WO2015166847A1

WO2015166847A1 - Method for producing trans-1-chloro-3,3,3-trifluoropropene

Info

Publication number: WO2015166847A1
Application number: PCT/JP2015/062147
Authority: WO
Inventors: 優竹内; 允彦中村; 岡本　秀一; 古田　昇二
Original assignee: 旭硝子株式会社
Priority date: 2014-04-28
Filing date: 2015-04-21
Publication date: 2015-11-05
Also published as: JP2017114766A

Abstract

　Provided is a method that makes it possible to easily produce trans-1-chloro-3,3,3-trifluoropropene (R-1233zd(E)) at high selectivity without generating metal salts. 1,1-Dichloro-3,3,3-trifluoropropane (R-243fa) is converted into trans-1-chloro-3,3,3-trifluoropropene by contact with an active carbon catalyst having a specific surface area of 10-3,000 m²/g.

Description

Process for producing trans-1-chloro-3,3,3-trifluoropropene

The present invention relates to a method for producing trans-1-chloro-3,3,3-trifluoropropene.

In the present specification, abbreviations (refrigerant numbers and the like) may be described in parentheses after the halogenated hydrocarbon compound name. In the present specification, abbreviations are used instead of compound names as necessary.
Of the cis-trans isomers, the trans isomer (E isomer) is indicated by adding (E) to the end of the abbreviation, and the cis isomer (Z isomer) is indicated by adding (Z) to the end of the abbreviation. To express. Further, a mixture of a trans isomer and a cis isomer is represented by adding (EZ) to the end of the abbreviation, and one of the trans isomer and the cis isomer is represented by adding (EorZ) to the end of the abbreviation.
Specifically, for example, the refrigerant number of 1-chloro-3,3,3-trifluoropropene is “R-1233zd”, and trans-1-chloro-3,3,3-trifluoropropene is “R −1233zd (E) ”, and cis-1-chloro-3,3,3-trifluoropropene is represented by“ R-1233zd (Z) ”. A mixture of trans-1-chloro-3,3,3-trifluoropropene and cis-1-chloro-3,3,3-trifluoropropene is represented by “R-1233zd (EZ)”, and trans-1 “R-1233zd (EorZ)” represents one of chloro-3,3,3-trifluoropropene and cis-1-chloro-3,3,3-trifluoropropene.

R-1233zd (E) is a greenhouse gas such as 1,1,1,2-tetrafluoroethane (refrigerant number: R-134a) and 1,1,1,3,3-pentafluoropropane (refrigerant number: In recent years, it has been expected as an alternative compound to R-245fa).

As a method for producing R-1233zd (E), for example, the following method has been proposed.
(1) A method of dehydrofluorinating 3-chloro-1,1,1,3-tetrafluoropropane (refrigerant number: R-244fa) in the presence of a catalyst (Patent Document 1).
(2) A method of dehydrochlorinating 1,1-dichloro-3,3,3-trifluoropropane (refrigerant number: R-243fa) in an alkaline solution (Non-patent Document 1).
(3) A method of dehydrochlorinating R-243fa in the presence of a metal catalyst (Patent Document 2).
(4) A method for dehydroiodination of 3-chloro-1,1,1-trifluoro-3-iodopropane in an alcohol solution of potassium hydroxide (Non-patent Document 2).
(5) A method of reacting R-245fa with hydrogen chloride in the gas phase in the presence of a solid catalyst (Patent Document 3).
(6) A method of reacting 1,1,1,3,3-pentachloropropane and hydrogen fluoride in the gas phase or liquid phase in the presence of a catalyst (Patent Documents 4 and 5).

In any of the methods (1) to (6), the reaction route of the following reaction (i), a combination of reactions (ii) and (i), or a combination of reactions (iii) and (i) To obtain R-1233zd (E). However, X is a halogen atom.

R-1233zd (E) is used as a substitute for R-134a and R-245fa, and is required to have a high purity. For this purpose, it is desirable to produce R-1233zd (E) with high selectivity.

However, in the method (1), it is difficult to selectively produce R-244fa as a raw material. In addition, the target R-1233zd (E) and the by-product R-245fa azeotrope, making separation difficult (see Patent Document 6).
In the method (2), an equimolar amount of an alkali metal compound and R-243fa are required, and an equimolar amount of an alkali metal salt is by-produced.
In the method (3), the preparation of the metal catalyst is complicated and the catalyst is expensive. Further, polymerization of the target product by metal catalyst and by-product olefins results in by-product formation of high-boiling products and the catalyst tends to be deactivated.
In the method (4), an equimolar amount of potassium hydroxide and 3-chloro-1,1,1-trifluoro-3-iodopropane are required, and an equimolar amount of potassium salt is by-produced. Also, 3-chloro-1,1,1-trifluoro-3-iodopropane is difficult to obtain.
In the methods (5) and (6), it is difficult to increase the selectivity of R-1233zd (E), and the yield is low. In the method (6), handling of dangerous hydrogen fluoride is not easy.

