WO2014208452A1 - トリフルオロエチレンの製造方法 - Google Patents
トリフルオロエチレンの製造方法 Download PDFInfo
- Publication number
- WO2014208452A1 WO2014208452A1 PCT/JP2014/066323 JP2014066323W WO2014208452A1 WO 2014208452 A1 WO2014208452 A1 WO 2014208452A1 JP 2014066323 W JP2014066323 W JP 2014066323W WO 2014208452 A1 WO2014208452 A1 WO 2014208452A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- reactor
- hfo
- tfe
- temperature
- heat medium
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/37—Preparation of halogenated hydrocarbons by disproportionation of halogenated hydrocarbons
-
- 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
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
- C07C17/269—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of only halogenated hydrocarbons
Definitions
- the present invention relates to a method for producing trifluoroethylene, and relates to a method for producing trifluoroethylene using tetrafluoroethylene and chlorofluoromethane as raw materials.
- HFO-1123 trifluoroethylene
- HFC-32 difluoromethane
- HFC- 1,1,1,2,2-pentafluoroethane
- a method for producing HFO-1123 a method in which chlorotrifluoroethylene (CTFE) is reduced with hydrogen in the presence of a palladium or platinum catalyst (see, for example, Patent Document 1), 1,1,1,2-tetra A method of dehydrofluorination using a metal fluoride or the like in which fluoroethane (HFC-134a) or 1,1,2,2-tetrafluoroethane (HFC-134) is supported on a carrier such as aluminum oxide as a catalyst (for example, Patent Document 2), a method of reducing 1,1,2-trichloro-1,2,2-trifluoroethane with hydrogen in the presence of a catalyst such as palladium (for example, see Patent Document 3), and the like are known. ing.
- CFE chlorotrifluoroethylene
- HFO-1132 (EFO ) E-1,2-difluoroethylene
- this HFO-1132 (E) has a boiling point very close to that of HFO-1123, and thus it is difficult to distill and separate them. And under certain conditions, this HFO-1132 (E) It was found that the by-product of E) can be suppressed.
- the present invention has been made from the above viewpoint, and uses HFO-1123, which is industrially useful in a synthesis reaction involving thermal decomposition, using raw materials that are easily procured and without using a catalyst,
- An object of the present invention is to provide an economically advantageous method for efficiently producing a high purity by suppressing the formation of by-products which are difficult to separate by distillation, particularly HFO-1132 (E).
- the present invention is a method for producing trifluoroethylene (HFO-1123) from tetrafluoroethylene (TFE) and chlorofluoromethane (R31), (A) mixing the TFE and the R31 in advance or separately supplying them to the reactor; (B) supplying a heat medium to the reactor; (C) generating the HFO-1123 by bringing the TFE, the R31, and the heat medium into contact with each other while the temperature in the reactor is controlled to 400 to 950 ° C. in the reactor.
- a method for producing HFO-1123 is provided.
- TFE and R31 which are easy to procure, are used as raw materials, and a synthesis reaction involving thermal decomposition controlled at a specific temperature without using a catalyst.
- a small and useful industrially useful HFO-1123 can be produced efficiently.
- HFO-1123 having high purity by suppressing the formation of by-products which are very difficult to separate due to their close boiling points.
- RHFO-1132 (E) has a boiling point of ⁇ 51 ° C. and very close to the boiling point of HFO-1123 ( ⁇ 54 ° C.).
- the use of a heat medium makes it easy to control production (reaction) conditions, particularly temperature conditions, and thus enables quantitative production of HFO-1123, which is an economic advantage. Is big. Furthermore, by-products that can generate difluorocarbene (F 2 C :) can be recycled and used as raw material components, which is useful as an industrial production method.
- the production method of the present invention can significantly reduce the cost required for raw materials and production equipment, compared with the conventional production method using an expensive metal catalyst or highly explosive hydrogen, for example. It is advantageous. Furthermore, as described above, since it is possible to suppress the formation of by-products that are difficult to be separated from HFO-1123 such as HFO-1132 (E), a known technique such as pressure distillation can be used without employing a special purification method. It is also useful as an industrial production method in that high-purity HFO-1123 can be obtained by carrying out the purification separation used.
- the present invention provides a method for producing HFO-1123 by a synthesis reaction involving thermal decomposition using TFE and R31 as raw materials. And this manufacturing method (A) mixing the TFE and the R31 in advance or separately supplying them to the reactor; (B) supplying a heat medium to the reactor; (C) in the reactor, with the temperature in the reactor controlled to 400 to 950 ° C., bringing the TFE, R31, and the heat medium into contact with each other to produce the HFO-1123. Have.
- the production method of the present invention may be a continuous production method or a batch production method.
