U.S. patent application number 10/171176 was filed with the patent office on 2003-01-23 for process for continuous production of acetylenediol.
Invention is credited to Fukuda, Hideo, Imanishi, Kazuhiro, Omori, Hideki, Sato, Tomohiko, Sawada, Goro.
Application Number | 20030018221 10/171176 |
Document ID | / |
Family ID | 19038485 |
Filed Date | 2003-01-23 |
United States Patent
Application |
20030018221 |
Kind Code |
A1 |
Omori, Hideki ; et
al. |
January 23, 2003 |
PROCESS FOR CONTINUOUS PRODUCTION OF ACETYLENEDIOL
Abstract
The present invention provides a process for producing an
acetylenediol continuously by reacting a ketone with acetylene in
the presence of an alkali catalyst, which process comprises
continuously feeding, into a first-stage reactor, a reaction
solvent, an alkali catalyst, a ketone and acetylene to give rise to
a reaction, continuously introducing the reaction mixture into a
second-stage reactor, and continuously feeding a fresh portion of
the same ketone into the second-stage reactor to give rise to a
reaction.
Inventors: |
Omori, Hideki;
(Ichihara-shi, JP) ; Sawada, Goro; (Ichihara-shi,
JP) ; Fukuda, Hideo; (Ichihara-shi, JP) ;
Imanishi, Kazuhiro; (Ichihara-shi, JP) ; Sato,
Tomohiko; (Ichihara-shi, JP) |
Correspondence
Address: |
Melvin I. Stoltz, Esq.
51 Cherry Street
Milford
CT
06460
US
|
Family ID: |
19038485 |
Appl. No.: |
10/171176 |
Filed: |
June 12, 2002 |
Current U.S.
Class: |
568/816 ;
568/855 |
Current CPC
Class: |
C07C 29/42 20130101;
C07C 29/42 20130101; C07C 29/42 20130101; C07C 33/042 20130101;
C07C 33/044 20130101 |
Class at
Publication: |
568/816 ;
568/855 |
International
Class: |
C07C 035/21; C07C
033/044 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 3, 2001 |
JP |
2001-201546 |
Claims
What is claimed is:
1. A process for producing an acetylenediol continuously by
reacting a ketone with acetylene in the presence of an alkali
catalyst, which process comprises continuously feeding, into a
first-stage reactor, a reaction solvent, an alkali catalyst, a
ketone and acetylene to give rise to a reaction, continuously
introducing the reaction mixture into a second-stage reactor, and
continuously feeding a fresh portion of the same ketone into the
second-stage reactor to give rise to a reaction.
2. A process for producing an acetylenediol continuously according
to claim 1, wherein the ketone is an aliphatic ketone or an
aromatic ketone.
3. A process for producing an acetylenediol continuously according
to claim 2, wherein the ketone is acetone, methyl ethyl ketone or
methyl isobutyl ketone.
4. A process for producing an acetylenediol continuously according
to claim 1, wherein the ketone is a cyclic ketone.
5. A process for producing an acetylenediol continuously according
to any of claims 1 to 4, wherein the alkali catalyst is an alkali
metal hydroxide.
6. A process for producing an acetylenediol continuously according
to any of claims 1 to 5, wherein the reaction solvent is a chain
aliphatic hydrocarbon, a cyclic aliphatic hydrocarbon, a mixture of
chain aliphatic hydrocarbons, a mixture of cyclic aliphatic
hydrocarbons or a mixture of a chain aliphatic hydrocarbon and a
cyclic aliphatic hydrocarbon.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a process for producing an
acetylenediol continuously. More particularly, the present
invention relates to a process for producing an acetylenediol
continuously and efficiently by reacting a ketone with
acetylene.
[0003] 2. Description of the Prior Art
[0004] An acetylenediol (hereinafter abbreviated to ADO in some
cases) represented by, for example, the general formula (III) or
(IV) shown below has been produced generally by reacting 2 moles of
a ketone with 1 mole of acetylene in the presence of an alkali
catalyst such as potassium hydroxide (see, for example, U.S. Pat.
Nos. 2,385,546 and 2,455,058). In this reaction, however, not only
ADO is produced but also an acetylenemonool (hereinafter
abbreviated to AMO in some cases) which is a reaction product
between 1 mole of the ketone and 1 mole of acetylene is formed as a
by-product.