In the methods (2) and (3), E-form (R-1233ze) of 3-chloro-1,3,3-trifluoropropene (refrigerant number: R-1233ze) is simultaneously formed with R-1233zd (E). (E)) and (Z) form (R-1233ze (Z)) are considered to be by-produced. Since R-1233zd (E) is difficult to be separated from R-1233ze (E) and R-1233ze (Z) by the methods (2) and (3), high-purity R-1233zd (E) ) Cannot be obtained.

In addition, when dehydrochlorinating R-243fa, 1,3-dichloro-1,3,3-trifluoropropane (refrigerant number: R-243fb), which is an isomer of R-243fa, is present in the reaction system. In this case, R-243fb can be dehydrochlorinated to produce R-1233ze (E) and R-1233ze (Z).

JP 2009-263365 A US Pat. No. 8,653,309 Japanese Patent No. 5277813 Japanese Patent No. 3516324 Japanese Patent No. 4746544 US Pat. No. 7,183,448

An object of the present invention is to provide a method capable of easily producing R-1233zd (E) with high selectivity without forming a metal salt.

The method for producing R-1233zd (E) of the present invention is characterized in that R-243fa is converted to R-1233zd (E) by contacting with R-233fa with an activated carbon catalyst having a specific surface area of 10 to 3000 m ² / g.
R-243fa is gaseous and can be brought into contact with the activated carbon catalyst, and the contact temperature is preferably 50 to 500 ° C. The R-243fa gas may be diluted with a compound inert gas, and an inert gas is preferable as the inert compound.
R-243fa is liquid and can be brought into contact with the activated carbon catalyst, and the contact temperature is preferably 0 to 250 ° C.
The specific surface area of the activated carbon catalyst is preferably 20 to 2500 m ² / g, the ash content of the activated carbon catalyst is preferably 15% or less, and the water content of the activated carbon catalyst is preferably 10% or less. .

When R-243fa contains R-243fb, the content ratio of R-243fb is preferably 5 mol% or less with respect to the total amount of R-243fa and R-243fb.
R-243fa including R-243fb is R-243fa obtained by reacting 1,1-difluoroethylene (hereinafter referred to as VdF) with dichlorofluoromethane (refrigerant number: R-21). Is preferred. Further, in this case, R-243fa obtained by removing R-243fb from the reaction mixture obtained by reacting VdF and R-21 is preferable.
R-243fa including R-243fb is preferably R-243fa obtained by reacting pentahalogenopropane with hydrogen fluoride. Further, in this case, R-243fa obtained by removing R-243fb from the reaction mixture obtained by reacting pentahalogenopropane with hydrogen fluoride is preferable.

According to the production method of R-1233zd (E) of the present invention, R-1233zd (E) can be easily produced with high selectivity without forming a metal salt.

It is a flowchart which shows an example of a gas phase reaction. It is a flowchart which shows an example of a liquid phase reaction. 10 is a graph showing the purification behavior in Example 11.

<Method for producing R-1233zd (E)>
The production method of the present invention is a method for obtaining R-1233zd (E) by contacting R-243fa with an activated carbon catalyst having a specific surface area of 10 to 3000 m ² / g to convert to R-1233zd (E). is there.

The reaction for converting R-1233zd (E) by contacting R-243fa with an activated carbon catalyst is represented by the following formula (1).

R-243fa may be in gaseous form and contacted with the activated carbon catalyst, or in liquid form and contacted with the activated carbon catalyst. The method of contacting R-243fa in gaseous form with the activated carbon catalyst is hereinafter referred to as a gas phase method, and the method of contacting the activated carbon catalyst with a liquid state is hereinafter referred to as a liquid phase method.
R-243fa may contain a compound inert to the above reaction. Examples of the compound inert to the reaction include inert gases such as nitrogen, carbon dioxide, rare gas, and water vapor, and organic compounds that do not dehydrochlorinate. As the organic compound that does not _{_{_{_{dehydrochlorination, C 3 F 8, CF 3}}}} CF 2 Cl, halogenated hydrocarbons containing fluorine atoms, such as _CF 3 CH ₂ F preferred. Furthermore, even a compound that may affect the above reaction may be contained in R-243fa if the effect is small due to its small amount.

Although R-243fa does not affect the above reaction, it may contain an impurity that reacts in the same manner as R-243fa to produce a compound other than R-1233zd (E). In the case where a product other than R-1233zd (E) produced from such a compound is easily separated from R-1233zd (E), purification of R-1233zd (E) results in purification of R-1233zd (E) having high purity. ) Can be manufactured. However, when products other than R-1233zd (E) are difficult to separate from R-1233zd (E), it is preferable that R-243fa has few impurities that produce such difficult-to-separate products. Specifically, for example, when R-243fa containing R-243fb by-produced in the production of R-243fa described later is used as a raw material, R-1233ze (E) generated by the dehydrochlorination reaction of R-243fb, R-1233ze (Z) is difficult to separate from R-1233zd (E). Therefore, R-243fa produced by the production method described later is preferably used as a raw material for R-1233zd (E) after reducing by-produced R-243fb.

