U.S. patent application number 14/663400 was filed with the patent office on 2015-07-09 for method for producing 1,2-dichloro-3,3,3-trifluoropropene.
The applicant listed for this patent is CENTRAL GLASS COMPANY, LIMITED. Invention is credited to Yoshio NISHIGUCHI, Satoru Okamoto, Fuyuhiko Sakyu.
Application Number | 20150191405 14/663400 |
Document ID | / |
Family ID | 50341551 |
Filed Date | 2015-07-09 |
United States Patent
Application |
20150191405 |
Kind Code |
A1 |
NISHIGUCHI; Yoshio ; et
al. |
July 9, 2015 |
METHOD FOR PRODUCING 1,2-DICHLORO-3,3,3-TRIFLUOROPROPENE
Abstract
The present invention has an object of providing a method for
producing 1,2-dichloro-3,3,3-trifluoropropene by a vapor-phase
reaction easily and in an industrial scale. A method for producing
1,2-dichloro-3,3,3-trifluoropropene of the present invention
includes putting 1,2-dichloro-1-halogeno-3,3,3-trifluoropropane
with an activated carbon catalyst in a vapor phase. According to
the present invention, 1,2-dichloro-3,3,3-trifluoropropene is
produced in an industrial scale at a high yield by use of
1,2-dichloro-1-halogeno-3,3,3-trifluoropropane, which is available
at low cost, as a material.
Inventors: |
NISHIGUCHI; Yoshio;
(Kawagoe-shi, JP) ; Okamoto; Satoru; (Kawagoe-shi,
JP) ; Sakyu; Fuyuhiko; (Kawagoe-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
CENTRAL GLASS COMPANY, LIMITED |
Ube City |
|
JP |
|
|
Family ID: |
50341551 |
Appl. No.: |
14/663400 |
Filed: |
March 19, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
PCT/JP2013/075541 |
Sep 20, 2013 |
|
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14663400 |
|
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Current U.S.
Class: |
570/156 |
Current CPC
Class: |
C07C 17/23 20130101;
B01J 21/18 20130101; C07C 17/25 20130101; C07C 17/25 20130101; C07C
21/18 20130101 |
International
Class: |
C07C 17/25 20060101
C07C017/25 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 21, 2012 |
JP |
2012-207929 |
Claims
1. A method for producing 1,2-dichloro-3,3,3-trifluoropropene
comprising: putting 1,2-dichloro-1-halogeno-3,3,3-trifluoropropane
represented by formula [1] into contact with an activated carbon
catalyst in a vapor phase: ##STR00003## (in the formula, X
represents fluorine, chlorine or bromine).
2. A method according to claim 1, wherein the activated carbon
catalyst is formed of activated carbon having no metal material
supported thereon.
3. A method according to claim 1, wherein the
1,2-dichloro-1-halogeno-3,3,3-trifluoropropane is in contact with
the activated carbon catalyst for a time that is longer than or
equal to 1 second and shorter than or equal to 300 seconds, and at
a temperature that is higher than or equal to 200.degree. C. and
lower than or equal to 350.degree. C.
4. A method according to claim 1, wherein the
1,2-dichloro-1-halogeno-3,3,3-trifluoropropane is
1,1,2-trichloro-3,3,3-trifluoropropane.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is based upon and claims the benefit of
priority from the prior Japanese Patent Application No.
2012-207929, filed on Sep. 21, 2012, and PCT Application No.
PCT/JP2013/075541, filed on Sep. 20, 2013, the entire contents of
which are incorporated herein by reference.
FIELD
[0002] The present invention relates to a method for producing
1,2-dichloro-3,3,3-trifluoropropene.
BACKGROUND
[0003] 1,2-dichloro-3,3,3-trifluoropropene includes an unsaturated
bond, and is expected to provide a function of a cleaner or a
coolant as hydrochlorofluorocarbon (HCFC), which is relatively
easily decomposed in the atmosphere.
[0004] There are various known methods for producing
1,2-dichloro-3,3,3-trifluoropropene. For example, A. L. Henne et
al., J. Am. Chem. Soc., 1941, pp. 3478-3479 discloses a method of
reacting 1,2,3,3,3-pentachloropropene with antimony trifluoride in
a liquid-phase.
[0005] A. M. Whaley et al., J. Am. Chem. Soc., 1948, pp. 1026-1027
discloses a method of reacting 1,1,2,3,3-pentachloropropene with
antimony trifluoride in a liquid phase by adding antimony
pentachloride. R. N. Haszeldine et al., J. Chem. Soc., 1951, pp.
