WO2014080779A1 - Procédé de production de 2,3,3,3-tétrafluoropropène et de 1,1-difluoroéthylène - Google Patents

Procédé de production de 2,3,3,3-tétrafluoropropène et de 1,1-difluoroéthylène Download PDF

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WO2014080779A1
WO2014080779A1 PCT/JP2013/080324 JP2013080324W WO2014080779A1 WO 2014080779 A1 WO2014080779 A1 WO 2014080779A1 JP 2013080324 W JP2013080324 W JP 2013080324W WO 2014080779 A1 WO2014080779 A1 WO 2014080779A1
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reactor
methane
tfe
raw material
tetrafluoropropene
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Japanese (ja)
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優 竹内
古田　昇二
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旭硝子株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton

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  • the present invention relates to a process for producing 2,3,3,3-tetrafluoropropene and 1,1-difluoroethylene, and in particular, 2,3,3,3-tetrafluoroethylene in a single reaction from a raw material containing methane.
  • the present invention relates to a process for producing fluoropropene and 1,1-difluoroethylene.
  • HFO-1234yf 2,3,3,3-tetrafluoropropene
  • HFC-134a 2-tetrafluoroethane
  • 1,1-dichloro-2,2,3,3,3-pentafluoropropane (HCFC-225ca) is dehydrofluorinated with an alkaline aqueous solution in the presence of a phase transfer catalyst.
  • HCFC-225ca 1,1-dichloro-2,2,3,3,3-pentafluoropropane
  • CFO-1214ya 1,1-dichloro-2,3,3,3-tetrafluoropropene
  • Patent Document 1 a mixture obtained by diluting methane and a hydrochlorocarbon having 2 carbon atoms (for example, 1-chloro-1,2,2,2-tetrafluoroethane) with air is used as a specific metal catalyst such as nickel.
  • a method for producing HFO-1234yf by heating to 600 to 650 ° C. in the presence of benzene is proposed.
  • Non-Patent Document 1 discloses that a mixture obtained by diluting methane and chlorodifluoromethane with nitrogen is subjected to normal heating such as an electric heater in a reactor.
  • a method of obtaining 1,1-difluoroethylene (VdF) industrially useful as a fluororesin raw material by heating and decomposing to a temperature of 400 to 800 ° C. by means is proposed.
  • Patent Document 1 has a problem in that it is necessary to prepare a special metal catalyst, which complicates the process, and that many hydrochlorocarbons that are raw materials are difficult to obtain.
  • Non-Patent Document 1 presents a method for obtaining 1,1-difluoroethylene (VdF) using methane and chlorodifluoromethane, which are easily available.
  • VdF 1,1-difluoroethylene
  • HFO-1234yf is used for the production of HFO-1234yf. It was not reached.
  • the present invention has been made from the above viewpoint, and it is possible to sufficiently control industrially useful HFO-1234yf and VdF in one reaction step involving thermal decomposition, using raw materials that are easily procured. It is an object to provide an economically advantageous process for producing in a state and efficiently.
  • the present invention includes (a) chlorodifluoromethane (R22) and / or tetrafluoroethylene (TFE) and methane, which are mixed in advance or separately supplied to the reactor, and (b) a heat medium. Supplying to the reactor; and (c) bringing the heat medium into contact with the R22 and / or the TFE and the methane in the reactor, and 2,3,3,3-tetrafluoropropene (HFO- 1234yf) and 1,1-difluoroethylene (VdF), A method for producing HFO-1234yf and VdF is provided.
  • HFO-1234yf and VdF are produced by reacting R22 and / or TFE, which can be easily procured, with methane as a raw material without taking out the intermediate product from the reaction system. Can be manufactured efficiently. Therefore, for example, compared with a method of manufacturing HFO-1234yf using HCFC-225ca as a raw material via CFO-1214ya, the cost required for the raw material and manufacturing equipment can be greatly reduced.
  • the production (reaction) conditions can be easily controlled, and thus quantitative HFO-1234yf and VdF can be produced, resulting in great economic merit. Furthermore, it is possible to recycle by-products, which has a great economic effect.