The content ratio of R-243fb in R-243fa is preferably 5 mol% or less, more preferably 3 mol% or less, still more preferably 1 mol% or less with respect to the total amount of R-243fa and R-243fb. When the content ratio of R-243fb is within this range, impurities in the product, particularly R-1233ze (E) and R-1233ze (Z) are small, and purification of R-1233zd (E) is facilitated.

Activated carbon catalyst:
The activated carbon catalyst in the present invention is a catalyst for dehydrochlorinating R-243fa to convert it into R-1233zd (E).

The specific surface area of the activated carbon catalyst is 10 to 3000 m ² / g. When the specific surface area of the activated carbon catalyst is 10 m ² / g or more, the reaction rate of R-243fa is improved. If the specific surface area of an activated carbon catalyst is 3000 m < ² > / g or less, an active site will reduce and it will be easy to suppress the production | generation of a by-product.
The specific surface area of the activated carbon catalyst, from the both of suppression of increase and by-products of the conversion to the desired product easiness, preferably 20 ~ 2500m ² / g, more preferably 50 ~ 2000m ² / g.
The specific surface area of the activated carbon catalyst is measured by a method based on the BET method.

Examples of the activated carbon catalyst include activated carbon prepared from charcoal, coal, coconut shell, and the like.
Examples of the shape of the activated carbon catalyst include formed coal having a length of about 2 to 5 mm, crushed coal having a size of about 4 to 50 mesh, granular coal, powdered coal and the like. In the case of a gas phase method, 4-20 mesh crushed coal or coal is preferable. In the case of the liquid phase method, powdered coal or granular coal is preferable.

The ash content of the activated carbon catalyst is preferably 15% or less, more preferably 10% or less, and even more preferably 8% or less. When the ash content of the activated carbon catalyst exceeds 15%, side reactions tend to occur.
The ash content of the activated carbon catalyst is measured according to ASTM D2866.
The ash content of the activated carbon catalyst can be removed by a known method such as washing with an acid. For example, even if the ash content of activated carbon made from coal or the like exceeds 15%, the activated carbon can be washed with an acid such as hydrochloric acid to reduce the ash content to 15% or less.

The activated carbon catalyst is preferably dried sufficiently before being used in the reaction. Specifically, the water content in the activated carbon catalyst before use is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 1% by mass or less, out of 100% by mass of the activated carbon (including moisture). preferable.

Examples of the gas phase method for producing R-1233zd (E) include a method of forming a catalyst layer filled with an activated carbon catalyst and introducing a gas containing R-243fa into the catalyst layer.
FIG. 1 is a flowchart showing an example of a gas phase method. R-243fa gas and, if necessary, a diluting gas are introduced into the reactor heated by the heating means, and the R-243fa gas is brought into contact with the activated carbon catalyst of the catalyst layer in the reactor. Product is continuously removed from the bottom of the reactor. A part of the product taken out from the lower part of the reactor may be collected and subjected to composition analysis by gas chromatography (GC). If necessary, the product is passed through a deoxidation tower to remove hydrogen chloride.

Examples of the reactor include known reactors capable of forming a catalyst layer, such as a fixed bed reactor and a fluidized bed reactor. A fixed bed reactor is preferred.
Examples of the material for the reactor include iron, nickel, alloys containing these as main components, and glass. An alloy containing iron (stainless steel or the like) is preferable.
The catalyst layer is formed by filling an activated carbon catalyst into the reactor. There may be two or more catalyst layers in the reactor.
Packing density of the activated carbon catalyst in the catalyst layer is preferably 0.2 ~ 1.0g / cm ^3, more preferably 0.25 ~ 0.7g / cm ^3. If the packing density of the activated carbon catalyst is 0.2 g / cm ³ or more, the amount of the activated carbon catalyst per unit volume is large, and the amount of gas to be reacted can be increased, so that productivity is improved. If the packing density of the activated carbon catalyst is 1.0 g / cm ³ or less, the temperature rise of the catalyst layer can be easily suppressed, and the reaction temperature can be easily managed.

Examples of the heating means include an electric furnace and an oil bath.
The diluent gas is introduced into the reactor together with R-243fa gas as necessary to extend the catalyst life of the activated carbon catalyst, improve the conversion rate, and improve the selectivity.
Examples of the diluent gas include inert gases (nitrogen, rare gases, etc.) and halogenated hydrocarbons that are inert to dehydrochlorination. Dilution gases other than these include hydrogen chloride and the like.
The ratio of the dilution gas is preferably 10 mol or less and more preferably 4 mol or less with respect to 1 mol of the raw material from the viewpoint of the recovery rate of the dilution gas.

