WO2016111227A1 - Method for producing (e)-1-chloro-3,3,3-trifluoropropene - Google Patents

Abstract

Provided is a method with which it is possible to produce (E)-1-chloro-3,3,3-trifluoropropene from 1,3-dichloro-1,1,3-trifluoropropane by using a catalyst that is economical and has excellent handleability. Disclosed is a method for producing (E)-1-chloro-3,3,3-trifluoropropene, wherein, by bringing a material including 1,3-dichloro-1,1,3-trifluoropropane as an essential component into contact with activated carbon, the 1,3-dichloro-1,1,3-trifluoropropane is converted, and (E)-1-chloro-3,3,3-trifluoropropene is obtained.

Description

(E) Process for producing 1-chloro-3,3,3-trifluoropropene

The present invention relates to a method for producing (E) -1-chloro-3,3,3-trifluoropropene (hereinafter also referred to as R-1233zd (E form)).

In this specification, an abbreviation (refrigerant number, etc.) may be described in parentheses after the halogenated hydrocarbon compound name. In the present specification, abbreviations may be used in place of compound names as necessary.

R-1233zd (E form) is a greenhouse gas such as 1,1,1,2-tetrafluoroethane (R-134a) and 1,1,1,3,3-pentafluoropropane (R-245fa). It is an alternative compound.

As a method for producing R-1233zd (E form), 1,1-difluoroethylene (vinylidene difluoride; hereinafter also referred to as VdF) and dichlorofluoromethane (hereinafter also referred to as R-21) are reacted. There is a method of dehydrochlorinating 1,1-dichloro-3,3,3-trifluoropropane (hereinafter also referred to as R-243fa) obtained in this manner.
For example, Non-Patent Document 1 discloses a method for dehydrochlorinating R-243fa in an alkaline solution.
Patent Document 1 discloses a method for dehydrochlorinating R-243fa in the presence of a metal catalyst.

In the reaction of VdF and R-21 described above, 1,3-dichloro-1,1,3-trifluoropropane (hereinafter also referred to as R-243fb) is also produced as an isomer of R-243fa.
However, the above document does not describe at all the production of R-1233zd from R-243fb. Under the conditions of the dehydrochlorination reaction described in the above document, the following formula (1) or (2) It is considered that such a reaction proceeds and R-1233zd is not generated.

The following method for producing R-1233zd (E form) from R-243fb has been attempted.
For example, Patent Document 2 discloses a method for producing R-1233zd (E-form) in which a composition containing R-243fb is contacted with a metal catalyst to convert R-243fb to R-1233zd (E-form). It is disclosed.

US Pat. No. 8,653,309 JP 2014-214123 A

J. et al. Am. Chem. Soc. 64, 1942, p. 1158

However, the metal catalyst described in Patent Document 2 is expensive and complicated to handle.
Accordingly, an object of the present invention is to provide a method capable of producing R-1233zd (E-form) from R-243fb using a catalyst that can be handled economically and easily.

