JP5780007B2 - Method for producing fluorine-containing propene - Google Patents

Description

The present invention relates to a method for producing a fluorine-containing propene represented by the general formula: CF ₃ CH═CHZ (Z is Cl or F).

1,3,3,3-Tetrafluoropropene represented by the chemical formula: CF ₃ CH═CHF (HFC-1234ze) is a useful compound as a propellant and a refrigerant. It has attracted attention as a component of mixed refrigerant.

As a method for producing HFC-1234ze, a method of de-HXing a compound represented by the general formula: CF ₃ CH ₂ CHFX (X is F, Cl, Br or I) (see Patent Documents 1 to 5, etc.) , chemical _{formula: CF 3 CHFCH 2 F (HFC} -245eb) by a method of the compound is de-HF represented (see Patent Document 6-7), the formula: CF ₃ CH = compound represented by CHCl (HCFC-1233zd) and A method of fluorination (Patent Document 8), a method of de-HXing a compound represented by the general formula: CF ₃ CHXCH ₂ F (X is Cl, Br or I) (Patent Document 9) and the like are known. . However, these methods have problems such as difficulty in the production of raw materials and difficulty in obtaining them, low yields, and multi-step processes, and improvements are required as industrial production methods. .

For example, Patent Document 1 describes a process for producing HFC-1234ze by de-HX reaction of a compound represented by CF ₃ CH ₂ CHFX (X is F, Cl, Br or I). As a method for producing a compound represented by the general formula: CF ₃ CH ₂ CHFX used as a raw material in the process, in the presence of a catalyst such as Cr ₂ O ₃ , CY ₃ CH ₂ CHY ₂ (Y is F, Cl, Br Or a compound represented by formula (I) is reacted with HF. However, to obtain 1,3,3,3-tetrafluoropropene by this method, a compound represented by CY ₃ CH ₂ CHY ₂ (Y is F, Cl, Br or I) is reacted with HF. The two steps of the step of removing and the step of removing HX are necessary, and the reaction step is complicated. Regarding the method for producing the compound represented by CF ₃ CH ₂ CHFX, which is an intermediate component of the reaction, in addition to the above method, CF ₃ X (X is Cl, Br or I) and vinyl fluoride are reacted. However, since this method uses an expensive compound called CF ₃ X, it is not an industrially effective production method.

On the other hand, 1-chloro-3,3,3-trifluoropropene (HCFC-1233zd) represented by the chemical formula: CF ₃ CH═CHCl is a compound useful as an intermediate for producing various fluorocarbons. It is also useful as a monomer component in various polymers.

  As a method for producing HCFC-1233zd, Non-Patent Documents 1, 2 and the like react 1,1,1,3,3-pentachloropropane (HCC-240fa) with HF in the presence of antimony halide in a liquid phase. A method is described. However, the material of the reactor that can be used under the reaction conditions of this method is limited, and generally an expensive corrosion-resistant material is required. Moreover, even if such an expensive corrosion resistant material is used, the corrosion resistance is not sufficient and frequent maintenance is required. Furthermore, the catalyst deteriorates due to moisture contained in the raw material, and it is necessary to regenerate it.

  Patent Document 10 describes a method in which 1,1,1,3,3-pentachloropropane (HCC-240fa) and HF are reacted in the liquid phase without a catalyst. This method can be carried out at a high temperature of 180 ° C. or higher (preferably 200 to 300 ° C.) under a pressure sufficient to allow HF or a product to exist as a liquid phase. 6 to 15 MPa) is a preferable pressure. As described above, this method requires a reaction under extremely high pressure and harsh conditions in which the HF or the product is in a liquid phase, and handling and safety in handling a large amount of HF in a liquid state. It also has the above issues. Moreover, since the reaction rate is slow and it takes a long time to obtain the desired product with a sufficient yield, it is unsuitable as a production method on an industrial scale.

  As another method for producing HCFC-1233zd, Patent Documents 11, 12, etc. describe a method of reacting 1,1,1,3,3-pentachloropropane (HCC-240fa) with HF in the presence of a catalyst in the gas phase. Has been. However, in this method, since the deterioration of the catalyst proceeds, it is necessary to frequently regenerate the catalyst and replace the catalyst, and it is necessary to improve the industrial production method.

US 2005/0245773 A1 US 2008/051611 A1 EP 2000/974571 A2 JP 11/140002 A US 2007/0129579 A1 WO 2008/002499 A2 WO 2008/002500 A1 JP 2007/320896 A WO 2005/108334 A1 JP 1999/180908 A JP 1998/67693 A JP 1997/194404 A

Journal of Fluorine Chemistry, 128 (3), 190-195; 2007 Journal of Molecular Catalysis A: Chemical, 233 (1-2), 99-104; 2005

The present invention has been made in view of the above-mentioned problems of the prior art, and its main object is a simple and efficient general formula: CF ₃ CH═CHZ (formula Wherein Z is Cl or F.).

