WO2018123911A1

WO2018123911A1 - Production method for chlorine-containing propene

Info

Publication number: WO2018123911A1
Application number: PCT/JP2017/046251
Authority: WO
Inventors: 優竹内; 和江戸田; 寺園　真二; 旭王
Original assignee: 旭硝子株式会社
Priority date: 2016-12-28
Filing date: 2017-12-22
Publication date: 2018-07-05

Abstract

Provided is a production method capable of efficiently producing a chlorine-containing propene, such as HCFO-1224yd. The production method for a chlorine-containing propene according to the present invention involves reacting a compound represented by formula (1) with hydrogen in the presence of a catalyst to produce a compound represented by formula (2). The catalyst is supported by a carrier, and contains at least one first element selected from Pd and Pt, and at least one second element selected from Ru, Cu, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, P, As, Sb, Bi, S, Se, Te, and Po. Formula (1): CX₃CY=CCl₂ (wherein each X independently represent F, Cl, or H, and Y represents F or H). Formula (2): CX₃CY=CHCl (wherein X and Y are the same as X and Y in formula (1)).

Description

Method for producing chlorine-containing propene

The present invention relates to a method for producing chlorine-containing propene, and in particular, a production method preferably used for producing 1-chloro-2,3,3,3-tetrafluoropropene (CF ₃ CF═CHCl (HCFO-1224yd)). About.

Chlorine-containing propene is very useful as a building block for organic compounds, as an intermediate for pharmaceuticals and agricultural chemicals, and as a monomer because of its reactivity derived from olefins. Among them, 2,3,3,3-tetrafluoro-1-propene (CF ₃ CF═CH ₂ (hereinafter also referred to as “HFO-1234yf”) is useful for refrigerants, solvents, and the like.
In the production of HFO-1234yf, which is known as an alternative refrigerant, the intermediate product 1-chloro-2,3,3,3-tetrafluoropropene (CF ₃ CF═CHCl (hereinafter “HCFO-1224yd”) is used. In recent years, it has been confirmed that it is useful as a refrigerant, a solvent, etc. Therefore, there is a demand for a method capable of producing HCFO-1224yd more efficiently, and HFO-1234yf and HCFO- 1224yd is useful as a foaming agent, a solvent, a cleaning agent, a refrigerant, a working fluid, a propellant, a fluororesin raw material, a medical and agrochemical intermediate for rigid polyurethane foam, and the like.

As a method for producing HCFO-1224yd, which is an example of chlorine-containing propene, 1,1-dichloro-2,3,3,3-tetrafluoropropene (CF ₃ CF═CCl ₂ (hereinafter also referred to as “HCFO-1214ya”)) Is known to react with hydrogen in the presence of Pd-supported activated carbon in which 0.5 part by mass of Pd is supported with respect to 100 parts by mass of the activated carbon support (Patent Document 1) However, in this method, 1224 yd The yield was low, which was disadvantageous for industrial production of 1224yd.

As another method for producing HCFO-1224yd, there is Pd / Cu-supported activated carbon in which HCFO-1214ya is loaded with 0.5 parts by mass of Pd and 8.5 parts by mass of Cu with respect to 100 parts by mass of the activated carbon support. It is known to react with hydrogen below (Patent Document 2). However, in this method, a catalyst carrying a large amount of metal must be used, and the environmental load is high. Further, in this method, although HCFO-1224yd is obtained in a larger amount than the above, the reaction is considered even if the total amount (HFO-1234yf + HCFO-1224yd) with HFO-1234yf that is simultaneously produced as the intended useful compound is considered. They were also disadvantageous for industrial production due to their low total selectivity in the product.

Therefore, there is a demand for a method for producing chlorine-containing propene such as 1224yd by an industrially advantageous method with a small environmental load.

International Publication No. 2011/162341 International Publication No. 2015/160532

An object of the present invention is to provide a production method for efficiently producing chlorine-containing propene such as HCFO-1224yd by an industrially advantageous method with a small environmental load.

In the method for producing a chlorine-containing propene of the present invention, a compound represented by the following formula (1) is reacted with hydrogen in the presence of a catalyst to obtain a compound represented by the following formula (2). Is the method. The catalyst is supported on a carrier and has at least one first element selected from the group consisting of Pd and Pt, Ru, Cu, Au, Zn, Cd, Hg, Al, Ga, In, And at least one second element selected from the group consisting of Si, Ge, Sn, Pb, P, As, Sb, Bi, S, Se, Te, and Po. The catalyst is 0.01 to 8 parts by mass with respect to 100 parts by mass of the carrier.
CX ₃ CY = CCl ₂ (1)
(In Formula (1), X represents F, Cl, or H each independently, and Y represents F or H.)
CX ₃ CY = CHCl (2)
(In formula (2), X and Y are the same as X and Y in formula (1).)

According to the method for producing chlorine-containing propene of the present invention, by using a specific catalyst, chlorine-containing propene such as HCFO-1224yd is efficiently produced, and the total amount of metals used as the catalyst is small.