2495-2504 discloses a method of adding potassium hydroxide in a
solid state to 1,2,2,-trichloro-3,3,3-trifluoropropane in a liquid
state and refluxing, while heating, the resultant substance to
produce 1,2-dichloro-3,3,3-trifluoropropene.
[0006] Regarding a vapor-phase reaction, Japanese Laid-Open Patent
Publication No. 2012-20992 discloses a method of producing a
fluorine-containing propene represented by general formula,
CF.sub.3CH.dbd.CHZ (Z is Cl or F), by a fluorination reaction and a
dehalogenation reaction by use of a chlorine-containing compound as
a material. In Example 4, it is described that
1,2-dichloro-3,3,3-trifluoropropene is generated as a byproduct of
a fluorination reaction and a dehalogenation reaction of
1,1,1,3,3-pentachloropropane (240fa).
[0007] According to the production method described in R. N.
Haszeldine et al., J. Chem. Soc., 1951, pp. 2495-2504, powdery
potassium hydroxide is dispersed in
1,2,2-trichloro-3,3,3-trifluoropropane in a liquid state to cause a
reaction. However, the yield is low (48%) and the reaction is not
uniform. Therefore, this method is not considered to be efficient
as an industrial production method.
[0008] As described in Japanese Laid-Open Patent Publication No.
2012-20992, it is known that 1,2-dichloro-3,3,3-trifluoropropene is
generated by a fluorination reaction and a dehalogenation reaction
of a chlorine-containing compound such as
1,1,1,3,3-pentachloropropane or the like in a vapor phase. However,
it is difficult to obtain 1,2-dichloro-3,3,3-trifluoropropene in an
industrially sufficient amount.
[0009] As can be seen from the above, it has been desired to
establish a method for producing
1,2-dichloro-3,3,3-trifluoropropene, which is a target compound of
the present invention, easily and in an industrial scale.
SUMMARY
[0010] The present invention has an object of providing a method
for producing 1,2-dichloro-3,3,3-trifluoropropene by a vapor-phase
reaction easily and in an industrial scale.
[0011] As a result of accumulating active studies to solve the
above-described problems, the present inventors found that
1,2-dichloro-3,3,3-trifluoropropene, which is a target compound, is
obtained at a high yield by putting
1,2-dichloro-1-halogeno-3,3,3-trifluoropropane into contact with an
activated carbon catalyst in a vapor phase.
[0012] Namely, the present invention includes inventions 1 through
invention 4 described below.
[0013] [Invention 1]
[0014] A method for producing 1,2-dichloro-3,3,3-trifluoropropene,
including: putting 1,2-dichloro-1-halogeno-3,3,3-trifluoropropane
represented by formula [1] below into contact with an activated
carbon catalyst in a vapor phase:
##STR00001##
(in the formula, X represents fluorine, chlorine or bromine).
[0015] According to the element of invention 1,
1,2-dichloro-3,3,3-trifluoropropene is selectively generated while
generation of a byproduct is suppressed. Thus,
1,2-dichloro-3,3,3-trifluoropropene can be obtained at a high
yield.
[0016] [Invention 2]
[0017] A method according to invention 1, wherein the activated
carbon catalyst is formed of activated carbon having no metal
material supported thereon. Herein, the "carbon having no metal
material supported thereon" refers to an activated carbon catalyst
containing a metal material at a content in the range that is lower
than or equal to 0.01% by mass including zero (0).
[0018] According to the element of invention 2,
1,2-dichloro-3,3,3-trifluoropropene can be obtained at a higher
yield.
[0019] [Invention 3]
[0020] A method according to invention 1 or 2, wherein the
1,2-dichloro-1-halogeno-3,3,3-trifluoropropane is in contact with
the activated carbon catalyst for a time that is longer than or
equal to 1 second and shorter than or equal to 300 seconds, and at
a temperature that is higher than or equal to 200.degree. C. and
lower than or equal to 350.degree. C.
[0021] According to the element of invention 3,
1,2-dichloro-3,3,3-trifluoropropene can be obtained at a higher
yield.
[0022] [Invention 4]
[0023] A method according to any one of inventions 1 through 3,
wherein the 1,2-dichloro-1-halogeno-3,3,3-trifluoropropane is
1,1,2-trichloro-3,3,3-trifluoropropane.
[0024] According to the element of invention 4,
1,2-dichloro-3,3,3-trifluoropropene can be obtained at a higher
yield.