  • the present invention uses, as a raw material, at least one of chlorodifluoromethane (R22) and tetrafluoroethylene (TFE) and methane, and in the presence of a heat medium, by a synthetic reaction involving thermal decomposition, HFO-1234yf and VdF A method of manufacturing the same is provided. And this manufacturing method (A) mixing the R22 and / or the TFE and the methane in advance or separately supplying them to the reactor; (B) supplying a heat medium to the reactor; (C) contacting the heating medium with the R22 and / or the TFE and the methane in the reactor to generate the HFO-1234yf and the VdF.
  • R22 chlorodifluoromethane
  • TFE tetrafluoroethylene
  • the production method of the present invention may be a continuous production method or a batch production method.
  • supply of a raw material containing R22 and / or TFE and methane to a reactor, supply of a heating medium to a reactor, and the reactor of a reaction mixture containing HFO-1234yf and VdF The removal from is performed continuously.
  • either the supply of the raw material in the step (a) or the supply of the heat medium in the step (b) may be earlier or at the same time. That is, when one of the raw material and the heat medium is supplied, even if the other is not supplied into the reactor, the component supplied later is retained during the retention of the previously supplied raw material or the heat medium.
  • the raw material and the heat medium that are supplied may be in contact with each other for a predetermined time in the reactor. From the viewpoint of reducing the possibility of carbonization of the raw material components when starting the raw material supply to the reactor, it is preferable that the heat medium that is also a dilution gas is supplied into the reactor first.
  • the production method of the present invention is preferably a continuous method in terms of production efficiency.
  • an embodiment in which the method of the present invention is applied to continuous production will be described unless otherwise specified as a batch type, but is not limited to a continuous type.
  • HFO-1234yf ⁇ Production reaction of HFO-1234yf>
  • a synthesis reaction involving thermal decomposition and dehydrochlorination shown in the following formula (1) occurs in the reactor, and HFO-1234yf and VdF Produces. Note that when the raw material does not contain both R22 and TFE but contains only one component, the same reaction occurs, and HFO-1234yf and VdF are generated.
  • the raw material containing R22 and / or TFE and methane is thermally decomposed and dehydrochlorinated in the reactor to produce a mixture containing difluorocarbene (F 2 C :) and TFE and methane, which is directly It is considered that it is converted to tetrafluoropropene (particularly HFO-1234yf) or VdF through an addition reaction or through one or more intermediates.
  • these thermal decomposition reactions to the purification reaction of HFO-1234yf and VdF are referred to as synthesis reactions involving thermal decomposition.
  • HFO-1234yf and VdF of the present invention uses at least one of R22 and TFE and methane as raw materials.
  • the raw material is a compound that can be decomposed by contact with a heat medium in the reactor to generate difluorocarbene (F 2 C :), such as hexafluoropropene (hereinafter referred to as HFP).
  • CTFE trifluoroethylene, octafluorocyclobutane (hereinafter referred to as RC318), hexafluoropropene oxide, and the like.
  • fluorine compounds other than R22 and TFE that can be thermally decomposed in a reactor to generate F 2 C: are referred to as “HFP and the like”.
  • the molar ratio of the supply amount of methane, which is one of the raw material components, and the total supply amount of R22 and TFE should be in the range of 0.01 to 10. preferable. A range of 0.2 to 5 is more preferable, and a range of 0.25 to 4 is particularly preferable.
  • methane / (R22 + TFE) By setting methane / (R22 + TFE) to 0.01 to 10, the conversion of methane can be increased and HFO-1234yf can be produced in high yield.
  • the supply amount of the other component is set to 0 (zero), and the supply amount of methane is adjusted so as to be in the above range.
  • the supply amount of each component of the raw material and the heat medium indicates the supply amount per unit time.
  • TFE / (R22 + TFE) The molar ratio between the TFE supply amount and the sum of the R22 and TFE supply amounts (hereinafter referred to as TFE / (R22 + TFE)) can be in the range of 0 to 1, but from the viewpoint of economy and safety Therefore, the range of 0 to 0.8 is more preferable, and the range of 0 to 0.5 is particularly preferable.