As a result of intensive studies by the present inventors, it has been found that R-243fb can be converted to R-1233zd (E form) with an activated carbon catalyst, and the present invention has been completed.
That is, the present invention has the following aspects [1] to [16].
[1] By bringing a raw material containing 1,3-dichloro-1,1,3-trifluoropropane as an essential component into contact with activated carbon, the 1,3-dichloro-1,1,3-trifluoropropane A process for producing (E) -1-chloro-3,3,3-trifluoropropene, which is converted to obtain (E) -1-chloro-3,3,3-trifluoropropene.
[2] The production method according to [1], wherein the raw material does not contain 1,1-dichloro-3,3,3-trifluoropropane.
[3] The production method according to [1], wherein the raw material contains 1,1-dichloro-3,3,3-trifluoropropane.
[4] The production method according to [3], wherein the raw material is a raw material obtained from a reaction product of vinylidene fluoride and dichlorofluoromethane.
[5] The 1,1-dichloro-3,3,3-trifluoropropane content in the raw material is 1,3-dichloro-1,1,3-trifluoropropane and 1,1-dichloro- The production method according to [3] or [4], which is more than 0 mol% and not more than 5 mol% with respect to the total molar amount of 3,3,3-trifluoropropane.
[6] The raw material contains 1,1-dichloro-3,3,3-trifluoropropane as an optional component, and the content of 1,3-dichloro-1,1,3-trifluoropropane in the raw material Is 5 mol% or more and 100 mol% or less with respect to the total molar amount of 1,3-dichloro-1,1,3-trifluoropropane and 1,1-dichloro-3,3,3-trifluoropropane The production method according to [1], wherein
[7] The production method according to any one of [1] to [6], wherein the activated carbon has a specific surface area of 10 to 3000 m ² / g.
[8] The production method according to any one of [1] to [7], wherein the raw material is a raw material in a gaseous state and is brought into contact with the activated carbon at 50 to 500 ° C.
[9] The production method according to [8], wherein the contact time is 1 to 1000 seconds.
[10] The conversion is performed while passing the gaseous raw material through the catalyst layer filled with the activated carbon, and the linear velocity of the gaseous raw material in the catalyst layer is 0.1 to 100 cm / sec. The production method according to [8] or [9].
[11] The production method according to any one of [8] to [10], wherein the activated carbon is 4 to 20 mesh crushed coal or formed coal.
[12] The production method according to any one of [1] to [7], wherein the raw material is a raw material in a liquid state and is brought into contact with the activated carbon at 0 to 250 ° C.
[13] The production method according to [12], wherein the pressure at the time of contact is 0 to 10 MPa (gauge pressure).
[14] The production method according to [12] or [13], wherein the contact is performed in a batch-type reaction vessel, and the contact time is 1 to 50 hours.
[15] The production method according to [12] or [13], wherein the contact is performed in a continuous reactor and the contact time is 1 to 3000 seconds.
[16] The production method according to any one of [12] to [15], wherein the activated carbon is powdered coal or granular coal.

According to the method for producing R-1233zd (E-form) of the present invention, R-1233zd (E-form) can be produced from R-243fb using an economical and excellent handleability catalyst.

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.

<Method for producing R-1233zd (E body)>
The method for producing R-1233zd (E form) is characterized in that R-243fb is converted by contacting a raw material containing R-243fb as an essential component with activated carbon to obtain R-1233zd (E form). And

Specific examples of the method for producing R-1233zd (E form) include, for example, a method of sequentially performing the following steps (a) to (d).
(A: Raw material acquisition step) Step of obtaining a raw material containing R-243fb (b: Raw material purification step) If necessary, the raw material obtained in the step (a) is purified, and the purity of R-243fb is high. Step of obtaining R-243fb raw material (c) Step of obtaining a product containing R-1233zd (E-form) by bringing R-243fb into contact with activated carbon and bringing R-243fb into contact with the raw material containing R-243fb (d) Necessary According to the process, the product containing R-1233zd (E form) is purified, and the purity of R-1233zd (E form) is increased.

(Process (a): Raw material acquisition process)
Preferred methods for obtaining the raw material containing R-243fb include the following method (a-1) and method (a-2). When a raw material containing R-243fb is obtained by the method (a-1) or the method (a-2), the raw material usually further contains R-243fa.
Of method (a-1) and method (a-2), the raw material is easily purified in step (b) to be described later, and a raw material having a low content of components other than R-243fb and R-243fa is obtained. From the viewpoint, the method (a-1) is preferable.
(A-1) Method of reacting VdF and R-21 (a-2) Method of reacting pentahalogenopropane and hydrogen fluoride

Method (a-1):
The reaction between VdF and R-21 is represented by the following formula (3).