- supply of TFE and R31, which are raw materials, to the reactor, supply of the heat medium to the reactor, contact between the raw material and the heat medium in the reactor, and a reaction including HFO-1123 Any removal of the mixture from the reactor is carried out continuously.
- the supply of the raw material in the step (a) and the supply of the heat medium in the step (b) may be performed earlier or simultaneously. 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 a reactor in which the internal temperature is controlled within the specific temperature range.
- the production method of the present invention is preferably a continuous method in terms of production efficiency.
- step (d) The step of taking out the reaction mixture containing HFO-1123 from the reactor is hereinafter referred to as step (d). Therefore, in the continuous production method, the step (a), the step (b), the step (c), and the step (d) are continuously performed.
- the raw materials TFE and R31 are difluorocarbene (F 2 C :), which is an intermediate produced from TFE, and fluoromethyl radical, which is an intermediate produced from R31, by thermal decomposition and dechlorination reaction in the reactor.
- a reaction intermediate such as H 2 FC ⁇
- H 2 FC ⁇ a reaction intermediate
- the reaction intermediates or the reaction intermediates and the raw material compounds are directly subjected to an addition reaction, or finally through one or more other intermediates.
- HFO-1123 the process from the thermal decomposition reaction to the formation reaction of HFO-1123 is referred to as a synthesis reaction involving thermal decomposition.
- the method for producing HFO-1123 of the present invention uses TFE and R31 as raw materials.
- the molar ratio of the supply amount of R31 to the supply amount of TFE supplied to the reactor (hereinafter referred to as “molar ratio R31 / TFE”) is preferably in the range of 0.01 to 100, and in the range of 0.05 to 20. Is more preferable, and the range of 0.1 to 10 is particularly preferable.
- the molar ratio R31 / TFE is 0.01 to 100, the conversion rate of the raw material, particularly the conversion rate of R31, is high, and HFO-1123 can be produced efficiently. Further, the ratio of HFO-1123 in the reaction mixture taken out from the reactor can be set to a certain level or more.
- the supply amount of each raw material and the heat medium indicates the supply amount per unit time.
- a fluorine-containing compound (excluding TFE) that can be thermally decomposed in a reactor as necessary to generate F 2 C :, for example, chlorodifluoromethane (R22 ), CTFE, hexafluoropropene (HFP), octafluorocyclobutane (RC318), hexafluoropropene oxide (HFPO), and the like.
- R22 chlorodifluoromethane
- CTFE hexafluoropropene
- RC318 octafluorocyclobutane
- HFPO hexafluoropropene oxide
- F 2 C is generated and reacts with R31, and finally HFO-1123 Is generated.
- a fluorine-containing compound that can be pyrolyzed in such a reactor to generate F 2 C: is used as a raw material
- a newly prepared fluorine-containing compound may be used, but it involves the above pyrolysis reaction.
- one or more fluorine-containing compounds by-produced in the synthesis reaction for example, one selected from HFP, RC318, and CTFE.
- F 2 C a fluorine-containing compound capable of generating a (excluding TFE.)
- "Other F 2 C: source compound” also referred to.
- the reaction mixture containing HFO-1123 is removed from the outlet of the reactor.
- the reaction mixture includes unreacted raw materials, reaction products, by-products and a heat medium.
- the heat medium and the target product, HFO-1123 are separated, and further, by-products are removed, and mainly composed of TFE and R31 as unreacted raw materials and other F 2 C: source compounds. Is obtained.
- Step (a) in the production method of the present invention is a step in which TFE and R31 are mixed in advance or separately supplied to the reactor.
- each raw material may be introduced into the reactor at room temperature, but in order to improve the reactivity in the reactor, the temperature at the time of introduction into the reactor is adjusted by heating or the like. May be.
- TFE and other F 2 C: source compounds and R31 have different temperature ranges suitable for improving the reactivity, it is preferable to perform temperature adjustment separately.
- the temperature of TFE supplied to the reactor is preferably 0 to 600 ° C., more preferably 25 to 600 ° C., and most preferably 100 to 500 ° C. from the viewpoint of further increasing the reactivity.
- TFE and the other F 2 C: source compounds have a certain degree of reactivity, but they are independently used in the reactor from the viewpoint of setting the temperature to be difficult to carbonize.
- the temperature is preferably 0 to 600 ° C, more preferably 25 to 600 ° C, and most preferably 100 to 500 ° C.
- the temperature of R31 supplied to the reactor is preferably 0 to 950 ° C. from the viewpoint of reactivity. From the viewpoint of increasing the reactivity, 25 to 900 ° C is preferable, and 100 to 800 ° C is more preferable. However, the temperature of each raw material component supplied to the reactor is set to be equal to or lower than the temperature in the reactor in the step (c) described later.