The present inventor has intensively studied to achieve the above-described object. As a result, according to the method of using a chlorine-containing compound represented by a specific general formula as a raw material and reacting it with hydrogen fluoride in the absence of a catalyst in the gas phase under heating, surprisingly, Production of a fluorinated propene represented by the general formula CF ₃ CH═CHZ (wherein Z is Cl or F) in a relatively short reaction time and in a high yield by a one-step reaction operation. I found out that I can do it. Then, according to this method, it has been found that it is possible to eliminate the drawbacks in the conventional method for producing fluorine-containing propene, and to efficiently produce fluorine-containing propene on an industrial scale, and the present invention is provided here. It came to be completed.

That is, this invention provides the manufacturing method of the following fluorine-containing propene.
1. In the absence of a catalyst, 1,1,1,3-tetrachloro-3-fluoropropane and hydrogen fluoride are reacted in the gas phase under heating, general formula (4): A method for producing a fluorinated propene represented by CF3CH = CHZ (wherein Z is Cl or F).
2 . 2. The method for producing a fluorinated propene according to item 1 , wherein the reaction is performed at 250 to 500 ° C. using 3 mol or more of hydrogen fluoride per mol of 1,1,1,3-tetrachloro-3-fluoropropane. .
3 . According to the method of the above item 1 or 2 , the general formula (4): CF3CH = CHZ (wherein Z is Cl
Or F. And a step of reusing 1,1,1,3-tetrachloro-3-fluoropropane as a raw material compound contained in the reaction product after the production of the fluorine-containing propene containing the compound represented by A method for producing fluorine propene.

  Hereinafter, the production method of the present invention will be specifically described.

Raw Material Compound In the present invention, the raw material compound is represented by the general formula (1): CClX ₂ CH ₂ CHClY (wherein each X is the same or different and Cl or F and Y is Cl or F). A chlorine-containing propane represented by the general formula (2): CClX ₂ CH═CHY (wherein each X is the same or different and Cl or F and Y is Cl or F). Chlorine propene and a chlorine-containing propene represented by the general formula (3): CX ₂ = CHCHClY (wherein each X is the same or different and Cl or F and Y is Cl or F) At least one chlorine-containing compound selected from the group is used. These chlorine-containing compounds are all known compounds and can be easily obtained by known methods.

In particular, the chlorine-containing propane represented by the general formula (1): CClX ₂ CH ₂ CHClY (wherein each X is the same or different and is Cl or F and Y is Cl or F), Examples of compounds that are readily available include 1,1,1,3-tetrachloro-3-fluoropropane (HCFC-241fb), 1,1,1,3,3-pentachloropropane (HCC-240fa ) And the like.

  1,1,1,3-Tetrachloro-3-fluoropropane (HCFC-241fb) and 1,1,1,3,3-pentachloropropane (HCC-240fa) are, for example, carbon tetrachloride and fluoride. It can be easily obtained under the same conditions by a reaction with vinyl or a reaction between carbon tetrachloride and vinyl chloride.

  Among these, the reaction of carbon tetrachloride and vinyl fluoride to obtain 1,1,1,3-tetrachloro-3-fluoropropane (HCFC-241fb) is, for example, the group consisting of metals and metal halides. In the presence of at least one component selected from the above, a nonpolar solvent inert to the reaction, for example, a solvent such as methylene chloride or carbon disulfide can be used as necessary. In this method, copper, iron, manganese or the like can be used as the metal, and aluminum chloride, cuprous chloride, cupric chloride, ferric chloride, manganese chloride, or the like can be used as the metal halide. . A metal and a metal halide can be used individually by 1 type or in mixture of 2 or more types.

  Further, in the reaction of carbon tetrachloride and vinyl fluoride, a compound containing pentavalent phosphorus as a reaction accelerator, for example, trimethyl phosphate, trimethyl phosphine, triethyl phosphate, triethyl phosphine, tributyl is used as necessary. A phosphate or the like can be used.

  In the above reaction, the amount of vinyl fluoride used may be about 0.1 to 10 moles per mole of carbon tetrachloride.

  The amount of at least one component selected from the group consisting of metals and metal halides may be about 0.001 to 2 moles per mole of carbon tetrachloride.

  Moreover, the usage-amount of the compound containing pentavalent phosphorus used as a reaction accelerator should just be about 0.1-10 mol with respect to 1 mol of total amounts of the added metal and metal halide.

