U.S. patent application number 09/895192 was filed with the patent office on 2002-04-18 for refining treatment method of liquid reaction mixture obtained from epoxidation reaction of 1,5,9-cyclododecatriene.
This patent application is currently assigned to Ube Industries, Ltd.. Invention is credited to Kaiso, Kohji, Kugimoto, Junichi, Ninomiya, Kouhei, Sugimoto, Tsunemi, Yamanaka, Mitsuo.
Application Number | 20020045791 09/895192 |
Document ID | / |
Family ID | 26595371 |
Filed Date | 2002-04-18 |
United States Patent
Application |
20020045791 |
Kind Code |
A1 |
Ninomiya, Kouhei ; et
al. |
April 18, 2002 |
Refining treatment method of liquid reaction mixture obtained from
epoxidation reaction of 1,5,9-cyclododecatriene
Abstract
After 1,5,9-cyclododecatriene is epoxidized with hydrogen
peroxide in the presence of a catalyst containing a tungsten
compound, a quaternary onium salt and a mineral acid, to obtain a
liquid reaction mixture containing the resultant
1,2-epoxy-5,9-cyclododecadiene, the catalyst, non-reacted hydrogen
peroxide and non-reacted 1,5,9-cyclododecatriene and being
phase-separated into an oil phase fraction and an aqueous phase
fraction, at least the oil phase fraction of the liquid reaction
mixture is treated with an aqueous alkali solution to deactivate
and remove the non-reacted hydrogen peroxide and the catalyst
contained in at least the oil phase fraction.
Inventors: |
Ninomiya, Kouhei; (Ube-shi,
JP) ; Sugimoto, Tsunemi; (Ube-shi, JP) ;
Kugimoto, Junichi; (Ube-shi, JP) ; Yamanaka,
Mitsuo; (Ube-shi, JP) ; Kaiso, Kohji;
(Ube-shi, JP) |
Correspondence
Address: |
MORGAN, LEWIS & BOCKIUS
1800 M STREET NW
WASHINGTON
DC
20036-5869
US
|
Assignee: |
Ube Industries, Ltd.
|
Family ID: |
26595371 |
Appl. No.: |
09/895192 |
Filed: |
July 2, 2001 |
Current U.S.
Class: |
585/700 ; 585/16;
585/940 |
Current CPC
Class: |
C07D 301/12
20130101 |
Class at
Publication: |
585/700 ; 585/16;
585/940 |
International
Class: |
C07C 005/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 4, 2000 |
JP |
2000-202688 |
May 18, 2001 |
JP |
2001-149699 |
Claims
1. A refining treatment method of a liquid reaction mixture
obtained from an epoxidation reaction of 1,5,9-cyclododecatriene
with hydrogen peroxide in the presence of a catalyst comprising a
tungsten compound, a quaternary onium salt and a mineral acid,
containing resultant 1,2-epoxy-5,9-cyclododecadiene, the catalyst,
non-reacted hydrogen peroxide and non-reacted
1,5,9-cyclododecatriene, and being phase-separated into an oil
phase fraction and an aqueous phase fraction, which method
comprises refining-treating at least the oil phase fraction of the
liquid reaction mixture with an aqueous alkali solution, to thereby
deactivate and remove the non-reacted hydrogen peroxide and the
catalyst contained in at least the oil phase fraction of the liquid
reaction mixture.
2. The refining treatment method of a liquid reaction mixture
obtained from an epoxidation reaction of 1,5,9-cyclododecatriene as
claimed in claim 1, wherein the aqueous alkali solution has a pH
value of 8 or more.
3. The refining treatment method of a liquid reaction mixture
obtained from an epoxidation reaction of 1,5,9-cyclododecatriene as
claimed in claim 1 or 2, wherein, in a system of the epoxidation
reaction, the 1,5,9-cyclododecatriene contained in the reaction
system serves as a reaction medium.
4. The refining treatment method of a liquid reaction mixture
obtained from an epoxidation reaction of 1,5,9-cyclododecatriene as
claimed in any of claims 1 to 3, wherein the refining treatment of
the liquid reaction mixture obtained from the epoxidation reaction,
with the aqueous alkali solution, is controlled so that after the
refining treatment, the aqueous phase fraction of the liquid
reaction mixture exhibits a pH value of 7.0 or more.
5. The refining treatment method of a liquid reaction mixture
obtained from an epoxidation reaction of 1,5,9-cyclododecatriene as
claimed in any of claims 1 to 4, wherein the oil phase fraction is
collected from the liquid reaction mixture obtained from the
epoxidation reaction and the collected oil phase fraction is
subjected to the refining treatment with the aqueous alkali
solution.
6. The refining treatment method of a liquid reaction mixture
obtained from an epoxidation reaction of 1,5,9-cyclododecatriene as
claimed in any of claims 1 to 4, wherein, after the refining
treatment of the liquid reaction mixture obtained from the
epoxidation reaction with the aqueous alkali solution is completed,
the oil phase fraction is collected from the refining-treated
liquid reaction mixture.
7. A method of isolating 1,2-epoxy-5,9-cyclododecadiene comprising
distilling the oil phase fraction collected and then
refining-treated, or refining-treated and then collected, in
accordance with the method as claimed in claim 5 or 6.
