Fluoroethane compound production method and fluoroolefin production method

Abstract

To provide a fluoroethane compound production method by which a fluoroethane compound, which is a target product, can be efficiently produced.SOLUTION: A fluoroethane compound production method comprises a step A for subjecting a chlorofluoroethane compound according to the present disclosure to a reduction reaction in the presence of a catalyst to obtain a fluoroethane compound-containing product, wherein, in the catalyst, at least one metal selected from the group consisting of Ni, Pd, Pt, Ru, and Rh is supported on activated carbon. According to this production method, a fluoroethane compound, which is a target product, can be efficiently produced.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a process for producing fluoroethane compounds and a process for producing fluoroolefins. [Background technology]

[0002] Fluoroethane, typified by 1,1,2-trifluoroethane (hereinafter sometimes referred to as "HFC-143"), is known as a raw material for producing various refrigerants. Various methods have been proposed for producing fluoroethane such as HFC-143.

[0003] For example, Patent Document 1 proposes a technology for producing HFC-143 by hydrogenating chlorotrifluoroethylene in the presence of a hydrogenation catalyst. Patent Document 2 discloses that HFC-143 and HCFC-133b are contained as by-products in the process for obtaining HFO-1123 by reacting chlorotrifluoroethylene (CTFE) with hydrogen. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 1-287044 [Patent Document 2] JP 2016-130236 A Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present disclosure is to efficiently produce the target product, a fluoroethane compound.

[0006] The present invention has been made in view of the above, and an object of the present invention is to provide a method for producing a fluoroethane compound, which can efficiently produce the target product, that is, a fluoroethane compound. [Means for solving the problem]

[0007] The present disclosure includes, for example, the inventions described in the following sections. Item 1 The process includes a step A of subjecting a chlorofluoroethane compound to a reduction reaction in the presence of a catalyst and hydrogen to obtain a product containing a fluoroethane compound, The method for producing a fluoroethane compound, wherein the catalyst is at least one metal selected from the group consisting of Ni, Pd, Pt, Ru and Rh supported on activated carbon. Section 2 The fluoroethane compound includes 1,1,2-trifluoroethane, Item 2. The method according to item 1, wherein the chlorofluoroethane compound comprises 1,1,2-trichloro-1,2,2-trifluoroethane. Section 3 The fluoroethane compound includes 1,1,2-trifluoroethane, Item 2. The method according to item 1, wherein the chlorofluoroethane compound comprises 1-chloro-1,1,2-trifluoroethane. Section 4 The fluoroethane compound includes 1,1-difluoroethane, The chlorofluoroethane compound includes 1-chloro-1,1,2-trifluoroethane. Item 1. The method for producing the present invention. Section 5 5. The method according to any one of items 1 to 4, wherein the product contains a compound selected from the group consisting of chlorotrifluoroethylene and trifluoroethylene as a by-product. Section 6 Item 3. The method according to item 2, further comprising the step of obtaining 1,1,2-trichloro-1,2,2-trifluoroethane by a liquid phase fluorination reaction of tetrachloroethylene. Section 7 A method for producing a fluoroolefin, comprising the steps of: A step of obtaining a fluoroethane compound by the production method according to any one of items 1 to 6, and a step of obtaining the fluoroolefin by a dehydrofluorination reaction of the fluoroethane compound obtained in the step; A method for producing a fluoroolefin, comprising: Effect of the Invention

[0008] According to the production method of the present disclosure, the target product, a fluoroethane compound, can be efficiently produced. [Brief description of the drawings]

[0009] [Figure 1] FIG. 1 is a schematic diagram illustrating an overall process including the method for producing fluoroethane compounds of the present disclosure. [Diagram 2] FIG. 2 is a schematic diagram illustrating another embodiment of an integrated process including the method for producing fluoroethane compounds of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] In the case of producing a fluoroethane compound by the hydrogenation reaction of chlorotrifluoroethylene, as described above, since chlorotrifluoroethylene is expensive, there has been a recent demand for using cheaper raw materials and producing a fluoroethane compound efficiently.

[0011] The present inventors have conducted extensive research in order to achieve the object of producing a target product, a fluoroethane compound, with high conversion and high selectivity. As a result, they have found that the above object can be achieved by subjecting a chlorofluoroethane compound to a gas-phase reduction reaction using hydrogen in the presence of a catalyst.

[0012] Hereinafter, embodiments of the present disclosure will be described in detail. In this specification, the expressions "containing" and "comprise" include the concepts of "containing", "comprises", "consists essentially of" and "consists only of".

[0013] In this specification, a numerical range indicated using "~" indicates a range including the numerical values ​​described before and after "~" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this specification, the upper limit or lower limit of a numerical range in a certain stage can be arbitrarily combined with the upper limit or lower limit of a numerical range in another stage. In the numerical ranges described in this specification, the upper limit or lower limit of the numerical range may be replaced with a value shown in an example or a value that can be unambiguously derived from an example.

[0014] 1. Method for producing fluoroethane compounds The method for producing a fluoroethane compound of the present disclosure includes the following step A. Step A: A step of obtaining a product containing a fluoroethane compound by subjecting a chlorofluoroethane compound to a reduction reaction in the presence of a catalyst.

[0015] In the method for producing a fluoroethane compound of the present disclosure, the catalyst is at least one metal selected from the group consisting of Ni, Pd, Pt, Ru, and Rh supported on activated carbon.

[0016] According to the production method of the present disclosure, the target product, a fluoroethane compound, can be efficiently produced. That is, the production method of the present disclosure has a high conversion rate and a high selectivity for the target product, a fluoroethane compound.

[0017] Hereinafter, in this specification, the method for producing a fluoroethane compound of the present disclosure will be referred to as "Production Method 1 of the present disclosure."

[0018] In the production method 1 of the present disclosure, a raw material containing a chlorofluoroethane compound is subjected to a reduction reaction in the presence of a catalyst and hydrogen in step A. By such a reduction reaction, a product containing a fluoroethane compound, which is the target product, is obtained.