- TFE and R31, as well as other F 2 C used as necessary may be supplied separately to the reactor for each raw material, or may be supplied after mixing each raw material. .
- the raw materials are preferably divided into groups.
- TFE and other F 2 C used as necessary may be divided into the source compound and the others, and each raw material may be mixed in each group and supplied separately to the reactor, or all raw materials may be mixed Then, it may be supplied.
- source compounds used as necessary are mixed, adjusted to the above preferable temperature conditions, and supplied to the reactor. It is preferable to adjust to the said preferable temperature conditions and to supply to a reactor.
- the temperature during introduction into the reactor is preferably 600 ° C. or lower, more preferably 500 ° C. or lower.
- Step (b) in the production method of the present invention is a step of supplying a heat medium to the reactor.
- the heat medium 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, is preferably a medium that does not undergo thermal decomposition at the reaction temperature (100 to 950 ° C.).
- Examples of the heat medium include water vapor, nitrogen, carbon dioxide, and the like.
- the heat medium is preferably at least one selected from the group consisting of water vapor, nitrogen and carbon dioxide, and more preferably a mixture containing 50% by volume or more of water vapor, with the balance being nitrogen and / or carbon dioxide.
- the content ratio of water vapor in the heat medium is preferably 50% by volume or more, more preferably 100% by volume (that is, only water vapor).
- the supply amount of the heat medium is preferably 20 to 98% by volume, more preferably 50 to 95% by volume with respect to the total amount of the heat medium and the raw material.
- the temperature of the heat medium supplied to the reactor is preferably 100 to 950 ° C. from the viewpoint of further improving the thermal decomposition and the reactivity of the raw material components. From the viewpoint of further increasing the reactivity of the raw material components, the temperature of the heat medium supplied to the reactor is more preferably 400 to 950 ° C, and most preferably 500 to 950 ° C.
- the temperature in the reactor in the step (c) is a temperature equal to or higher than the temperature of each raw material component supplied to the reactor, that is, R31, TFE and other F 2 C: source compound used as necessary, and 400-950 ° C.
- the temperature in the reactor in step (c) is more preferably 500 to 950 ° C., and most preferably 600 to 950 ° C.
- the reaction rate of the synthesis reaction accompanied by thermal decomposition represented by the above formula (1) is increased, and the production of by-products, particularly HFO-1132 (E), is suppressed.
- HFO-1123 can be obtained efficiently.
- 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 (600 to 950 ° 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.
- the contact time of the heat medium and the raw material in the reactor is preferably 0.01 to 10 seconds, and more preferably 0.01 to 3.0 seconds. When the contact time is 0.01 to 10 seconds, the synthesis reaction of HFO-1123 can sufficiently proceed.
- the contact time between the heat medium and the raw material corresponds to the residence time of the raw material in the reactor, 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 reaction apparatus 20 has a reactor 1 provided with heating means such as an electric heater. Connected to the reactor 1 are a supply line 2 for R31 as a first raw material component, a supply line 3 for TFE as a second raw material component, and a supply line 4 for steam as a heat medium as shown below. Has been. In addition, installation of the heating means in the reactor 1 is not essential.
- the R31 supply line 2 and the TFE supply line 3 are provided with preheaters (preheaters) 2a and 3a each equipped with an electric heater or the like, and after each raw material component to be supplied is preheated to a predetermined temperature. It is supplied to the reactor 1.
- the steam supply line 4 is provided with a heated steam generator 4a, and the temperature and pressure of the steam supplied are adjusted.
- These supply lines 2, 3, and 4 may be separately connected to the reactor 1, but some or all of the supply lines may be connected before the reactor 1 and connected to the reactor. Good.
- the raw material mixture in which all raw material components are mixed is reacted from the raw material mixing supply line 5 by connecting the supply lines 2 and 3 after passing through the respective preheaters 2 a and 3 a.
- the steam supplied to the reactor 1 may be supplied from the steam supply line 4 to the reactor 1 separately from the raw material mixing supply line 5.
- it can also comprise so that TFE, R31, and water vapor
- the outlet line 7 in which a cooling means 6 such as a water cooler is installed is connected to the outlet of the reactor 1.
- the outlet line 7 is further provided with a water vapor and acidic liquid recovery tank 8, an alkali cleaning device 9, and a dehydration tower 10 in this order.
- an analyzer such as gas chromatography (GC).
- GC gas chromatography
- a reaction mixture containing HFO-1123 is taken out of the reactor 1, and the gas obtained by removing acidic substances such as hydrogen chloride, water vapor, water, etc. by the treatment after the outlet line 7 as described above, Hereinafter, it is called outlet gas.
- the outlet gas contains the target product HFO-1123.
