object, the present inventors
have found that unreacted cyclohexanone can be efficiently separated and purified
in a second distillation column by recovering a side-cut fraction containing unreacted
cyclohexanone in a high concentration from a first distillation column, and that
ε-caprolactone can be produced in a high yield by recycling the unreacted cyclohexanone.
Specifically, the present invention provides, in an aspect, a process
for producing ε-caprolactone by the oxidation of cyclohexanone, including
the steps of feeding a crude reaction mixture to a first distillation column; and
recovering a first side-cut fraction containing unreacted cyclohexanone from an
intermediate tray of the first distillation column.
The present invention also provides, in another aspect, a process for producing
ε-caprolactone by the oxidation of cyclohexanone, including the steps of
feeding a crude reaction mixture to a first distillation column; distilling off
a first distillate from the top of the first distillation column, the first distillate
containing low boiling components including unreacted cyclohexanone; recovering
a first side-cut fraction from an intermediate tray of the first distillation column,
the first side-cut fraction containing unreacted cyclohexanone in a higher concentration
than in the first distillate; recovering a first bottom liquid from the bottom
of the first distillation column, the first bottom liquid containing high boiling
components including ε-caprolactone; introducing the first side-cut fraction
to a second distillation column; recovering a second bottom liquid containing unreacted
cyclohexanone from the bottom of the second distillation column; recycling the
second bottom liquid into the raw material cyclohexanone; introducing the first
bottom liquid to a third distillation column to thereby yield a third distillate
containing ε-caprolactone from the third distillation column.
According to the present invention, a side-cut fraction containing unreacted
cyclohexanone in a high concentration is recovered from an intermediate tray other
than the top and bottom of the first distillation column and is fed to the second
distillation column. Therefore, the burden on the processing in the second distillation
column can be mitigated, and high-quality ε-caprolactone can be economically
produced in a high yield without changing reaction conditions.
In the production processes of the present invention, cyclohexanone may be oxidized
using a peracid. The peracid is preferably an organic peracid and more preferable
peracetic acid.
The crude reaction mixture may mainly contain the peracid, an acid derived from
the peracid, a solvent for the peracid, cyclohexanone, ε-caprolactone, adipic
acid, and a polymerized product of ε-caprolactone. The first side-cut fraction
may mainly contain the peracid, an acid derived from the peracid, a solvent for
the peracid, and cyclohexanone. The first distillate may mainly contain the peracid,
an acid derived from the peracid, a solvent for the peracid, and cyclohexanone.
The first bottom liquid may mainly contain ε-caprolactone, adipic acid, and
a polymerized product of ε-caprolactone. The second bottom liquid may mainly
contain an acid derived from the peracid and unreacted cyclohexanone. The third
distillate may mainly contain ε-caprolactone.
Further objects, features and advantages of the present invention will become
apparent from the following description of the preferred embodiments with reference
to the attached drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic flow chart of a process for producing ε-caprolactone
as an embodiment of the present invention; and
FIG. 2 is a schematic flow chart of a process for producing ε-caprolactone
as Comparative Example 1.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 is a schematic flow chart of a process for producing ε-caprolactone
as an embodiment of the present invention, in which abbreviations in frames represent
main components of a distillate or bottom liquid.
Reaction
In this embodiment, ε-caprolactone is produced by the oxidation of cyclohexanone
with a peracid. The peracid can be any of inorganic peracids and organic peracids,
of which organic peracids are preferred. Such organic peracids include, for example,
organic peroxoacids having -CO-OOH group, such as peroxyacetic acid (peracetic
acid), peroxypropionic acid, and peroxyisobutyric acid, of which peracetic acid
is typically preferred. The peracid is generally used in the form of a solution
in a solvent such as acetone, ethyl acetate or acetic acid. For example, the organic
peracid serves to oxidize cyclohexanone to yield ε-caprolactone and is generally
converted into an acid having a boiling point lower than ε-caprolactone,
such as acetic acid, propionic acid or isobutyric acid.