Description
BACKGROUND OF THE INVENTION
[0001] (1) Field of the Invention
[0002] The present invention relates to a method of
refining-treating a liquid reaction mixture obtained from an
epoxidation reaction of 1,5,9-cyclododecatriene. More particularly,
the method of the present invention relates to a method of
refining-treating a liquid reaction mixture obtained from an
epoxidation reaction of 1,5,9-cyclododecatriene with hydrogen
peroxide in the presence of a catalyst. The refining-treatment
method of the present invention is useful for the production of
1,2-epoxy-5,9-cyclododecadiene usable as an intermediate for
laurolactam which is usable as a material for the production of
nylon 12.
[0003] (2) Description of the Related Art
[0004] A method of epoxidizing an olefin compound with hydrogen
peroxide is generally well known. For example, various methods of
epoxidizing an olefin with hydrogen peroxide in the presence of a
catalyst comprising, as examples, a tungsten compound, a quaternary
onium salt and a mineral acid are disclosed in Japanese Examined
Patent Publication No. 1-33,471 and No. 3-74235, and Japanese
Unexamined Patent Publication No. 5-213,919, No. 62-230,778 and No.
62-234,550.
[0005] However, none of the above-mentioned publications discloses
an industrial treating method for isolating an epoxy compound as a
target product from a liquid reaction mixture obtained by an
epoxidation reaction of the olefin compound with high safety and
with high efficiency.
[0006] Usually, as a method of treating a liquid reaction mixture
obtained from an epoxidation reaction of the olefin compound with
hydrogen peroxide, a method in which an oil phase fraction and an
aqueous phase fraction contained in the liquid reaction mixture are
separated from each other by using a separator, and the separated
oil phase fraction is subjected to distillation to collect the
target epoxy compound, is utilized.
[0007] In the liquid reaction mixture obtained by an epoxidation
reaction of 1,5,9-cyclododecatriene with hydrogen peroxide in the
presence of a catalyst comprising a tungsten compound, a quaternary
onium salt and a mineral acid, however, the oil phase fraction
containing the resultant 1,2-epoxy-5,9-cyclododecadiene and the
aqueous phase fraction exhibit a low liquid phase separation
property from each other, and a portion of the aqueous phase
fraction in several % is mixed with and suspended in the form of a
plurality of liquid particles in the oil phase fraction. The
portion of aqueous phase fraction suspended in the oil phase
fraction is difficult to completely separate from the oil phase
fraction, even after the oil phase fraction is left to stand for a
long period.
[0008] The liquid particles, of the aqueous phase fraction mixed in
the oil phase fraction, contain the tungsten compound and the
mineral acid for the catalyst and the non-reacted hydrogen peroxide
are dissolved therein. Therefore, when the oil phase fraction
containing the aqueous phase fraction particles is subjected to
distillation, the target product, namely
1,2-epoxy-5,9-cyclododecadiene is undesirably polymerized in the
presence of the above-mentioned catalyst, and thus, a
disadvantageous decrease in the yield of the target compound
occurs.
[0009] Further, when the particles of the aqueous phase fraction
mixed into the oil phase fraction contain a extremely strong acid
compound, for example, phosphotungstic acid
(H.sub.3PW.sub.12O.sub.40), a phenomenon that the target
1,2-epoxy-5,9-cyclododecadiene vigorously reacts with the
phosphotungstic acid (H.sub.3PW.sub.120.sub.40) to generate
exothermic heat, may be created.
[0010] Also, a phenomenon that, in the distillation procedure, the
non-reacted hydrogen peroxide and a by-product consisting of
organic peroxide compounds which are dissolved in the aqueous phase
fraction and the oil phase fraction, are respectively thermally
decomposed, may be generated, and thus, the method in which the oil
phase fraction of the liquid reaction mixture obtained from the
epoxidation reaction of 1,5,9-cyclododecatriene is directly
subjected to the distillation is not always safe in industrial
practice.
[0011] Therefore, it is necessary to deactivate the non-reacted
hydrogen peroxide and the residual catalyst compound contained in
the oil phase fraction of the liquid reaction mixture and/or to
remove them from the oil phase fraction by extraction, before the
distillation of the oil phase fraction.
SUMMARY OF THE INVENTION
[0012] An object of the present invention is to provide a refining
treatment method of a liquid reaction mixture obtained from an
epoxidation reaction of 1,5,9-cyclododecatriene with hydrogen
peroxide in the presence of a catalyst comprising a tungsten
compound, a quaternary onium salt and a mineral acid, to obtain a
liquid refined mixture from which the target 1,2-epoxy
-5,9-cyclododecadiene can be collected, by distillation with an
enhanced safety and with a high yield.
[0013] The above-mentioned object can be attained by the method of
the present invention.