Hereinafter, the manufacturing method of the chlorine containing propene of this invention is demonstrated concretely, referring one embodiment.
In the method for producing a chlorine-containing propene according to the present embodiment, a compound represented by the following formula (1) is reacted with hydrogen in the presence of a catalyst to obtain a compound represented by the following formula (2). It is a manufacturing method. The catalyst is supported on a carrier and has at least one first element selected from the group consisting of Pd and Pt, Ru, Cu, Au, Zn, Cd, Hg, Al, Ga, In, And at least one second element selected from the group consisting of Si, Ge, Sn, Pb, P, As, Sb, Bi, S, Se, Te, and Po. The catalyst is used in an amount of 0.01 to 8 parts by mass with respect to 100 parts by mass of the carrier.
CX ₃ CY = CCl ₂ (1)
(In Formula (1), X represents F, Cl, or H each independently, and Y represents F or H.)
CX ₃ CY = CHCl (2)
(In formula (2), X and Y are the same as X and Y in formula (1).)

<Compound represented by Formula (1)>
In the compound represented by the formula (1), X is independently composed of F, Cl, or H, and Y is composed of F or H. Here, all three Xs may be composed of the same element, or may be composed of two or three different elements.

According to the method for producing a chlorine-containing propene of this embodiment, one of the olefin-terminated Cls can be selectively reduced to H.
In the present specification, reduction means replacing a halogen atom with H. In this embodiment, it means that specific Cl is substituted with H, and when other Cl is reduced, a compound other than the compound of formula (2), which is the target product, is produced. Compared with Cl, F, which is inactive in the reduction reaction, is extremely difficult to reduce, and the reductant H does not cause any further reduction reaction. Therefore, since the reduction reaction other than Cl at the olefin end is suppressed and the compound other than the target compound of the formula (2) is reduced, in the formula (1), each X is independently F or H. Yes, it is preferable that Y is F or H, and since a product excellent in cooling efficiency and friendly to the global environment is obtained, X is all F, and Y is F. CFO-1214ya is more preferable.

CFO-1214ya can be produced by a known method. For example, 1,1-dichloro-2,2,3,3,3-pentafluoropropane (CF ₃ CF ₂ CHCl ₂ (hereinafter also referred to as “HCFC-225ca”)) such as tetrabutylammonium bromide (TBAB) It can be produced by a dehydrofluorination reaction in contact with an aqueous alkali solution in the presence of a phase transfer catalyst.

In the dehydrofluorination reaction, dichloropentafluoropropane containing HCFC-225ca (hereinafter also referred to as “HCFC-225”) can be used. In the dehydrofluorination reaction, only the HCFC-225ca in the HCFC-225 is selectively dehydrofluorinated by the phase transfer catalyst. After the dehydrofluorination reaction, CFO-1214ya can be separated and recovered by a known method such as distillation.

HCFC-225 including HCFC-225ca can be produced by reacting tetrafluoroethylene and dichlorofluoromethane in the presence of a catalyst such as aluminum chloride. HCFC-225 obtained by the above reaction includes HCFC-225ca and 1,3-dichloro-1,2,2,3,3-pentafluoropropane (CHClFCF ₂ CClF ₂ (hereinafter also referred to as “HCFC-225cb”). .)) As a main component.

Commercially available HCFC-225 including HCFC-225ca may be used. As a commercially available product, Asahi Clin (trademark) AK225 (manufactured by Asahi Glass Co., Ltd., a mixture of 48 mol% of HCFC-225ca and 52 mol% of HCFC-225cb; hereinafter referred to as “AK225”) can be mentioned.

<Chlorine-containing propene represented by formula (2)>
Specifically, in the chlorine-containing propene represented by the formula (2), X in the formula (1) is maintained as it is. In addition, since there are three Xs, they are each independently F, Cl, or H, and each X in the formula (1) is maintained.

Moreover, Y in the formula (1) is maintained as it is.

For example, when the compound represented by the formula (1) is CFO-1214ya, HCFO-1224yd can be obtained as represented by the following formula (3).
CF ₃ CF = CCl ₂ + H ₂ → CF ₃ CF = CHCl + HCl (3)

<Catalyst>
The catalyst includes a first element and a second element. As a typical form, the first element and the second element may form an alloy or may be in a mixed state. Here, an alloy means a metal-like thing which consists of a some metallic element or a metallic element, and a nonmetallic element, A state does not ask | require.

<First element>
The first element is at least one selected from the group consisting of Pd and Pt. When the first element is Pd and Pt, Pd and Pt may form an alloy, or may not form an alloy and may simply be in a mixed state.

If the first element is Pd, the compound represented by the formula (2) can be efficiently generated. On the other hand, Pt has a long catalyst life from the viewpoint of acid resistance. From the viewpoint of efficiently generating the compound represented by the formula (2), the first element preferably contains Pd. The content ratio of Pd is preferably 90 mol% or more, more preferably 95 mol% or more, and most preferably 100 mol% in a total of 100 mol% of Pd and Pt.

<Second element>
The second element is made of Ru, Cu, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, P, As, Sb, Bi, S, Se, Te, and Po. It is at least one selected from the group.