The above reaction yields a crude reaction mixture A containing ε-caprolactone
(hereinafter briefly referred to as "CL-M") as a product, unreacted cyclohexanone
(hereinafter briefly referred to as "ANO"), unreacted peracid (hereinafter briefly
referred to as "AP"), a solvent for the peracid (hereinafter briefly referred to
as "AE"), an acid corresponding to the peracid (hereinafter briefly referred to
as "AC"), a polymerized product of ε-caprolactone (hereinafter briefly referred
to as "HB") such as a caprolactone oligomer and/or caprolactone polymer, a by-product
derived from cyclohexanone such as oxycaproic acid or adipic acid (hereinafter
briefly referred to as "ADA"), and other by-products. From the crude reaction mixture
A, individual components are separated and recovered according to the steps exemplified
in FIG.
1.
In a co-oxidation process, ε-caprolactone is produced by the oxidation
of
cyclohexanone with air using acetaldehyde instead of the peracid, where necessary,
in the presence of a catalyst. In this process, unreacted acetaldehyde corresponds
to the unreacted peracid AP and acetic acid derived from acetaldehyde corresponds
to the acid derived from the peracid AC in the process using the peracid.
First Distillation Column
According to the embodiment of FIG. 1, the crude reaction mixture A formed
as a result of the above reaction is fed to a first distillation column. A first
bottom liquid A
3 mainly comprising high boiling components, ε-caprolactone
CL-M, adipic acid ADA, and a polymerized product of ε-caprolactone HB, is
recovered from the bottom of the first distillation column; a first distillate
A
1 mainly comprising low boiling components, unreacted cyclohexanone ANO,
unreacted peracid AP, a solvent for the peracid AE, and an acid corresponding to
the peracid AC, is recovered from the top, and a first side-cut fraction A
2
mainly comprising low boiling components ANO, AP, AE, and AC is recovered from
an intermediate tray other than the top and the bottom.
The distillation conditions in the first distillation column may be such that
cyclohexanone can be recovered as a side-cut fraction from an intermediate tray
of the distillation column and are preferably such that the concentration of cyclohexanone
in the first side-cut fraction A
2 is higher than that in the first distillate
(first overhead) A
1. They are more preferably such that the first distillate
A
1, the first side-cut fraction A
2 and the first bottom liquid A
3
have the compositions shown in FIG. 1, respectively. More specifically, in the
first distillation column, the bottom temperature is, for example, from about 100°
C. to about 200° C., and the column top pressure is, for example, lower than
the normal atmospheric pressure and is preferably about 100 mmHg (13.3 kPa) or
less. The distillation under reduced pressure can inhibit loss of ε-caprolactone
due to polymerization in the crude reaction mixture A that contains multiple components
and is thermally unstable with time.
The first side-cut fraction A
2 can be recovered from any intermediate
tray of the first distillation column, namely from any position other than the
column top and bottom and is preferably recovered from a portion where the concentration
of unreacted cyclohexanone is high, such as an intermediate tray between the column
top and a tray from which the crude reaction mixture A is charged. The first side-cut
fraction A
2 can be extracted in any form of a liquid, a gas or a mixture thereof.
As a result of the above distillation procedure, substantially all of unreacted
cyclohexanone contained in the crude reaction mixture A is distilled as the first
distillate A
1 and the first side-cut fraction A
2. Even if the bottom
liquid A
3 contains unreacted cyclohexanone, the amount thereof is trivial.
According to this embodiment, the first side-cut fraction A
2 containing
cyclohexanone in a higher concentration than in the first distillate A
1
recovered from the column top is recovered and is fed to the second distillation
column, thus mitigating the burden on the subsequent separation and purification
procedure in the second distillation column.
The above-recovered first side-cut fraction A
2 is introduced into the
second distillation column to thereby recover unreacted cyclohexanone, and the
first bottom liquid A
3 is introduced into a third distillation column to
thereby yield ε-caprolactone.
Second Distillation Column
In the embodiment shown in FIG. 1, the first side-cut fraction A
2 recovered
from the first distillation column is introduced into the second distillation column.
A second distillate A
21 mainly comprising low boiling components including
the unreacted peracid AP, the solvent for the peracid AE, and the acid corresponding
to the peracid AC is distilled off from the column top. A second bottom liquid
A
22 mainly comprising the unreacted cyclohexanone ANO and AC is recovered
from the bottom and is then recycled into the raw material cyclohexanone.
The distillation conditions in the second distillation column may be such that
cyclohexanone can be recovered from the bottom and are preferably such that the
second distillate A
21 and the second bottom liquid A
22 have the compositions
shown in FIG.