The contact temperature is preferably 50 to 500 ° C., more preferably 100 to 400 ° C., and even more preferably 170 to 380 ° C. from the viewpoint of excellent reaction rate.
The pressure in the reactor may be ordinary pressure, increased pressure, or reduced pressure. Normal pressure or pressurization is preferred.
In order to control the conversion rate and selectivity of the raw material, the contact time can be shortened if the contact temperature is high, and can be lengthened if the contact temperature is low. More preferably, it is preferably ˜300 seconds, particularly preferably 10 to 100 seconds.

The gas linear velocity in the catalyst layer is preferably 0.1 to 100 cm / second, more preferably 0.3 to 30 cm / second. If the linear velocity is 0.1 cm / second or more, productivity is improved. When the linear velocity is 100 cm / second or less, the reaction rate of the raw material is improved.
The linear velocity u is calculated by the following equation from the amount of the raw material gas introduced into the reactor and the volume of the catalyst layer.
u = V / S.
However,
V is the flow rate (cm ³ / sec) of the total gas introduced into the catalyst layer,
S is a cross-sectional area (cm ² ) with respect to the gas flow direction of the catalyst layer.

In addition to the target product, the product includes unreacted raw materials and by-products. By-products include hydrogen chloride.
Hydrogen chloride contained in the product can be easily removed by distillation. If necessary, the product may be removed by contacting with a metal hydroxide or an aqueous solution thereof to neutralize. Examples of the metal hydroxide include sodium hydroxide and potassium hydroxide.

The liquid phase method for producing R-1233zd (E) may be a batch method or a continuous method. From the viewpoint of production efficiency, the continuous type is preferable.
FIG. 2 is a flowchart showing an example of the liquid phase method.
R-243fa is continuously supplied to a reactor containing an activated carbon catalyst and, if necessary, a liquid medium inert to the reaction, and the activated carbon catalyst and R-243fa are brought into contact with each other in a liquid phase in the reactor. . The product is recovered from the reactor. When the product is recovered from the liquid phase in the reactor, the product is cooled by cooling. If necessary, the product is passed through a deoxidation tower to remove hydrogen chloride.

Examples of the reactor include known reactors capable of bringing activated carbon catalyst into contact with liquid R-243fa.
Examples of the material for the reactor include iron, nickel, alloys containing these as main components, and glass. If necessary, lining treatment such as resin lining and glass lining may be performed.

As the activated carbon catalyst, powdered or granular charcoal is preferable.
In the liquid phase method, a liquid medium may be used or a liquid medium may not be used. It is preferable not to use a liquid medium. The liquid medium is a liquid inert to the dehydrochlorination reaction, and examples thereof include water and organic solvents (alcohols, fluorine-containing solvents, etc.).
When a liquid medium is used, the amount of the medium is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the raw material.

The contact temperature is preferably 0 to 250 ° C, more preferably 20 to 150 ° C. When the contact temperature is 0 ° C. or higher, the reaction rate is improved. If a contact temperature is 250 degrees C or less, it will be easy to suppress a by-product.
The pressure in the reaction vessel is preferably 0 to 10 MPa [gage], more preferably 0.05 to 5 MPa [gage], and still more preferably 0.15 to 3 MPa [gage]. The reaction pressure is preferably not less than the vapor pressure of R-243fa at the reaction temperature.
The contact time is preferably 1 to 50 hours for the batch method, and preferably 1 to 3000 seconds for the continuous method.

The product may be recovered from the gas phase or may be recovered from the liquid phase. It is preferable to recover from the gas phase. When recovering the product from the gas phase, a cooling device may be attached to the extraction site. By attaching a cooling device, unreacted raw materials can be returned to the reactor, and R-1233zd (E), R-1233zd (Z) and hydrogen chloride having low boiling points can be selectively removed from the reaction system. Excellent conversion and selectivity.

R-1233zd (E) obtained by a gas phase method or a liquid phase method can be purified to give R-1233zd (E) with few impurities.
Examples of the purification method include distillation, extractive distillation, adsorption, washing, dehydration, and two-layer separation. Distillation is preferred because it can be carried out easily. Examples of washing include washing with an acidic aqueous solution, a neutral aqueous solution, or a basic aqueous solution.

When R-243fa with reduced R-243fb is used, R-1233ze (E) and R-1233ze (Z) are difficult to separate from R-1233zd (E) in the product (eg, distillation separation). The content ratio of is reduced. Therefore, high-purity R-1233zd (E) can be obtained from the reaction product by separation and purification by general distillation.

Examples of the method for obtaining the raw material R-243fa include the following method (a-1) and method (a-2). The method (a-1) is preferred because R-243fa having a small content of impurities other than R-243fb can be obtained.
(A-1) A method of reacting VdF with R-21.
(A-2) A method of reacting pentahalogenopropane with hydrogen fluoride.