  • the temperature of R22 and TFE supplied to the reactor is preferably 0 to 600 ° C. from the viewpoint of making the temperature somewhat reactive but difficult to carbonize.
  • the temperature is preferably 0 to 600 ° C.
  • R22, TFE, HFP, and the like are preferably heated to room temperature (25 ° C.) or higher and 600 ° C. or lower before being introduced into the reactor, and heated to 100 to 500 ° C. Is more preferable.
  • the temperature of methane supplied to the reactor is preferably 0 to 1200 ° C. from the viewpoint of reactivity. From the viewpoint of further increasing the reactivity, methane is preferably heated to normal temperature (25 ° C.) or higher and 1200 ° C. or lower, more preferably 100 to 800 ° C. before being introduced into the reactor.
  • Feeding to the reactor such as R22 and / or TFE as raw material components, methane, and HFP used as necessary may be separate, or may be fed after mixing each component. .
  • groups for example, fluorinated compounds and other components, mix each component in each group, and supply each component separately to the reactor Alternatively, all components may be mixed and then supplied.
  • methane is adjusted to the preferred temperature and supplied to the reactor. It is preferable to supply.
  • the temperature at the time of supplying to the reactor is preferably less than 600 ° C, and particularly preferably less than 500 ° C.
  • R22 and / or TFE since methane reacts only in the presence of R22 and / or TFE, in the case of batch production, after mixing methane and R22 and / or TFE, is the mixed gas supplied to the reactor? Alternatively, it is preferable that R22 and / or TFE is supplied to the reactor before methane is supplied. In the case of such a configuration, the timing of supplying the heat medium to the reactor, which will be described later, is not particularly limited, and after the supply of R22 and / or TFE, before the supply of methane, or after the supply of methane. But you can.
  • the heat medium in the present invention is supplied to the reactor so as to be in contact with the raw material for a certain time in the reactor.
  • the heat medium is a medium that does not undergo thermal decomposition at the temperature in the reactor, and specifically, a medium that does not undergo thermal decomposition at a temperature of 100 to 1200 ° C. is preferable.
  • Examples of the heat medium include one or more gases selected from water vapor, nitrogen, and carbon dioxide, and it is preferable to use a gas that contains 50% by volume or more of water vapor and the balance is nitrogen and / or carbon dioxide.
  • the content ratio of water vapor in the heat medium is preferably 50% by volume or more, and a gas substantially consisting of only water vapor (100% by volume) Use is particularly preferred.
  • the supply amount of the heat medium is preferably 20 to 98% by volume and more preferably 50 to 95% by volume with respect to the total supply amount of the heat medium and the raw material.
  • the temperature of the heat medium supplied to the reactor is preferably 100 to 1200 ° C. from the viewpoint of thermal decomposition and reactivity of raw material components. From the viewpoint of further increasing the reactivity of the raw material components, the temperature of the heat medium introduced into the reactor is more preferably 600 to 900 ° C, and particularly preferably 700 to 900 ° C.
  • the contact time of the heat medium supplied in this manner with the raw material in the reactor is preferably 0.01 to 10 seconds, and more preferably 0.2 to 3.0 seconds. By setting the contact time to 0.01 to 10 seconds, the production reaction of HFO-1234yf and VdF can sufficiently proceed and the production of by-products can be suppressed.
  • the contact time between the heat medium and the raw material corresponds to the residence time of the raw material in the reactor in the continuous production method, and can be controlled by adjusting the supply amount (flow rate) of the raw material to the reactor.
  • the shape of the reactor is not particularly limited as long as it can withstand the temperature and pressure in the reactor described later, and examples thereof include a cylindrical vertical reactor.
  • Examples of the material of the reactor include glass, iron, nickel, or an alloy mainly composed of iron and nickel.
  • the temperature in the reactor in the step (c) is preferably higher than the supply temperature of R22 and / or TFE and methane, which are raw materials supplied to the reactor, and 400 to 1200 ° C.
  • a range of 600 to 900 ° C. is more preferable, and a range of 710 to 900 ° C. is particularly preferable.
  • the temperature in the reactor can be controlled by adjusting the temperature and pressure of the heat medium supplied to the reactor. Further, the inside of the reactor can be supplementarily heated with an electric heater or the like so that the temperature in the reactor falls within a particularly preferable temperature range (710 to 900 ° C.).