[0005] Hence, it was attempted to minimize the amount of AMO formed
as a by-product and increase the amount of ADO produced. In, for
example, JP-A-63-258823, is disclosed a process for producing an
alkynediol, wherein a particular ether type solvent and a
particular ratio of raw materials are employed to suppress the
amount of AMO formed as a by-product.
[0006] Meanwhile, in all of the processes for ADO production
proposed heretofore, a batch process is employed. As compared with
this batch process, a continuous process apparently shows a high
production efficiency when a reactor of a given capacity is used.
However, the continuous process, as compared with the batch
process, is not always advantageous in selectivity of intended
product. This is because the production of ADO is a successive
reaction via the formation of AMO and, in the case of the
continuous process, AMO (an intermediate product) and part of the
raw materials introduced are discharged per se and contained in the
reaction mixture, reducing the proportion of ADO produced.
SUMMARY OF THE INVENTION
[0007] Hence, the object of the invention is to alleviate the
above-mentioned drawbacks of the prior art and provide a process
for producing ADO by reacting a ketone with acetylene in the
presence of an alkali catalyst, which can minimize the amount of
the AMO formed as a by-product and increase the proportion of the
ADO produced and which can produce the ADO continuously and
efficiently.
[0008] In order to achieve the above object, the present inventors
made a study. As a result, the present inventors found out that by
employing a two-stage continuous process which comprises conducting
a reaction between a ketone and acetylene in a first reactor,
introducing the reaction mixture into a second reactor, and adding
a fresh portion of the ketone thereto to give rise to a reaction,
ADO can be produced efficiently with the ADO/AMO ratio in the
reaction mixture being kept at a high level. The present invention
has been completed based on the above finding.
[0009] The present invention lies in a process for producing an
acetylenediol continuously by reacting a ketone with acetylene in
the presence of an alkali catalyst, which process comprises
continuously feeding, into a first-stage reactor, a reaction
solvent, an alkali catalyst, a ketone and acetylene to give rise to
a reaction, continuously introducing the reaction mixture into a
second-stage reactor, and continuously feeding a fresh portion of
the same ketone into the second-stage reactor to give rise to a
reaction.
DETAILED DESCRIPTION OF THE INVENTION
[0010] The present invention is described in detail below.
[0011] A ketone is used as one of the main raw materials in the
continuous ADO production of the present invention. The ketone is
an aliphatic or aromatic ketone represented by the following
general formula (I) 1
[0012] (wherein R.sup.1 and R.sup.2 are each independently an alkyl
group, an arylalkyl group, an aryl group or an alkylaryl group each
having 1 to 12 carbon atoms), or a cyclic ketone represented by the
following general formula (II) 2
[0013] (wherein R.sup.3 is an alkylene group having 5 to 12 carbon
atoms).
[0014] As specific examples of the ketone represented by the
general formula (I), there can be mentioned acetone, methyl ethyl
ketone, methyl isobutyl ketone, 2-hexanone, 2-octanone,
acetophenbne, ethyl phenyl ketone and ethyl tolyl ketone. As
specific examples of the ketone represented by the general formula
(II), there can be mentioned cyclopentanone, cyclohexanone,
methylcyclohexanone and cyclooctanone.
[0015] As to the amount of the ketone used, there is no particular
restriction. However, the amount is generally 2 to 50% by weight,
preferably 5 to 30% by weight based on the reaction solvent
(described later) used.
[0016] In the present invention, the above ketone is reacted with
acetylene in the presence of an alkali catalyst. The alkali
catalyst usable herein can be selected from an alkali metal, an
alkali metal hydroxide and an alkali metal alkoxide.
[0017] Of the above alkali catalysts, as the alkali metal, there
can be mentioned, for example, metal sodium and metal potassium; as
the alkali metal hydroxide, there can be mentioned, for example,
sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium
hydroxide and cesium hydroxide; as the alkali metal alkoxide, there
can be mentioned, for example, alkali metal aliphatic alkoxides
such as potassium methoxide, potassium ethoxide, potassium
isobutoxide, potassium tert-butoxide, sodium methoxide, sodium
ethyoxide and the like. There can also be used alkali metal
alicyclic alkoxides such as potassium cyclohexyloxide and the
like.