1. More specifically, in the second distillation column, the
bottom temperature is, for example, from about 120° C. to about 200°
C., and the column top pressure is, for example, about 50 mmHg (6.67 kPa) or less.
The distillation under these conditions can prevent thermally unstable cyclohexanone
contained in the first side-cut fraction A
2 from deterioration.
The second bottom liquid A
22 contains unreacted cyclohexanone in a high
concentration and can be recycled, as intact, into the reaction system.
Third Distillation Column
According to the embodiment of FIG. 1, the first bottom liquid A
3
recovered from the first distillation column is fed to the third distillation column.
A third bottom liquid A
32 containing high boiling components including adipic
acid ADA and a polymerized product of ε-caprolactone HB is drained from the
bottom of the third distillation column, and a third distillate A31 containing
ε-caprolactone CL-M is recovered as a product.
The distillation conditions in the third distillation column may be such that
ε-caprolactone can be recovered as a distillate (including a distillate from
an intermediate tray) They are preferably such that the third distillate A
31
and the third bottom liquid A
32 have, for example, the compositions shown
in FIG.
1. More specifically, in the third distillation column, the bottom
temperature is, for example, from about 100° C. to about 200° C., and
the column top pressure is, for example, about 50 mmHg (6.67 kPa) or less. For
avoiding the polymerization of ε-caprolactone, the third distillate A
31
is preferably recovered not from the column top but from an intermediate tray such
as an intermediate tray between the column top and a tray from which the first
bottom liquid A
3 is charged. While not shown in FIG. 1, when ε-caprolactone
is recovered from an intermediate tray, a third distillate A
30 recovered
from the column top may be introduced into the first distillation column for removing
low boiling components. The third bottom liquid A
32 contains multiple components
such as ADA and HB, does not have a constant composition and is thereby generally disposed.
The present invention will be illustrated in further detail with reference to
an example below, which is not intended to limit the scope of the invention. All
percentages are by weight.
REFERENCE EXAMPLE 1
Into a flow reactor with a reaction inner capacity of 2 liters were fed cyclohexanone
at 60 g/hr, a 30% solution of peracetic acid in ethyl acetate at 170.5 g/hr (at
51.4 g/hr in terms of pure peracetic acid, 1.1 times by mole that of cyclohexanone)
for performing a continuous reaction at a reaction temperature of 50° C. The
resulting crude reaction mixture was analyzed and was found to contain 28.78% of
ε-caprolactone CL-M, 0.52% of unreacted cyclohexanone ANO, 1.31% of unreacted
peracetic acid, 0.59% of by-produced adipic acid ADA, 0.30% of a polymerized product
of caprolactone HB, 21.16% of acetic acid, 47.34% of ethyl acetate, and 0% of water.
EXAMPLE 1
According to the flow chart of FIG. 1, ε-caprolactone was produced.
Initially, a crude reaction mixture A produced according to the procedure of Reference
Example 1 was fed to a first distillation column and was subjected to distillation
for removing low boiling components at a bottom temperature of 180° C. and
a column top pressure of 90 mmHg (12.0 kPa). In the first distillation column,
low boiling components including unreacted cyclohexanone ANO, unreacted peracetic
acid, ethyl acetate and acetic acid were distilled as a first distillate A1
and a first side-cut fraction A2. The first side-cut fraction A2
contained ANO in a higher concentration than in the first overhead distillate A1.
The first side-cut fraction A2 was introduced into a second distillation
column, was subjected to distillation at a bottom temperature of 100° C. and
a column top pressure of 225 mmHg (30.0 kPa) and thereby yielded a second distillate
A21 containing unreacted peracetic acid, ethyl acetate, and acetic acid
from the column top and a second bottom liquid A22 containing ANO and part
of acetic acid from the bottom. The recovered second bottom liquid A22 was
recycled as a reaction raw material to the reaction system. In the first distillation
column, a first bottom liquid A3 containing the target ε-caprolactone
CL-M, by-produced adipic acid ADA and a polymerization product of ε-caprolactone
HB was recovered from the bottom. The recovered first bottom liquid A3 was
introduced into a third distillation column and was subjected to distillation at
a bottom temperature in a range from 120° C. to 200° C. and a column
top pressure of 5 mmHg (0.67 kPa). In the third distillation column, the target
ε-caprolactone was yielded as a third side-cut fraction A31 not from
the column top but from an intermediate tray between the column top and a tray
from which the first bottom liquid A3 was charged. A third bottom liquid
A32 containing by-produced adipic acid ADA and a polymerized product of
ε-caprolactone HB was drained from the bottom. Separately, a third overhead
distillate A30 was recovered from the column top and was introduced into
the first distillation column for removing low boiling components.