- HFO-1132 E / Z
- CTFE 1-chloro- 2,2-difluoroethylene
- HCFO-1122 E / Z-1,2-dichlorofluoroethylene
- HCFO-1122a E / Z
- 1,1,2-trifluoroethane HFC-143
- methane E / Z-1-chloro-2-fluoroethylene
- fluoroethylene HFO-1141
- 3,3-difluoropropene HFO-1252zf
- HFO-1243zf 3,3,3- Trifluoropropene
- HFO-1234yf E / Z-1, , 3,3-tetrafluoropropene
- HFP hydrogen fluorine atoms
- CTFE CTFE
- HFO-1123 HFO-1225, RC318, VdF, etc.
- TFE TFE
- HFO-1123 is a compound derived from RFE and a compound derived from R31.
- the above components other than HFO-1123 contained in the outlet gas can be removed to a desired extent by known means such as distillation.
- a general distillation method can be used without using a special purification method or apparatus.
- High-purity HFO-1123 can be produced with an apparatus or the like.
- the separated TFE and R31 can be recycled as a part of the raw material components.
- HFP, CTFE and RC318 are F 2 C: source compounds and can be recycled as part of the raw material components.
- the obtained VdF, TFE, HFP, CTFE, etc. are PVdF (VdF polymer), PTFE (TFE polymer), FEP (TFE-HFP copolymer), VdF-HFP copolymer, It can be used as a raw material for fluororesins such as PCTFE (CTFE polymer) and ECTFE (ethylene-CTFE copolymer).
- HFO-1132 (E) has a boiling point of ⁇ 51 ° C. and very close to the boiling point of HFO-1123 ( ⁇ 54 ° C.).
- R31 and TFE are used as raw materials, and the temperature in the synthesis reaction involving thermal decomposition of these raw materials is controlled within a specific range. By controlling the temperature in the above specific range, the ratio of the production amount of HFO-1132 (E) to the production amount of HFO-1123 can be greatly reduced, and HFO-1123 with higher purity can be obtained. Can do.
- Examples 1 to 4 are examples, and example 5 is a comparative example.
- Example 1 Using the reaction apparatus shown in FIG. 1, crude HFO-1123 was obtained as follows from a raw material gas composed of TFE and R31.
- R31 was continuously introduced into the stainless steel tube preheater 2a in the electric furnace set to a furnace temperature of 300 ° C, and R31 was heated to 300 ° C. Further, TFE was continuously introduced into a preheater 3a made of a stainless steel tube in an electric furnace set at a furnace temperature of 300 ° C., and the TFE was heated to 300 ° C.
- 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 0.2 seconds, 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 750 ° C., and the actually measured value of the reactor internal pressure was 0.04 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. These results are shown in Table 1 together with the reaction conditions.
- the preheating temperature of R31 and TFE is a set temperature in each electric furnace for preheating
- the water vapor temperature is a set temperature in an electric furnace for water vapor heating.
- the water vapor pressure is a set pressure.
- the molar ratio of TFE, R31, and HFO-1123 in the outlet gas was calculated based on the molar composition of the outlet gas obtained by gas chromatography analysis. Furthermore, the conversion rate (reaction rate) of R31, the selectivity of each component derived from R31, the conversion rate of TFE (reaction rate), and HFO-1123 / HFO-1132 (E) (molar ratio) were determined. These results are shown in the lower column of Table 1.
- R31-derived component methyl group (—CH 3 ), methylene group (—CH 2 —, ⁇ CH 2 ) or methine group ( ⁇ CH, —CH ⁇ ) in the exit gas, one fluorine atom and hydrogen It means the proportion (mol%) of each compound other than R31 in the compound having a moiety (—CFH—, ⁇ CFH) in which one atom is bonded to one carbon.
- R31 conversion rate reaction rate
- TFE conversion rate (reaction rate)
- TFE conversion rate (reaction rate)
- HFO-1123 / HFO-1132 (E) This is the ratio of the abundance ratio of HFO-1123 to the abundance ratio of HFO-1132 (E) in the outlet gas. It is obtained by “Mole composition of outlet gas of HFO-1123” / “Mole composition of outlet gas of HFO-1132 (E)”. This represents the ratio (molar ratio) of HFO-1123 to the HFO-1132 (E) in the outlet gas.
- Example 2 The reaction was carried out under the same conditions as in Example 1 except that the set temperature of the electric furnace for heating the steam was 800 ° C. and the internal temperature of the reactor was controlled to 800 ° C. 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 the obtained outlet gas was analyzed in the same manner as in Example 1. The results are shown in Table 1 together with the reaction conditions.
- Example 3 The reaction was carried out under the same conditions as in Example 1 except that the set temperature of the electric furnace for heating the steam was 850 ° C. and the internal temperature of the reactor was controlled at 850 ° C. 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 the obtained outlet gas was analyzed in the same manner as in Example 1. The results are shown in Table 1 together with the reaction conditions.