By using the second element together with the first element, the catalytic activity of the first element is adjusted, and the generation of a compound other than the compound represented by the formula (2) is suppressed, which is represented by the formula (2). Can be produced efficiently.

The first element and the second element may be mixed in the catalyst or may be in an alloy state. The formation of the alloy state may be performed in the production process of the catalyst-supported carrier, in an atmosphere of an inert gas such as nitrogen gas, carbon dioxide gas or argon gas before use in the reaction, in a reducing atmosphere containing a trace amount of hydrogen, or oxygen. It can carry out by heat treatment in the contained oxidizing atmosphere.

The second element preferably contains at least one selected from the group consisting of Ru, Cu, Au, Sn, Zn, Bi, S, and Te. By containing at least one of these elements, the production of compounds other than the compound represented by formula (2) can be effectively suppressed. From the viewpoint of selectivity, it is preferable to include at least one selected from Bi and S. From the viewpoint of valuable material selectivity, it is more preferable that the second element includes at least one selected from the group consisting of Au, Zn, Bi, S, and Te. Moreover, from the viewpoint of yield and valuable material selectivity, the second element preferably contains at least one selected from the group consisting of Sn, Zn, Bi, S, and Te, and Zn, Bi, It is more preferable to include at least one selected from the group consisting of S and Te, and it is most preferable to include at least one selected from the group consisting of Bi and S.

The second element is preferably contained in an amount of 0.1 to 400 mol% with respect to 100 mol% of the first element. When the content of the second element is 0.1 mol% or more, the catalytic activity of the first element is effectively adjusted, and production other than the compound represented by the formula (2) is further suppressed. Can do. From the viewpoint of effectively adjusting the catalytic activity of the first element, the content is more preferably 1 mol% or more, and further preferably 5 mol% or more. Moreover, the excessive fall of catalyst activity is suppressed as content of a 2nd element is 400 mol% or less, and the metal amount to be used can be reduced. From the viewpoint of suppressing an excessive decrease in catalyst activity, the content is more preferably 200 mol% or less, and even more preferably 100 mol% or less.

The catalyst can contain other elements other than the first element and the second element as long as the effects of the present invention are not impaired. Examples of other elements include metal elements such as Fe, Co, and Ni. As for other elements, only 1 type may be contained and 2 or more types may be contained. For example, the other element may form an alloy with or both of the first element and the second element, or may be mixed. The other elements are preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 1 part by mass or less with respect to a total of 100 parts by mass of the first element and the second element.

<Carrier>
The catalyst is supported on a carrier. In the present specification, a catalyst carrying carrier is referred to as a catalyst carrying carrier. By using a support, the catalyst can be dispersed. Examples of the carrier include carbon materials such as activated carbon, carbon black, and carbon fiber, and oxide materials such as alumina, silica, titania, zirconia, alkali metal oxides, and alkaline earth metal oxides. Silica, zirconia, alkali metal oxides and alkaline earth metal oxides are preferred. Among these, activated carbon, alumina, and zirconia are more preferable because they have a large specific surface area and easily support the catalyst. Moreover, activated carbon is particularly preferable because generation of a compound other than the compound represented by the formula (2) is suppressed.

Examples of the activated carbon include activated carbon prepared from fruit shells such as wood, charcoal, and coconut shells, peat, lignite, and coal. Examples of the activated carbon include aggregates of formed coal having a length of about 2 to 7 mm, crushed coal having a size of about 4 to 50 mesh, and granular coal. Among these, aggregates of forming coal or crushed coal of 4 to 30 mesh are preferable.

Examples of alumina include those having different crystal states such as α-alumina, γ-alumina, and θ-alumina. The crystal state is not particularly limited, and can be used widely from γ-alumina having a large specific surface area to α-alumina having a high crystallinity and a small specific surface area. The shape of the alumina is not necessarily limited, but is preferably formed into a spherical shape or a pellet shape because the filling property when filling the reactor, the flowability of the reaction gas, and the like are good.

Examples of zirconia include monocrystalline, tetragonal, cubic, and purely stable tetragonal crystal forms having different crystal states, as well as amorphous hydrated zirconium oxide. There is no particular limitation, and any zirconia can be used widely. The shape of zirconia is not necessarily limited, but is preferably formed into a spherical shape or a pellet shape because the filling property when filling the reactor, the flowability of the reaction gas, and the like are good.

The catalyst content is 0.01 parts by mass or more with respect to 100 parts by mass of the carrier. Reaction can be effectively advanced as this content is 0.01 mass part or more. From the viewpoint of allowing the reaction to proceed effectively, the content is preferably 0.05 parts by mass or more, and more preferably 0.1 parts by mass or more. Further, from the viewpoint of suppressing the total amount of metal and suppressing environmental load, the content is 8 parts by mass or less, preferably 5 parts by mass or less, and more preferably 3 parts by mass or less.