  The reaction temperature for the reaction between carbon tetrachloride and vinyl fluoride is usually about room temperature to 150 ° C, preferably about 80 to 120 ° C.

  The reaction pressure may be any of normal pressure, pressurization, and reduced pressure, but can usually be performed under pressure in a sealed container.

  1,1,1,3,3-Pentachloropropane (HCC-240fa) can also be produced in the same manner as 1,1,1,3-tetrachloro-3-fluoropropane (HCFC-241fb).

  In these methods, carbon tetrachloride, vinyl fluoride, and vinyl chloride as raw materials are all relatively inexpensive materials, and the manufacturing method is simple. Therefore, HCFC-241fb and HCC as raw materials in the method of the present invention are used. -240fa is available cheaply.

  Furthermore, 1,1,1,3,3-pentachloropropane (HCC-240fa) is, for example, Journal of Molecular Catalysis, 77, 51-60; 1992, US 2001/6313360 B1, US 2004/6720466 B2, US 2008 / 0091053 It can also be easily produced by the method described in A1 and the like.

Production method of the present invention In the production method of the fluorinated propene of the present invention, in the absence of a catalyst, the above general formula (1): CClX ₂ CH ₂ CHClY (wherein each X is the same or different is Cl or F, Y is Cl or F.) Chlorinated propane represented by the general formula (2): CClX ₂ CH = CHY (wherein each X is the same or different and Cl or F, Y is Cl or F.) and a general formula (3): CX ₂ = CHCHClY (wherein each X is the same or different and Cl or F and Y is Cl or F.) At least one chlorine-containing compound selected from the group consisting of chlorine-containing propenes represented by the following formula may be reacted with anhydrous hydrogen fluoride in a gas phase state under heating. Thereby, the fluorine-containing propene represented by the general formula (4): CF ₃ CH═CHZ (wherein Z is Cl or F) can be produced.

As described above, the raw material compound used in the above method is an inexpensive substance. In particular, the chlorine-containing propane represented by the general formula (1) is an easily available and inexpensive compound. Therefore, according to the method of the present invention, both a fluorination reaction and a dehydrohalogenation reaction can be efficiently advanced by a substantially one-step reaction using an inexpensive raw material, and the general formula (4) : A fluorine-containing propene represented by CF ₃ CH═CHZ (wherein Z is Cl or F) can be obtained in high yield. Moreover, the method of the present invention is a production method utilizing a gas phase reaction suitable for continuous production. For this reason, the method of the present invention is a highly industrially useful method.

  In the method of the present invention, the target fluorine-containing propene is produced in a substantially one-step reaction without using a catalyst by reacting in the gas phase state under heating using the above-mentioned specific raw materials. It is possible to do. This eliminates the disadvantages of the conventional method for producing fluorine-containing propene.

  In the production method of the present invention, it is important to react the raw material compound and hydrogen fluoride in a gas phase state. In this case, it is only necessary that the raw material compound and hydrogen fluoride can be brought into contact with each other in a gas state in a reaction temperature region described later, and the raw material compound may be in a liquid state when the raw material compound is supplied. For example, when the raw material compound is liquid at room temperature and normal pressure, the raw material compound is vaporized using a vaporizer (vaporization region), then passed through the preheating region and supplied to the mixing region where it is brought into contact with anhydrous hydrogen fluoride. By doing so, the reaction can be performed in a gas phase state. In the mixing region, fillers (beads, plates, flakes, etc.) may be present from the viewpoints of mixing of source gases, improving heat transfer, and uniforming the temperature distribution in the reaction tube. This filler is preferably made of a material having good thermal conductivity and stable against hydrogen fluoride, for example, a Ni-based material such as nickel, hastelloy, or inconel. Alternatively, the raw material compound may be supplied to the reaction apparatus in a liquid state and vaporized and reacted when reaching the reaction region with hydrogen fluoride. The method for vaporizing the raw material compound in the reaction region is not particularly limited, but the region containing the above-described packing is heated to a temperature higher than the vaporization temperature of the raw material compound, and the raw material compound in a liquid state is supplied to the region. The raw material compound may be vaporized to form a gas phase.

Hydrogen fluoride is usually supplied to the reactor in a gas phase together with the raw material compound. The supply amount of hydrogen fluoride is usually about 3 mol or more with respect to 1 mol of the above-described raw material compound (chlorine-containing compound). , More preferably in the range of about 5 to 30 mol. By setting the amount in such a range, the conversion rate of the raw material compound and the fluorine-containing propene represented by the general formula (4): CF ₃ CH═CZ (wherein Z is Cl or F) Both selectivities can be kept within a good range.

  The raw materials described above may be supplied to the reactor as they are, or may be supplied after being diluted with an inert gas such as nitrogen, helium, or argon.