Method (a-1):
The reaction between VdF and R-21 is represented by the following formula (2).

As shown by the above formula (2), R-243fb is produced together with R-243fa by the reaction of VdF and R-21.
The content ratio of R-243fb in the mixture obtained by the reaction varies depending on the reaction conditions (especially the reaction temperature and the type of catalyst), but usually 5 mol out of a total of 100 mol% of R-243fa and R-243fb. % Or more.
The mixture contains chloroform, 1,1,1-trifluoroethane (refrigerant number: R-143a), etc., in addition to R-243fa and R-243fb.

The reaction between VdF and R-21 is preferably performed using a catalyst. Examples of the catalyst include aluminum chloride; modified zirconium chloride treated with trichlorofluoromethane or the like (see JP-A-4-253828); Lewis acid catalyst and the like. Examples of the Lewis acid catalyst include a halide containing at least one element selected from the group consisting of Al, Sb, Nb, Ta, W, Re, B, Sn, Ga, In, Zr, Hf, and Ti. .

Method (a-2):
The reaction between pentahalogenopropane and hydrogen fluoride is represented by the following formula (3). Here, m is an integer of 1 to 3.

The content ratio of R-243fb in the mixture obtained by the reaction varies depending on the reaction conditions (especially the reaction temperature and the type of catalyst), but usually 5 mol out of a total of 100 mol% of R-243fa and R-243fb. % Or more.

The reaction mixture obtained by the method (a-1), the method (a-2) or the like contains at least R-243fa and R-243fb, and may contain other components.
Other components include chloroform, tetrachloromethane, 1,2-dichloroethane, 1,1-dichloroethane, 1,1,2-trichloro-3,3-difluoroethane (refrigerant number: R-122), 1,1, 2-trichloroethylene, R-244fa, 1-chloro-1,1,3,3-tetrafluoropropane (refrigerant number: R-244fb), 1,3-dichloro-3,3-difluoropropene (refrigerant number: R- 1232zd E and Z), R-1233ze (E), R-1233ze (Z), R-1233zd (Z), 3,3-dichloro-1,1,3-trifluoropropene (refrigerant number: R −1233zc), chlorodifluoromethane (refrigerant number: R-22), R-21, R-143a, and the like.

The content of R-243fa in the reaction mixture is preferably 30 mol% or more, more preferably 50 mol% or more, and further preferably 70 mol% or more in the reaction mixture (100 mol%).
The content of R-243fb in the reaction mixture is preferably 15 mol% or less, more preferably 10 mol% or less, and even more preferably 7 mol% or less in the reaction mixture (100 mol%).

As described above, the content ratio of R-243fb in R-243fa is preferably 5 mol% or less, more preferably 3 mol% or less, more preferably 1 mol% with respect to the total amount of R-243fa and R-243fb. The following is more preferable. Therefore, when the reaction mixture obtained by the method (a-1), the method (a-2), etc. contains R-243fb exceeding this ratio, the method (a-1), the method (a-2), etc. The obtained reaction mixture is purified, and the ratio of R-243fb in R-243fa is preferably within the above range.
Examples of the purification method include distillation, extractive distillation, adsorption and the like. Distillation is preferred because it can be carried out easily.
Distillation may be performed under normal pressure, may be performed under pressure, or may be performed under reduced pressure. It is preferable to carry out under normal pressure.

(Use of R-1233zd (E))
R-1233zd (E) is useful as a refrigerant, a foaming agent, a foam, a preform mix, a solvent, a cleaning agent, a propellant and a compatibilizer, and a raw material monomer of a functional material and an intermediate for synthesis.
When R-1233zd (E) is used as a raw material monomer of a functional material or an intermediate for synthesis, it is preferably highly pure (for example, 99.0 mol% or more).

(Other forms)
The method for producing R-1233zd (E) of the present invention is not limited to the method described above as long as it is a method for bringing R-243fa into contact with a specific activated carbon catalyst.
For example, R-243fa may be obtained by methods other than the method (a-1) and the method (a-2), and the obtaining method is not particularly limited.

(Mechanism of action)
In the production method of R-1233zd (E) of the present invention described above, R-243fa is dehydrochlorinated by bringing R-243fa into contact with a specific activated carbon catalyst to obtain R-1233zd (E). Therefore, R-1233zd (E) can be easily produced with high selectivity without producing a metal salt.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

(Example 1)
Adjustment of modified zirconium chloride catalyst:
A cooler having a height of 15 cm was connected to the top, and 256.9 g of zirconium tetrachloride was placed in a four-necked flask (material: glass, capacity: 1 L) containing a magnetic stirrer. While cooling the condenser and flask with dry ice to −78 ° C., 636 g of R-21 was gradually added. While stirring with a magnetic stirrer, the temperature of the cooler and the flask was gradually raised to 0 ° C., and the stirring was continued for 2.5 hours after the internal temperature reached 0 ° C. The cooling of the condenser and flask was stopped, and drying was performed under reduced pressure at room temperature overnight. After the drying, 236.1 g of modified zirconium chloride catalyst was recovered.