The specific surface area of the catalyst-loaded support is preferably 10 ~ 2000m ² / g, more preferably 30 ~ 1500m ² / g. When the specific surface area is 10 m ² / g or more, the reaction can be effectively advanced. The production | generation of compounds other than the compound represented by Formula (2) can be suppressed as a specific surface area is 2000 m < ² > / g or less. The specific surface area of the catalyst-supported carrier is measured by a method based on an N ₂ gas adsorption method, for example, the BET method.

(Method for producing catalyst-supported carrier)
The catalyst-supported carrier can be produced by a known method. Examples of such a method include an impregnation method and a colloid method. Although the example of the manufacturing method of these catalysts is shown below, it is not restricted to this.

The impregnation method is a general method for supporting a catalyst on a carrier. The impregnation method can be performed as follows. First, the catalyst metal salt solution is impregnated with the carrier, and the catalyst metal salt is adsorbed on the surface of the carrier. Then, after the carrier is dried, the catalytic metal salt is reduced by bringing a reducing agent into contact with the catalytic metal salt on the surface. Thereby, the catalyst can be supported on the carrier.

Examples of the reducing agent include ammonia, hydrazine, reducing compounds such as sodium borohydride, reducing gases such as hydrogen, alcohols, aldehydes, organic acids and salts thereof, borohydrides and salts thereof, and hydrazines. A reducing liquid is mentioned.

In the colloid method, the metal fine particle dispersion is brought into contact with the surface of the carrier, and then dried, thereby supporting the metal fine particles on the surface of the carrier. The metal fine particle dispersion can be obtained by dissolving a metal salt in a solvent and then reducing with a reducing agent. At this time, a high molecular organic compound can be used in order to enhance dispersibility. Examples of such high molecular organic compounds include polyvinylpyrrolidone, polyethyleneimine, polyallylamine, poly (N-carboxymethyl) allylamine, poly (N, N-dicarboxymethyl) allylamine, poly (N-carboxymethyl) ethyleneimine, etc. Is mentioned.

<Reaction method>
As a method of reacting the compound represented by the formula (1) with hydrogen, the following method (α) or method (β) may be mentioned.
Method (α): A method of reacting in the gas phase.
Method (β): A method of reacting in a liquid phase.
The raw material may contain components other than the compound represented by the formula (1).

<Method (α)>
Examples of the method (α) include a method in which a compound represented by the formula (1) and hydrogen are introduced into a reactor filled with a catalyst-supporting carrier and reacted in the gas phase. As such a method, for example, a gas of a compound represented by the formula (1) and hydrogen gas are mixed to form a raw material mixed gas, and then this raw material mixed gas is introduced into a reactor, or a formula ( Examples thereof include a method in which a liquid of a compound represented by 1), hydrogen gas, and a dilution gas are introduced into a reactor, gasified in the reactor, and then contacted with a catalyst-supported carrier. As a method for introducing the raw material into the reactor, it may be introduced as a gas or may be introduced as a liquid and gasified in the reactor. Dilution gas may or may not be introduced.

As the dilution gas, for example, an inert gas can be mentioned. Examples of the inert gas include nitrogen gas, rare gas, carbon dioxide, and chlorofluorocarbons inert to hydrogenation reaction. Moreover, hydrogen chloride, oxygen, etc. are mentioned as dilution gas other than an inert gas.

The amount of the diluent gas introduced is determined from the number of moles of the diluent gas and the number of moles of the compound represented by the formula (1) from the viewpoint of adjusting the reaction temperature described later, extending the catalyst life, and improving the selectivity and the conversion rate. The ratio (diluted gas / compound represented by formula (1)) is preferably 0.1 or more, and more preferably 0.5 or more. Further, from the viewpoint of suppressing an excessive decrease in volumetric efficiency, the above ratio (diluted gas / compound represented by formula (1)) is preferably 100 or less, and more preferably 10 or less.

For example, the catalyst-supporting carrier is filled in a reactor to form a catalyst layer. The packing density of the catalyst-supporting carrier varies depending on the carrier. For example, in the case of activated carbon, 0.2 to 1 g / cm ³ is preferable, and 0.4 to 0.8 g / cm ³ is more preferable. Reaction can be advanced effectively as it is 0.4 g / cm < ³ > or more. On the other hand, when it is 1 g / cm ³ or less, an excessive increase in temperature of the catalyst layer is suppressed, and the production of compounds other than the compound represented by Formula (2) can be suppressed.

As the reactor, a general flow reactor used for gas-solid heterogeneous catalytic reaction in which the catalyst-supporting carrier is solid and the reaction fluid is gas can be used. Flow-type reactors can be roughly classified into fixed bed reactors and fluidized bed reactors.

In a fixed bed reactor, it is preferable to fill various shaped bodies as a catalyst support in order to reduce the pressure loss of the reaction fluid. In addition, a system in which a catalyst-carrying support is packed, moved by gravity, and extracted from the bottom of the reactor and regenerated is called a moving bed reactor as in the fixed bed reactor. In the moving bed reactor, the catalyst-supporting carrier is dispersed in the reaction fluid and moves in the reactor.