DESCRIPTION OF EMBODIMENTS
[0025] Hereinafter, the present invention will be described in
detail. In a reaction according to present invention,
1,2-dichloro-1-halogeno-3,3,3-trifluoropropane is put into contact
with an activated carbon catalyst in a vapor phase to cause
dehydrochlorination. Specifically, this reaction is caused by
filling a reactor with an activated carbon catalyst and putting
1,2-dichloro-1-halogeno-3,3,3-trifluoropropane into contact with
the activated carbon catalyst in a vapor phase at a predetermined
temperature. The vapor-phase reaction may be a fixed-bed
vapor-phase reaction, a fluidized-bed vapor-phase reaction or of
any other appropriate system. Selection of any system of the
vapor-phase reaction does not prevent a person of ordinary skill in
the art from easily adjusting the reaction conditions.
[0026] 1,2-dichloro-1-halogeno-3,3,3-trifluoropropane, which is a
starting material of the present invention, is represented by
formula [1].
##STR00002##
In formula [1], "X" specifically represents fluorine, chlorine or
bromine. Specific compounds usable as
1,2-dichloro-1-halogeno-3,3,3-trifluoropropane include
1,1,2-trichloro-3,3,3-trifluoropropane,
1,2-dichloro-1,3,3,3-tetrafluoropropane, and
1-bromo-1,2-dichloro-3,3,3-trifluoropropane. Among these compounds,
1,1,2-trichloro-3,3,3-trifluoropropane is preferably usable for
easy availability thereof and usefulness of a resultant
compound.
[0027] Activated carbon catalysts include plant-based catalysts
formed of wood, charcoal, palm shell charcoal, palm kernel
charcoal, pure ash or the like; coal-based catalysts formed of
peat, lignite, brown coal, bituminous coal, anthracite coal or the
like; petroleum-based catalysts formed of petroleum residue, oil
carbon or the like; or synthetic resin-based catalysts such as
carbonized poly(vinylidene chloride) or the like. As the activated
carbon catalyst used in the present invention, any of such
commercially available activated carbon catalysts may be selected.
Preferably usable activated carbon catalysts include, for example,
palm shell charcoals for gas purification or for catalyst/catalyst
support (Granulated Shirasagi GX, SX, CX and XRC produced by Japan
EnviroChemicals, Ltd.; PCB produced by Toyo Calgon; Yashicoal
produced by Taihei Chemical Industrial Co, Ltd.; and Kuraray Coal
GG and GC) and the like. For the activated carbon catalyst
according to the present invention, activated carbon having a metal
material supported thereon or activated carbon having no metal
material supported thereon may be used. Activated carbon having no
metal material supported thereon is advantageous from the viewpoint
of costs and ease of abolishment. In the present invention, the
"carbon having no metal material supported thereon" refers to an
activated carbon catalyst containing a metal material at a content
that is at least 0 and lower than or equal to 0.01% by mass.
[0028] In the case where activated carbon having a metal material
supported thereon is used, the supported metal material may be
aluminum, chromium, titanium, manganese, iron, nickel, cobalt,
copper, magnesium, zirconium, molybdenum, zinc, tin, lanthanum,
antimony or the like. Such a metal material may be supported in the
form of fluoride, chloride, fluorochloride, oxyfluoride,
oxychloride, oxyfluorochloride, or the like. A combination of two
or more of metal compounds may be supported.
[0029] The activated carbon catalyst is usually used in the form of
granules, but may be used in a usually set form that is compatible
to the reactor, such as spheres, fibers, powders, honeycomb-like
components or the like. The specific surface area and the pore
capacity of the activated carbon may be in the range of the
standards for the commercially available products. The specific
surface area is preferably larger than 400 m.sup.2/g, and more
preferably larger than or equal to 800 m.sup.2/g and smaller than
or equal to 3000 m.sup.2/g. The pore capacity is preferably larger
than 0.1 cm.sup.3/g, and more preferably larger than or equal to
0.2 cm.sup.3/g and smaller than or equal to 1.0 cm.sup.3/g.
[0030] The reaction temperature for the present invention is
usually higher than or equal to 200.degree. C. and lower than or
equal to 350.degree. C., and preferably higher than or equal to
220.degree. C. and lower than or equal to 320.degree. C. When the
reaction temperature is lower than 200.degree. C., the reaction
does not advance almost at all or the reaction is extremely slow,
which is not preferable. When the reaction temperature is higher
than 350.degree. C., the decomposition reaction or the like
advances and the resultant product may possibly be contaminated
with a large amount of byproducts, which is not preferable.