The content ratio of R-243fb in the raw material obtained by the reaction varies depending on the reaction conditions (particularly the reaction temperature and the type of catalyst), but usually 5 mol out of a total of 100 mol% of R-243fb and R-243fa. It is about 15 mol% higher than%. In addition to R-243fb and R-243fa, the product may include chloroform, 1,1,1-trifluoroethane (hereinafter also referred to as R-143a) and the like.

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 Lewis acid catalysts include oxides or halides 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. Is mentioned. Particularly preferred is an oxide or halide containing at least one element selected from the group consisting of Al, Zr, Hf and Ti. When this catalyst is used, the reaction temperature is preferably −30 ° C. to 80 ° C., the reaction time is preferably 0.5 hours to 50 hours, and the amount of the catalyst used is 0.1% relative to 100% by mass of VdF and R-21. 0001 mass% to 5 mass% is preferable.

Method (a-2):
The reaction between pentahalogenopropane and hydrogen fluoride is represented by the following formula (4). Here, m is an integer of 1 to 3.

The content ratio of R-243fb in the product obtained by the reaction varies depending on the reaction conditions (especially the reaction temperature and the type of catalyst), but is usually 5% of the total 100 mol% of R-243fb and R-243fa. Higher than mol%.

Product composition:
The product obtained in step (a) may further contain other components.
Other components include chloroform, tetrachloromethane, 1,2-dichloroethane, 1,1-dichloroethane, 1,1,2-trichloro-3,3-difluoroethane (R-122), 1,1,2-trichloroethylene 1-chloro-1,3,3,3-tetrafluoropropane (R-244fa), 1-chloro-1,1,3,3-tetrafluoropropane (R-244fb), (EZ) -1,3 -Dichloro-3,3-difluoropropene (R-1232zd (EZ form)), R-1233ze (EZ form), (Z) -1-chloro-3,3,3-trifluoropropene (hereinafter referred to as R-1233zd) (Also referred to as Z form)), 3,3-dichloro-1,1,3-trifluoropropene, chlorodifluoromethane (hereinafter also referred to as R-22), R-21, R- 43a, and the like.
The raw material of the present invention may not contain 1,1-dichloro-3,3,3-trifluoropropane.

R-243fa and other components can be produced as by-products in the process of producing R-243fb.
The content of R-243fb in the product is 5 mol% out of the total 100 mol% of R-243fb and R-243fa from the viewpoint that the subsequent step (b) can be omitted and the production efficiency can be further improved. Higher is preferred.

(Process (b))
Step (b) is an optional step for purifying the product obtained in step (a) to obtain a raw material containing R-243fb having a higher concentration of R-243fb.
In step (b), the product in step (a) contains R-243fb and R-243fa, and the content of R-243fb in the product is 100 mol% in total of R-243fb and R-243fa. Of these, it is carried out when it is 5 mol% or less.
The product obtained in step (a) contains R-243fb and R-243fa, and the content ratio of R-243fb in the raw material is 5 mol% out of the total 100 mol% of R-243fb and R-243fa. If higher, the product obtained in the step (a) may be used as a raw material in the subsequent step (c) as it is, and if necessary, the content of R-243fb in the product is increased and the subsequent step You may use for (c).
If the product obtained in step (a) does not contain R-243fa, step (b) may or may not be performed. In this case, it is preferable to perform the step (b) from the viewpoint of increasing the content ratio of R-243fb in the raw material and increasing the production efficiency.

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 perform under normal pressure.
An appropriate fraction in distillation may be used as a raw material containing R-243fb used in step (c).

(Process (c))
In the present invention, a raw material containing R-243fb as an essential component is brought into contact with activated carbon to carry out a conversion reaction to obtain a product containing R-1233zd (E form).
The conversion reaction in the step (c) is represented by the following formula (5).

Raw materials containing R-243fb:
The raw material used here may be any material that contains R-243fb as an essential component. The content of R-243fb in the raw material is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 30% by mass or more with respect to the raw material (100% by mass) from the viewpoint of excellent production efficiency. Preferably, 50% by mass or more is particularly preferable, and 80% by mass or more is most preferable. Further, a material having a R-243fb content of 100% by mass in the raw material can be used.