As the reactor, a fixed bed reactor is preferable. According to the fixed bed reactor, the reaction temperature can be appropriately controlled. Thereby, the production | generation of compounds other than the compound represented by Formula (2) can be suppressed, and deterioration of a catalyst can also be suppressed.

Examples of the fixed bed reactor include a tubular reactor and a tank reactor. Among these, a tubular reactor is preferable because the reaction temperature can be easily controlled. Examples of the tubular reactor include a multi-tube heat exchange type in which a large number of reaction tubes having a small diameter are arranged in parallel and a heat medium is circulated outside. Note that only one catalyst layer may be provided in the flow direction, or two or more catalyst layers may be provided.

The reaction temperature is preferably 30 ° C. or higher, more preferably 35 ° C. or higher, and further preferably 40 ° C. or higher, from the viewpoint of allowing the reaction to proceed effectively. Moreover, from the point which suppresses production | generation of compounds other than the compound represented by Formula (2), 350 degrees C or less is preferable, 300 degrees C or less is more preferable, 250 degrees C or less is more preferable, 200 degrees C or less is especially preferable.

Here, the reaction temperature is the temperature of the highest temperature portion of the catalyst layer. Since the reaction region generates heat due to the reaction, the temperature becomes the highest, but the size of the local heat generation varies depending on the type of the catalyst-supporting carrier and the reaction conditions.

The reaction temperature can be measured by providing a thermometer in the catalyst layer. Note that the catalyst gradually deteriorates from the upstream side to the downstream side of the catalyst layer. In accordance with this, the reaction region also gradually moves from the upstream side to the downstream side of the catalyst layer. For this reason, the measurement of the reaction temperature is performed by moving the measurement position in accordance with the movement of the reaction region.

Examples of the method for adjusting the reaction temperature include a method (α1) in which hydrogen is dividedly introduced into the catalyst layer. According to the method (α1), by dividing and introducing hydrogen, the reaction region can be dispersed and the reaction temperature can be lowered. Further, the temperature of the catalyst layer can be made uniform, and the productivity can be improved.

Hydrogen may be introduced at one location or multiple locations. In the case of two places, two places of the entrance of a catalyst layer and the midway introduction part provided in the middle of a catalyst layer are mentioned. In this case, it is preferable that the compound represented by the formula (1) and hydrogen are introduced into the inlet of the catalyst layer, and only hydrogen is introduced into the midway introduction portion.

Two hydrogen introduction points are preferable from the viewpoint of simplifying the reactor. On the other hand, from the viewpoint of lowering the reaction temperature, three or more locations are preferred. Usually, it is preferable to introduce hydrogen evenly into each introduction site.

Also, as a method for adjusting the reaction temperature, a method using a dilution gas (α2) can be mentioned. In the method (α2), a diluent gas is introduced together with the compound represented by the formula (1) and hydrogen. Thereby, the concentration of the compound represented by the formula (1) and hydrogen can be lowered, and the reaction temperature can be lowered.

Examples of adjustment methods other than the method (α1) and the method (α2) include a method (α3) of adjusting the temperature of the heat medium used for heating the reactor and the like. According to the method (α3), heat can be removed quickly by lowering the temperature of the heat medium, and the reaction can be promoted by increasing the temperature of the heat medium.

As described above, the method (α1), the method (α2), and the method (α3) are exemplified as methods for adjusting the reaction temperature. However, these methods may be used alone, or two or three. May be used in combination.

The reaction pressure is preferably an absolute pressure of 0 to 1.0 MPa, more preferably 0 to 0.5 MPa from the viewpoint of workability. From the viewpoint of workability, the absolute pressure is more preferably 0.1 to 0.4 MPa. The contact time, which is the time during which the compound represented by formula (1) is in contact with the catalyst, is preferably 0.1 to 10,000 seconds, and more preferably 1 to 100 seconds. However, this preferred contact time varies depending on the volume of the catalyst layer and is not limited to this numerical range. The contact time can be calculated from the amount of substance per unit time introduced into the reactor and the volume of the catalyst layer.

In the reaction of the compound represented by formula (1) with hydrogen, the ratio (H ₂ / Cl) of the number of moles of chlorine atoms to the number of moles of hydrogen in the compound represented by formula (1) is 0.1. It is preferable to adjust the introduction amount of the compound represented by the formula (1) and hydrogen so as to be ˜3.0. When the ratio (H ₂ / Cl) is 0.1 to 3.0, it becomes easy to obtain the compound represented by the formula (2). The ratio (H ₂ / Cl) is more preferably 0.2 to 2.0. In addition, when hydrogen is introduced in a divided manner, it may be within the above range when hydrogen is introduced from all introduction locations.

The rate of introducing the compound represented by the formula (1) is such that the linear velocity u in the catalyst layer represented by the following formula is preferably 0.1 to 100 cm / sec, more preferably 1 to 50 cm / sec. preferable. Productivity will become favorable in it being 0.1 cm / sec or more. Moreover, the compound and hydrogen which are represented by Formula (1) can fully be reacted as it is 100 cm / sec or less.

u = V / S
In the formula, V represents the total gas flow rate (cm ³ / second) per unit time introduced into the reactor, and S represents the cross-sectional area (cm ² ) of the catalyst layer with respect to the gas flow direction.