  • the pressure in the reactor is preferably 0 to 2 MPa in gauge pressure, and more preferably in the range of 0 to 0.5 MPa.
  • FIG. 1 shows an example of a reaction apparatus used for producing HFO-1234yf and VdF in the present invention.
  • This reaction apparatus 20 has a reactor 1 provided with heating means such as an electric heater.
  • the reactor 1 includes a methane supply line 2 as a first raw material component, an R22 supply line 3 as a second raw material component, a TFE supply line 4 as a third raw material component, and a steam supply line. 5 are connected as shown below. When only one component of R22 and TFE is supplied, the supply line of the other component is not used. Moreover, installation of the heating means in the reactor 1 is not essential.
  • the methane supply line 2, the R22 supply line 3 and the TFE supply line 4 are respectively provided with preheaters (preheaters) 2a, 3a and 4a equipped with electric heaters, etc. After being preheated to a predetermined temperature, it is supplied to the reactor 1.
  • the steam supply line 5 is provided with a superheated steam generator 5a, and the temperature and pressure of the steam supplied are adjusted.
  • installation of the preheater (preheater) 2a, 3a, 4a is not essential.
  • raw material supply lines 2, 3, and 4 may be separately connected to the reactor 1, but as shown in FIG. 2, R22 and TFE in which the raw material supply line 3 and the raw material supply line 4 are connected.
  • a raw material supply line 6 may be connected to the reactor 1. Further, for example, as shown in FIG. 1, after passing through each preheater 3a, 4a, the R22 supply line 3 and the TFE supply line 4 are connected, and the connected R22 and TFE raw material supply line 6 are connected.
  • the methane supply line 2 after passing through the preheater 2a may be further connected. That is, after preheating R22 and TFE are mixed, preheated methane is further mixed with the raw material mixture of R22 and TFE, and all the raw material components are mixed in this way.
  • the steam may be supplied to the reactor 1 after being mixed with some or all of the raw materials, but it is preferable to supply the water vapor to the reactor separately from the raw materials. That is, as shown in FIG. 1, it is preferable that the steam is supplied from the steam supply line 5 to the reactor 1 separately from the raw material mixture.
  • An outlet line 9 provided with a cooling means 8 such as a heat exchanger is connected to the outlet of the reactor 1.
  • a water vapor and acidic liquid recovery tank 10 In the outlet line 9, a water vapor and acidic liquid recovery tank 10, an alkali cleaning device 11 and a dehydration tower 12 are further installed in this order. Then, after dehydration by the dehydration tower 12, each component of the obtained gas is analyzed and quantified by an analyzer such as gas chromatography (GC).
  • GC gas chromatography
  • outlet gas A gas obtained by removing a reaction mixture containing HFO-1234yf and VdF from the reactor 1 and removing acidic substances such as hydrogen chloride, water vapor, and water by the treatment after the outlet line 9 as described above.
  • HFO-1234yf and VdF can be obtained as components of the outlet gas.
  • Compounds other than HFO-1234yf and VdF contained in the outlet gas include R22, methane, ethylene, TFE, HFP, CTFE, trifluoroethylene, RC318, 3,3,3-trifluoropropene (CF 3 CH ⁇ CH 2 : HFO-1243zf) and the like.
  • HFO-1234yf and VdF are compounds derived from R22 and / or TFE, as well as compounds derived from methane.
  • HFP, CTFE, trifluoroethylene, and RC318 are also compounds that can generate a difluorocarbene radical (CF 2 :), and can be recycled as part of the raw material.
  • the global warming potential (GWP) is as small as 4 in a single reaction, and HFO-1234yf useful as a new refrigerant is sufficient.
  • the production method of the present invention can not only reduce the cost required for raw materials and production equipment, but also significantly reduce the energy required for production, compared to the conventional method for producing HFO-1234yf. can do.
  • VdF which is a raw material for polyvinylidene fluoride, which is industrially used as a water treatment filter, for example, can be manufactured. And can be manufactured simultaneously.