R-243fa, which is an isomer of R-243fb, may be contained in the raw material. That is, R-243fa is an optional component.
Considering this R-243fa, when the content ratio of R-243fb in the raw material is expressed, the content ratio is 5 mol% or more and 100 mol% relative to the total molar amount of R-243fb and R-243fa. Mole% is preferred. If the content is 5 mol% or more with respect to the total molar amount of R-243fb and R-243fa, the raw material containing R-243fb obtained in step (a) may be used as it is. The raw material containing R-243fb at a high concentration obtained in (1) may be used.
The content of R-243fb in the raw material is preferably 7 mol% or more, more preferably 10 mol% or more with respect to the total molar amount of R-243fb and R-243fa. When the content ratio is equal to or higher than the lower limit, the amount of R-243fb is increased, and thus productivity is excellent.

If the raw material may contain R-243fa, the product obtained in the step (a) can be used as it is. If R-243fa is contained, R-243fa comes into contact with activated carbon, and the following formula (6) Is obtained from R-243fa, the yield of R-1233zd (E-form) is also improved. At this time, the content of R-243fa in the raw material is preferably more than 0 mol% and 5 mol% or less with respect to the total molar amount of R-243fb and R-243fa.

Activated carbon:
Activated carbon is a catalyst that converts R-243fb to R-1233zd (E form). The activated carbon exchanges fluorine atoms and chlorine atoms of R-243fb (isomerization reaction) and dehydrochlorinates to obtain R-1233zd (E form).

The specific surface area of the activated carbon is preferably 10 to 3000 m ² / g, more preferably 20 to 2500 m ² / g, and further preferably 50 to 2000 m ² / g. When the specific surface area of the activated carbon is not less than the lower limit, the reaction rate of R-243fb is improved. If the specific surface area of the activated carbon is not more than the above upper limit value, the active sites are decreased and the production of by-products can be easily suppressed.
The specific surface area of the activated carbon is measured by a method based on the BET method.

Examples of the activated carbon include activated carbon prepared from charcoal, coal, coconut shell, and the like.
Examples of the shape of the activated carbon 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 reaction, 4-20 mesh crushed coal or coal is preferred. In the case of a liquid phase reaction, powdered coal or granular coal is preferred.

The ash content of the activated carbon is preferably 15% or less, more preferably 10% or less, and even more preferably 8% or less. If the ash content of the activated carbon exceeds 15%, an unintended side reaction tends to occur.
The ash content of the activated carbon is measured according to ASTM D2866.
The ash content of the activated carbon 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.

It is preferable to dry the activated carbon sufficiently before use in the reaction. Specifically, the moisture in the activated carbon 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). .

Conversion reaction:
In the production method of the present invention, when the conversion reaction of R-243fb occurs, the target compound R-1233zd (E form) is obtained. Further, when the raw material contains R-243fa, R-1233zd (E form) can be obtained also by the dehydrochlorination reaction of R-243fa, so that a decrease in yield can be suppressed.
In the above conversion reaction, dehydrochlorination and isomerization are considered to occur. It is not clear which of dehydrochlorination and isomerization occurs first or simultaneously, but it is considered that the reaction of the present invention proceeds by any one of the following reaction mechanisms (7) and (8). .

In the present invention, specific examples of the method of contacting with activated carbon include the following methods.
(Gas phase reaction method) Method of bringing the raw material in a gaseous state into contact with activated carbon (Liquid phase reaction method) Method of bringing the raw material in a liquid phase into contact with activated carbon

Gas phase reaction method:
The gas phase reaction method in this specification is a method in which a raw material in a gaseous state and activated carbon are brought into contact with each other. Examples of the gas phase reaction method include a method of forming a catalyst layer filled with activated carbon, introducing a gas containing a raw material into the catalyst layer, and performing conversion while passing through the catalyst layer.