[0014] The refining treatment method of the present invention for a
liquid reaction mixture obtained from an epoxidation reaction of
1,5,9-cyclododecatriene with hydrogen peroxide in the presence of a
catalyst comprising a tungsten compound, a quaternary onium salt
and a mineral acid, containing resultant
1,2-epoxy-5,9-cyclododecadiene, the catalyst, non-reacted hydrogen
peroxide and non-reacted 1,5,9-cyclododecatriene, and being
phase-separated into an oil phase fraction and an aqueous phase
fraction, comprises refining-treating at least the oil phase
fraction of the liquid reaction mixture with an aqueous alkali
solution, to thereby deactivate and remove the non-reacted hydrogen
peroxide and the catalyst contained in at least the oil phase
fraction of the liquid reaction mixture.
[0015] In the refining treatment method of the present invention,
for a liquid reaction mixture obtained from an epoxidation reaction
of 1,5,9-cyclododecatriene, the aqueous alkali solution preferably
has a pH value of 8 or more.
[0016] In the refining treatment method of the present invention,
for a liquid reaction mixture obtained from an epoxidation reaction
of 1,5,9-cyclododecatriene, in a system of the epoxidation
reaction, the 1,5,9-cyclododecatriene contained in the reaction
system serves as a reaction medium.
[0017] In the refining treatment method of the present invention,
for a liquid reaction mixture obtained from an epoxidation reaction
of 1,5,9-cyclododecatriene, the refining treatment of the liquid
reaction mixture obtained from the epoxidation reaction with the
aqueous alkali solution, is preferably controlled so that after the
refining treatment, the aqueous phase fraction of the liquid
reaction mixture exhibits a pH value of 7.0 or more.
[0018] In the refining treatment method of the present invention,
for a liquid reaction mixture obtained from an epoxidation reaction
of 1,5,9-cyclododecatriene, preferably the oil phase fraction is
collected from the liquid reaction mixture obtained from the
epoxidation reaction, and the collected oil phase fraction is
subjected to the refining treatment with the aqueous alkali
solution.
[0019] In the refining treatment method of the present invention,
for a liquid reaction mixture obtained from an epoxidation reaction
of 1,5,9-cyclododecatriene, and preferably after the refining
treatment of the liquid reaction mixture obtained from the
epoxidation reaction with the aqueous alkali solution is completed,
the oil phase fraction is collected from the refining-treated
liquid reaction mixture.
[0020] The method of the present invention for isolating
1,2-epoxy-5,9-cyclododecadiene comprises distilling the oil phase
fraction collected and then refining-treated, or refining-treated
and then collected, in accordance with the refining treatment
method as mentioned above.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0021] The refining treatment method of the present invention for
the liquid reaction mixture obtained from the catalytic epoxidation
reaction of 1,5,9-cyclododecatriene with hydrogen peroxide will be
explained in detail as follows.
[0022] The tungsten compounds usable for the epoxidation catalyst
for the epoxidation reaction are preferably selected from inorganic
acids containing tungsten atoms and salts thereof. The tungsten
atom-containing acids and salts thereof include, for example,
tungstic acid (wolframic acid) and salts thereof, for example,
sodium tungstate, potassium tungstate, lithium tungstate, ammonium
tungstate; and dodecatungstates, for example, sodium
dodecatungstate, potassium dodecatungstate and ammonium
dodecatungstate; and heteropoly-acids and salts thereof, for
example, phosphotungstic acid, sodium phosphotungstate,
silicotungstic acid, sodium silicotungstate, phosphovadadotungstic
acid: and phosphomolybdotungstic acid, preferably tungstic acid,
sodium tungstate, potassium tungstate, and phosphotungstic acid.
There tungsten compounds may be employed alone or in a mixture of
two or more thereof.
[0023] The tungsten compound for the epoxidation reaction of the
method of the present invention is preferably employed in an amount
of 0.0007 to 5% by weight, more preferably 0.002 to 3% by weight,
in terms of tungsten atoms, based on the amount of
1,5,9-cyclododecatriene.
[0024] In the method of the present invention, the quaternary onium
salts usable for the epoxidation catalyst include quaternary
ammonium halides, for example, trioctylmethyl ammonium chloride,
tridecylmethyl ammonium chloride, trioctylmethyl ammonium bromide,
benzyldimethyltetradecyl ammonium chloride, benzyltriethyl ammonium
chloride, dimethyldidodecyl ammonium chloride, benzyltributyl
ammonium chloride, benzyltributyl ammonium iodide and
phenyltrimethyl ammonium chloride; quaternary ammonium hydrogen
sulfates; for example, trioctylmethyl ammonium hydrogen sulfate;
quaternary ammonium perchlorates, for example, trioctylmethyl
ammonium perchlorate; quaternary ammonium dihydrogen phosphates,
for example, trioctylmethyl ammonium dihydrogen phosphate;
quaternary ammonium nitrate, for example, trioctylmethyl ammonium
nitrate; quaternary ammonium hydrosilicofluorate, for example,
trioctylmethyl ammonium hydrosilicofluorate; and quaternary
ammonium acetates, for example, trioctylmethyl ammonium acetate.
Among the above-mentioned quaternary onium salts, preferably
quaternary ammonium halides, more preferably trioctylmethyl
ammonium chloride and tridecylmethyl ammonium chloride are
employed.
[0025] The content of the quaternary onium salt in the epoxidation
catalyst is preferably 0.0003 to 4% by weight, more preferably
0.003 to 2.5% by weight, based on the amount in weight of
1,5,9-cyclododecatriene.