[0019] (raw materials) The raw material used in step A includes a chlorofluoroethane compound. The chlorofluoroethane compound is a compound having two carbon atoms and both a chloro group and a fluoro group. The chlorofluoroethane compound preferably has two or more fluoro groups, more preferably has three or more fluoro groups, and even more preferably has three fluoro groups.

[0020] Specific examples of the chlorofluoroethane compound include at least one selected from the group consisting of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), 1-chloro-1,1,2-trifluoroethane (HCFC-133b), 1-chloro-1-fluoroethane (HCFC-151), 1,2-dichloro-1,2-difluoroethane (HCFC-132), 2-chloro-1,1-difluoroethane (HCFC-142), 1-chloro-1,2-difluoroethane (HCFC-142a), 2-chloro-1,1,2-trifluoroethane (HCFC-133), 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123), and 1,2-dichloro-1,2,2-trifluoroethane (HCFC-123a).

[0021] Among them, the chlorofluoroethane compound more preferably contains one selected from the group consisting of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) and 1-chloro-1,1,2-trifluoroethane (HCFC-133b), and particularly preferably contains 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113). That is, it is particularly preferable that the raw material used in step A contains 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113). In this case, the fluoroethane compound can be obtained efficiently, and the conversion rate can be increased.

[0022] The chlorofluoroethane compound used in step A preferably contains 50% by mass or more of CFC-113, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more. The chlorofluoroethane compound used in step A may be CFC-113 alone.

[0023] The chlorofluoroethane compound used in step A preferably contains 50% by mass or more of HCFC-133b, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more. The chlorofluoroethane compound used in step A may be HCFC-133b alone.

[0024] The raw material used in step A may consist of only a chlorofluoroethane compound, and may contain other compounds other than a chlorofluoroethane compound as long as the effect of the present disclosure is not impaired. It may also contain the components:

[0025] The amount of water in the chlorofluoroethane compound used in step A is preferably 100 mass ppm or less, more preferably 70 mass ppm or less, even more preferably 60 mass ppm or less, and particularly preferably 50 mass ppm or less, based on the total mass of the chlorofluoroethane compound. In this case, the deterioration of the catalyst is suppressed, so that the catalyst life can be improved. The lower limit of the amount of water in the chlorofluoroethane compound is not particularly limited as long as the effect of the manufacturing method 1 of the present disclosure is not inhibited. For example, in the manufacturing method 1 of the present disclosure, the chlorofluoroethane compound introduced into the reactor may not contain water. Alternatively, the lower limit of the content of water in the chlorofluoroethane compound introduced into the reactor can be 0.1 mass ppm. From the viewpoint that the process for removing water in the chlorofluoroethane compound introduced into the reactor is not likely to become complicated, the lower limit of the content of water in the chlorofluoroethane compound introduced into the reactor is preferably 1 mass ppm. The content of water in the chlorofluoroethane used in the manufacturing method 1 of the present disclosure indicates a value obtained by the Karl Fischer moisture measurement method.

[0026] (catalyst) In the production method 1 of the present disclosure, a catalyst is used in step A. Specifically, as described above, a catalyst in which at least one metal selected from the group consisting of Ni, Pd, Pt, Ru, and Rh is supported on activated carbon is used in step A. Among them, in terms of being able to obtain a fluoroethane compound more efficiently, it is preferable to use a catalyst in which at least one metal selected from the group consisting of Pd, Pt, and Ru is supported on activated carbon, it is more preferable to use a catalyst in which at least one metal selected from the group consisting of Pd and Pt is supported on activated carbon, and it is even more preferable to use a catalyst in which Pd is supported on activated carbon.

[0027] In the catalyst, the amount of the metal carried is not particularly limited, but from the viewpoint of easily and efficiently obtaining fluoroethane compounds, the content ratio of the metal to the total amount of the carrier (activated carbon) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and particularly preferably 0.5% by mass or more. Also, from the viewpoint of easily and efficiently obtaining fluoroethane compounds, the content ratio of the metal to the total amount of the carrier (activated carbon) is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less.

[0028] The method for preparing the catalyst is not particularly limited, and a wide variety of known preparation methods can be used. For example, the catalyst can be obtained by immersing the activated carbon carrier in a solution containing at least one metal selected from the group consisting of Ni, Pd, Pt, Ru, and Rh to impregnate the carrier with the solution, and then, if necessary, neutralizing and calcining the carrier. In this case, the amount of precious metal supported on the carrier can be controlled by adjusting the concentration of the solution, the impregnation time, etc.

[0029] The type of activated carbon is not particularly limited, and for example, various commercially available activated carbons can be used. Activated carbons such as charcoal-based activated carbon, coal-based activated carbon, coconut shell activated carbon, oil carbon activated carbon, and phenol resin activated carbon can be mainly used preferably, and among them, charcoal-based activated carbon, coal-based activated carbon, and coconut shell activated carbon are more preferably used.

[0030] In step A, the amount of catalyst used is not particularly limited and may be the same as that used in known hydrogenation reactions. For example, the amount of catalyst used in the reduction reaction in step A may be appropriately set depending on the size of the reactor used, the amount of raw material used, etc.

[0031] (Reduction reaction) In step A, a raw material containing a chlorofluoroethane compound is subjected to a gas-phase reduction reaction using hydrogen in the presence of a catalyst. One embodiment of such a reduction reaction is a so-called hydrodehalogenation reaction in which a halogen element in a molecule is replaced by hydrogen and hydrogen halide is eliminated. Another embodiment of the reduction reaction is a so-called hydrogenation reaction in which a hydrogen molecule is added to a double bond in a molecule to produce an alkane from an alkene. In step A, either or both of the above reactions proceed.