[0018] The alkali catalyst is used in an amount of 0.1 to 20 moles,
preferably 0.5 to 10 moles per mole of the raw material ketone.
When the amount of the alkali catalyst is less than 0.1 mole per
mole of the ketone, the reaction rate is low and the conversion
rate is low. When the amount of the alkali catalyst is more than 20
moles per mole of the ketone, the amount of the alkali catalyst is
unnecessarily excessive. Therefore, such amounts are
uneconomical.
[0019] As to the reaction solvent used in the present invention,
there is no particular restriction. As the reaction solvent, there
can be used a chain or cyclic aliphatic hydrocarbon, an aromatic
hydrocarbon, an aliphatic ether, etc. As the chain aliphatic
hydrocarbon, there can be mentioned, for example, saturated
hydrocarbons such as hexane, heptane, octane, nonane, decane and
the like; and unsaturated hydrocarbons such as diisobutylene,
triisobutylene, tetraisobutylene and the like. As the cyclic
aliphatic hydrocarbon (alicyclic hydrocarbon), there can be
mentioned, for example, cyclohexane, methylcyclohexane, decalin and
the like. Further, a mixture of chain aliphatic hydrocarbons, a
mixture of cyclic aliphatic hydrocarbons, or a mixture of a chain
aliphatic hydrocarbon and a cyclic aliphatic hydrocarbon (a
so-called naphthenic solvent) can also be used as the reaction
solvent of the present invention.
[0020] As the aromatic hydrocarbon among the reaction solvent,
there can be mentioned, for example, benzene, toluene, xylene,
ethylbenzene, cumene, mesitylene, indene, fluorene and the like. As
the aliphatic ether, there can be mentioned, for example, diethyl
ether, methyl tert-butyl ether, ethyl tert-butyl ether, diisopropyl
ether and the like.
[0021] The continuous production of ADO according to the present
process is conducted using a two-stage reaction apparatus
constituted mainly by two reactors. As the reactors, a tank type is
used generally, but a tube type may also be used.
[0022] In the flow of the production steps, first, a reaction
solvent and an alkali catalyst are fed continuously into a first
reactor; then, acetylene and a ketone are continuously fed; in this
state, a reaction is allowed to proceed. Part of the reaction
mixture formed in the first reactor is continuously withdrawn into
a second reactor with the liquid level of the first reactor being
kept constant; a fresh portion of the same ketone is continuously
fed into the second reactor; and a reaction is further allowed to
proceed. Part of the reaction mixture formed in the second reactor
is continuously withdrawn at a given rate and treated in a
separation and recovery step to recover an ADO (an intended
product). Thus, all of the production steps are conducted
continuously and thereby a high production efficiency is made
possible.
[0023] The reaction temperature in the first reactor or the second
reactor is 0 to 100.degree. C., preferably 10 to 80.degree. C., and
the reaction pressure is ordinarily 0 to 1 MPa (gauge pressure),
preferably 0 to 0.2 MPa (gauge pressure) in terms of acetylene
partial pressure. A high acetylene partial pressure gives a high
reaction rate; however, it is preferred to use a low acetylene
partial pressure in order to prevent the decomposition and
explosion of gaseous acetylene. Incidentally, in order to prevent
the decomposition and explosion, it is possible to dilute acetylene
by introducing an inert gas such as nitrogen, argon, propane or the
like.
[0024] In the above production steps, the molar ratio of acetylene
to ketone may be at least 0.6 mole of acetylene relative to mole of
the ketone. Generally, the reaction is allowed to proceed in a
large excess of acetylene.
[0025] The residence time in the reaction system varies depending
upon the ratio of raw materials, the temperature of reaction
system, the partial pressure of acetylene and other conditions, but
is ordinarily 0.5 to 1 hour, preferably 1 to 6 hours.
[0026] According to the process of the present invention, there are
formed mainly an ADO represented by the following general formula
(III) when a ketone of the general formula (I) is used: 3
[0027] (wherein R.sup.1 and R.sup.2 have the same definitions as
given above), and an ADO represented by the following general
formula (IV) when a ketone of the general formula (II) is used:
4
[0028] (wherein R.sup.3 has the same definition as given
above).
[0029] The reaction mixture withdrawn from the second reactor is
ordinarily subjected first to removal of the alkali catalyst
contained therein.