  • Example 1 Using the reaction apparatus shown in FIG. 1, crude HFO-1234yf and crude VdF were obtained from a raw material gas composed of R22 and methane as follows.
  • Methane was continuously introduced into a stainless steel tube in an electric furnace set at a furnace temperature of 300 ° C., and the methane was heated to 300 ° C. Moreover, R22 was continuously introduce
  • the amount of raw material components supplied from these raw material gases preheated and adjusted to the above temperature and steam (water vapor) heated by an electric furnace set at a furnace temperature of 850 ° C.
  • Gauge pressure It was supplied to a reactor controlled at 0.04 MPa and an internal temperature of 800 ° C. Hereinafter, all the pressures are assumed to be gauge pressures.
  • the flow rate of the raw material gas (amount supplied per unit time) was controlled so that the residence time of the raw material gas in the reactor was 1.0 second, and the gas of the reaction mixture was taken out from the outlet of the reactor.
  • the actually measured value of the reactor internal temperature was 800 ° C.
  • the actually measured value of the reactor internal pressure was 0.042 MPa.
  • the gas of the reaction mixture taken out from the outlet of the reactor includes unreacted source gas in addition to the gas generated or by-produced by the reaction.
  • the gas of the reaction mixture taken out from the outlet of the reactor is cooled to 100 ° C. or lower, and after performing steam and acidic liquid recovery and alkali washing in order, dehydration treatment is performed, the obtained outlet gas is subjected to gas chromatography. Analysis was performed to calculate the molar composition of the gas component contained in the outlet gas.
  • reaction rate the conversion rate of methane (reaction rate), the selectivity of each component derived from methane, the conversion rate of R22 (reaction rate), and the selection of each component derived from R22
  • reaction rate the conversion rate of methane
  • R22 the conversion rate of R22
  • selection of each component derived from R22 Each rate was determined.
  • Table 1 the preheat temperatures of methane and R22 are set temperatures in each preheat electric furnace, and the water vapor temperature is a set temperature in an electric furnace for water vapor heating.
  • the water vapor pressure is a set pressure.
  • methane conversion rate When the methane yield is X%, (100-X)% is referred to as methane conversion (reaction rate). It means the ratio (mol%) of reacted methane.
  • the methane yield refers to the proportion (mol%) occupied by methane among the methane-derived components (components having a methylene group or methyl group) in the outlet gas.
  • the selectivity of each component derived from methane is the percentage.
  • the selectivity of each component is obtained by “yield of each component derived from methane” / “conversion rate of methane (reaction rate)”.
  • the yield of each component derived from methane refers to the proportion (mol%) of each compound other than methane among the components derived from methane in the outlet gas.
  • R22 conversion rate (reaction rate)
  • the conversion rate (reaction rate) of R22. It means the ratio (mol%) of reacted R22.
  • R22 yield says the ratio (mol%) which R22 accounts among the components derived from R22 (component which has a fluorine atom) in outlet gas.
  • the percentage converted to each component other than R22 is the percentage of each.
  • the selectivity of each component is obtained by “yield of each component derived from R22” / “conversion rate (reaction rate) of R22”.
  • the yield of each component derived from R22 refers to the proportion (mol%) of each compound other than R22 among the components derived from R22 in the outlet gas.
  • Example 2 to 4 The temperature in the reactor was changed as shown in Table 1. Otherwise, the reaction was carried out under the same conditions as in Example 1. Next, the gas taken out from the outlet of the reactor was treated in the same manner as in Example 1 and then analyzed in the same manner. The results are shown in Table 1 together with the reaction conditions.
  • Example 5 to 7 The supply ratio of water vapor to the total gas supply amount was changed as shown in Table 2 by volume% (water vapor / (methane + R22 + water vapor) ⁇ 100). Otherwise, the reaction was carried out under the same conditions as in Example 1. Subsequently, the gas of the reaction mixture taken out from the outlet of the reactor was treated in the same manner as in Example 1, and then analyzed in the same manner. The results are shown in Table 2 together with the reaction conditions.