[0032] In the reduction reaction of step A, the amount of hydrogen used is not particularly limited, and for example, hydrogen can be 3 moles or more and 60 moles or less per mole of chlorofluoroethane compound in the raw material. Since the selectivity of HFC-143 is increased and the effect of suppressing catalyst deterioration can be expected, it is preferable to supply hydrogen in an amount equal to or more than the raw material to the reactor together with the raw material. The amount of hydrogen is preferably 5 moles or more, more preferably 7 moles or more, per mole of chlorofluoroethane compound in the raw material. By using an appropriate amount of hydrogen, the selectivity of HFC-143 is high and the effect of suppressing catalyst deterioration can be expected. On the other hand, since the supply of an excessive amount of hydrogen leads to the loss of hydrogen and HFC-143, the excess amount of hydrogen needs to be within a moderate range from the viewpoint of efficient plant operation. Therefore, the amount of hydrogen is preferably 55 moles or less, more preferably 40 moles or less, even more preferably 25 moles or less, and particularly preferably 21 moles or less per mole of chlorofluoroethane compound in the raw material. As described above, the chlorofluoroethane compound used in step A may contain water. When the water content is 100 ppm by mass or less relative to the total mass of the chlorofluoroethane compound, the amount of hydrogen per mole of chlorofluoroethane compound in the raw material is preferably 15 moles or more, more preferably 20 moles or more, and is preferably 60 moles or less, more preferably 55 moles or less, and even more preferably 40 moles or less, in order to easily suppress catalyst deterioration.

[0033] The method of carrying out the reduction reaction is not particularly limited. For example, in a state where a catalyst is accommodated in a reactor, a raw material containing a chlorofluoroethane compound and hydrogen gas are introduced into the reactor and brought into contact with the catalyst, thereby carrying out a gas-phase reduction reaction. After that, a product containing the target fluoroethane compound is collected outside the reactor, for example, as a mixed gas. In addition to the target product, the fluoroethane compound, the mixed gas may also contain by-products described below and unreacted raw materials. In the reduction reaction, the raw material containing the chlorofluoroethane compound and hydrogen gas may be introduced into the reactor from the same line (piping), or may be introduced into the reactor from different lines (piping).

[0034] In the reduction reaction, the reaction temperature (the atmospheric temperature when the raw material comes into contact with the catalyst) is not particularly limited and can be, for example, 50 to 400°C, preferably 100 to 380°C, more preferably 100 to 350°C, and particularly preferably 150 to 330°C.

[0035] The reaction time of the reduction reaction is not particularly limited. For example, the contact time represented by the ratio of the catalyst loading amount in the reactor W (g) to the total flow rate of the chlorofluoroethane compound and hydrogen gas flowing into the reactor F: W / F can be 1 to 50 g·sec / cc, preferably 5 g·sec / cc or more, more preferably 10 g·sec / cc or more, preferably 40 g·sec / cc or less, more preferably 30 g·sec / cc or more, and even more preferably 20 g·sec / cc or less.

[0036] The reduction reaction in step A can be carried out in either a continuous or batch manner. The (gas phase) reduction reaction in step A can be carried out under reduced pressure, atmospheric pressure, or pressure. For example, from the viewpoint of reactivity, the pressure during the reaction is preferably 2 MPaG or less, more preferably 1.5 MPaG or less, and particularly preferably 1 MPaG or less. The "G" in "MPaG" means gauge pressure, and indicates the pressure gauge reading based on atmospheric pressure (i.e., atmospheric pressure is 0 MPaG). Reduction reactions can also be carried out by making inert gases such as helium, nitrogen, and argon coexist with the reaction gas.

[0037] The reactor used in the reduction reaction may be, for example, a tubular flow reactor. Examples of the flow reactor include an adiabatic reactor and a multi-tubular reactor that can adjust the temperature by heating using a heat medium and can adjust the reaction temperature by removing the heat of reaction. The reactor is preferably made of a material that is resistant to corrosion, and is particularly preferably made of stainless steel (SUS), Hastelloy, Inconel, Monel, or the like.

[0038] The reactor may be equipped with a jacket for adjusting the temperature inside the reactor, and for example, a heat transfer medium or the like may be circulated inside the jacket, thereby making it possible to adjust the temperature of the gases (for example, the raw materials, chlorofluoroethane compound and hydrogen, and the reaction products, such as hydrogen chloride, fluoroethanes, and fluoroethylenes) inside the reactor.

[0039] The target fluoroethane compound can be obtained by collecting the mixed gas obtained by carrying out the reduction reaction in the above-mentioned step A. In addition to step A, the production method 1 of the present disclosure can also include other steps as necessary. The reactor outlet gas contains unreacted raw materials chlorofluoroethane and hydrogen, as well as reaction products such as hydrogen chloride, fluoroethanes, and fluoroethylenes. Therefore, the production method 1 of the present disclosure can include steps for facilitating separation of these gases, such as a compression step for pressurizing the gas, a cooling step for separation, a distillation step, a deoxidization step, a dehydration step, and the like.

[0040] (product) The product of the manufacturing method 1 of the present disclosure includes the fluoroethane compound. In this specification, the fluoroethane compound is a saturated hydrocarbon having two carbon atoms and containing one or more fluorines. The type is not particularly limited as long as it corresponds to the type of the chlorofluoroethane compound used in step A. The fluoroethane compound can have a chloro group, that is, the fluoroethane compound may be a chlorofluoroethane compound, but it is preferable that the fluoroethane compound does not have a chloro group.

[0041] In the production method 1 of the present disclosure, one or more of the fluoroethane compounds are produced. That is, in the production method 1 of the present disclosure, the product contains one or more of the fluoroethane compounds.

[0042] Specific examples of chlorofluoroethane compounds and / or fluoroethane compounds obtained by Production Method 1 of the present disclosure include 1,1,2-trifluoroethane (HFC-143), fluoroethane (HFC-161), 1,2-difluoroethane (HFC-152), 1,1-difluoroethane (HFC-152a), 2-chloro-1,1,2-trifluoroethane (HCFC-133), 1-chloro-1,1,2-trifluoroethane (HCFC- 133b), 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123), 1,2-dichloro-1,2,2-trifluoroethane (HCFC-123a), 1,1,1-trifluoroethane (HFC-143a), 1,1,2-trifluoroethane (HFC-143), 1,1,2,2-tetrafluoroethane (HFC-134), and 1,1,1,2-tetrafluoroethane (HFC-134a).