[0031] In this specification, the term "contact time" is defined as
follows. The "volume of the filler (activated carbon)" is set as
"A". The "volume of the material gas that is introduced into the
reactor per second" is set as "B". Considering that the material
gas is ideal gas, the value of B is calculated from the molar
number per second and the pressure of the introduced material and
nitrogen and the temperature. A value obtained by dividing A with B
(=A/B) is referred to as the "contact time". In the reactor, HCl or
other types of gas is produced as a byproduct and thus the molar
number is changed. Such a change in the molar number is not
considered for calculation of the "contact time".
[0032] The contact time varies in accordance with the temperature
of the reactor (reaction temperature), the shape of the reactor,
and the type of filler in the reactor. Therefore, it is desirable
to adjust the supply rate of the material (contact time) for each
of set temperatures, each of shapes of the reactor, and each of
types of fillers, so that an optimal value is determined as the
contact time. Usually, the contact time is preferably set such that
a conversion rate of the material of at least 25% is obtained and
is more preferably set such that a conversion rate of the material
of at least 50% is obtained, from the viewpoint of recoverability
and recyclability of an unreacted part of the material.
[0033] In a preferable example, in the case where the reaction
temperature is kept in the range that is higher than or equal to
200.degree. C. and lower than or equal to 350.degree. C., the
contact time is preferably longer than or equal to 1 second and
shorter than or equal to 300 seconds, and more preferably longer
than or equal to 20 seconds second and shorter than or equal to 150
seconds. When the contact time exceeds 300 seconds, a side reaction
is easily caused, which is not preferable. When the contact time is
shorter than 1 second, the conversion rate is too low, which is not
preferable. In one preferable embodiment,
1,2-dichloro-1-halogeno-3,3,3-trifluoropropane is caused to pass
the reactor, filled with activated carbon heated to a temperature
that is higher than or equal to 200.degree. C. and lower than or
equal to 350.degree. C., with a contact time that is longer than or
equal to 1 second and shorter than or equal to 300 seconds.
[0034] The reaction pressure may be lower than, equal to, or higher
than the atmospheric pressure. In general, the reaction pressure is
preferably the atmospheric pressure. The reaction may be caused in
the presence of inert gas such as nitrogen, argon or the like,
which is stable under the reaction conditions.
[0035] The dehydrochlorination reaction according to the present
invention may be caused in a vapor phase by use of a common
chemical engineering device. A reactor, a related material
introduction system, a flow-out system, and a related unit are
formed of a substance that is durable against hydrogen chloride.
Typical such substances include, for example, stainless steel,
especially austenite-type stainless steel; high nickel alloys such
as Monel.TM., Hastelloy.TM., Inconel.TM. and the like; and
copper-clad steel, but are not limited to these.
[0036] 1,2-dichloro-3,3,3-trifluoropropene produced by the method
according to the present invention exists in the form of a liquid
at room temperature and normal pressure. The gas obtained by the
reaction may be caused to flow in a cooled condenser to be
condensed, and precision-distilled, so that highly pure
1,2-dichloro-3,3,3-trifluoropropene is obtained.
1,2-dichloro-3,3,3-trifluoropropene generated by the reaction is a
mixture of geometric isomers such as cis and trans isomers.
Nonetheless, the mixture can be precision-distilled to provide
highly pure cis-1,2-dichloro-3,3,3-trifluoropropene and
trans-1,2-dichloro-3,3,3-trifluoropropene.
[0037] The cis isomer and the trans isomer can be mutually
converted by an isomerization reaction. There is no specific
limitation on the method of isomerization. The isomerization may be
caused by a known vapor-phase reaction using a solid acid catalyst
such as fluorinated alumina, fluorinated chromia, fluorinated
titania, fluorinated zirconia or the like.
[0038] Hereinafter, the present invention will be described in more
detail by way of examples. The present invention is not limited to
the following examples. Herein, "%" used for a composition analysis
value represents the "surface area %" of each of components of a
reaction mixture measured by direct use of gas chromatography
(unless otherwise specified, the detector is FID).
Example 1
[0039] Example 1 will be described hereinafter. In example 1,
1,2-dichloro-3,3,3-trifluoropropene was synthesized by use of
activated carbon having no metal material supported thereon as a
catalyst. Table 1 shows the synthesis results of
1,2-dichloro-3,3,3-trifluoropropene.