Production of R-243fa:
In an autoclave (material: Hastelloy, capacity: 10 L), an initial solvent (R-243fa: 71.4 mol%, R-243fb: 8.7 mol%, chloroform: 1.3 mol%, R-22: 0.1) Mol%, R-21: 1.3 mol%, other components: 17.2 mol%) and 78 g of the modified zirconium chloride catalyst were added. The autoclave was cooled to -15 ° C. While cooling and stirring, 7202 g of R-21 was slowly added at such a rate that the internal temperature remained below -10 ° C. While cooling and stirring, 4480 g of VdF was added over 10 hours so that the internal temperature was kept below 0 ° C. After stirring for another 30 minutes, the gas phase was replaced with nitrogen to complete the reaction. While stirring, the reaction crude liquid was extracted from the bottom of the autoclave. The amount of the reaction crude liquid was 12822 g. The reaction crude liquid was filtered with a pressure filter set with filter paper (4 μm diameter) to obtain 12277 g of a uniform organic layer. As a result of partially collecting the organic layer and analyzing the composition by GC, the composition ratio of the organic layer was as follows.
R-243fa: 67.9 mol%,
R-243fb: 9.3 mol%,
Chloroform: 1.1 mol%,
R-143a: 3.2 mol%,
R-21: 2.2 mol%,
Other ingredients: 16.3 mol%.

Purification of R-243fa:
In a distillation column (material: glass, inner diameter: 3 cm, height: 97 cm) equipped with a kettle (material: glass, capacity: 10 L), a magnetic reflux device, a reflux timer and a Dimroth cooler that can be heated with a mantle heater, A filling for distillation (manufactured by Takenaka Wire Mesh Co., Ltd., Helipac No. 1) was filled (measured number of stages: 43 stages).
11,000 g of the reaction crude liquid obtained in the production of R-243fa was put in a kettle of a distillation column, and the ratio of reflux time / distillation time was adjusted to 50/1 to 300/1 by a reflux timer at normal pressure. Distillation was performed. As a result, 2220 g of a composition having R-243fa of more than 99.9 mol% and R-243fb of less than 0.1 mol% (hereinafter also referred to as R-243-containing composition 1) was obtained. In addition, 3870 g of a composition having R-243fa of 94.0 mol% and R-243fb of 5.9 mol% (hereinafter also referred to as R-243-containing composition 2) was obtained.
In Examples 1 to 8 below, R-243fa-containing composition 1 was used as a raw material.

Production of R-1233zd (E):
A vertical fixed bed reactor (material: SUS316, inner diameter 23.0 mm × height 200 mm) was used as the reaction apparatus. An insertion tube (material: SUS316, diameter: 4 mm) was introduced into the center of the reactor, a K-type thermocouple was inserted therein, and the internal temperature was measured. The central part of the reactor was filled with an activated carbon catalyst, which was used as a catalyst layer. The catalyst layer was heated by an electric furnace. A raw material preheating mixing line heated to 100 ° C. connected to a gas feed line and a raw material supply line heated to 100 ° C. was connected to the upper part of the reactor. Nitrogen was supplied from the gas feed line to the raw material preheating mixing line by adjusting the gas flow rate using a mass flow controller. The raw material containing R-243fa was vaporized through a raw material supply line heated to 100 ° C. using a plunger pump, and then supplied to the raw material preheating mixing line. Product was continuously removed from the bottom of the reactor. A part of the product taken out from the lower part of the reactor was collected and subjected to composition analysis by gas chromatography (GC). Hereinafter, the product taken out from the lower part of the reactor is referred to as outlet gas.

The reactor activated carbon catalyst (Japan EnviroChemicals Chemicals Inc., Shirasagi activated carbon C2x, specific surface area: 1260m ² / g, ash content: 1.2 wt%) was charged with 81.2ML (41.2 g) of.
Nitrogen and raw materials were introduced into the reactor under the conditions shown in Table 1, and the reaction was continued for 4 hours. Immediately before the end of the reaction, a part of the outlet gas was sampled and analyzed by gas chromatography (GC). The results are shown in Table 1.

(Examples 2-7)
Under the conditions shown in Table 1, nitrogen and raw materials or only raw materials were introduced into the reactor and reacted continuously for 4 hours. Immediately before the end of the reaction, a part of the outlet gas was sampled and subjected to composition analysis by gas chromatography (GC). The results are shown in Table 1.

(Example 8)
The raw materials were introduced into the reactor under the same reaction conditions as in Example 6 and reacted continuously for 256 hours. Immediately before the end of the reaction, a part of the outlet gas was sampled and subjected to composition analysis by gas chromatography (GC). The results are shown in Table 1. Further, after extracting the catalyst after this reaction from the reactor, the specific surface area was measured by using a continuous flow type surface area meter SA-9601 manufactured by Horiba Seisakusho, and it was 78 m ² / g.