FIG. 1 is a flowchart showing an example of a gas phase reaction.
A raw material gas and, if necessary, a dilution gas are introduced into the reactor heated by the heating means, and the raw material gas is brought into contact with the activated carbon of the catalyst layer in the reactor. The resulting crude product is continuously removed from the bottom of the reactor. Further, if necessary, the crude product recovered from the outlet of the reactor is passed through a deoxidation tower to remove hydrogen chloride, thereby obtaining a product. A part of the crude product taken out from the reactor may be collected and subjected to composition analysis by gas chromatography (hereinafter also referred to as “GC”).

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 activated carbon into the reactor. There may be two or more catalyst layers in the reactor.
Packing density of the activated carbon 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 activated carbon is 0.2 g / cm ³ or more, the amount of activated carbon 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 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 the raw material gas as necessary to extend the catalyst life of the activated carbon, improve the conversion rate, and improve the selectivity.
Examples of the dilution gas include inert gases (nitrogen, rare gases, chlorofluorocarbons inert to dehydrochlorination, etc.). Examples of the diluent gas other than the inert gas include hydrogen chloride.
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 inert gas.

The contact temperature is preferably 50 to 500 ° C., more preferably 100 to 400 ° C., and further preferably 170 to 380 ° C. If a contact temperature is more than the said lower limit, a reaction rate will improve. If a contact temperature is below the said upper limit, it can suppress that the by-product by dehydrofluorination etc. produces | generates.
The inside of the reactor may be at normal pressure, in a pressurized state, or in a reduced pressure state. Normal pressure or a pressurized state is preferred.
The contact time can be adjusted to control the conversion rate and selectivity of the raw material, and the contact time can be shortened if the contact temperature is high, and the contact time can be lengthened if the contact temperature is low. For example, the contact time is preferably 1 to 1000 seconds, more preferably 5 to 300 seconds, and particularly preferably 10 to 100 seconds.

The linear velocity of the raw material gas in the catalyst layer is preferably from 0.1 to 100 cm / second, more preferably from 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 = (W / 100) × V / S
However,
W is the concentration (mol%) of the raw material gas in the total gas introduced into the catalyst layer,
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.

The crude product recovered from the outlet of the reactor contains unreacted raw materials and by-products in addition to the target product. By-products include hydrogen chloride.
Hydrogen chloride contained in the crude product can be easily removed by distillation in a deoxidation tower. If necessary, the crude 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.

Liquid phase reaction method:
The liquid phase reaction method in the present specification is a method in which a raw material in a liquid state and activated carbon are brought into contact with each other.
The conversion reaction in the liquid phase reaction method may be a batch type or a continuous type. From the viewpoint of production efficiency, the continuous type is preferable.

FIG. 2 is a flowchart showing an example of a liquid phase reaction.
A raw material is continuously supplied to a reactor containing activated carbon, a liquid raw material, and a liquid medium as necessary, and the activated carbon and the raw material are brought into contact in the reactor. The crude product produced by the reaction is recovered from the reactor. When the crude product is recovered from the gas phase in the reactor, the crude product may be cooled with a cooler. Further, if necessary, the crude product is passed through a deoxidation tower to remove hydrogen chloride, whereby the product is obtained. Although GC is not shown in FIG. 2, in this example as well, as in the example of the gas phase reaction in FIG. 1, a part of the crude product recovered from the reactor is collected and subjected to composition analysis by GC. May be.

As a reactor, the well-known reactor which can contact activated carbon and the raw material of a liquid state is mentioned.
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.