  The form of the reactor used in the method of the present invention is not particularly limited.For example, it is an adiabatic reactor for an empty column or for improving the gas phase mixing state of hydrogen fluoride and a starting material (porous or An adiabatic reactor filled with metal or medium may be used (although it may not be porous). Also, a multi-tube reactor or the like in which the heat distribution is made uniform by using a heat medium and the temperature distribution in the reactor is made uniform can be used. As the reactor, it is preferable to use a reactor made of a material that is resistant to the corrosive action of hydrogen fluoride, such as HASTELLOY, INCONEL, MONEL, and INCOLLOY. .

In the method of the present invention, the reaction temperature is suitably about 250 to 600 ° C., more preferably about 300 to 500 ° C. as the temperature in the reactor. When the temperature is higher than this temperature range, the selectivity of the fluorinated propene represented by the general formula (4): CF ₃ CH═CHZ (wherein Z is Cl or F) decreases, and at a lower temperature, the raw material compound Since the conversion rate of is reduced, neither is preferable. If the reaction is performed at a temperature higher than 500 ° C, corrosion of the reactor is likely to proceed, and carbides may be generated and adhere to and accumulate on the reaction tube wall and filler. In such cases, it is possible to entrain oxygen in the reaction system, or to temporarily remove the carbides remaining in the reaction tube by stopping the reaction and circulating oxygen or air. it can.

  The pressure during the reaction is not particularly limited as long as the above-described raw material compound and hydrogen fluoride can exist in a gas phase state, and may be any of normal pressure, pressurized pressure and reduced pressure. That is, the production method of the present invention can be carried out under reduced pressure or atmospheric pressure (0.1 MPa), and can also be carried out under a pressure that does not cause the raw material to be in a liquid state.

  Thus, in the method of the present invention, the reaction under high pressure is unnecessary, and the reaction can usually be performed under atmospheric pressure or a relatively low pressure up to about 2 MPa. For this reason, the method of the present invention is an industrially very advantageous method in that the reaction can be performed under mild conditions. In addition, for the product obtained by the method of the present invention, in the case where hydrogen fluoride and the like are subsequently separated by liquid separation treatment, in consideration of the efficiency of the liquid separation operation, a pressure condition slightly higher than atmospheric pressure, for example, The reaction is preferably performed under a pressure of about 0.2 to 1 MPa.

  Although there is no particular limitation on the reaction time, generally, the total flow rate Fo (0 ° C., 0) The flow rate at 0.1 MPa: cc / sec): The contact time represented by V / Fo may be in the range of 0.1 to 100 sec, preferably about 1 to 50 sec.

  In the method of improving heat transfer efficiency using a reaction tube having a small inner diameter, for example, the relationship between the flow rate of the raw material and the inner diameter of the reaction tube is preferably such that the linear velocity is large and the heat transfer area is large. .

  Further, when introducing a packing material, for example, hastelloy pieces, nickel beads or the like may be used as materials satisfying the above-described conditions, and these materials may be charged into the reaction tube. The shape of the material to be filled is not particularly limited, and may be any shape that can uniformly fill the reaction tube such as powder or pellets according to the shape of the reaction tube.

Reaction Product According to the reaction conditions described above, at the outlet of the reactor, a reaction containing a fluorine-containing propene represented by the general formula (4): CF ₃ CH═CHZ (wherein Z is Cl or F) A product can be obtained.

As the fluorine-containing propene represented by the general formula (4) obtained by this method: CF ₃ CH═CHZ (wherein Z is Cl or F), the general formula (1) or (3) when using the compounds, usually, CF ₃ CH = in CHF (HFC-1234ze) represented by 1,3,3,3 and _{CF 3 CH = CHCl (HCFC-} 1233zd) Both of the represented 1-chloro-3,3,3-trifluoropropenes are obtained. In addition, when the compound of the general formula (2) is used as a raw material compound, when Y is F, 1,3,3,3-tetra represented by CF ₃ CH═CHF (HFC-1234ze) Although tetrafluoropropene is obtained, when Y is Cl _{are, CF 3 CH = CHF (HFC} -1234ze) represented by 1,3,3,3 and _{CF 3 CH = CHCl (HCFC-} 1233zd Both 1-chloro-3,3,3-trifluoropropene represented by Incidentally, as 1,3,3,3-tetrafluoropropene represented by CF ₃ CH═CHF (HFC-1234ze), E-form (bp.−19 ° C.) and Z-form (bp. + 9) are usually used. Both 1-chloro-3,3,3-trifluoropropene represented by CF ₃ CH═CHCl (HCFC-1233zd) and E-form (bp. + 17 ° C.) and Z- Both bodies (bp. + 44 ° C) are obtained.