- Example 4 The temperature of the electric furnace for heating the steam is set to 650 ° C., the internal temperature of the reactor is controlled to 650 ° C., and the flow rate of the raw material gas is set so that the residence time of the raw material gas in the reactor is 0.61 seconds.
- the reaction was carried out under the same conditions as in Example 1 except that the control was performed. 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 the obtained outlet gas was analyzed in the same manner as in Example 1. The results are shown in Table 1 together with the reaction conditions.
- Example 5 The reaction was carried out under the same conditions as in Example 1 except that the set temperature of the electric furnace for heating the steam was 980 ° C. and the internal temperature of the reactor was controlled at 980 ° C. 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 the obtained outlet gas was analyzed in the same manner as in Example 1. The results are shown in Table 1 together with the reaction conditions.
- HFO-1123 can be efficiently produced with high purity by suppressing the formation of by-products that are difficult to be separated from HFO-1123 such as HFO-1132 (E).
- a method of manufacturing can be provided. It should be noted that the entire content of the specification, claims, drawings and abstract of Japanese Patent Application No. 2013-136611 filed on June 28, 2013 is cited here as the disclosure of the specification of the present invention. Incorporated.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
(a)前記TFEと前記R31とを、予め混合しまたは別々に反応器に供給する工程と、
(b)熱媒体を前記反応器に供給する工程と、
(c)前記反応器内で、該反応器内の温度を400~950℃に制御した状態で、前記TFEと前記R31と前記熱媒体とを接触させて前記HFO-1123を生成させる工程と
を有することを特徴とするHFO-1123の製造方法を提供する。
本発明は、原料としてTFEとR31を用い、熱分解を伴う合成反応により、HFO-1123を製造する方法を提供する。そして、この製造方法は、
(a)前記TFEと前記R31とを、予め混合しまたは別々に反応器に供給する工程と、
(b)熱媒体を前記反応器に供給する工程と、
(c)前記反応器内で、該反応器内の温度を400~950℃に制御した状態で、前記TFEと前記R31と前記熱媒体とを接触させて前記HFO-1123を生成させる工程とを有する。
本発明の製造方法は、製造効率の点で連続式の方法であるのが好ましい。以下、本発明の方法を連続式の製造に適用する実施形態について説明するが、本発明はこれに限定されない。なお、前記反応器からHFO-1123を含む反応混合物を取り出す工程を、以下、工程(d)という。したがって、上記連続的な製造方法においては、上記工程(a)、工程(b)、工程(c)および工程(d)は連続的に行われる。
本発明の製造方法における、反応器内の主な反応を下記式(1)に示す。
本発明のHFO-1123の製造方法は、TFEとR31とを原料として用いる。
反応器に供給するTFEの供給量に対するR31の供給量のモル比(以下、「モル比R31/TFE」と示す。)は、0.01~100の範囲が好ましく、0.05~20の範囲がより好ましく、0.1~10の範囲が特に好ましい。モル比R31/TFEが0.01~100であると、原料の転化率、特にR31の転化率が高く、HFO-1123を効率よく製造できる。また、反応器から取り出される反応混合物における、HFO-1123の割合を一定以上とすることができる。
なお、原料および熱媒体を、反応器内を連続的に流通させて反応を行わせる本発明において、各原料および熱媒体の供給量は、単位時間当たりの供給量を示すものとする。