Synthesis of 1,2-dichloro-3,3,3-trifluoropropene
[0040] Nitrogen was caused to flow, at a rate of 10 ml/min., into a
vapor-phase reaction device (formed of SUS304, inner diameter: 25
mm; length: 300 mm) formed of a cylindrical reactor equipped with a
metal electric heater filled with 50 ml of granulated activated
carbon (Shirasagi G2x; produced by Japan EnviroChemicals, Ltd.;
specific surface area: 1200 m.sup.2/g; pore capacity: 0.86
cm.sup.3/g), while the temperature of the reactor was gradually
raised. When the temperature of the reactor reached 250.degree. C.,
1,1,2-trichloro-3,3,3-trifluoropropane was vaporized and was
supplied to the reactor at a flow rate of about 0.25 g/min.
1,1,2-trichloro-3,3,3-trifluoropropane was supplied for 3 hours,
and 44.5 g thereof was put into the reactor (contact time: 107
seconds). The temperature of the reactor during this period was
higher than or equal to 240.degree. C. and lower than or equal to
250.degree. C. Generated gas flowing out from the reactor was
caused to flow into a water-containing gas washing bottle formed of
a fluorine resin that had been cooled in an iced water bath. Thus,
hydrogen chloride was absorbed and the reaction product was
collected. 33.4 g of organic substance that was collected and
analyzed by gas chromatography to find the following composition
ratio. The organic substance contained
1,2-dichloro-3,3,3-trifluoropropene at a content of 97.82% (in more
detail, cis-1,2-dichloro-3,3,3-trifluoropropene was contained at a
content of 92.74%, and trans-1,2-dichloro-3,3,3-trifluoropropene
was contained at a content of 5.08%). The yield of
1,2-dichloro-3,3,3-trifluoropropene was 91.4%.
TABLE-US-00001 TABLE 1 Reaction Contact Composition ratio of
product temperature time (GC surface area) Catalyst (.degree. C.)
(s) 1223xd (Z) 1223xd (E) 233da Example 1 Activated carbon 250 107
92.74 5.08 0.02 1223xd (Z): cis-1,2-dichloro-3,3,3-trifluoropropene
1223xd (E): trans-1,2-dichloro-3,3,3-trifluoropropene 233da:
1,1,2-trichloro-3,3,3-trifluoropropane
[0041] As described in Japanese Laid-Open Patent Publication No.
2012-20992 mentioned above, it is known that
1,2-dichloro-3,3,3-trifluoropropene (1223xd) is generated by a
fluorination reaction and a dehalogenation reaction of a
chlorine-containing compound such as 1,1,1,3,3-pentachloropropane
or the like in a vapor phase in the absence of a catalyst. However,
1,2-dichloro-3,3,3-trifluoropropene (1223xd) obtained by a
fluorination reaction and a dehalogenation reaction of a
chlorine-containing compound such as 1,1,1,3,3-pentachloropropane
or the like in a vapor phase in the absence of a catalyst is in an
extremely small amount. 1,2-dichloro-3,3,3-trifluoropropene is not
obtained in an industrially sufficient amount by the method
described in Japanese Laid-Open Patent Publication No. 2012-20992.
As can be seen from a comparison of the results of example 1
against the known method described in Japanese Laid-Open Patent
Publication No. 2012-20992, the conversion ratio into
1,2-dichloro-3,3,3-trifluoropropene is higher when the method for
producing 1,2-dichloro-3,3,3-trifluoropropene according to the
present invention is used.
[0042] According to the present invention,
1,2-dichloro-3,3,3-trifluoropropene is produced in an industrial
scale at a high yield by use of
1,2-dichloro-1-halogeno-3,3,3-trifluoropropane, which is available
at low cost, as a material.
[0043] According to the present invention, the amount of generated
byproducts, which are not 1,2-dichloro-3,3,3-trifluoropropene as
the target compound, is very small. In addition, no byproduct
having a boiling point close to that of the target compound is
generated. Therefore, the resultant product can be easily purified
by distillation or the like, which is a process that is
economically advantageous and also has little environmental
load.
[0044] 1,2-dichloro-3,3,3-trifluoropropene, which is a target
compound of the present invention, is usable as a heat transfer
medium usable for a heat pump cycle or a rankine cycle, a
functional material such as a cleaner or the like, a
physiologically active substance, an intermediate of a functional
material, or a monomer of a polymer compound.
* * * * *