As the reactor, a known reactor used for a gas phase reaction can be used. Examples of the material for the reactor include iron, nickel, alloys containing these as main components, and glass.

The product gas obtained by the reaction of the compound represented by the formula (1) and hydrogen includes the compound represented by the formula (2), the compound represented by the formula (1), and the compound represented by the formula (1). A compound in which hydrogen is added to the bond (CX ₃ -CYH-CCl ₂ H), a compound in which hydrogen is added to the double bond of formula (2) (CX ₃ -CYH-CClH ₂ ), and a terminal chlorine in formula (2) A reduced compound (CX ₃ -CY = CH ₂ ), a compound in which hydrogen is added to the double bond of the compound of formula (2) in which the terminal chlorine is reduced (CX ₃ -CYH-CH ₃ ), hydrogen chloride, etc. included. Hydrogen chloride can be removed by blowing the product gas into an alkaline aqueous solution to neutralize it. Examples of the alkali used in the alkaline aqueous solution include sodium hydroxide and potassium hydroxide.

The compound represented by the formula (1) and the compound represented by the formula (2) can be separated by a known method such as distillation. The compound represented by the formula (1) can be used again for the reaction with hydrogen.

<Method (β)>
In the method (β), it is preferable to use a solvent. Examples of the solvent include organic solvents such as water and alcohol. The amount of the solvent used is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the compound represented by the formula (1).

Examples of the method (β) include a method in which hydrogen gas is blown into a solution composed of the compound represented by the formula (1), a catalyst support, and a solvent. In addition, as the method (β), for example, hydrogen is dissolved in a first solvent under pressure to prepare a first solution, and separately, a compound represented by the formula (1), a catalyst-supporting carrier, and There is a method in which a second solution composed of a second solvent is prepared, and the first solution is added to the second solution. The method (β) may be a batch method or a continuous method.

The reaction temperature is preferably 0 to 300 ° C, more preferably 20 to 200 ° C. When the reaction temperature is 0 ° C. or higher, the reaction can proceed effectively, and when it is 300 ° C. or lower, the production of compounds other than the compound represented by formula (2) is suppressed.

The reaction pressure is preferably an absolute pressure of 0 to 10.0 MPa, more preferably 0 to 8.0 MPa from the viewpoint of workability. From the viewpoint of workability, the reaction time of 0.1 to 5.0 MPa in terms of absolute pressure is more preferable. The batch time is preferably 1 to 50 hours, and the continuous time is preferably 0.1 to 1000 minutes.

In the reaction of the compound represented by the formula (1) and hydrogen, in the continuous formula, the ratio of the number of moles of chlorine atoms to the number of moles of hydrogen in the compound represented by the formula (1) (H ₂ / Cl ) Is preferably adjusted to 0.1 to 3.0, and the amount of the compound represented by the formula (1) and hydrogen is adjusted. When the ratio (H ₂ / Cl) is 0.1 to 3.0, it becomes easy to obtain the compound represented by the formula (2). The ratio (H ₂ / Cl) is more preferably 0.2 to 2.0. In the batch system, the ratio (H ₂ / Cl) changes with time, and is not limited to this.

The reaction solution after the reaction includes a compound represented by the formula (1), hydrogen chloride, and the like together with a compound represented by the formula (2). Hydrogen chloride can be removed by blowing the product gas into an alkaline aqueous solution to neutralize it. Examples of the alkali used in the alkaline aqueous solution include sodium hydroxide and potassium hydroxide. In addition, you may add an alkali previously to the reaction liquid used for reaction.

The compound represented by the formula (1) and the compound represented by the formula (2) can be separated by a known method such as distillation. The compound represented by formula (1) can be used again for the reaction.

As the reactor, a known reactor used for a liquid phase reaction can be used. Examples of the material for the reactor include iron, nickel, alloys containing these as main components, and glass.

In the production method of the present embodiment, the compound represented by the formula (2) usually contains a trans isomer and a cis isomer that are geometric isomers. Therefore, in order to obtain a desired geometric isomer, it is preferable to perform separation by a known separation method such as distillation, membrane separation, extractive distillation, azeotropic separation, or two-layer separation. Hereinafter, among geometric isomers, the compound name of the trans isomer is represented by (E), and the compound name of the cis isomer is represented by (Z).

As described above, according to this embodiment, the compound represented by the formula (2) can be efficiently produced. Specifically, by using a specific second element together with at least one first element selected from the group consisting of Pd and Pt, the catalytic activity of the first element can be reduced, and the formula Generation of compounds other than the compound represented by (2) can be suppressed.

Therefore, according to this embodiment, the selectivity and yield of the target compound can be improved. Furthermore, the selectivity (valuable material selectivity) of the compound group (valuable material) in which the target compound and the target compound are different from each other only in the presence or absence of reduction of Cl at the olefin end is also good. I can do it.