本発明の製造方法における工程(a)は、TFEとR31とを予め混合し、または別々に反応器に供給する工程である。
工程(a)において、各原料は、常温のまま反応器に導入してもよいが、反応器内での反応性を向上させるために、反応器に導入する際の温度を加熱等により調整してもよい。ただし、TFEおよび他のF2C:源化合物とR31とは、反応性を向上させるのに好適な温度範囲が異なるので、温度調整を別々に行うことが好ましい。
他のF2C:源化合物を使用する場合には、TFEと他のF2C:源化合物は反応性がある程度高いが、カーボン化はしにくい温度とするという観点からそれぞれ独立に反応器に供給することが好ましく、その温度は、0~600℃が好ましく、25~600℃がより好ましく、100~500℃が最も好ましい。
ただし、反応器に供給する上記各原料成分の温度はそれぞれ、後述する工程(c)における反応器内の温度以下に設定される。
本発明の製造方法における工程(b)は、熱媒体を前記反応器に供給する工程である。
本発明の工程(b)において、熱媒体は、前記原料と反応器内で一定の時間接触するように、反応器に供給される。熱媒体は、反応器内の温度で熱分解が生じない媒体であり、具体的には反応温度(100~950℃)で熱分解しない媒体であるのが好ましい。熱媒体としては、水蒸気、窒素、二酸化炭素等が挙げられる。熱媒体としては、水蒸気、窒素および二酸化炭素からなる群から選ばれる少なくとも1種からなることが好ましく、水蒸気を50体積%以上含み、残部が窒素および/または二酸化炭素である混合物がより好ましい。各原料の熱媒体との接触による反応に伴い生成する塩化水素を塩酸にして除くため、熱媒体における水蒸気の含有割合は50体積%以上が好ましく、100体積%(すなわち、水蒸気のみ)がより好ましい。
本発明において、HFO-1123の製造に使用される反応装置の一例を、図1および図2に示す。
反応装置20は、電気ヒータ等の加熱手段を備えた反応器1を有する。反応器1には、第1の原料成分であるR31の供給ライン2、第2の原料成分であるTFEの供給ライン3、および熱媒体としての水蒸気の供給ライン4が、以下に示すように接続されている。なお、反応器1における加熱手段の設置は必須ではない。
また、図2に示す反応装置20のように、TFE、R31および水蒸気が別個に反応器1に供給されて反応器1の入り口付近でこれらが一体に混合されるように構成することもできる。
出口ガスには、目的生成物であるHFO-1123が含まれる。出口ガスに含有されるHFO-1123および未反応原料成分(TFE、R31)以外の化合物としては、HFO-1132(E/Z)、1,1-ジフルオロエチレン(VdF)、CTFE、1-クロロ-2,2-ジフルオロエチレン(HCFO-1122)、E/Z-1,2-ジクロロフルオロエチレン(HCFO-1122a(E/Z))、1,1,2-トリフルオロエタン(HFC-143)、メタン、E/Z-1-クロロ-2-フルオロエチレン(HCFO-1131(E/Z))、フルオロエチレン(HFO-1141)、3,3-ジフルオロプロペン(HFO-1252zf)、3,3,3-トリフルオロプロペン(HFO-1243zf)、2,3,3,3-テトラフルオロプロペン(HFO-1234yf)、E/Z-1,3,3,3-テトラフルオロプロペン(HFO-1234ze(E/Z))、HFP、E/Z-1,2,3,3,3-ペンタフルオロプロペン(HFO-1225ye(E/Z))、1,1,3,3,3-ペンタフルオロプロペン(HFO-1225zc)、HFC-125、HFC-134、HFC-134a、1,1,1-トリフルオロエタン(HFC-143a)、1-クロロ-1,2,2,2-テトラフルオロエタン(HCFC-124)、1-クロロ-1,1,2,2-テトラフルオロエタン(HCFC-124a)、1,1,1,2,2,3,3-ヘプタフルオロプロパン(HFC-227ca)、1,1,1,2,3,3,3-ヘプタフルオロプロパン(HFC-227ea)、1,1,1,3,3,3-ヘキサフルオロプロパン(HFC-236fa)、1,1,1,2,3,3-ヘキサフルオロプロパン(HFC-236ea)、ジクロロジフルオロメタン(CFC-12)、HFC-32、トリフルオロメタン(HFC-23)、フルオロメタン(HFC-41)、クロロメタン、およびRC318等が挙げられる。なお、上記においてE/ZはE体とZ体の混合物を意味する。
図1に示す反応装置を用い、TFEとR31とからなる原料ガスから、以下に示すようにして粗HFO-1123を得た。
なお、R31およびTFEの予熱温度は、予熱用の各電気炉における設定温度であり、水蒸気温度は、水蒸気加熱用の電気炉における設定温度である。また、水蒸気圧力は設定圧力である。
(R31由来の各成分の収率)
出口ガス中のR31由来成分(メチル基(-CH3)、メチレン基(-CH2-、=CH2)またはメチン基(≡CH、-CH=)を有する化合物、およびフッ素原子1個と水素原子1個がひとつの炭素に結合した部分(-CFH-、=CFH)をもつ化合物のうちのR31以外の各化合物の占める割合(モル%)を意味する。
(R31転化率(反応率))
出口ガス中のR31由来成分のうちで、R31の占める割合(R31収率)がX%であるとき、(100-X)%をR31の転化率(反応率)という。反応したR31の割合(モル%)を意味する。
(R31由来の各成分の選択率)
反応したR31のうちで、R31以外の各成分に転化したのは各々何%かをいう。各成分の選択率は、「R31由来の各成分の収率」/「R31の転化率(反応率)」で求められる。
出口ガス中のTFE由来成分(フッ素原子2個以上がひとつの炭素に結合した部分をもつ化合物)のうちで、TFEの占める割合(TFE収率)がX%であるとき、(100-X)%をTFEの転化率(反応率)という。反応したTFEの割合(モル%)を意味する。