The activated carbon is preferably powdered or granular charcoal.
In the liquid phase reaction method, a liquid medium may or may not be used. It is preferable not to use a medium. Examples of the medium include water, an organic solvent (alcohol, etc.) and the like.
When a 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. If a contact temperature is more than the said lower limit, a reaction rate will improve. If a contact temperature is below the said upper limit, it can suppress that the by-product by dehydrofluorination etc. produces | generates.
The pressure in the reaction vessel is preferably 0 to 10 MPa [gauge pressure], more preferably 0.05 to 5 MPa [gauge pressure], and further preferably 0.15 to 3 MPa [gauge pressure]. The reaction pressure is preferably not less than the vapor pressure of R-243fb 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 crude product produced by the reaction may be recovered from the gas phase or recovered from the liquid phase. It is preferable to recover from the gas phase. When recovering the crude 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-form), R-1233zd (Z-form) and hydrogen chloride having a low boiling point can be selectively removed from the reaction system. Therefore, the conversion rate and selectivity are excellent.

The crude product includes unreacted raw materials and by-products in addition to the target product. By-products include hydrogen chloride.
Hydrogen chloride contained in the crude product can be easily removed by distillation in a deoxidation tower. If necessary, the crude 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.

(Process (d))
The product obtained in the step (c) may be purified to obtain a purified product in which the concentration of R-1233zd (E form) is increased. Step (d) is an optional step.
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.

(Use of R-1233zd (E body))
R-1233zd (E-form) 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-form) is used as a raw material monomer for 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 body) of the present invention is not limited to the above-described steps.
For example, the method for obtaining the raw material containing R-243fb is not limited to the above method.

(Function and effect)
According to the method for producing R-1233zd (E-form) of the present invention, R-1233zd (E-form) can be produced from R-243fb using an economical and excellent handleability catalyst.

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

<Evaluation method>
(Composition analysis)
GC was used for the composition analysis of the organic layer obtained in step (a), the R-243fb-containing composition obtained in step (b), and the crude product recovered from the outlet of the reactor. As a column, DB-1301 (manufactured by Agilent Technologies, length 60 m × inner diameter 250 μm × thickness 1 μm) was used.

(R-243fb conversion)
The R-243fb conversion rate X (%) was determined from the following equation.
X = 100 × (Xa−Xb) / Xa
However, in the formula:
Xa: R-243fb content ratio (mol%) in the raw material,
Xb: R-243fb content ratio (mol%) in the crude product recovered from the outlet of the reactor.

(R-243fa conversion)
The R-243fa conversion rate Y (%) was determined from the following equation.
Y = 100 × (Ya−Yb) / Ya
However, in the formula:
Ya: R-243fa content ratio (mol%) in the raw material,
Yb: R-243fa content ratio (mol%) in the crude product recovered from the outlet of the reactor.

(R-1233zd selectivity)
The R-1233zd (E-form) selectivity Z (E) (%) and the R-1233zd (Z-form) selectivity Z (Z) (%) were determined from the following equations.
Z (E) = 100 × Ze / (Xa + Ya−Xb−Yb)
Z (Z) = 100 × Zz / (Xa + Ya−Xb−Yb)
However, in the formula:
Ze: R-1233zd (E-form) content ratio (mol%) in the crude product recovered from the outlet of the reactor,
Zz: R-1233zd (Z form) content ratio (mol%) in the crude product recovered from the outlet of the reactor.

From the values of Z (E) and Z (Z), according to the following formula, “R-1233zd (E-form) selectivity + R-1233zd (Z-form) selectivity” (hereinafter referred to as “(E) + (Z)”) (%), “R-1233zd (E-form) selectivity / {R-1233zd (E-form) selectivity + R-1233zd (Z-form) selectivity} × 100” (hereinafter referred to as “(E) / ( E) + (Z) ".) (%).
(E) + (Z) = Z (E) + Z (Z)
(E) / (E) + (Z) = 100 × Z (E) / (Z (E) + Z (Z))

<Manufacture of raw materials containing R-243fb>
(Process (a))
The catalyst of step (a) was prepared as follows.
A cooler having a height of 15 cm was connected to the top, and 499.9 g of zirconium tetrachloride was placed in a four-necked flask (material: glass, capacity: 1 L) containing a magnetic stirring bar. While cooling the condenser and flask with dry ice to −78 ° C., 1350 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 completion of drying, 477.1 g of modified zirconium chloride catalyst was recovered.