Quantitative operation conditions on charge, reflux, overhead distillation,
side cut, and bottom liquid recovery in the first distillation column, those on
reflux, distillation, and bottom liquid recovery (ANO recovery) in the second distillation
column, and those on reflux, overhead distillation, side cut (product recovery)
and bottom liquid drain in the third distillation column are shown in Tables 1-1,
1-2, and 1-3, respectively.
COMPARATIVE EXAMPLE 1
According to the flow chart shown in FIG. 2, ε-caprolactone was produced.
Initially, a crude reaction mixture B prepared according to the procedure of Reference
Example 1 was fed to a first distillation column and was subjected to distillation
for removing low boiling components at a bottom temperature of 200° C. and
a column top pressure of 100 mmHg (13.3 kPa). In the first distillation column,
low boiling components including unreacted cyclohexanone ANO, unreacted peracetic
acid, ethyl acetate, and acetic acid was distilled as a first distillate B1.
The first distillate B1 was introduced into a second distillation column
and was subjected to distillation at a bottom temperature of 200° C. and a
column top pressure of 100 mmHg (13.3 kPa). In this procedure, a second distillate
B11 containing unreacted peracetic acid, ethyl acetate, and acetic acid
was distilled off from the column top, and a second bottom liquid B12 containing
unreacted cyclohexanone ANO and part of acetic acid was recovered from the bottom.
A part of the second bottom liquid B12 was recycled as a reaction raw material
to the reaction system, and the remainder was disposed. Separately, a first bottom
liquid B2 containing the target product ε-caprolactone CL-M, by produced
adipic acid ADA, and a polymerized product of ε-caprolactone HB was recovered
from the bottom of the first distillation column. The recovered first bottom liquid
B2 was introduced into a third distillation column and was subjected to
distillation at a bottom temperature in a range from 120° C. to 200°
C. and a column top pressure of 50 mmHg (6.67 kPa). In this procedure, the target
ε-caprolactone CL-M was recovered as a third distillate B21 not from
the column top but from an intermediate tray between the column top and a tray
from which the first bottom liquid B2 was charged, and a third bottom liquid
B22 containing by-produced adipic acid ADA and a polymerized product of
ε-caprolactone HB was drained from the bottom. A third overhead distillate
B20 was recovered from the column top and was introduced into the first
distillation column for removing low boiling components.
Quantitative operation conditions on charge, reflux, distillation, and
bottom liquid recovery in the first distillation column, those on reflux, distillation,
bottom liquid recovery (ANO recovery), and bottom liquid disposal (partial disposal)
in the second distillation column, and those on reflux, overhead distillation,
side cut (product recovery) and bottom liquid drain in the third distillation column
are shown in Tables 2-1, 2-2, and 2-3, respectively.
In the tables below, the term "AP" means unreacted peracetic acid, the term "AE"
means ethyl acetate, the term "AC" means acetic acid, and the term "LB" means other
low-boiling components. And composition is referred to as the abbreviation "comp.".