[0043] Just to be sure, the raw material used in step A and the product are different raw materials in production method 1. For example, if the raw material used in step A is HCFC-133b, the product is a compound other than HCFC-133b.

[0044] The fluoroethane compound obtained by Production Method 1 of the present disclosure preferably contains 1,1,2-trifluoroethane (HFC-143), and in particular, the fluoroethane compound obtained by Production Method 1 of the present disclosure preferably contains HFC-143 as the main product. This is because if 1,1,2-trifluoroethane is the main product, the conversion rate and selectivity are particularly high. When HFC-143 is the main product, the chlorofluoroethane compound as the raw material is 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) or 1-chloro-1,1,2-trifluoroethane (HCFC-133b).

[0045] In this specification, the term "main product" refers to a component that is contained in the product in an amount of 50 mol % or more.

[0046] When HFC-143 is the main product, the content of HFC-143 in the product is preferably 60 mol % or more, and more preferably 70 mol % or more.

[0047] The fluoroethane compound obtained by Production Method 1 of the present disclosure may be 1,1-difluoroethane (HFC-152a). That is, the fluoroethane compound obtained by Production Method 1 of the present disclosure may be HFC-152a as the main product. When HFC-152a is the main product, the raw material chlorofluoroethane compound is 1-chloro-1,1,2-trifluoroethane (HCFC-133b).

[0048] The product obtained by Production Method 1 of the present disclosure may contain by-products, unreacted raw materials, etc. In the product obtained by Production Method 1 of the present disclosure, the content of the by-products can be, for example, 40 mol % or less based on the total amount of the product, more preferably 30 mol % or less, and even more preferably 20 mol % or less.

[0049] The type of the by-product is not particularly limited. For example, the by-product may include a compound selected from the group consisting of chlorotrifluoroethylene and trifluoroethylene. That is, the product obtained in step A may include a compound selected from the group consisting of chlorotrifluoroethylene and trifluoroethylene as a by-product.

[0050] For example, when CFC-113 is used as the raw material chlorofluoroethane compound, the main product is HFC-143, and at this time, compounds selected from the group consisting of chlorotrifluoroethylene and trifluoroethylene are likely to be produced as by-products. Note that chlorotrifluoroethylene and trifluoroethylene are intermediates in the reduction reaction for obtaining HFC-143 from CFC-113, for example.

[0051] More specifically, when the main component in the product obtained by Production Method 1 of the present disclosure is HFC-143, 1,2-dichloro-1,2,2-trifluoroethane (HCFC-123a) may be generated as a by-product. When HFC-143 is the main product, the content of the by-product in the product is preferably less than 40 mol%, more preferably less than 30 mol%, and even more preferably less than 20 mol%.

[0052] In addition, when the main component in the product obtained by Production Method 1 of the present disclosure is HFC-152a, 1,2-dichloro-1,2,2-trifluoroethane (HCFC-123a) may be generated as a by-product. When HFC-152a is the main product, the content of the by-product in the product is preferably less than 40 mol%, more preferably less than 30 mol%, and even more preferably less than 20 mol%.

[0053] The by-product is selected from the group consisting of chlorotrifluoroethylene and trifluoroethylene. When the product contains compounds that are easily soluble in water, the total content of chlorotrifluoroethylene and trifluoroethylene can be less than 40 mol%, more preferably less than 30 mol%, and even more preferably less than 20 mol%, based on the total amount of the product.

[0054] The product obtained by the manufacturing method 1 of the present disclosure may be purified to increase the purity of the target compound, or the product obtained without purification may be used as the target compound. In addition, when the product contains unreacted raw materials, the raw materials can be separated by an appropriate method and used again as raw materials for reaction. In other words, in the manufacturing method 1, the crude product can be recycled as a raw material.

[0055] By the manufacturing method 1 of the present disclosure, for example, a composition containing HFC-143 and HCFC-123a can be obtained. In such a composition, the content of HFC-143 is preferably 60 mol% or more, and more preferably 70 mol% or more, based on the total amount of HFC-143 and HCFC-123a. The content of HCFC-123a can be less than 40 mol%, more preferably less than 30 mol%, and even more preferably less than 20 mol%, based on the total amount of HFC-143 and HCFC-123a.

[0056] Moreover, by the manufacturing method 1 of the present disclosure, for example, a composition containing HFC-152a and HCFC-123a can be obtained. In such a composition, the content of HFC-152a is preferably 60 mol% or more, more preferably 70 mol% or more, based on the total amount of HFC-152a and HCFC-123a. The content of HCFC-123a can be less than 40 mol%, more preferably less than 30 mol%, and even more preferably less than 20 mol%, based on the total amount of HFC-152a and HCFC-123a.

[0057] (Production method of raw materials) The method for producing the chlorofluoroethane compound used as the raw material in step A is not particularly limited, and for example, a wide variety of known production methods can be adopted. Among them, it is preferable to produce the chlorofluoroethane compound by a method including step A0 of reacting tetrachloroethylene with a fluorinating agent. In this case, for example, 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) is likely to be produced as the chlorofluoroethane compound.

[0058] In step A0, the reaction between tetrachloroethylene and a fluorinating agent is, for example, a liquid-phase fluorination reaction. That is, the production method 1 of the present disclosure can also include a step of obtaining the 1,1,2-trichloro-1,2,2-trifluoroethane by a liquid-phase fluorination reaction of tetrachloroethylene.