[0026] The mineral acids usable for the epoxidation catalyst
include, for example, phosphoric acids, sulfuric acids,
hydrochloric acid, perchloric acid, hexafluorosilicic acid, nitric
acid and tetrafluorosilicic acid. Preferably, phosphoric acid and
sulfuric acid, more preferably phosphoric acid, are employed for
the epoxidation catalyst. The above-mentioned mineral acids may be
employed alone or in a mixture of two or more thereof.
[0027] The content of the mineral acid in the epoxidation catalyst
is preferably 0.001 to 5% by weight, more preferably 0.005 to 3% by
weight, based on the amount (by weight) of
1,5,9-cyclododecatriene.
[0028] There is no limitation to the concentration of hydrogen
peroxide in the aqueous solution thereof usable for the epoxidation
reaction for the method of the present invention. In consideration
of safety in handling and economy of the epoxidation reaction, the
aqueous hydrogen peroxide solution preferably has a concentration
of hydrogen peroxide of 10 to 70% by weight. The aqueous hydrogen
peroxide solution is preferably employed in a molar amount of
hydrogen peroxide, of 0.05 to 1.2 times, more preferably 0.05 to
1.0 time, still more preferably 0.1 to 0.8 time the molar amount of
1,5,9-cyclododecatriene. 1,5,9-cyclododecatriene usable as a
starting material for the epoxidation reaction may be a commercial
grade, and the commercial grade 1,5,9-cyclododecatriene may be
directly subjected to the epoxidation reaction without
pre-treatment, or may be refined and then subjected to the
epoxidation reaction. The 1,5,9-cyclododecatriene may be in any
isomer form, for example, a cis-form or trans-form. The isomers may
be mixed with each other.
[0029] In the epoxidation reaction in accordance with the method of
the present invention, an organic solvent may be contained as a
reaction medium in the reaction system. There is no limitation to
the type of the organic solvent as long as the organic solvent
cannot be evenly dissolved in water and does not obstruct the
epoxidation reaction. The organic solvent for the reaction medium
includes aliphatic halogenated hydrocarbons, for example,
chloroform, dichloroethane, and dichloromethane; aliphatic
non-halogenated hydrocarbons, for example, cyclohexane and
n-heptane; and aromatic hydrocarbons, for example, benzene, toluene
and xylene. The above-mentioned organic solvents may be employed
alone or in a mixture of two or more thereof.
[0030] When the organic solvent is employed, the amount in weight
of the organic solvent preferably does not exceeding 20 times, and
more preferably does not exceeding 10 times, the weight of
1,5,9-cyclododecatriene.
[0031] Preferably, the epoxidation reaction is carried out in a two
liquid phase system consisting a liquid phase comprising
1,5,9-cyclododecadiene and an other liquid phase comprising the
aqueous hydrogen peroxide solution, phase-separated from each
other. For example, the epoxidation reaction is carried out by
mixing 1,5,9-cyclododecatriene, an aqueous hydrogen peroxide
solution and a catalyst comprising a tungsten compound, a
quaternary onium salt and a mineral acid with each other in an
atmosphere consisting of an inert gas, for example, nitrogen gas,
and by heating the resultant mixture under the ambient atmospheric
pressure or an increased pressure, while agitating the mixture.
There is no limitation to the reaction temperature. Usually, the
reaction temperature is preferably 20 to 120.degree. C., more
preferably 30 to 120.degree. C.
[0032] In the refining treatment method of the present invention
for the liquid reaction mixture obtained from the epoxidation
reaction, an aqueous alkali solution may be directly added to the
liquid reaction mixture. Otherwise, preferably, the liquid reaction
mixture is subjected to a phase-separation procedure to separate an
oil phase fraction from an aqueous phase fraction in the liquid
reaction mixture, and then the oil phase fraction is subjected to
the refining treatment procedure with the aqueous alkali solution.
In the former, the resultant liquid mixture treated with the
aqueous alkali solution is subjected to a phase-separation
procedure to collect the treated oil phase fraction from the
treated liquid mixture.
[0033] The aqueous alkali solution usable for the method of the
present invention is an aqueous solution of at least one member
selected from basic organic compounds of alkali metals and alkaline
earth metals and ammonia. The aqueous alkali solution has a pH
value of more than 7, preferably of 8 or more, more preferably 10
or more, still more preferably 11 or more. The basic organic
compound includes hydroxides of alkali metals, carbonates of alkali
metals, bicarbonates of alkali metals, sulfites of alkali metals,
hydroxides of alkaline earth metals, carbonates of alkaline earth
metals, bicarbonates of alkaline earth metals and sulfites of
alkaline earth metals. Preferably the hydroxides of alkali metals,
carbonates of alkali metals, bicarbonates of alkali metals and
sulfites of alkali metals are employed and more preferably the
hydroxides of alkali metals are employed.
[0034] Practical examples of the alkali metal hydroxides and
alkaline earth metal hydroxides are potassium hydroxide, sodium
hydroxide, magnesium hydroxide, barium hydroxide and calcium
hydroxide.