| TABLE 1-1 |
| First Distillation Column (removal of low boiling components) |
| |
Charge |
Reflux |
distillation |
[to 2nd column] |
[to 3rd column] |
| Compo- |
Rate |
Comp. |
Rate |
Comp. |
Rate |
Comp. |
Rate |
Comp. |
Rate |
Comp. |
| nent |
kg/hr |
wt. % |
kg/hr |
wt. % |
kg/hr |
wt. % |
kg/hr |
wt. % |
kg/hr |
wt. % |
| AE |
4449.9 |
45.5 |
4495.0 |
82.9 |
4086.3 |
82.9 |
363.6 |
18.2 |
0.0 |
0.0 |
| AC |
2249.4 |
23.0 |
879.2 |
16.2 |
799.3 |
16.2 |
1450.1 |
72.5 |
0.0 |
0.0 |
| AP |
117.4 |
1.2 |
47.1 |
0.9 |
42.8 |
0.9 |
74.6 |
3.7 |
0.0 |
0.0 |
| ANO |
78.2 |
0.8 |
1.74 |
0.0 |
1.6 |
0.0 |
76.6 |
3.8 |
0.0 |
0.0 |
| CL-M |
2840.0 |
29.0 |
0.0 |
0.0 |
0.0 |
0.0 |
35.1 |
1.8 |
2804.9 |
98.3 |
| H2O |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
| LB |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
| ADA |
48.9 |
0.5 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
48.9 |
1.7 |
| HB |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
| Total |
9780.0 |
100 |
5423 |
100 |
4930.0 |
100 |
1999.9 |
100 |
2853.8 |
100 |
| TABLE 1-2 |
| Second Distillation Column (ANO recovery) |
| |
Reflux |
Distillation |
[ANO recovery] |
| Compo- |
Rate |
Comp. |
Rate |
Comp. |
Rate |
Comp. |
| nent |
kg/hr |
wt. % |
kg/hr |
wt. % |
kg/hr |
wt. % |
| AE |
363.6 |
21.4 |
363.6 |
21.4 |
0.0 |
0.0 |
| AC |
1264.7 |
74.4 |
1264.7 |
74.4 |
185.5 |
61.8 |
| AP |
71.2 |
4.2 |
71.2 |
4.2 |
3.3 |
1.1 |
| ANO |
0.5 |
0.0 |
0.5 |
0.0 |
76.1 |
25.4 |
| CL-M |
0.0 |
0.0 |
0.0 |
0.0 |
35.1 |
11.7 |
| H2O |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
| LB |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
| ADA |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
| HB |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
| Total |
1700.0 |
100 |
1700.0 |
100 |
300.0 |
100 |
| TABLE 1-3 |
| Third Distillation Column (product recovery) |
| |
Overhead |
|
| |
distillation |
|
| |
[recycled |
|
| |
for removing |
|
Side cut |
| |
low boiling |
|
[product |
| |
Reflux |
components] |
Bottom |
recovery] |
| Compo- |
Rate |
Comp. |
Rate |
Comp. |
Rate |
Comp. |
Rate |
Comp. |
| nent |
kg/hr |
wt. % |
kg/hr |
wt. % |
kg/hr |
wt. % |
kg/hr |
wt. % |
| AE |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
| AC |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
| AP |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
| ANO |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
| CL-M |
3724.5 |
100 |
120.0 |
100 |
86.0 |
63.8 |
2718.9 |
100 |
| H2O |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
| LB |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
| ADA |
0.0 |
0.0 |
0.0 |
0.0 |
48.9 |
36.2 |
0.0 |
0.0 |
| HB |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
0.0 |
| Total |
3724.5 |
100 |
120.0 |
100 |
134.9 |
100 |
2598.9 |
100 |
| TABLE 2-1 |
| First Distillation Column (removal of low boiling components) |
| |
Charge |
Reflux |
[to 2nd column] |
[to 3rd column] |
| Compo- |
Rate |
Comp. |
Rate |
Comp. |
Rate |
Comp. |
Rate |
Comp. |
| nent |
kg/hr |
wt. % |
kg/hr |
wt. % |
kg/hr |
wt. % |
kg/hr |
wt. % |