[0059] In step A0, the fluorinating agent is not particularly limited, and for example, a fluorinating agent (fluorination catalyst) such as HF or a metal halide is used. An example of the fluorinating agent (fluorination catalyst) is SbCl 5 , SbCl 3 , SnCl 4 , TaCl 5 , TiCl 4 , NbCl 5 , MoCl 6 , FeCl 3 , and those in which part or all of the Cl bonded to these fluorinating agents have been replaced with fluorine, and mixtures or combinations of these. Among these, antimony pentachloride and antimony pentachloride in which part of the Cl has been replaced with fluorine are preferred, and a liquid-phase fluorination reaction using HF is suitably used for this reaction. Taking the liquid-phase fluorination reaction as an example, this reaction is carried out at a reaction temperature of 50°C to 200°C and a reaction pressure of 0.2 to 1.5 MPaG. In order to maintain the valence of antimony, which is the fluorinating agent, at 5, chlorine can also be added appropriately. The reaction gas flowing out from the reactor may contain unreacted HF, HCl, CFC-112 which is an intermediate, chlorine, etc., in addition to the target CFC-113. The reaction carried out in step A0 is a reaction of a commonly used corrosion-resistant material, etc. For example, a material containing nickel, such as Hastelloy, Inconel, or Monel, can be used.

[0060] As described above, the manufacturing method 1 of the present disclosure can include the step A0 before the step A.

[0061] 2. Fluoroolefin manufacturing method A fluoroolefin can also be obtained by subjecting the fluoroethane compound obtained by Production Method 1 of the present disclosure to a dehydrohalogenation reaction. That is, the present disclosure also includes a method for producing a fluoroolefin by a dehydrofluorination step of the fluoroethane compound obtained by Production Method 1 of the present disclosure. Hereinafter, such a production method is referred to as "Production Method 2 of the present disclosure." In addition, the dehydrofluorination step carried out in Production Method 2 of the present disclosure is referred to as "Step B."

[0062] According to the production method 2 of the present disclosure, for example, a compound represented by the following general formula (4) CX 11 X 21 =CX 31 X 41 (4) (In formula (4), X 11 , X 21 , X 31 and X 41 are the same or different and represent a hydrogen atom, a fluorine atom or a chlorine atom; X 11 , X 21 , X 31 and X 41 At least one of the X represents a hydrogen atom; 11 , X 21 , X 31 and X 41 At least one of the groups represents a fluorine atom. It is possible to obtain a fluoroolefin represented by the formula:

[0063] In the dehydrofluorination step, the method of the dehydrofluorination reaction is not particularly limited, and for example, the dehydrofluorination reaction can be carried out under the same conditions as those of known dehydrofluorination reactions. For example, the dehydrofluorination reaction can be carried out in the gas phase in the presence of a dehydrofluorination catalyst.

[0064] In Production Method 2 of the present disclosure, when 1,1,2-trifluoroethane (HFC-143) is used as the fluoroethane, the dehydrofluorination reaction follows the following reaction formula. CF 2 HCFH 2 → CHF=CHF + HF

[0065] The dehydrofluorination catalyst is not particularly limited, and a wide variety of known catalysts can be used, such as chromium oxide, chromium oxide fluoride, aluminum oxide, and aluminum oxide fluoride.

[0066] The dehydrofluorination catalyst may be supported on a carrier. Examples of the carrier include carbon, alumina (Al 2 O 3 ), zirconia (ZrO 2 ), silica (SiO 2 ), titania (TiO 2 ) and the like. As the carbon, activated carbon, amorphous carbon, graphite, diamond, and the like can be used.

[0067] In the production method 2 of the present disclosure, the dehydrofluorination reaction can also be carried out in the presence of an oxidizing agent. In order to increase the effect of suppressing catalyst deterioration in the dehydrofluorination reaction, it is preferable to supply the oxidizing agent together with the reaction gas. Examples of the oxidizing agent include oxygen, chlorine, bromine, and iodine, and oxygen is particularly preferable. The concentration of the oxidizing agent is not particularly limited, and can be the same as that of a known dehydrofluorination reaction, for example.

[0068] The reaction temperature of the dehydrofluorination reaction is not particularly limited and can be the same as that of known dehydrofluorination reactions, and can be, for example, 300° C. or higher, preferably 320° C. or higher, more preferably 340° C. or higher, and particularly preferably 350° C. or higher. In addition, the reaction temperature of the dehydrofluorination reaction can be 600° C. or lower, preferably 550° C. or lower, more preferably 500° C. or lower, and particularly preferably 450° C. or lower.

[0069] The reaction time and pressure during the dehydrofluorination reaction are not particularly limited, and known conditions can be widely adopted. The dehydrofluorination reaction can be carried out in the presence of an inert gas, air, or oxygen. The dehydrofluorination reaction can be carried out in either a continuous or batch system.

[0070] The production method 2 of the present disclosure may include other steps as necessary in addition to the dehydrofluorination step. Note that, in the production method 2 as well, the raw materials can be separated from the crude product obtained in the production method 2 and recycled.

[0071] The dehydrofluorination step produces a fluoroolefin, which is the target product of Production Method 2 of the present disclosure, for example, a compound represented by general formula (4). The fluoroolefin produced by the dehydrofluorination step may be one or more types.

[0072] The fluoroolefin obtained may depend on the fluoroethane used in the dehydrofluorination step. Examples of the fluoroolefin include 1,2-difluoroethylene (HFO-1132), 1,1-difluoroethylene (HFO-1132a), trifluoroethylene (HFO-1123), fluoroethylene (HFO-1141), and the like.

[0073] In the production method 2 of the present disclosure, when HFC-143 is used as the fluoroethane, the resulting fluoroolefin is HFO-1132. In the production method 2 of the present disclosure, when HFC-143a is used as the fluoroethane, the resulting fluoroolefin is HFO-1132a. In the production method 2 of the present disclosure, when HFC-134a is used as the fluoroethane, the resulting fluoroolefin is HFO-1123. HFO-1132 may include trans-1,2-difluoroethylene [(E)-HFO-1132] and cis-1,2-difluoroethylene [(Z)-HFO-1132].