  • Example 8 to 11 The molar ratio of methane supply to R22 supply (methane / R22) was changed as shown in Table 3. Otherwise, the reaction was carried out under the same conditions as in Example 1. Subsequently, the gas of the reaction mixture taken out from the outlet of the reactor was treated in the same manner as in Example 1 and then analyzed in the same manner. The results are shown in Table 3 together with the reaction conditions.
  • Example 12 to 14 The pressure in the reactor was changed as shown in Table 4. Otherwise, the reaction was carried out under the same conditions as in Example 1. Subsequently, the gas of the reaction mixture taken out from the outlet of the reactor was treated in the same manner as in Example 1, and then analyzed in the same manner. The results are shown in Table 4 together with the reaction conditions.
  • Example 15 to 19 The residence time in the reactor was changed as shown in Table 5. Otherwise, the reaction was performed under the same conditions as in Example 1. Subsequently, the gas of the reaction mixture taken out from the outlet of the reactor was treated in the same manner as in Example 1, and then analyzed in the same manner. The results are shown in Table 5 together with the reaction conditions.
  • Example 20 Using the same reaction apparatus as in Example 1, crude HFO-1234yf and crude VdF were obtained from a raw material gas composed of TFE and methane as shown below.
  • Methane was continuously introduced into a stainless steel tube in an electric furnace set at a furnace temperature of 300 ° C., and the methane was heated to 300 ° C. Moreover, TFE was continuously introduce
  • these raw material gases (methane and TFE) that have been preheated and adjusted to the above temperature and water vapor that has been heated by an electric furnace set at a furnace temperature of 850 ° C. are used as moles of the supply amount of the raw material components.
  • the gauge pressure was supplied to a reactor controlled at 0.04 MPa and an internal temperature of 800 ° C.
  • the flow rate of the source gas (amount supplied per unit time) was controlled so that the residence time of the source gas in the reactor was 1 second, and the gas of the reaction mixture was taken out from the outlet of the reactor.
  • the actually measured value of the reactor internal temperature was 800 ° C.
  • the actually measured value of the reactor internal pressure was 0.042 MPa.
  • the gas of the reaction mixture taken out from the outlet of the reactor was treated in the same manner as in Example 1, and the molar composition of the gas components contained in the outlet gas was calculated in the same manner.
  • the conversion rate of methane reaction rate
  • the selectivity of each component derived from methane the conversion rate of TFE (reaction rate)
  • the selection of each component derived from TFE each rate was determined.
  • the conversion rate (reaction rate) of TFE and the selectivity of each component derived from TFE mean the following.
  • TFE conversion rate (reaction rate)
  • reaction rate When the TFE yield is X%, (100-X)% is referred to as TFE conversion (reaction rate). It means the ratio (mol%) of reacted TFE.
  • the TFE yield refers to the proportion (mol%) occupied by TFE in the TFE-derived component (component having a fluoro group) in the outlet gas.
  • the percentage converted to each component other than TFE is the percentage of each.
  • the selectivity of each component is determined by “yield of each component derived from TFE” / “conversion rate of TFE (reaction rate)”.
  • the yield of each component derived from TFE refers to the ratio (mol%) of each compound other than TFE among the TFE-derived components in the outlet gas.
  • Example 21 Using the same reactor as in Example 1 except that there are three raw material supply lines, crude HFO-1234yf and crude VdF are obtained from the raw material composition comprising R22, methane and TFE as shown below. It was.
  • Methane was continuously introduced into a stainless steel tube in an electric furnace set to a furnace temperature of 300 ° C., and the methane was heated to 300 ° C. (preheating).
  • R22 was continuously introduce
  • TFE was continuously introduced into the stainless steel tube in the electric furnace set to a furnace temperature of 300 ° C., and the TFE was preheated to 300 ° C.
  • the molar ratio of methane to the total of R22 and TFE (methane / (R22 + TFE) is 0.75 as described above, but among the components constituting the raw material composition, as a compound containing fluorine. From the viewpoint of working, since 1 mole of TFE can be counted as 2 equivalents corresponding to 2 moles of R22, the equivalent ratio of methane to the sum of R22 and TFE (methane / (R22 + TFE ⁇ 2) is 0. 5
  • the flow rate of the raw material gas (amount supplied per unit time) was controlled so that the residence time of the raw material gas in the reactor was 1.0 second, and the gas of the reaction mixture was taken out from the outlet of the reactor.