Here, the selectivity refers to the ratio of the production amount of the target compound to the consumption of the raw material compound in the reaction, and the yield refers to the production amount of the target compound relative to the maximum reaction product (mixture) that can be obtained in the reaction. The ratio of The valuable substance selectivity refers to the ratio of the amount of valuable substances produced to the consumption of raw material compounds in the reaction.

The yield is preferably more than 5%, more preferably more than 8%, and most preferably more than 10%.
The valuable material selectivity is preferably 82% or more, more preferably 87% or more, and most preferably 92% or more.
Further, the valuable material selectivity is preferably 87% or more and the yield is more than 5%, the valuable material selectivity is more than 82% and the yield is more than 8%, and the valuable material selectivity is 87% or more. It is even more preferable that the yield is more than 8%, and it is most preferable that the valuables selectivity is 92% or more and the yield is more than 10%.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples.
However, the present invention is not limited to the examples.

(Production of compound represented by formula (1))
CFO-1214ya was produced as a compound represented by the formula (1). CFO-1214ya was produced by the following method using AK225.

A 1 L glass reactor equipped with a Dimroth cooled to 0 ° C was charged with 3 g of TBAB as a phase transfer catalyst, 83 g (1.485 mol) of potassium hydroxide, 180 g of water, and 609 g (3.0 mol) of AK225. Then, the temperature was gradually raised while stirring, and the reaction was carried out at 45 ° C. for 1 hour. The reaction solution thus obtained was separated into two phases, an organic phase and an aqueous phase. The organic phase was separated from this reaction solution and charged into a distillation column having a capacity of 1 L in a kettle and a theoretical plate number of 10 to carry out distillation. As a result of distillation, 262 g (1.43 mol) of CFO-1214ya (boiling point: 45 ° C.) having a purity of 99.5% was obtained.

Example 1
A catalyst-supported carrier was prepared in which a catalyst made of an alloy of Pd as the first element and Bi as the second element was supported on the surface of the carrier made of activated carbon. The activated carbon used was coconut shell crushed charcoal having 4 to 30 mesh and a specific surface area of about 1000 to 1200. The catalyst was 0.75 part by mass with respect to 100 parts by mass of the carrier. At this time, the content ratio of the first element is 0.5 parts by mass with respect to 100 parts by mass of the carrier. The content ratio of the second element is 25 mol% with respect to 100 mol% of the first element.

Separately, a U-shaped reaction tube made of SUS304 and having an inner diameter of 21.4 mm was prepared as a reactor. The reaction tube has a sheath tube into which a thermometer for measuring the internal temperature is inserted. The reaction tube was filled with 141 mL of the catalyst-supporting carrier at a packing density of 0.4 g / cm ³ .

The reaction tube was immersed in an oil bath whose temperature was controlled at 110 to 130 ° C. After soaking, nitrogen was introduced into the reaction tube to dry the catalyst support. The amount of nitrogen introduced was 600 NmL / min, and the introduction time was 16 hours. Thereby, the water content of the outlet gas of the reaction tube became 23 ppm.

Thereafter, the temperature of the oil bath was lowered to 45 ° C., and CFO-1214ya and nitrogen were introduced. The amount introduced was 149 NmL / min for CFO-1214ya and 447 NmL / min for nitrogen. The raw material was introduced in liquid form up to the reactor inlet. All reactions were performed at atmospheric pressure.

Due to the introduction of CFO-1214ya and nitrogen, an exothermic peak due to adsorption was observed on the inlet side of the catalyst layer. As the adsorption progressed, the exothermic peak moved from the inlet side to the outlet side of the catalyst layer. After the exothermic peak reached the outlet side of the catalyst layer, CFO-1214ya and nitrogen were further supplied for 30 minutes or more.

Next, a raw material mixed gas composed of CFO-1214ya, hydrogen, and nitrogen was introduced into the reaction tube. As a result, CFO-1214ya and hydrogen were reacted to produce HCFO-1224yd.

Regarding the introduction of hydrogen, the flow rate was divided into three stages to reach the target flow rate in order to suppress rapid heat generation due to reaction heat. At that time, the total flow rate of CFO-1214ya, hydrogen, and nitrogen was kept constant. Specifically, the total flow rate of CFO-1214ya, hydrogen, and nitrogen was kept constant by lowering the nitrogen flow rate by this amount as the hydrogen flow rate increased with the introduction of hydrogen.

Final introduction amounts of each component were 149 NmL / min for CFO-1214ya, 149 NmL / min for hydrogen, and 298 NmL / min for nitrogen. At this time, the ratio (H ₂ / Cl) is 0.5, and the ratio (dilution gas / CFO-1214ya) is 2. The reaction temperature could be kept at 250 ° C. or lower by starting the hydrogen supply stepwise.

During the reaction, the oil bath temperature was maintained at 45 ° C. Five hours after the start of the reaction, the product gas was collected from the outlet of the reaction tube. Then, the composition was analyzed using a gas chromatograph, and the selectivity of HCFO-1224yd was determined from the peak area as the analysis result by the following formula. The results are shown in Table 1. The reaction temperature at this time was 46 ° C.