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 10.5 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, and a crude reaction solution was obtained. While stirring, the reaction crude liquid was extracted from the bottom of the autoclave. The reaction crude liquid was filtered with a pressure filter set with filter paper (4 μm diameter) to obtain 11,210 g of uniform organic layers. 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: 69.2 mol%,
R-243fb: 9.8 mol%,
Chloroform: 1.0 mol%,
R-143a: 0.2 mol%,
R-21: 1.2 mol%,
Other ingredients: 18.6 mol%.

(Process (b))
A distillation column (material: glass, inner diameter: 3 cm, height: 97 cm) equipped with a kettle (material: glass, capacity: 20 L) that can be heated with a mantle heater, a magnetic reflux device, a reflux timer and a Dimroth cooler A filling for distillation (manufactured by Takenaka Wire Mesh Co., Ltd., Helipac No. 1) was filled (measured number of stages: 43 stages).
Step (a) was carried out twice, and 22,740 g of the obtained organic layer was put in a distillation column kettle, and the reflux time / distillation time ratio was adjusted to 50/1 to 300/1 by a reflux timer. The distillation was carried out at normal pressure. The content ratio of each of R-243fa and R-243fb relative to the total molar amount was 13,517 g, R-243fa of a composition in which R-243fa was more than 99.9 mol% and R-243fb was less than 0.1 mol%. Of the composition (hereinafter also referred to as R-243fb-containing composition 1) 1689 g, R-243fa is 4.7 mol%, and R-243fb is R-243fb is 89.37 mol% and R-243fb is 10.55 mol%. A composition (hereinafter, referred to as R-243fb-containing composition 2) (608 g), R-243fa (0.43 mol%) and R-243fb (99.48 mol%) (hereinafter referred to as R-243fb-containing composition 2). R-243fb-containing composition 3)) was obtained.
In Example 1 below, R-243fb-containing composition 3 was used, in Examples 2 and 3, R-243fb-containing composition 1 was used, and in Example 4, R-243fb-containing composition 2 was used.

<Example 1>
(Process (c))
As the reaction apparatus in the step (c), a vertical fixed bed reactor (material: SUS316, inner diameter 23.0 mm × height 200 mm) was used. 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 activated carbon (Osaka Gas Chemical Co., Ltd., Shirasagi activated carbon C2x, specific surface area: 1260 m ² / g, ash content: 1.2% by mass), and this was used as a catalyst layer. The catalyst layer was heated by an electric furnace. A gas feed line and a raw material supply line heated to 100 ° C. were connected, and a raw material preheating mixing 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 R-243fb-containing composition 3 was supplied to the raw material preheating mixing line after the liquid flow rate was adjusted using a plunger pump, vaporized through the raw material supply line heated to 100 ° C.
The crude product at the reactor outlet was collected and made into a product.

In this example, nitrogen and raw materials were introduced into the reactor under the conditions shown in Table 1, and the reaction was continued for 4 hours. From the result of composition analysis of the crude product at the outlet of the reactor, R-243fb conversion (%), “(E) + (Z)” (%), “(E) / (E) + (Z)” (% ) Production conditions and results are shown in Table 1.

As shown in Table 1, in the production method of the present invention, R-243fb in the raw material caused a conversion reaction, and R-1233zd could be generated by activated carbon. Further, R-1233zd (E form) could be selectively produced from the analysis results of the isomers in the product.

<Examples 2 and 3>
(Process (c))
Except for using R-243fb-containing composition 1 as a raw material containing R-243fb and under the conditions shown in Table 2, nitrogen and the raw material were introduced into the reactor in the same manner as in Example 1 and allowed to react for 4 hours. It was. From the results of composition analysis, R-243fb conversion rate (%), R-243fa conversion rate (%), “(E) + (Z)” (%), “(E) / (E) + (Z)” (%) Was calculated. Production conditions and results are shown in Table 2.