  • the actually measured value of the reactor internal temperature was 800 ° C., and the actually measured value of the reactor internal pressure was 0.042 MPa.
  • the gas of the reaction mixture taken out from the outlet of the reactor was treated in the same manner as in Example 1, and the molar composition of the gas components contained in the outlet gas was calculated in the same manner.
  • the conversion rate of methane reaction rate
  • the selectivity of each component derived from methane the conversion rate of R22 and / or TFE (reaction rate)
  • R22 and / or Alternatively the selectivity of each component derived from TFE was determined.
  • the conversion rate (reaction rate) of R22 and TFE and the selectivity of each component derived from R22 and / or TFE mean the following.
  • R22 and / or TFE conversion (reaction rate) Among the components derived from R22 and / or TFE, which are fluorine-containing compounds in the outlet gas (components having fluorine atoms), the proportion of R22 and / or TFE (R22 and / or TFE recovery rate) is X%. (100-X)% is referred to as the conversion rate (reaction rate) of R22 and / or TFE. It means the ratio (mol%) of reacted R22 and / or TFE.
  • each component derived from R22 and / or TFE selectivity of each component derived from R22 and / or TFE
  • the selectivity of each component is determined by “yield of each component derived from R22 and / or TFE” / “conversion rate (reaction rate) of R22 and / or TFE”.
  • the yield of each component derived from R22 and / or TFE refers to the proportion (mol%) of each component other than R22 in the components derived from R22 and / or TFE in the outlet gas.
  • Example 22 to 25 The molar ratio (TFE / (TFE + R22)) of the supply amount of TFE and the total supply amount of TFE and R22 is 0.1 in Example 22, 0.3 in Example 23, and 0.7 in Example 24. In Example 25, it was set to 0.9. In addition, the molar ratio of methane / (TFE + R22) was 0.55 in Example 22 so that the equivalent ratio of methane to the sum of R22 and TFE (methane / (R22 + TFE ⁇ 2) was 0.5). Example 23 was 0.65, Example 24 was 0.85, and Example 25 was 0.95. Otherwise, the reaction was performed under the same conditions as in Example 1.
  • HFO-1234yf and VdF can be produced by using a raw material composition containing at least one of R22 and TFE and methane.
  • R22 and / or TFE which can be easily procured, and methane as raw materials are reacted as they are without taking intermediate products from the reaction system, and industrially useful HFO-1234yf and VdF can be produced efficiently. Therefore, for example, compared with a method of manufacturing HFO-1234yf using HCFC-225ca as a raw material via CFO-1214ya, the cost required for the raw material and manufacturing equipment can be greatly reduced.
  • the production (reaction) conditions can be easily controlled, so that quantitative production of HFO-1234yf and VdF is possible, resulting in great economic merit. Furthermore, it is possible to recycle by-products, which has a great economic effect.

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Abstract

L'invention concerne un procédé économiquement avantageux de production de HFO-1234yf, qui est une substance utile comme nouveau milieu de refroidissement, présentant un rendement élevé satisfaisant par une réaction à un cycle impliquant une décomposition thermique. Le procédé de production de 2,3,3,3-tétrafluoropropène et de 1,1-difluoroéthylène selon l'invention comprend les étapes consistant à : (a) mélanger au préalable du chlorodifluorométhane et/ou du tétrafluoroéthylène avec du méthane puis alimenter un réacteur en ce mélange ou alimenter le réacteur, séparément, en chlorodifluorométhane et/ou en tétrafluoroéthylène et en méthane; (b) alimenter le réacteur en milieu de chauffage; et (c) amener le chlorodifluorométhane et/ou le tétrafluoroéthylène et le méthane en contact avec le milieu de chauffage dans le réacteur, en vue de produire du 2,3,3,3-tétrafluoropropène et du 1,1-difluoroéthylène.
PCT/JP2013/080324 2012-11-22 2013-11-08 Procédé de production de 2,3,3,3-tétrafluoropropène et de 1,1-difluoroéthylène WO2014080779A1 (fr)

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