[0074] When a fluoroolefin is obtained by the above-mentioned Production Method 2 of the present disclosure, the above-mentioned Production Method 1 of the present disclosure and Production Method 2 of the present disclosure may be carried out continuously or independently. In Production Method 2 of the present disclosure, after a product containing a fluoroethane compound is obtained by the above-mentioned step A, a fluoroolefin can be produced by a dehydrofluorination step of the fluoroethane compound.

[0075] As described above, Production Method 2 of the present disclosure is a production method of a fluoroolefin, and includes a step of obtaining a fluoroethane compound by Production Method 1 of the present disclosure, and a step of obtaining the fluoroolefin by a dehydrofluorination reaction of the fluoroethane compound obtained in the above step.

[0076] 3. Overall process The present disclosure encompasses an integrated process including the above-mentioned steps A0, A, and B. Such an integrated process is referred to as "integrated process 1." The concept of integrated process 1 is shown in FIG. 1. In FIG. 1, PCE stands for perchloroethylene (tetrachloroethylene). This figure is a conceptual diagram of integrated process 1, and does not show all of the flows and steps.

[0077] Another embodiment of the integrated process may include the above-mentioned steps A0, A', A2, and B. Such another embodiment of the integrated process is referred to as "integrated process 2." The concept of integrated process 2 is shown in FIG. 2. In FIG. 2, PCE means perchloroethylene (tetrachloroethylene). This figure is a conceptual diagram of integrated process 2, and does not show all flows and steps.

[0078] In the comprehensive process 2, step A' and step A2 are as follows. Step A': A step of extracting a fluoroethylene compound as an intermediate in the reduction reaction of the step A. Step A2: A step of obtaining a fluoroethane compound by a gas phase hydrogenation reaction of the fluoroethylene compound.

[0079] In the integrated process 2, step A0 is the same as step A0 in the integrated process 1, and step B is the same as step B in the integrated process 1.

[0080] In step A', the fluoroethylene compound is preferably at least one selected from the group consisting of fluoroethylene (HFO-1141), 1,2-dichloro-1,2-difluoroethylene (CFO-1112), 1,1-difluoroethylene (HFO-1132a), 1,2-difluoroethylene (HFO-1132), chlorotrifluoroethylene (CTFE, CFO-1113), trifluoroethylene (HFO-1123), 2-chloro-1,1-difluoroethylene (HCFO-1122), 1-chloro-1,2-difluoroethylene (HCFO-1122a), and tetrafluoroethylene (FO-1114). Of these, the fluoroethylene more preferably includes at least one selected from the group consisting of chlorotrifluoroethylene (CTFE, CFO-1113) and tetrafluoroethylene (FO-1114), and particularly preferably includes chlorotrifluoroethylene (CTFE, CFO-1113).

[0081] In step A2, the method for producing a fluoroethane compound by the gas-phase hydrogenation reaction of the fluoroethylene compound is not particularly limited, and a wide variety of known gas-phase hydrogenation reactions can be adopted. For example, the hydrogenation reaction can be carried out by introducing the fluoroethylene compound obtained in step A' and hydrogen gas into a reactor filled with a catalyst and bringing them into contact with the catalyst. This produces a fluoroethane compound. The type of such a fluoroethane compound is the same as the type of the fluoroethane compound produced by the reduction reaction in the above-mentioned step A. When the gas-phase hydrogenation reaction of chlorotrifluoroethylene (CTFE, CFO-1113) is carried out in step A', HFC-143 is obtained as the fluoroethane compound.

[0082] The fluoroethane compound obtained in the step A2 can be subjected to a dehydrohalogenation reaction in the above-mentioned step B to obtain a fluoroolefin.

[0083] In specifying the invention included in the present disclosure, the configurations (properties, structures, functions, etc.) described in each embodiment of the present disclosure may be combined in any manner. In other words, the present disclosure includes all subject matter consisting of all combinations of the configurations that can be combined as described in this specification. EXAMPLES

[0084] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the embodiments of these examples.

[0085] Example 1 A reactor with an inner diameter of 1.5 cm and a length of 50 cm was prepared, and 10 g of a catalyst in which 0.5 mass % of palladium (Pd) was supported on activated carbon was packed in the reactor. CFC-113 and hydrogen were supplied into the reactor from the raw material supply port of the reactor, and passed through the catalyst to carry out a reduction reaction. In this reduction reaction, CFC-113 was supplied in a gaseous state at a flow rate of 20 ml / min, and hydrogen gas was supplied so that the molar ratio of hydrogen:CFC-113 was 9:1 (i.e., the hydrogen / CFC-113 molar ratio was 9). In the reduction reaction, the amount of catalyst packed in the reactor was W (g), and the total flow rate of CFC-113 and hydrogen gas flowing into the reactor was The contact time expressed as W / F was 3 g·sec / cc, and the temperature at which CFC-113 and hydrogen passed through the catalyst (reaction temperature, i.e., temperature inside the reactor) was 300°C. HFC-143 was obtained with a conversion rate of 97% and a selectivity for HFC-143 of 77%. The selectivity for useful compounds, including intermediates that can be converted to HFC-143, was 85%.

[0086] Example 2 Except for changing the catalyst to one supporting 2 mass % of palladium (Pd) on activated carbon, HFC-143 was obtained in the same manner as in Example 1. The conversion rate was 98%, and the selectivity for HFC-143 was 95%.

[0087] Example 3 Except for changing the catalyst to one in which palladium (Pd) was supported at 3 mass % on activated carbon, HFC-143 was obtained in the same manner as in Example 1. The conversion rate was 99%, and the selectivity for HFC-143 was 98%.

[0088] (Examples 4 to 9) HFC-143 was obtained in the same manner as in Example 2, except that the reaction temperature and the hydrogen / CFC-113 molar ratio were set as shown in Table 1.

[0089] Example 10 HFC-143 was obtained in the same manner as in Example 4, except that the catalyst was changed to a catalyst in which 2% by mass of Pt was supported on activated carbon.

[0090] Example 11 HFC-143 was obtained in the same manner as in Example 4, except that the catalyst was changed to a catalyst in which 2% by mass of Ru was supported on activated carbon.