出口ガス中のHFO-1132(E)の存在比に対するHFO-1123の存在比の割合である。「HFO-1123の出口ガスモル組成」/「HFO-1132(E)の出口ガスモル組成」で求められる。出口ガス中にHFO-1123がHFO-1132(E)に対してどのくらいの割合(モル比)で存在しているかを表す。
スチームを加熱する電気炉の設定温度を800℃とし、反応器の内温を800℃に管理した以外は例1と同様な条件で反応を行なわせた。次いで、反応器の出口より取り出した反応混合物のガスを、例1と同様に処理した後、得られた出口ガスを例1と同様に分析した。結果を反応の条件とともに表1に示す。
スチームを加熱する電気炉の設定温度を850℃とし、反応器の内温を850℃に管理した以外は例1と同様な条件で反応を行なわせた。次いで、反応器の出口より取り出した反応混合物のガスを、例1と同様に処理した後、得られた出口ガスを例1と同様に分析した。結果を反応の条件とともに表1に示す。
スチームを加熱する電気炉の設定温度を650℃とし、反応器の内温を650℃に管理し、反応器内の原料ガスの滞留時間が0.61秒間となるように、原料ガスの流量を制御した以外は例1と同様な条件で反応を行なわせた。次いで、反応器の出口より取り出した反応混合物のガスを、例1と同様に処理した後、得られた出口ガスを例1と同様に分析した。結果を反応の条件とともに表1に示す。
スチームを加熱する電気炉の設定温度を980℃とし、反応器の内温を980℃に管理した以外は例1と同様な条件で反応を行なわせた。次いで、反応器の出口より取り出した反応混合物のガスを、例1と同様に処理した後、得られた出口ガスを例1と同様に分析した。結果を反応の条件とともに表1に示す。
なお、2013年6月28日に出願された日本特許出願2013-136611号の明細書、特許請求の範囲、図面及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (9)
- テトラフルオロエチレンとクロロフルオロメタンから、トリフルオロエチレンを製造する方法であって、
(a)前記テトラフルオロエチレンと前記クロロフルオロメタンとを、予め混合してまたは別々に反応器に供給する工程と、
(b)熱媒体を前記反応器に供給する工程と、
(c)前記反応器内で、該反応器内の温度を400~950℃に制御した状態で、前記テトラフルオロエチレンと前記クロロフルオロメタンと前記熱媒体とを接触させて前記トリフルオロエチレンを生成させる工程と、
を有することを特徴とするトリフルオロエチレンの製造方法。 - 前記クロロフルオロメタンの供給量が、前記テトラフルオロエチレンの1モルに対して0.01~100モルである、請求項1に記載のトリフルオロエチレンの製造方法。
- 前記反応器に供給する前記クロロフルオロメタンの温度が0~950℃である、請求項1または2に記載のトリフルオロエチレンの製造方法。
- 前記反応器に供給する前記テトラフルオロエチレンの温度が0~600℃である、請求項1~3のいずれか1項に記載のトリフルオロエチレンの製造方法。
- 前記反応器に供給する前記熱媒体の温度が100~950℃である、請求項1~4のいずれか1項に記載のトリフルオロエチレンの製造方法。
- 前記熱媒体が、水蒸気、窒素および二酸化炭素からなる群から選ばれる少なくとも1種からなる、請求項1~5のいずれか1項に記載のトリフルオロエチレンの製造方法。
- 前記熱媒体の供給量が、前記反応器に供給する全気体中の20~98体積%である、請求項1~6のいずれか1項に記載のトリフルオロエチレンの製造方法。
- 工程(c)における接触時間が0.01~10秒間である、請求項1~7のいずれか1項に記載のトリフルオロエチレンの製造方法。
- 前記反応器への原料の供給から前記反応器からの反応混合物の取り出しまでを連続的に行う、請求項1~8のいずれか1項に記載のトリフルオロエチレンの製造方法。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201480036749.XA CN105339331A (zh) | 2013-06-28 | 2014-06-19 | 三氟乙烯的制造方法 |
JP2015524016A JP6217750B2 (ja) | 2013-06-28 | 2014-06-19 | トリフルオロエチレンの製造方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013136611 | 2013-06-28 | ||
JP2013-136611 | 2013-06-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014208452A1 true WO2014208452A1 (ja) | 2014-12-31 |
Family
ID=52141792
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/066323 WO2014208452A1 (ja) | 2013-06-28 | 2014-06-19 | トリフルオロエチレンの製造方法 |
Country Status (3)
Country | Link |
---|---|
JP (1) | JP6217750B2 (ja) |
CN (1) | CN105339331A (ja) |
WO (1) | WO2014208452A1 (ja) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09104647A (ja) * | 1995-06-06 | 1997-04-22 | Solvay & Cie | 1,1,2−トリクロロ−1,2,2−トリフルオロエタンで開始するクロロトリフルオロエチレン及びトリフルオロエチレンの製造方法、並びにこの方法で使用する触媒組成物 |