[0035] Practical examples of the alkali metal carbonates and
alkaline earth metal carbonates are potassium carbonate, sodium
carbonate, magnesium carbonate and calcium carbonate.
[0036] Practical examples of the alkali metal bicarbonates are
potassium bicarbonate and sodium bicarbonate.
[0037] Practical examples of the alkali metal sulfites are
potassium sulfite and sodium sulfite.
[0038] Preferably, sodium hydroxide, potassium hydroxide and sodium
sulfite, more preferably sodium hydroxide and potassium hydroxide
are employed. The above-mentioned alkali metal compounds and
alkaline earth metal compounds may be employed alone or in a
mixture of two or more thereof.
[0039] The treatment procedure of the liquid reaction mixture with
the aqueous alkali solution is not limited to a specific procedure.
The treatment may be carried out by procedures in which at least
the oil phase fraction of the liquid reaction mixture obtained from
the epoxidation reaction is added with a solid alkali compound and
then with water, or by procedures in which a solid alkali compound
is dissolved in water to provide an aqueous alkali solution, and
the aqueous alkali solution is mixed into the liquid reaction
mixture obtained from the epoxidation reaction. In view of the ease
of the procedures, preferably, an aqueous alkali solution is
prepared and then the aqueous alkali solution is mixed into the
liquid reaction mixture.
[0040] In the aqueous alkali solution, the concentration of the
alkali compound is preferably 0.01 to 60% by weight, more
preferably 0.1 to 30% by weight, still more preferably 0.5 to 10%
by weight. The amount of the aqueous alkali solution to be added
into the liquid reaction mixture is preferably controlled to an
extent such that after the refining treatment is completed, the
resultant treated liquid mixture has a pH value of 7 or more, more
preferably 8.0 or more, still more preferably from 8 to 13.
[0041] Usually, the amount of the aqueous alkali solution used for
the refining treatment for the liquid reaction mixture is
preferably 1 to 20% by weight, more preferably 0.5 to 10% by
weight, still more preferably 1.0 to 5% by weight, based on the
total weight of the oil phase fraction in the liquid reaction
mixture. If the alkali compound is employed in too large an amount,
a new problem, that the aqueous phase fraction separated from the
oil phase fraction must be specifically treated to remove the
alkali, may occur.
[0042] In the refining treatment of the present invention, there is
no limitation to the treatment temperature. Usually, the treatment
temperature is preferably 0 to 120.degree. C., more preferably 15
to 80.degree. C., still more preferably 20 to 60.degree. C. If the
treatment temperature is too high, a trend that the yield of the
target 1,2-epoxy-5,9-cyclododecadiene decreases may be
observed.
[0043] The treatment apparatus usable for the refining treatment
method of the present invention is not limited to specific types of
apparatus, as long as the apparatus is provided with a stirring
device enabling at least the oil phase fraction of the liquid
reaction mixture obtained from the epoxidation reaction to be fully
contacted with the aqueous alkali solution. For example, a vessel
type reactor or a static type line mixer is preferably utilized for
the refining treatment.
[0044] The refining treatment time for the method of the present
invention is variable in response to the type of treatment
apparatus. When the vessel type reactor is employed, the treatment
time is preferably 1 to 90 minutes, more preferably 2 to 60
minutes, still more preferably 5 to 40 minutes. When the static
mixer type reactor is employed, the treatment time is preferably
0.01 to 5 second, more preferably 0.05 to 3 seconds, still more
preferably 0.1 to 2 seconds.
[0045] The refining treatment in accordance with the method of the
present invention is usually carried out under the ambient
atmospheric pressure, or optionally under increased pressure or
reduced pressure.
[0046] The refining treatment of the liquid epoxidation reaction
mixture in accordance with the method of the present invention can
be carried out in a batch type reactor system or a continuous
reactor system. In order to fully exhibit the effect of the present
invention on an industrial scale, the method of the present
invention is preferably carried out by using a continuous treating
system comprising one or more treating apparatuses.
[0047] By applying the refining treatment in accordance with the
method of the present invention, the deactivation and extraction of
the residual catalyst contained in the liquid epoxidation reaction
mixture and the decomposition of the non-reacted peroxide compounds
remaining in the liquid epoxidation reaction mixture are promoted,
and particularly, the residual catalyst is fully extracted and
removed from the liquid reaction mixture.
[0048] Therefore, when the resultant alkali-treated liquid mixture
is subjected to distillation, loss of the target compound, namely
1,2-epoxy-5,9-cyclododecadiene due to undesired polymerization
and/or thermal decomposition of the target compound during the
distillation is minimized and thus the target compound can be
collected with high safety and with a high yield.
[0049] The target 1,2-epoxy-5,9-cyclododecadiene contained in the
oil phase fraction of the liquid reaction mixture treated in
accordance with the method of the present invention can be refined
and collected by conventional distillation. The distilling
apparatus usable for the alkali-treated liquid reaction mixture
includes a conventional snider-type simple distilling apparatus, a
regular packed column-type distilling apparatus, a perforated plate
column-type distilling apparatus and a bubble cap tower type
distilling apparatus.