_{CF 3 CH = CHF (HFC-} 1234ze) represented by 1,3,3,3 and _{CF 3 CH = CHCl (HCFC-} 1233zd) represented by 1-chloro-3,3,3 The production ratio of trifluoropropene varies depending on the reaction conditions and the like, but usually the production amount of 1-chloro-3,3,3-trifluoropropene increases.

  The product obtained by the above-mentioned method may be used for the intended use as a mixture, or may be purified by distillation or the like, separated and recovered, and used for the intended use. It can also be converted to a compound.

In the production method of the present invention, in the reaction product, other than the fluorine-containing propene represented by the target general formula (4): CF ₃ CH═CHZ (wherein Z is Cl or F). A chlorine-containing propane represented by the general formula (1): CClX ₂ CH ₂ CHClY (wherein each X is the same or different and Cl or F and Y is Cl or F), A chlorine-containing propene represented by the formula (2): CClX ₂ CH═CHY (wherein each X is the same or different and is Cl or F and Y is Cl or F), 3): Chlorine-containing propene represented by CX ₂ = CHCHClY (wherein each X is the same or different and Cl or F and Y is Cl or F) may be contained. . These compounds contain a target represented by the general formula (4): CF ₃ CH═CHZ (wherein Z is Cl or F), depending on the type of raw materials used and reaction conditions. It occurs as a precursor of fluorine propene, and any of them can be used as a raw material for the production method of the present invention.

In the production method of the present invention, these precursors and unreacted raw materials contained in the reaction product, that is, the general formula (1): CClX ₂ CH ₂ CHClY (wherein each X is the same or different). , Cl or F, and Y is Cl or F.) General formula (2): CClX ₂ CH = CHY (wherein each X is the same or different, Cl or F and Y is Cl or F.) and a general formula (3): CX ₂ = CHCHClY (wherein each X is the same or different, Cl or F And Y is Cl or F.) For a chlorine-containing compound selected from the group consisting of chlorine-containing propenes represented by the following general formula (4): CF ₃ CH═CHZ (wherein Z is Cl or F.) After separating and recovering the fluorine-containing propene represented by the following formula, it can be returned to the reactor again and recycled to be reused as a raw material compound. Thus, by recycling the precursor of the target product and the unreacted raw material, high productivity can be maintained even when the raw material conversion rate is low.

  According to the method of the present invention, a target fluorine-containing compound can be obtained by a substantially one-step reaction using a simple reaction apparatus using a specific chlorine-containing compound, which is an easily available compound, and hydrogen fluoride as raw materials. Propene can be obtained.

  Further, the production method of the present invention can be carried out under mild conditions such as normal pressure and reduced pressure, and is a production method utilizing a gas phase reaction suitable for continuous production. Furthermore, in the method of the present invention, since the reaction is carried out in the gas phase, it is possible to eliminate problems in terms of safety and operation, such as when handling HF in a liquid state.

For this reason, the method of the present invention is industrially very advantageous as a method for producing a fluorinated propene represented by the general formula (4): CF ₃ CH═CHZ (wherein Z is Cl or F). Can be said.

Schematic of the reactor used in Examples 1-6.

  Hereinafter, the present invention will be described in more detail with reference to production examples of 1,1,1,3-tetrachloro-3-fluoropropane (HCFC-241fb) used as a raw material and examples of the present invention.

Production Example 1
1,1,1,3-Tetrachloro-3-fluoropropane (HCFC-241fb) synthesis thermometer, vacuum line, nitrogen purge line, preparation line, gauge and pressure relief valve installed in a 1000ml autoclave with soft iron powder 4 .5 g (79.2 mmol), triethyl phosphate 20 g (79.2 mmol), ferric chloride 100 mg, and carbon tetrachloride 420 g (2.73 mol) were charged and purged 5 times with nitrogen and once with vinyl fluoride. . Next, the inside of the autoclave was evacuated and charged with vinyl fluoride until the gauge pressure became 0.4 MPa while stirring. The reaction started when heated to 120 ° C., the internal temperature increased to 127 ° C., and the pressure decreased from 0.9 MPa to 0.4 MPa. While maintaining the pressure of vinyl fluoride at 0.8 MPa, the mixture was stirred at an internal temperature of 120 ° C. for 8 hours. Thereafter, 10 g (39.6 mmol) of triethyl phosphate was injected and further reacted at 120 ° C. for 10 hours.