[0030] The removal of the alkali catalyst is generally conducted by
addition of water to the reaction mixture and extraction of the
alkali catalyst therewith. Depending upon the case, it is possible
to add an inorganic or organic acid to the organic phase to
neutralize and remove a very small amount of the alkali catalyst
remaining in the organic phase.
[0031] The mixture obtained after the removal treatment of the
alkali catalyst contains the reaction solvent, the unreacted
ketone, ADO, AMO and a small amount of water used in the removal
treatment of the alkali catalyst, is subjected to distillation to
remove the unreacted ketone, AMO and a small amount of water,
whereby an intended ADO can be obtained.
[0032] The ADO obtained by the present invention has a triple bond
of high electron density and two hydroxyl groups adjacent thereto.
Since these hydroxyl groups synergistically act as highly polar
groups, the ADO or its derivative shows strong orientation to
metals, antifoaming property, wettability, etc. and are utilized in
nonionic surfactants, metal surface-treating agents, medicines,
etc.
[0033] The present invention is described in more detail below by
way of Example. However, the present invention is in no way
restricted to the Example.
EXAMPLE 1
[0034] Into a first reactor having an internal volume of 10 liters
were continuously fed 95 g/hr of a potassium hydroxide powder
(purity: 95%) and 800 g/hr of a naphthenic solvent (boiling point
range: 210 to 230.degree. C., sp. gr.: 0.79). Acetylene was
introduced up to a pressure of 0.02 MPa (gauge pressure). Further,
100 g/hr of methyl isobutyl ketone (a raw material ketone) was
introduced. The mixture was allowed to react at a temperature of
25.degree. C. with stirring while the acetylene pressure was kept
constant. Then, continuous operation was conducted while part of
the reaction mixture being withdrawn so that the residence time
became 4.4 hr.
[0035] The reaction mixture withdrawn from the first reactor was
introduced into a second reactor. Separately, 3.4 g/hr of methyl
isobutyl ketone was continuously fed into the second reactor. In
this stage, the mixture was further allowed to react. Successively,
the mixture in the second reactor was continuously withdrawn so
that the residence time became 4.0 hr.
[0036] The mixture withdrawn was washed with water and neutralized
to remove the catalyst. The resulting material was analyzed by gas
chromatography. As a result, the material contained 9.3% by weight
of an ADO, i.e. 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 0.5% by
weight of an AMO, i.e. 3,5-dimethyl-1-hexyne-3-ol, and 3.6% by
weight of unreacted methyl isobutyl ketone.
Comparative Example 1
[0037] Into a first reactor having an internal volume of 10 liters
were continuously fed 95 g/hr of a potassium hydroxide powder
(purity: 95%) and 800 g/hr of a naphthenic solvent (boiling point
range: 210 to 230.degree. C., sp. gr.: 0.79). Acetylene was
introduced up to a pressure of 0.02 MPa (gauge pressure). Further,
100 g/hr of methyl isobutyl ketone (a raw material ketone) was
introduced. The mixture was allowed to react at a temperature of
25.degree. C. with stirring while the acetylene pressure was kept
constant. Then, continuous operation was conducted while part of
the reaction mixture being withdrawn so that the residence time
became 4.4 hr.
[0038] The mixture withdrawn was washed with water and neutralized
to remove the catalyst. The resulting material was analyzed by gas
chromatography. As a result, the material contained 6.1% by weight
of an ADO, i.e. 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 4.2% by
weight of an AMO, i.e. 3,5-dimethyl-1-hexyne-3-ol, and 2.1% by
weight of unreacted methyl isobutyl ketone.
[0039] As seen above, the ADO/AMO ratio (molar ratio) in the
continuous two-stage process of Example 1 is 10.4 while the ADO/AMO
ratio (molar ratio) in the one-stage process of Comparative Example
1 is 1.6. Thus, the ADO/AMO ratio is significantly improved in the
process of the present invention.
[0040] In the present process for continuous production of the
acetylenediol, a continuous two-stage reaction and particular
conditions are employed; as a result, the formation of an
acetylenemonool (a by-product) can be suppressed, and an
acetylenediol can be produced continuously and efficiently with the
acetylenediol/acetylenemonool ratio (ADO/AMO ratio) in the product
being kept at a high level.
* * * * *