[0050] There is no limitation to the distillation conditions for
the alkali-treated liquid reaction mixture. The distillation can be
carried out under the ambient atmospheric pressure, a certain
increased pressure or a reduced pressure. The distillation
temperature is variable in response to the distillation pressure.
Usually, the distillation temperature is preferably 200.degree. C.
or less more preferably 180.degree. C. or less.
EXAMPLES
[0051] The present invention will be further illustrated by the
following examples in comparison with the following comparative
examples.
[0052] In the examples and comparative examples, the pH value of an
aqueous alkali solution was determined by the following
measurement.
[0053] An alkali compound in an amount of 1 mole was dissolved in 1
liter of ion-exchanged water, the pH value of the aqueous alkali
solution was measured by a pH meter (model: D-24, made by HORIBA
SEISAKUSHO) at room temperature.
[0054] Separately, the pH value of the ion-exchanged water was
measured in the same manner as above.
Example 1
[0055] To prepare a typical liquid reaction mixture from an
epoxidation reaction of 1,5,9-cyclododecatriene, 4500 g (27.8
moles) of 1,5,9-cyclododecatriene, 1.14 g (250 ppm) of
trioctylmethyl ammonium chloride as an onium salt were placed in a
glass flask with a capacity of 5000 ml, the resultant mixture was
heated to a temperature of 75.degree. C. while the flask was sealed
with a nitrogen gas stream and the mixture was stirred.
[0056] After the temperature of the mixture reached 75.degree. C.,
an aqueous solution of 393 g (6.9 moles) of a 60% by weight
hydrogen peroxide, 1.14 g (250 ppm) of sodium tungstate and 1.14 g
(250 ppm) of phosphoric acid was added dropwise to the
1,5,9-cyclododecatriene mixture over a time of 25 minutes. Then the
resultant liquid reaction mixture was heated at a temperature of
75.degree. C. for 90 minutes to complete the epoxidation reaction
of 1,5,9-cyclododecatriene, and then cooled to room
temperature.
[0057] A target typical liquid reaction mixture prepared by an
epoxidation reaction of 1,5,9-cyclododecatriene was obtained in an
amount of 4890 g.
[0058] The whole amount of the resultant liquid reaction mixture
was placed in a separatory funnel with a capacity of 5,000 ml. The
liquid reaction mixture was phase-separated into 4611 g of an oil
phase fraction and 279 g of an aqueous phase fraction.
[0059] A glass flask having a capacity of 5,000 ml and equipped
with a stirrer was charged with a portion of the oil phase fraction
obtained by the phase-separation, in an amount of 750 g, and with
20 g of an aqueous solution containing 2.0% by weight of sodium
hydroxide, and the resultant mixture in the glass flask was stirred
at a temperature of 45.degree. C. for 20 minutes.
[0060] Then the resultant alkali-treated mixture was cooled to room
temperature and phase-separated by using a separatory funnel into
an oil phase fraction and an aqueous phase fraction consisting of
an aqueous solution containing sodium hydroxide. The separated
aqueous phase fraction exhibited a pH value of 9.5.
[0061] The separated oil phase fraction was subjected to a plasma
excitation emission spectroscopic analysis (ICP-AE S analysis) to
determine the concentrations of catalytic elements, namely tungsten
(W) and phosphorus (P). Also, the concentration of peroxide
compounds in the oil phase fraction was determined by an Iodometry
titration method. The analysis results are shown in Table 1.
[0062] As Table 1 shows, the alkali-treated, separated oil phase
fraction had a W concentration of 10 ppm, a P concentration of 1
ppm or less and a peroxide concentration of 0.0056 millimole/g.
[0063] The alkali-treated, separated oil phase fraction in an
amount of 500 g was distilled in a Sneader type distillator. In the
distillation conditions, the distillation temperature for
1,5,9-cyclododecatriene was 76.degree. C. under a pressure of 0.25
kPa, the distillation temperature for
1,2-epoxy-5,9-cyclododecadiene was 97.degree. C under a pressure of
0.25 kPa. As a distillation result, the target
1,2-epoxy-5,9-cyclododecad- iene was collected in an amount of
163.1 g corresponding to a distillation yield of 99.4%.
Example 2
[0064] The same typical liquid reaction mixture obtained by the
epoxidation reaction of 1,5,9-cyclododecatriene as in Example 1 was
refining treated in the same manner as in Example 1, with the
following exceptions.
[0065] An oil phase fraction, in an amount of 750 g, separated from
the liquid reaction mixture and obtained from the epoxidation
reaction, was placed, together with 75 g of an aqueous solution of
4.0% by weight of potassium hydroxide, in a glass flask having a
capacity of 1000 ml and equipped with a stirrer. The mixture in the
flask was stirred at a temperature of 25.degree. C. for 10 minutes,
and phase-separated into an oil phase fraction and an aqueous phase
fraction.
[0066] The separated aqueous phase fraction and the separated oil
phase fraction were separately subjected to the same analysis as in
Example 1.
[0067] In the analysis results, the aqueous phase fraction had a pH
value of 10.8, and the oil phase fraction had a W concentration of
8 ppm, a P concentration of 1 ppm or less, and a peroxide
concentration of 0.0048 m mole/g.
[0068] The alkali-treated, separated oil phase fraction in an
amount of 500 g was distilled in the same manner as in Example 1.