  After completion of the reaction, the crude product was analyzed by gas chromatography to confirm that carbon tetrachloride was completely consumed. HCFC-241fb with a gas chromatographic purity of 88.9% was obtained by washing twice with water 3 times the amount of the crude product and drying the organic layer over magnesium sulfate. The by-products were ethylene and vinyl fluoride oligomer. The obtained crude product was distilled under reduced pressure (10 mmHg) to collect a fraction of 63 to 65 ° C., thereby obtaining 467 g (2.35 mol, yield 86%) of HCFC-241fb having a purity of 99% or more. .

Example 1
Fluorination of 1,1,1,3-tetrachloro-3-fluoropropane (HCFC-241fb)
A schematic diagram of the reactor used in this example is shown in FIG. This equipment is a line that preheats and supplies anhydrous hydrogen fluoride (HF) in a gas phase, a raw material compound vaporizer and a preheating line, and a mixture that mixes anhydrous hydrogen fluoride (HF) and a raw material compound in a gas phase. And a preheating line for heating up to the reactor inlet after mixing of anhydrous hydrogen fluoride (HF) and the raw material compound.

As the reaction tube, an Inconel 600 tube with an outer diameter of 1/4 inch (thickness 1.0 mm) and a length of 200 cm was used. All the reaction tubes were placed inside the muffle furnace so that the reaction temperature was almost uniform. installed. Nothing was filled in the reaction tube, and it was used as an empty cylinder. A tube made of Hastelloy 22 (outer diameter 1/8 inch) was used for the connection between the reaction tube and the mixing section and a reaction outlet line from the reaction tube, and a joint made of Inconel 600 was used for joining. The volume in the reaction tube was 29.4 cm ³ , and this was defined as the reaction volume (V). Since the volume of the connection part other than the reaction tube in the muffle furnace is small, the reaction volume is not considered, and the following examples are also the same.

  Maintain the atmospheric pressure (0.1MPa) and the temperature in the muffle furnace at 400 ℃ in this reactor, and dry air (nitrogen: oxygen = 79: 21) at 100 cc / min (0 ℃, 0.1 MPa) The flow rate was continuously supplied to the reactor and maintained for 10 hours, and then the temperature in the muffle furnace was lowered to room temperature. After that, the supply of dry air was stopped and the temperature in the muffle furnace was maintained at 400 ° C while continuously supplying nitrogen to the reactor at 100 cc / min (flow rate at 0 ° C, 0.1 MPa) for 2 hours. I let you. Thereafter, the supply of nitrogen was stopped and anhydrous hydrogen fluoride (HF) was continuously supplied to the reactor at 140 cc / min (flow rate at 0 ° C. and 0.1 MPa) and maintained for 2 hours. 1,3-tetrachloro-3-fluoropropane (HCFC-241fb, purity 99.4%) was continuously supplied at 7.0 cc / min (flow rate at 0 ° C., 0.1 MPa) in the gas phase to start the reaction. .

The reaction pressure at the time of continuing the reaction was 0.007 MPa (gauge pressure). When the reaction was continued, nitrogen (N ₂ ) was supplied from the outlet side of the reactor at 60 cc / min (flow rate at 0 ° C., 0.1 MPa) and extracted together with the reaction product. The outer wall temperature of the reaction tube was measured at a regular interval of 5 points from the reactor inlet side to the outlet side, and the average temperature was taken as the reaction temperature. In the following examples, the reaction temperature was determined by performing the same measurement.

The molar ratio of HF to 1,1,1,3-tetrachloro-3-fluoropropane (HF / 1,1,1,3-tetrachloro-3-fluoropropane) was 20. The residence time (V / F ₀ ) was V / F ₀ = 12.1 sec based on the reaction volume (V) and the total flow rate (F ₀ ) of the gas supplied to the reactor. In the following examples, the residence time (V / F ₀ ) was calculated based on the same concept.

  The reactor outlet effluent 3 hours after the start of the reaction was analyzed using a gas chromatograph.

  Among the reaction products, high-boiling products having a boiling point of 50 ° C. or higher were quantified by the method described below. That is, HCFC-225 (225ca: 225cb = 43: 57) in which a predetermined amount of perchlorethylene was dissolved as an internal standard substance and ice water were mixed and separated into liquids, and the reactor outlet component was kept for a certain period of time. The organic matter was extracted with the HCFC-225 layer, and the acid content of hydrogen fluoride and hydrogen chloride was dissolved in ice water. The extract was heated to 20 ° C., and the HCFC-225 layer was analyzed by gas chromatography (FID). DB-624 (60m) capillary column is used as the column, and each product is generated by taking into account the coefficient in the gas chromatograph from the detection area ratio between perchlorethylene, which is the internal standard substance, and each product. The amount was converted to a molar ratio.