[0091] Example 12 HFC-143 was obtained in the same manner as in Example 4, except that the catalyst was changed to a catalyst in which 2% by mass of Rh was supported on activated carbon.

[0092] Comparative Example 1 HFC-143 was obtained in the same manner as in Example 1, except that the catalyst was changed to one supporting 2% by mass of Pd on aluminum oxide. In this case, the conversion rate was 64% and the selectivity was 40%. After 36 hours of reaction, the conversion rate decreased to 40% and the selectivity to 32%.

[0093] Table 1 shows the reaction conditions (reaction temperature, hydrogen / CFC-113 molar ratio) and the addition rate and selectivity after the reaction in the reactions carried out in each Example.

[0094] [Table 1]

[0095] Example 13 A reactor with an inner diameter of 0.97 cm and a length of 55 cm was prepared, and 2 g of a catalyst in which palladium (Pd) was supported at 2.0 mass% on activated carbon was filled in the reactor. CFC-113 with a moisture content of 41.8 mass ppm and hydrogen were supplied into the reactor from the raw material supply port of the reactor and passed through the catalyst to carry out a reduction reaction. In this reduction reaction, CFC-113 was supplied in a gaseous state at a flow rate of 4.7 ml / min, and hydrogen gas was supplied so that the molar ratio of hydrogen:CFC-113 was 12:1 (i.e., the hydrogen / CFC-113 molar ratio was 12). In the above reduction reaction, the catalyst loading in the reactor was W (g), the total flow rate of CFC-113 and hydrogen gas flowing into the reactor was F (flow rate at 25°C and 0.1013 MPa), the contact time expressed as W / F was 2 g·sec / cc, and the temperature when CFC-113 and hydrogen passed through the catalyst (reaction temperature, i.e., temperature inside the reactor) was 285°C. As a result, HFC-143 was obtained, with a conversion rate of 100% and a selectivity for HFC-143 of 80%. The selectivity for useful compounds, including intermediates that can be converted to HFC-143, was 80%. The catalyst life under these conditions was about 46 hours, and about 0.4 months when W / F was 12.

[0096] Example 14 A reactor with an inner diameter of 0.97 cm and a length of 55 cm was prepared, and 1.76 g of a catalyst in which palladium (Pd) was supported at 2.0 mass% on activated carbon was filled in the reactor. CFC-113 with a moisture content of 41.8 mass ppm and hydrogen were supplied into the reactor from the raw material supply port of the reactor and passed through the catalyst to carry out a reduction reaction. In this reduction reaction, CFC-113 was supplied in a gaseous state at a flow rate of 3.1 ml / min, and hydrogen gas was supplied so that the molar ratio of hydrogen:CFC-113 was 20:1 (i.e., the hydrogen / CFC-113 molar ratio was 20). In the above reduction reaction, the catalyst loading in the reactor was W (g), the total flow rate of CFC-113 and hydrogen gas flowing into the reactor was F (flow rate at 25°C and 0.1013 MPa), and the contact time expressed as W / F was 1.65 g·sec / cc. The temperature when CFC-113 and hydrogen passed through the catalyst (reaction temperature, i.e., temperature inside the reactor) was 175°C. As a result, HFC-143 was obtained, with a conversion rate of 100% and a selectivity for HFC-143 of 56%. The selectivity for useful compounds, including intermediates that can be converted to HFC-143, was 88.5%. The catalyst life under these conditions was about 903 hours, and W / When F was set to 12, the time was approximately 9.1 months.

[0097] Example 15 A reactor with an inner diameter of 0.97 cm and a length of 55 cm was prepared, and 1.76 g of a catalyst in which palladium (Pd) was supported at 2.0 mass% on activated carbon was filled in the reactor. CFC-113 with a moisture content of 41.8 mass ppm and hydrogen were supplied into the reactor from the raw material supply port of the reactor and passed through the catalyst to carry out a reduction reaction. In this reduction reaction, CFC-113 was supplied in a gaseous state at a flow rate of 1.4 ml / min, and hydrogen gas was supplied so that the molar ratio of hydrogen:CFC-113 was 25:1 (i.e., the hydrogen / CFC-113 molar ratio was 25). In the above reduction reaction, the catalyst loading in the reactor was W (g), the total flow rate of CFC-113 and hydrogen gas flowing into the reactor was F (flow rate at 25°C and 0.1013 MPa), the contact time expressed as W / F was 3 g·sec / cc, and the temperature when CFC-113 and hydrogen passed through the catalyst (reaction temperature, i.e., temperature inside the reactor) was 300°C. As a result, HFC-143 was obtained, with a conversion rate of 100% and a selectivity for HFC-143 of 87%. The selectivity for useful compounds, including intermediates that can be converted to HFC-143, was 91.3%. The catalyst life under these conditions was about 952 hours, and about 9.5 months when W / F was 12.

[0098] (Example 16) A reactor with an inner diameter of 0.97 cm and a length of 55 cm was prepared, and 1.76 g of a catalyst in which palladium (Pd) was supported at 2.0 mass% on activated carbon was filled in the reactor. CFC-113 with a moisture content of 41.8 mass ppm and hydrogen were supplied into the reactor from the raw material supply port of the reactor and passed through the catalyst to carry out a reduction reaction. In this reduction reaction, CFC-113 was supplied in a gaseous state at a flow rate of 0.7 ml / min, and hydrogen gas was supplied so that the molar ratio of hydrogen:CFC-113 was 51:1 (i.e., the hydrogen / CFC-113 molar ratio was 51). In the above reduction reaction, the catalyst loading in the reactor was W (g), the total flow rate of CFC-113 and hydrogen gas flowing into the reactor was F (flow rate at 25°C and 0.1013 MPa), the contact time expressed as W / F was 3 g·sec / cc, and the temperature when CFC-113 and hydrogen passed through the catalyst (reaction temperature, i.e., temperature inside the reactor) was 300°C. As a result, HFC-143 was obtained, with a conversion rate of 100% and a selectivity for HFC-143 of 83%. The selectivity for useful compounds, including intermediates that can be converted to HFC-143, was 86.1%. The catalyst life under these conditions was about 1120 hours, and about 11.2 months when W / F was 12.