(Product composition analysis)
A gas chromatogram was used for composition analysis of the product. DB-1 (manufactured by Agilent Technologies, length 60 m × inner diameter 250 μm × thickness 1 μm) was used as the column.

(R-243fa conversion)
The R-243fa conversion rate X (%) was determined from the following equation.
X = 100 × (Xa−Xb) / Xa.
However,
Xa: R-243fa content ratio (mol%) in the raw material,
Xb: R-243fa content ratio (mol%) in the outlet gas after the reaction.

(R-1233zd selectivity)
The R-1233zd (E) selectivity Y (E) (%) and the R-1233zd (Z) selectivity Y (Z) (%) were obtained from the following equations.
Y (E) = 100 × Ya / (Xa−Xb).
Y (Z) = 100 × Yb / (Xa−Xb).
However,
Ya: R-1233zd (E) content ratio (mol%) in the outlet gas after the reaction,
Yb: R-1233zd (Z) content ratio (mol%) in the outlet gas after the reaction.

From the results of Examples 1 to 8, it can be seen that according to the production method of R-1233zd (E) of the present invention, R-1233zd (E) can be produced with high selectivity.
Further, comparison between Example 3 and Example 6 shows that the R-1233zd (E) selectivity is hardly lowered even if R-243fa is not diluted with nitrogen.

(Example 9)
After adding 19.3 g of tetrabutylammonium chloride (TBAC) and 3861.9 g (23.1 mol) of R-243fa-containing composition 2 as raw materials to an autoclave (material: Hastelloy, capacity: 10 L) While maintaining the internal temperature at 5 to 10 ° C., 6907.7 g (NaOH: 34.7 mol) of a 20 mass% sodium hydroxide aqueous solution was added. After replacing the gas phase with nitrogen, the internal temperature was raised to 25 ° C. and stirred for 2 hours, and the internal temperature was further raised to 40 ° C. and stirred for 8 hours. After cooling the internal temperature to 5 ° C., the mixture was allowed to stand for 2 hours and recovered in the order of the organic layer and the aqueous layer from the bottom of the autoclave. The recovery amount of the organic layer was 2835.4 g, and the recovery amount of the aqueous layer was 7733.7 g. About the organic layer, the composition by gas chromatography (GC) was performed. The results and other reaction results are shown in Table 2.

In Table 2, R-243fa conversion rate X (%), R-1233zd (E) selectivity Y (%), and R-1233ze (EorZ) in R-1233zd (E): isomer A content Z ( %) Is obtained by the following equation.

(R-243fa conversion)
X = 100 × (Xa−Xb) / Xa.
However,
Xa: R-243fa content ratio (mol%) in the raw material,
Xb: R-243fa content ratio (mol%) in the outlet gas after the reaction.

(R-1233zd (E) selectivity)
Y = 100 × Ya / (Xa−Xb).
However,
Ya: R-1233zd (E) content ratio (mol%) in the outlet gas after the reaction.

(R-1233ze (EorZ) in R-1233zd (E): isomer A content)
Z = 100 × Za / (Za + Zb).
However,
Za: R-1233ze (EorZ) in the exit gas after the reaction: Content ratio of isomer A (mol%)
Zb: R-1233zd (E) content ratio (mol%) in the outlet gas after the reaction.

The dehydrochlorination reaction was carried out twice, and the resulting composition was mixed to obtain 5564 g of R-1233zd (E) -containing composition 1 having the following composition.
R-1233zd (E): 86.0 mol%,
R-1233zd (Z): 6.4 mol%,
3,3,3-trifluoropropyne: 1.0 mol%,
R-243fa: 3.8 mol%,
R-1233ze (EorZ): Isomer A: 2.2 mol%
R-1233ze (EorZ): Isomer B: 0.4 mol%
R-1233zc: 0.3 mol%.

Purification:
Heatable kettle (material: SUS, capacity: 5 L), reflux column, reflux timer, multi-tube cooling condenser, nitrogen gas line, back pressure valve and dry ice cooled low boiling point substance recovery trap (material: SUS, inner diameter: 2.7 cm, height: 300 cm, packing height: 250 cm) were packed with a fine distillation packing (manufactured by Takenaka Wire Mesh Co., Ltd., Helipack No. 3) (measured number of stages: 30 stages).
5564 g of the obtained R-1233zd (E) -containing composition 1 was put in a distillation column kettle, and the ratio of reflux time / distillation time was adjusted to 300/1 to 600/1 by a reflux timer to adjust the back pressure valve. Then, distillation was performed under a pressure of 0.2 MPa with nitrogen. As a result, a composition having R-1233zd (E) exceeding 99.0 mol% was not obtained, but a composition having R-1233zd (E) and R-1233ze (EorZ): isomer A was obtained. The yield of the mixed composition (R-1233zd (E) + R-1233ze (EorZ): isomer A is more than 99.0 mol%) was 3630 g, and the composition was 98.3 mol% R-1233zd (E). , R-1233ze (EorZ): The isomer A was 1.7 mol%. In addition, 559 g of the composition was recovered as the kettle residue. The distillation behavior is shown in FIG.
As is clear from FIG. 3, separation of R-1233zd (E) and R-1233ze (EorZ): isomer A was very difficult.