On the other hand, low boiling point substances having a boiling point of 50 ° C. or less were quantified by the method described below. That is, two washing towers containing water were connected and connected to the outlet of the reactor, immersed in a water bath and preheated to 60 ° C., then the reactor effluent was poured and bubbled to wash the acid content. Thereafter, the dehydrated gas components were collected through a CaCl ₂ tube and analyzed by gas chromatography (FID). At this time, a predetermined amount of HFC-32 was caused to accompany the washing tower from the outlet side of the reactor as an internal standard substance. As the column, a gsgaspro (60m) capillary column was used, and the amount of each product produced, taking into account the coefficient in the gas chromatograph from the detection area ratio between the internal standard substance HFC-32 and each product. Was converted to a molar ratio. In Examples 1 to 6 shown below, all were quantified by this analysis method. Table 1 shows the reaction conditions and analysis results at the time of analysis.

The products in this example are as follows. Of the following five compounds, compounds other than HFC-1234ze and HCFC-1233zd are all precursors thereof, and are considered useful because they can be recycled and used as raw materials.
CF ₃ CH = CHF (HFC-1234ze E body + Z body)
CF ₃ CH = CHCl (HCFC-1233zd E body + Z body)
CF ₃ CH ₂ CHFCl (HCFC-244fa)
CF ₂ ClCH = CHCl (HCFC-1232zd E body + Z body)
CF ₂ ClCH ₂ CHFCl (HCFC-243fb)
The following compounds are regarded as impurities generated by this reaction.
CF ₃ CH ₂ CHF ₂ (HFC-245fa)
CF ₃ CH = CH ₂ (HFC-1243zf).

Example 2
The experiment was performed in the same manner as in Example 1 except that the reaction tube (length: 200 cm) used in Example 1 was used and the reaction temperature was changed to 451 ° C. The molar ratio of HF to 1,1,1,3-tetrachloro-3-fluoropropane (HF / 1,1,1,3-tetrachloro-3-fluoropropane) is 20, and the volume in the reaction tube is 29.4. Since it was cm ³ , the residence time (V / F ₀ ) was 12.1 sec. The reaction pressure at the time of continuing the reaction was 0.008 MPa (gauge pressure).

  The outlet effluent from the reactor 2 hours after the start of the reaction was analyzed using a gas chromatograph. Table 1 shows the reaction conditions and analysis results at the time of analysis.

Example 3
Except for changing the reaction tube length to 250 cm, changing the reaction temperature to 363 ° C, and changing the flow rate of anhydrous hydrogen fluoride (HF) to 105 cc / min (flow rate at 0 ° C, 0.1 MPa) The experiment was performed in the same manner as in Example 1. The molar ratio of HF to 1,1,1,3-tetrachloro-3-fluoropropane (HF / 1,1,1,3-tetrachloro-3-fluoropropane) is 15, and the volume in the reaction tube is 37.1 Since it was cm ³ , the residence time (V / F ₀ ) was 19.9 sec. The reaction pressure at the time of continuing the reaction was 0.008 MPa (gauge pressure).

  The reactor outlet effluent 3 hours after the start of the reaction was analyzed using a gas chromatograph. Table 1 shows the reaction conditions and analysis results at the time of analysis.

Example 4
Fluorination of 1,1,1,3,3-pentachloropropane (HCC-240fa) In the reactor used in Example 1, the reaction tube had an outer diameter of 1/4 inch (thickness: 1.0 mm). , Use a 520 cm long Inconel 600 tube, connect the reaction tube to the mixing section, and use a Hastelloy 22 tube (outer diameter 1/8 inch) for the reaction outlet line from the reaction tube. Used a reactor having the same structure as in Example 1 except that a joint made of Inconel 600 was used. The volume in the reaction tube was 77.2 cm ³ , and this was defined as the reaction volume (V). Since the volume of the connection part other than the reaction tube in the muffle furnace is small, the reaction volume is not considered, and the following examples are also the same.

  Maintain the atmospheric pressure (0.1MPa) and the temperature in the muffle furnace at 400 ℃ in this reactor, and dry air (nitrogen: oxygen = 79: 21) at 100 cc / min (0 ℃, 0.1 MPa) The flow rate was continuously supplied to the reactor and maintained for 10 hours, and then the temperature in the muffle furnace was lowered to room temperature. Thereafter, the supply of dry air was stopped, the temperature in the muffle furnace was maintained at 400 ° C. for 2 hours while continuously supplying nitrogen to the reactor at 100 cc / min, and then the flow rate of nitrogen was 7.0 cc. , continuously supplying anhydrous hydrogen fluoride (HF) to the reactor at 140 cc / min (flow rate at 0 ° C, 0.1 MPa) and maintaining for 2 hours, 1,1,1,3 , 3-pentachloropropane (HCC-240fa, purity 99.8%) was continuously supplied at a gas phase of 7.0 cc / min (flow rate at 0 ° C. and 0.1 MPa) to initiate the reaction.