Selectivity = (ratio of peak area of HCFO-1224yd in total area of peak of product gas [%]) ÷ (ratio of area of peak of CFO-1214ya in total area of peak of mixed gas of raw material [%]) -(Proportion of peak area of CFO-1214ya in the total area of peak of product gas [%]))

Furthermore, using the obtained selectivity, the yield of HCFO-1224yd and the selectivity for valuable resources were determined by the following formulas. The results are also shown in Table 1. Valuables selectivity can be calculated by adding the respective selectivity of HCFO-1224yd and HFO-1234yf, and the ratio of the raw material compound that could be converted into useful compounds HCFO-1224yd and HFO-1234yf. Show.

Yield = selectivity × ((ratio of peak area of CFO-1214ya in total area of peak of mixed gas of raw material [%]) − (ratio of peak area of CFO-1214ya in total area of peak of product gas [% ]))

Valuables selectivity = selectivity + (ratio of peak area of HFO-1234yf in total area of peak of product gas [%]) / ((peak area of CFO-1214ya in total area of peak of mixed gas of raw material) Ratio [%])-(Proportion of peak area of CFO-1214ya in total area of peak of product gas [%]))

Next, HCFO-1224yd (Z) was separated.
First, the produced gas is washed with water, then passed through a 10% by weight potassium hydroxide (KOH) aqueous solution to remove acidic components, and further passed through a dehydration tower packed with synthetic zeolite (Molecular Sieves 4A) for dehydration. Went. After dehydration, the generated gas was trapped in a cylinder cooled with dry ice.

Thereafter, this product gas was distilled to obtain a distillate containing HCFO-1224yd (Z). Distillation was carried out using a distillation column having about 40 theoretical plates, supplying the product gas to the bottom of the column, and performing batch distillation at an operating pressure of 0.05 MPa (gauge pressure). By such distillation, a distillate containing 99.3% by mass of HCFO-1224yd (Z) could be obtained from the top of the distillation column.

(Examples 2 to 22)
As shown in Table 1, HCFO-1224yd was produced by reacting CFO-1214ya with hydrogen in the same manner as in Example 1 except that the composition of the catalyst support and the oil bath temperature were changed. The selectivity, yield and valuable material selectivity of the obtained HCFO-1224yd were determined. The results are shown in Table 1. The amount introduced at each oil bath temperature was calculated using a gas equation of state so that the contact times would be equal without changing the ratio of each component.

(Comparative Examples 1 and 2)
As shown in Table 1, HCFO-1224yd was produced by reacting CFO-1214ya with hydrogen in the same manner as in Example 1 except that the composition of the catalyst support and the oil bath temperature were changed. The selectivity, yield and valuable material selectivity of the obtained HCFO-1224yd were determined. In Comparative Examples 1 and 2, a catalyst-supporting carrier that does not have the second element is used. The results are also shown in Table 1.

As is apparent from Table 1, it was found that the selectivity and yield of HCFO-1224yd can be improved by using a catalyst-supporting carrier having the second element. It was also found that the selectivity for valuable materials including HFO-1234yf was good. Therefore, according to the manufacturing method of the chlorine containing propene of this invention, the target chlorine containing propene can be manufactured efficiently.

Claims

A method for producing a chlorine-containing propene, wherein a compound represented by the following formula (1) is reacted with hydrogen in the presence of a catalyst to obtain a compound represented by the following formula (2),
The catalyst is supported on a support, and includes at least one first element selected from the group consisting of Pd and Pt, Ru, Cu, Au, Zn, Cd, Hg, Al, Ga, In Si, Ge, Sn, Pb, P, As, Sb, Bi, S, Se, Te, and at least one second element selected from the group consisting of Po, and with respect to 100 parts by mass of the carrier A method for producing chlorine-containing propene, wherein the catalyst is 0.01 to 8 parts by mass.
CX 3 CY = CCl 2 (1)
(In Formula (1), X represents F, Cl, or H each independently, and Y represents F or H.)
CX 3 CY = CHCl (2)
(In Formula (2), X and Y are the same as Formula (1) and X and Y.)
The method for producing a chlorine-containing propene according to claim 1, wherein the second element includes at least one selected from the group consisting of Ru, Cu, Au, Sn, Zn, Bi, S, and Te.
3. The method for producing chlorine-containing propene according to claim 1, wherein the second element is 0.1 to 400 mol% with respect to 100 mol% of the first element.
The method for producing a chlorine-containing propene according to any one of claims 1 to 3, wherein the first element contains Pd.
The method for producing a chlorine-containing propene according to any one of claims 1 to 4, wherein, in the formula (1), X is independently F or H, and Y is F or H.
The method for producing a chlorine-containing propene according to any one of claims 1 to 4, wherein, in the formula (1), X is F and Y is F.
The inclusion according to any one of claims 1 to 6, wherein the carrier contains at least one selected from the group consisting of activated carbon, alumina, silica, zirconia, alkali metal oxides, and alkaline earth metal oxides. A method for producing chlorine propene.
The method for producing a chlorine-containing propene according to any one of claims 1 to 7, wherein the reaction temperature of the reaction is 30 to 350 ° C.