[0099] (Example 17) A reactor with an inner diameter of 0.97 cm and a length of 55 cm was prepared, and 1.42 g of a catalyst in which palladium (Pd) was supported at 2.0 mass% on activated carbon was filled in the reactor. CFC-113 with a moisture content of 510 mass ppm and hydrogen were supplied into the reactor from the raw material supply port of the reactor and passed through the catalyst to carry out a reduction reaction. In this reduction reaction, CFC-113 was supplied in a gaseous state at a flow rate of 4.1 ml / min, and hydrogen gas was supplied so that the molar ratio of hydrogen:CFC-113 was 10:1 (i.e., the hydrogen / CFC-113 molar ratio was 10). In the above reduction reaction, the catalyst loading in the reactor was W (g), the total flow rate of CFC-113 and hydrogen gas flowing into the reactor was F (flow rate at 25°C and 0.1013 MPa), the contact time expressed as W / F was 1.72 g·sec / cc, and the temperature when CFC-113 and hydrogen passed through the catalyst (reaction temperature, i.e., temperature inside the reactor) was 175°C. As a result, HFC-143 was obtained, with a conversion rate of 85% and a selectivity for HFC-143 of 50%. The selectivity for useful compounds, including intermediates that can be converted to HFC-143, was 86%. The catalyst life under these conditions was about 540 hours, and about 5.2 months when W / F was 12.

[0100] (Example 18) A reactor with an inner diameter of 0.97 cm and a length of 55 cm was prepared, and 1.42 g of a catalyst in which palladium (Pd) was supported at 2.0 mass% on activated carbon was filled in the reactor. CFC-113 with a moisture content of 173 mass ppm and hydrogen were supplied into the reactor from the raw material supply port of the reactor and passed through the catalyst to carry out a reduction reaction. In this reduction reaction, CFC-113 was supplied in a gaseous state at a flow rate of 4.1 ml / min, and hydrogen gas was supplied so that the molar ratio of hydrogen:CFC-113 was 10:1 (i.e., the hydrogen / CFC-113 molar ratio was 10). In the above reduction reaction, the catalyst loading in the reactor was W (g), the total flow rate of CFC-113 and hydrogen gas flowing into the reactor was F (flow rate at 25°C and 0.1013 MPa), the contact time expressed as W / F was 1.72 g·sec / cc, and the temperature when CFC-113 and hydrogen passed through the catalyst (reaction temperature, i.e., temperature inside the reactor) was 175°C. As a result, HFC-143 was obtained, with a conversion rate of 99.9% and a selectivity for HFC-143 of 57.5%. The selectivity for useful compounds, including intermediates that can be converted to HFC-143, was 89.1%. The catalyst life under these conditions was about 455 hours, and about 4.4 months when W / F was 12.

[0101] (Example 19) A reactor with an inner diameter of 0.97 cm and a length of 55 cm was prepared, and 1.46 g of a catalyst in which palladium (Pd) was supported at 2.0 mass% on activated carbon was filled in the reactor. The pressure inside the reactor tube was adjusted to 0.20 MPaG, and CFC-113 with a moisture content of 173 mass ppm and hydrogen were supplied into the reactor from the raw material supply port of the reactor and passed through the catalyst to carry out a reduction reaction. In this reduction reaction, CFC-113 was supplied in a gaseous state at a flow rate of 4.7 ml / min, and hydrogen gas was supplied so that the molar ratio of hydrogen:CFC-113 was 10:1 (i.e., the hydrogen / CFC-113 molar ratio was 10). In the above reduction reaction, the catalyst loading in the reactor was W (g), the total flow rate of CFC-113 and hydrogen gas flowing into the reactor was F (flow rate at 25°C and 0.1013 MPa), the contact time expressed as W / F was 1.70 g·sec / cc, and the temperature when CFC-113 and hydrogen passed through the catalyst (reaction temperature, i.e., temperature inside the reactor) was 175°C. As a result, HFC-143 was obtained, with a conversion rate of 99.9% and a selectivity for HFC-143 of 50.9%. The selectivity for useful compounds, including intermediates that can be converted to HFC-143, was 89.8%. The catalyst life under these conditions was about 569 hours, and about 5.6 months when W / F was 12.

Claims

1. The process includes a step A of subjecting a chlorofluoroethane compound to a reduction reaction in the presence of a catalyst and hydrogen to obtain a product containing a fluoroethane compound, The method for producing a fluoroethane compound, wherein the catalyst is at least one metal selected from the group consisting of Ni, Pd, Pt, Ru and Rh supported on activated carbon.

2. The fluoroethane compound includes 1,1,2-trifluoroethane, The method according to claim 1, wherein the chlorofluoroethane compound comprises 1,1,2-trichloro-1,2,2-trifluoroethane.

3. The fluoroethane compound includes 1,1,2-trifluoroethane, The method according to claim 1, wherein the chlorofluoroethane compound comprises 1-chloro-1,1,2-trifluoroethane.

4. The fluoroethane compound includes 1,1-difluoroethane, The method according to claim 1, wherein the chlorofluoroethane compound comprises 1-chloro-1,1,2-trifluoroethane.

5. The method according to claim 2, wherein the product contains a by-product selected from the group consisting of chlorotrifluoroethylene and trifluoroethylene.

6. The method according to claim 2, further comprising a step of obtaining the 1,1,2-trichloro-1,2,2-trifluoroethane by a liquid phase fluorination reaction of tetrachloroethylene.

7. A method for producing a fluoroolefin, comprising the steps of: Obtaining a fluoroethane compound by the process according to any one of claims 1 to 6; obtaining said fluoroolefin by dehydrofluorination of the fluoroethane compound obtained in said step; A method for producing a fluoroolefin, comprising:

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