The production method of R-1233zd (E) of the present invention can be suitably used for the production of R-1233zd (E) because R-1233zd (E) can be obtained with high selectivity.
In addition, the entire content of the specification, claims, abstract, and drawings of Japanese Patent Application No. 2014-093092 filed on April 28, 2014 is cited here as disclosure of the specification of the present invention. Incorporated.

Claims

1,1-dichloro-3,3,3-trifluoropropane is converted to trans-1-chloro-3,3,3-trifluoropropene by contacting with an activated carbon catalyst having a specific surface area of 10 to 3000 m 2 / g. A process for producing trans-1-chloro-3,3,3-trifluoropropene.
The process for producing trans-1-chloro-3,3,3-trifluoropropene according to claim 1, wherein 1,1-dichloro-3,3,3-trifluoropropane is brought into contact with the activated carbon catalyst in a gaseous state. .
The process for producing trans-1-chloro-3,3,3-trifluoropropene according to claim 2, wherein the contact temperature with the activated carbon catalyst is 50 to 500 ° C.
4. Trans-1-chloro-3, according to claim 2 or 3, wherein the 1,1-dichloro-3,3,3-trifluoropropane gas is diluted with a gas of a compound inert to the reaction. A method for producing 3,3-trifluoropropene.
The method for producing trans-1-chloro-3,3,3-trifluoropropene according to claim 4, wherein the compound inert to the reaction is an inert gas.
The process for producing trans-1-chloro-3,3,3-trifluoropropene according to claim 1, wherein 1,1-dichloro-3,3,3-trifluoropropane is brought into contact with the activated carbon catalyst in a liquid state.
The process for producing trans-1-chloro-3,3,3-trifluoropropene according to claim 6, wherein the contact temperature with the activated carbon catalyst is 0 to 250 ° C.
The process for producing trans-1-chloro-3,3,3-trifluoropropene according to any one of claims 1 to 7, wherein the activated carbon catalyst has a specific surface area of 20 to 2500 m 2 / g.
The process for producing trans-1-chloro-3,3,3-trifluoropropene according to any one of claims 1 to 8, wherein the activated carbon catalyst has an ash content of 15% or less.
The process for producing trans-1-chloro-3,3,3-trifluoropropene according to any one of claims 1 to 9, wherein the activated carbon catalyst has a water content of 10% or less.
The 1,1-dichloro-3,3,3-trifluoropropane comprises 1,3-dichloro-1,3,3-trifluoropropane;
The content ratio of 1,3-dichloro-1,3,3-trifluoropropane is such that 1,1-dichloro-3,3,3-trifluoropropane and 1,3-dichloro-1,3,3-trifluoro The process for producing trans-1-chloro-3,3,3-trifluoropropene according to any one of claims 1 to 10, which is 5 mol% or less based on the total amount of propane.
1,1-dichloro-3,3,3-trifluoropropane containing 1,3-dichloro-1,3,3-trifluoropropane reacts 1,1-difluoroethylene with dichlorofluoromethane. The process for producing trans-1-chloro-3,3,3-trifluoropropene according to claim 11, which is the obtained 1,1-dichloro-3,3,3-trifluoropropane.
1,1-dichloro-3,3,3-trifluoropropane containing 1,3-dichloro-1,3,3-trifluoropropane reacts 1,1-difluoroethylene with dichlorofluoromethane. 13. 1,1-dichloro-3,3,3-trifluoropropane obtained by removing 1,3-dichloro-1,3,3-trifluoropropane from the obtained reaction mixture, A process for producing the trans-1-chloro-3,3,3-trifluoropropene described.
1,1-dichloro-3,3,3-trifluoropropane containing 1,3-dichloro-1,3,3-trifluoropropane was obtained by reacting pentahalogenopropane with hydrogen fluoride. The process for producing trans-1-chloro-3,3,3-trifluoropropene according to claim 11, which is 1,1-dichloro-3,3,3-trifluoropropane.
1,1-dichloro-3,3,3-trifluoropropane containing 1,3-dichloro-1,3,3-trifluoropropane was obtained by reacting pentahalogenopropane with hydrogen fluoride. 15. The trans of claim 14, which is 1,1-dichloro-3,3,3-trifluoropropane obtained by removing 1,3-dichloro-1,3,3-trifluoropropane from the reaction mixture. A process for producing 1-chloro-3,3,3-trifluoropropene.