| AE |
4210.8 |
46.32 |
2105.4 |
65.51 |
4210.8 |
65.51 |
0.0 |
0.00 |
| AC |
1954.8 |
21.51 |
977.2 |
30.41 |
1954.3 |
30.41 |
0.5 |
0.02 |
| AP |
150.0 |
1.65 |
75.0 |
2.33 |
150.0 |
2.33 |
0.0 |
0.00 |
| ANO |
94.8 |
1.04 |
47.4 |
1.48 |
94.8 |
1.48 |
0.3 |
0.01 |
| CL-M |
2623.2 |
28.86 |
4.2 |
0.13 |
8.4 |
0.13 |
2725.9 |
97.95 |
| H2O |
9.6 |
0.11 |
4.5 |
0.14 |
9.0 |
0.14 |
1.1 |
0.04 |
| LB |
0.1 |
0.00 |
0.1 |
0.00 |
0.1 |
0.00 |
0.0 |
0.00 |
| ADA |
27.6 |
0.30 |
0.0 |
0.00 |
0.0 |
0.00 |
27.6 |
0.99 |
| HB |
19.2 |
0.21 |
0.0 |
0.00 |
0.0 |
0.00 |
27.6 |
0.99 |
| Total |
9090.1 |
100 |
3213.7 |
100 |
6427.4 |
100 |
2783.0 |
100 |
| TABLE 2-2 |
| Second Distillation Column (ANO recovery) |
| |
Reflux |
Distillation |
[ANO recovery] |
[partial disposal] |
| Compo- |
Rate |
Comp. |
Rate |
Comp. |
Rate |
Comp. |
Rate |
Comp. |
| nent |
kg/hr |
wt. % |
kg/hr |
wt. % |
kg/hr |
wt. % |
kg/hr |
wt. % |
| AE |
1263.2 |
67.65 |
4210.8 |
67.65 |
0.0 |
0.00 |
0.0 |
0.00 |
| AC |
556.3 |
29.79 |
1854.3 |
29.79 |
80.0 |
49.23 |
20.0 |
49.14 |
| AP |
45.0 |
2.41 |
150.0 |
2.41 |
0.0 |
0.00 |
0.0 |
0.00 |
| ANO |
0.0 |
0.00 |
0.0 |
0.00 |
75.8 |
46.65 |
19.0 |
46.68 |
| CL-M |
0.0 |
0.00 |
0.0 |
0.00 |
6.7 |
4.12 |
1.7 |
4.18 |
| H2O |
2.7 |
0.15 |
9.0 |
0.15 |
0.0 |
0.00 |
0.0 |
0.00 |
| LB |
0.0 |
0.00 |
0.1 |
0.00 |
0.0 |
0.00 |
0.0 |
0.00 |
| ADA |
0.0 |
0.00 |
0.0 |
0.00 |
0.0 |
0.00 |
0.0 |
0.00 |
| HB |
0.0 |
0.00 |
0.0 |
0.00 |
0.0 |
0.00 |
0.0 |
0.00 |
| Total |
1867.2 |
100 |
6224.2 |
100 |
162.5 |
100 |
40.7 |
100 |
| TABLE 2-3 |
| Third Distillation Column (product recovery) |
| |
Overhead |
|
| |
distillation |
|
| |
[recycled |
|
| |
for removing |
|
Side cut |
| |
low boiling |
|
[product |
| |
Reflux |
components] |
Bottom |
recovery] |
| Compo- |
Rate |
Comp. |
Rate |
Comp. |
Rate |
Comp. |
Rate |
Comp. |
| nent |
kg/hr |
wt. % |
kg/hr |
wt. % |
kg/hr |
wt. % |
kg/hr |
wt. % |
| AE |
0.0 |
0.00 |
0.0 |
0.00 |
0.0 |
0.00 |
0.0 |
0.00 |
| AC |
0.0 |
0.00 |
0.0 |
0.00 |
0.0 |
0.00 |
0.5 |
0.02 |
| AP |
0.0 |
0.00 |
0.0 |
0.00 |
0.0 |
0.00 |
0.0 |
0.00 |
| ANO |
0.0 |
0.00 |
0.3 |
0.25 |
0.0 |
0.00 |
0.0 |
0.00 |
| CL-M |
3602.4 |
99.54 |
119.5 |
99.33 |
33.0 |
23.88 |
2523.4 |
99.96 |
| H2O |
15.6 |
0.43 |
0.5 |
0.42 |
0.0 |
0.00 |
0.6 |
0.02 |
| LB |
1.2 |
0.03 |
0.0 |
0.00 |
0.0 |
0.00 |
0.0 |
0.00 |
| ADA |
0.0 |
0.00 |
0.0 |
0.00 |
27.1 |
19.61 |
0.0 |
0.00 |
| HB |
0.0 |
0.00 |
0.0 |
0.00 |
78.1 |
56.51 |
0.0 |
0.00 |
| Total |
3619.2 |
100 |
120.3 |
100 |
138.2 |
100 |
2524.5 |
100 |
While the present invention has been described with reference to what are presently
considered to be the preferred embodiments, it is to be understood that the invention
is not limited to the disclosed embodiments. On the contrary, the invention is
intended to cover various modifications and equivalent arrangements included within
the spirit and scope of the appended claims. The scope of the following claims
is to be accorded the broadest interpretation so as to encompass all such modifications
and equivalent structures and functions.
*