The reaction pressure at the time of continuing the reaction was 0.010 MPa (gauge pressure). When the reaction was continued, nitrogen (N ₂ ) was supplied from the outlet side of the reactor at 60 cc / min (flow rate at 0 ° C., 0.1 MPa) and extracted together with the reaction product. The outer wall temperature of the reaction tube was measured at a regular interval of 5 points from the reactor inlet side to the outlet side, and the average temperature was taken as the reaction temperature. In the following examples, the reaction temperature was determined by performing the same measurement. The molar ratio of HF to 1,1,1,3,3-pentachloropropane (HF / 1,1,1,3,3-pentachloropropane) was 20. The residence time (V / F ₀ ) was V / F ₀ = 30.1 sec from the reaction volume (V) and the total flow rate (F ₀ ) of the gas supplied to the reactor. In the following examples, the residence time (V / F ₀ ) was calculated based on the same concept.

  The reactor outlet effluent 3 hours after the start of the reaction was analyzed using a gas chromatograph. Table 2 shows the reaction conditions and analysis results at the time of analysis.

The products in this example are as follows. Of the following eight compounds, compounds other than HFC-1234ze and HCFC-1233zd are all precursors thereof, and are considered useful because they can be recycled and used as raw materials.
CF ₃ CH = CHF (HFC-1234ze E body + Z body)
CF ₃ CH = CHCl (HCFC-1233zd E body + Z body)
CF ₂ ClCH = CHCl (HCFC-1232zd)
CHCl ₂ CH = CF ₂ (HCFC-1232zc)
CFCl ₂ CH = CHCl (HCFC-1231zd)
CHCl ₂ CH = CFCl (HCFC-1231zb)
CFCl ₂ CH ₂ CHCl ₂ (HCFC-241fa)
CCl ₂ = CHCHCl ₂ (HCC-1230za)
The following compounds are regarded as impurities generated by this reaction.
CF ₃ CCl = CH ₂ (HCFC-1233xf)
CF ₂ ClCCl = CH ₂ (HCFC-1232xf)
CF ₃ CCl = CHCl (HCFC-1223xd)
CF ₂ ClCCl = CHCl (HCFC-1222xd).

Example 5
The experiment was conducted in the same manner as in Example 4 except that the reaction tube length was changed to 335 cm and the anhydrous hydrogen fluoride (HF) flow rate was changed to 105 cc / min (0 ° C, 0.1 MPa flow rate). It was. The molar ratio of HF to 1,1,1,3,3-pentachloropropane (HF / 1,1,1,3,3-pentachloropropane) is 15, and the volume in the reaction tube is 49.8 cm ³ The residence time (V / F ₀ ) was 25.1 sec. The reaction pressure at the time of continuing the reaction was 0.009 MPa (gauge pressure).

  The reactor outlet effluent 3 hours after the start of the reaction was analyzed using a gas chromatograph. Table 2 shows the reaction conditions and analysis results at the time of analysis.

Example 6
The experiment was performed in the same manner as in Example 5 except that the reaction tube (length 335 cm) used in Example 5 was used and the reaction temperature was changed to 435 ° C. The molar ratio of HF to 1,1,1,3,3-pentachloropropane (HF / 1,1,1,3,3-pentachloropropane) is 15, and the volume in the reaction tube is 49.8 cm ³ The residence time (V / F ₀ ) was 25.1 sec. The reaction pressure at the time of continuing the reaction was 0.009 MPa (gauge pressure).

  The outlet effluent from the reactor 2 hours after the start of the reaction was analyzed using a gas chromatograph. Table 2 shows the reaction conditions and analysis results at the time of analysis.

Claims (3)

In the absence of a catalyst, 1,1,1,3-tetrachloro-3-fluoropropane and hydrogen fluoride are reacted in the gas phase under heating, general formula (4): A method for producing a fluorinated propene represented by CF ₃ CH═CHZ (wherein Z is Cl or F). The method for producing a fluorinated propene according to claim 1, wherein 3 mol or more of hydrogen fluoride is used per 1 mol of 1,1,1,3-tetrachloro-3-fluoropropane , and the reaction is performed at 250 to 500 ° C. . After producing a fluorinated propene containing a compound represented by the general formula (4): CF ₃ CH═CHZ (wherein Z is Cl or F) by the method according to claim 1 or 2 , a reaction product is produced. A method for producing fluorine-containing propene, comprising a step of reusing 1,1,1,3-tetrachloro-3-fluoropropane contained in a product as a raw material compound.

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