As a result, 1,2-epoxy-5,9-cyclododecadiene was obtained in an
amount of 163.5 g corresponding to a distillation yield of
99.7%.
[0069] The distillation yield is calculated in accordance with the
following equation. 1 Distillation yield ( % ) = [ Amount in gram
of product collected by distillation ] [ Amount in gram of product
contained in treated liquid reaction mixture subjected to
distillation ] .times. 100
Example 3
[0070] The same typical liquid reaction mixture obtained by the
epoxidation reaction of 1,5,9-cyclododecatriene as in Example 1 was
refining treated in the same manner as in Example 2, with the
following exceptions.
[0071] In the alkali treatment, the aqueous alkali solution
contained 50 g of an aqueous solution of 10% by weight of sodium
sulfite in place of the aqueous potassium hydroxide solution.
[0072] In the analysis results, the aqueous phase fraction had a pH
value of 10.1, and the oil phase fraction had a W concentration of
15 ppm, a P concentration of 1 ppm or less, and a peroxide
concentration of 0.0081 m mole/g.
[0073] The alkali-treated, separated oil phase fraction in an
amount of 500 g was distilled in the same manner as in Example 1.
As a result, 1,2-epoxy-5,9-cyclododecadiene was obtained in an
amount of 162.5 g corresponding to a distillation yield of
99.2%.
Comparative Example 1
[0074] The same typical liquid reaction mixture obtained by the
epoxidation reaction of 1,5,9-cyclododecatriene as in Example 1 was
directly subjected to the same phase-separating procedure as in
Example 1.
[0075] The separated oil phase fraction contained a portion of the
aqueous phase fraction suspended therein and had a pH value of 3.6.
The oil phase fraction was subjected to the same quantitative
analysis for concentrations of W, P and peroxides as in Example
1.
[0076] In the analysis results, the oil phase fraction had a W
concentration of 117 ppm, a P concentration of 4.1 ppm, and a
peroxide concentration of 0.0163 m mole/g.
[0077] The non-alkali-treated, separated oil phase fraction in an
amount of 500 g was directly distilled in the same manner as in
Example 1. As a result, 1,2-epoxy-5,9-cyclododecadiene was obtained
in an amount of 160.6 g corresponding to a distillation yield of
97.9%.
Comparative Example 2
[0078] The same typical liquid reaction mixture obtained by the
epoxidation reaction of 1,5,9-cyclododecatriene as in Example 1 was
refining treated in the same manner as in Example 2, except that
the 4% by weight aqueous potassium hydroxide solution was replaced
by a distilled water, and then phase-separated and analized in the
same manner as in Example 2.
[0079] The separated aqueous phase fraction had a pH value of 6.2
and the separated oil phase fraction had a W concentration of 102
ppm, a P concentration of 3.6 ppm and a peroxide concentration of
0.0147 m mole/g.
[0080] The water-treated, separated oil phase fraction in an amount
of 500 g was distilled under the same distillation conditions. The
target 1,2-epoxy-5,9-cyclododecadiene was obtained in an amount of
161.2 g corresponding to a distillation yield of 98.2%.
[0081] In Table 1, the treatment conditions and results of Examples
1 to 3 and Comparative Examples 1 and 2 are shown.
1 TABLE 1 Item Refining treatment with alkali Analysis results
Amount of Aqueous alkali of oil phase fraction oil phase solution W
P Peroxide Distillation fraction of Alkali Alkali treatment concen-
concen- concen- yield liquid reaction concen- Amount Temperature
Time tration tration tration of ECD" Example No mixture (ml)
tration (g) (.degree. C.) (min.) (ppm) (ppm) (m mole/g) (%) Example
1 750 2% NaOH 20 45 20 10 <1 0.0056 99.4 2 750 4% KOH 75 25 10 8
<1 0.0048 99.7 3 750 10% Na.sub.2SO.sub.3 50 25 10 15 <1
0.0081 99.2 Comparative Example 1 750 None None -- -- 117 4.1
0.0163 97.9 2 750 Distilled 75 25 10 102 3.6 0.0147 98.2 water
Note: ECD" - 1,2-epoxy-cyclododecadiene
Example 4
[0082] From a liquid reaction mixture obtained by an epoxidation
reaction in a pilot plant scale, an oil phase fraction containing
22.0% by weight of 1,2-epoxy -cyclododecadiene, 80.2 ppm of
tungsten (W), 8.2 ppm of phosphorus (P), 0.0179 m mole of peroxides
and 76% by weight of non-reacted 1,5,9-cyclododecatriene which
served as a reaction medium, was prepared.
[0083] The oil phase fraction in an amount of 200 g was mixed with
20 g of an aqueous solution of 1 mole/liter of sodium hydroxide
(having a measured pH value of 13.6), and the resultant mixture was
shaken at room temperature for 3 minutes, and then left to stand to
allow it to phase-separate. The separated oil phase fraction was
subjected to the same analysis as in Example 1. As a result, it was
confirmed that the peroxide concentration of the oil phase fraction
was reduced to 0.010 g m mole/g, the W concentration was reduced to
7.3 ppm and the P concentration was reduced to 1 ppm or less.