As shown in Table 2, in the production method of the present invention, R-243fb in the raw material caused a conversion reaction, and R-1233zd could be generated by activated carbon. Further, R-1233zd (E form) could be selectively produced from the analysis results of the isomers in the product.

<Example 4>
(Process (c))
Using R-243fb-containing composition 2 as a raw material containing R-243fb, nitrogen and the raw material were introduced into the reactor under the conditions shown in Table 3, and the reaction was continued for 4 hours. From the results of composition analysis, R-243fb conversion rate (%), R-243fa conversion rate (%), “(E) + (Z)” (%), “(E) / (E) + (Z)” (%) Was calculated. Production conditions and results are shown in Table 3.

As shown in Table 3, in the production method of the present invention, R-243fb in the raw material caused a conversion reaction, and R-1233zd could be generated by activated carbon. Further, R-1233zd (E form) could be selectively produced from the analysis results of the isomers in the product.

The method for producing R-1233zd (E-form) of the present invention can be suitably used for production of R-1233zd (E-form) since it can obtain R-1233zd (E-form) with high selectivity.

Claims (16)

By bringing a raw material containing 1,3-dichloro-1,1,3-trifluoropropane as an essential component into contact with activated carbon, the 1,3-dichloro-1,1,3-trifluoropropane is converted. (E) A process for producing (E) -1-chloro-3,3,3-trifluoropropene, which comprises obtaining (E) -1-chloro-3,3,3-trifluoropropene. The production method according to claim 1, wherein the raw material does not contain 1,1-dichloro-3,3,3-trifluoropropane. The production method according to claim 1, wherein the raw material contains 1,1-dichloro-3,3,3-trifluoropropane. The method according to claim 3, wherein the raw material is a raw material obtained from a reaction product of vinylidene difluoride and dichlorofluoromethane. The 1,1-dichloro-3,3,3-trifluoropropane content in the raw material is 1,3-dichloro-1,1,3-trifluoropropane and 1,1-dichloro-3,3 The production method according to claim 3 or 4, wherein the amount is more than 0 mol% and not more than 5 mol%, based on the total molar amount of 1,3-trifluoropropane. The raw material contains 1,1-dichloro-3,3,3-trifluoropropane as an optional component, and the content of 1,3-dichloro-1,1,3-trifluoropropane in the raw material is 1 , 3-dichloro-1,1,3-trifluoropropane and 1,1-dichloro-3,3,3-trifluoropropane are characterized by being 5 mol% or more and 100 mol% or less The manufacturing method according to claim 1. The production method according to any one of claims 1 to 6, wherein the activated carbon has a specific surface area of 10 to 3000 m ² / g. The manufacturing method according to any one of claims 1 to 7, wherein the raw material is a raw material in a gaseous state and is brought into contact with the activated carbon at 50 to 500 ° C. The manufacturing method according to claim 8, wherein the contact time is 1 to 1000 seconds. The gaseous raw material is converted while passing through the catalyst layer filled with the activated carbon, and the linear velocity of the gaseous raw material in the catalyst layer is 0.1 to 100 cm / second. The manufacturing method of Claim 8 or 9. The production method according to any one of claims 8 to 10, wherein the activated carbon is 4 to 20 mesh crushed coal or formed coal. The production method according to any one of claims 1 to 7, wherein the raw material is a raw material in a liquid state and is brought into contact with the activated carbon at 0 to 250 ° C. The manufacturing method according to claim 12, wherein the pressure at the time of contact is 0 to 10 MPa (gauge pressure). The production method according to claim 12 or 13, wherein the contact is performed in a batch-type reaction vessel, and the contact time is 1 to 50 hours. The production method according to claim 12 or 13, wherein the contact is performed in a continuous reactor and the contact time is 1 to 3000 seconds. The production method according to any one of claims 12 to 15, wherein the activated carbon is powdered coal or granular coal.

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