[0084] The analysis results are shown in Table 2.
Example 5
[0085] The same procedures as in Example 4 were carried out to
refining treat the oil phase fraction, with the following
exceptions.
[0086] The aqueous solution of 1 mole/liter of sodium hydroxide in
an amount of 20 g (having a measured pH value of 13.6) was replaced
by 20 g of an aqueous solution of 1 mole/liter of potassium
hydroxide (having a measured pH value of 13.7).
[0087] The analysis results are shown in Table 2.
Example 6
[0088] The same procedures as in Example 4 were carried out to
refining treat the oil phase fraction, with the following
exceptions.
[0089] The aqueous solution of 1 mole/liter of sodium hydroxide in
an amount of 20 g (having a measured pH value of 13.6) was replaced
by 20 g of an aqueous solution of 1 mole/liter of sodium sulfite
(having a measured pH value of 10.3).
[0090] The analysis results are shown in Table 2.
Example 7
[0091] The same procedures as in Example 4 were carried out to
refining treat the oil phase fraction, with the following
exceptions.
[0092] The aqueous solution of 1 mole/liter of sodium hydroxide in
an amount of 20 g (having a measured pH value of 13.6) was replaced
by 20 g of an aqueous solution of 1 mole/liter of sodium hydrogen
carbonate (having a measured pH value of 7.9).
[0093] The analysis results are shown in Table 2.
Comparative Example 3
[0094] The same procedures as in Example 4 were carried out to
refining treat the oil phase fraction, with the following
exceptions.
[0095] The aqueous solution of 1 mole/liter of sodium hydroxide in
an amount of 20 g (having a measured pH value of 13.6) was replaced
by 20 g of an aqueous solution of 1 mole/liter of sodium hydrogen
sulfite (having a measured pH value of 3.8).
[0096] The analysis results are shown in Table 2.
Comparative Example 4
[0097] The same procedures as in Example 4 were carried out to
refining treat the oil phase fraction, with the following
exceptions.
[0098] The aqueous solution of 1 mole/liter of sodium hydroxide in
an amount of 20 g (having a measured pH value of 13.6) was replaced
by 20 g of an aqueous solution of 1 mole/liter of sodium
thiosulfate (having a measured pH value of 6.7).
[0099] The analysis results are shown in Table 2.
Comparative Example 5
[0100] The same procedures as in Example 4 were carried out to
refining treat the oil phase fraction, with the following
exceptions.
[0101] The aqueous solution of 1 mole/liter of sodium hydroxide in
an amount of 20 g (having a measured pH value of 13.6) was replaced
by 20 g of an ion-exchanged water (having a measured pH value of
6.7).
[0102] The analysis results are shown in Table 2.
[0103] The treatment conditions of Examples 4 to 7 and Comparative
Examples 3 to 5 are shown, together with the analysis results, in
Table 2.
2 TABLE 2 Item Analysis result of treated Refining treatment with
alkali oil phase fraction Amount of oil Aqueous alkali solution W P
Peroxide phase fraction Concentration Alkali treatment concen-
concen- concen- of liquid reaction Type of Amount of alkali pH Time
tration tration tration Example No mixture (ml) alkali (g)
(mole/liter) value Temperature (min.) (ppm) (ppm) (in mole/g) Oil
phase -- -- -- -- -- -- -- 80.2 8.2 0.0179 fraction before refining
treatment Example 4 200 NaOH 20 1 13.6 Room temp. 3 7.3 <1
0.0109 5 200 KOH 20 1 13.7 Room temp. 3 9.2 <1 0.0103 6 200
Na.sub.2SO.sub.3 20 1 10.3 Room temp. 3 15.2 <1 0.0169 7 200
NaHCO.sub.3 20 1 7.9 Room temp. 3 26.5 4.3 0.0151 Comparative
Example 3 200 NaHSO.sub.3 20 1 3.8 Room temp. 3 63.2 4.1 0.0138 4
200 Na.sub.2S.sub.2O.sub.3 20 1 6.7 Room temp. 3 14.2 3.7 0.0181 5
200 Distilled 20 1 6.7 Room temp. 3 81.2 8.2 0.0180 water
[0104] When the refining treatment method, of the present
invention, with an aqueous alkali solution is applied to at least
an oil phase fraction of a liquid reaction mixture obtained from an
epoxidation reaction of 1,5,9-cyclododecatriene with hydrogen
peroxide in the presence of a catalyst comprising a tungsten
compound, a quaternary onium salt and a mineral acid, containing
the resultant 1,2-epoxy-5,9-cyclododecadiene, the catalyst,
non-reacted hydrogen peroxide and non-reacted
1,5,9-cyclododecatriene, and being phase-separated into an oil
phase fraction and an aqueous phase fraction, peroxide compounds
and the catalyst contained in at least the oil phase fraction of
the liquid reaction mixture are deactivated and removed and the
target 1,2-epoxy-5,9-cyclododecadiene can be collected from the
treated reaction mixture or oil phase fraction with high safety and
with a high yield. Also, by the refining treatment method, the
catalyst remaining in the liquid reaction mixture can be
extract-treated with a high efficiency.
* * * * *