JP2010533151A (ja) * | 2007-07-13 | 2010-10-21 | ゾルファイ フルーオル ゲゼルシャフト ミット ベシュレンクテル ハフツング | 金属フッ化物触媒上でのハロゲンおよび水素を有するアルケンの製造 |
JP2011201877A (ja) * | 2010-03-03 | 2011-10-13 | Daikin Industries Ltd | テトラフルオロエチレンの還元体の製造方法 |
WO2013146709A1 (ja) * | 2012-03-30 | 2013-10-03 | 旭硝子株式会社 | 2,3,3,3-テトラフルオロプロペンおよび1,1-ジフルオロエチレンの製造方法 |
-
2014
- 2014-06-19 CN CN201480036749.XA patent/CN105339331A/zh active Pending
- 2014-06-19 WO PCT/JP2014/066323 patent/WO2014208452A1/ja active Application Filing
- 2014-06-19 JP JP2015524016A patent/JP6217750B2/ja not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09104647A (ja) * | 1995-06-06 | 1997-04-22 | Solvay & Cie | 1,1,2−トリクロロ−1,2,2−トリフルオロエタンで開始するクロロトリフルオロエチレン及びトリフルオロエチレンの製造方法、並びにこの方法で使用する触媒組成物 |
JP2010533151A (ja) * | 2007-07-13 | 2010-10-21 | ゾルファイ フルーオル ゲゼルシャフト ミット ベシュレンクテル ハフツング | 金属フッ化物触媒上でのハロゲンおよび水素を有するアルケンの製造 |
JP2011201877A (ja) * | 2010-03-03 | 2011-10-13 | Daikin Industries Ltd | テトラフルオロエチレンの還元体の製造方法 |
WO2013146709A1 (ja) * | 2012-03-30 | 2013-10-03 | 旭硝子株式会社 | 2,3,3,3-テトラフルオロプロペンおよび1,1-ジフルオロエチレンの製造方法 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2014208452A1 (ja) | 2017-02-23 |
CN105339331A (zh) | 2016-02-17 |
JP6217750B2 (ja) | 2017-10-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2826765B1 (en) | Production method for 2,3,3,3-tetra-fluoropropene and 1,1-difluoroethylene | |
CN115160988B (zh) | 包含三氟乙烯的组合物 | |
EP2826766B1 (en) | Production method for 2,3,3,3-tetra-fluoropropene | |
JP7081596B2 (ja) | 2-クロロ-1,1,1,2-テトラフルオロプロパンおよび/または3-クロロ-1,1,1,2-テトラフルオロプロパンの製造方法、ならびに2,3,3,3-テトラフルオロプロペンの製造方法 | |
JP2016199569A (ja) | フッ素化オレフィンを製造するための統合プロセス | |
JP5975096B2 (ja) | 2,3,3,3−テトラフルオロプロペンおよび1,1−ジフルオロエチレンの製造方法 | |
KR20080066853A (ko) | 플루오르화 유기 화합물의 제조 방법 | |
WO2014080916A1 (ja) | 2,3,3,3-テトラフルオロプロペンの製造方法 | |
JP6217750B2 (ja) | トリフルオロエチレンの製造方法 | |
JP6549553B2 (ja) | フッ素化オレフィンの製造プロセス | |
JP6217749B2 (ja) | トリフルオロエチレンの製造方法 | |
JP6197637B2 (ja) | (e)−1,3,3,3−テトラフルオロプロペンの製造方法 | |
WO2014080779A1 (ja) | 2,3,3,3-テトラフルオロプロペンおよび1,1-ジフルオロエチレンの製造方法 | |
JP2015010058A (ja) | トリフルオロエチレンの製造方法 | |
JP2015117188A (ja) | トリフルオロエチレンの製造方法 | |
JP2014101326A (ja) | 2,3,3,3−テトラフルオロプロペンの製造方法 | |
JP2013227244A (ja) | 2,3,3,3−テトラフルオロプロペンの製造方法 | |
JP2014129260A (ja) | 2,3,3,3−テトラフルオロプロペンの製造方法 | |
JP6176182B2 (ja) | トリフルオロエチレンの製造方法 | |
JP2015110533A (ja) | 2,3,3,3−テトラフルオロプロペンおよび1,1−ジフルオロエチレンの製造方法 | |
KR20190016284A (ko) | 기상 촉매를 이용한 1,1,1-트리플루오로-2-클로로프로펜과 1,1,1,2-테트라플루오로프로펜의 동시 제조 방법 | |
JP2014129273A (ja) | 2,3,3,3−テトラフルオロプロペンの製造方法 | |
JP2014129259A (ja) | 2,3,3,3−テトラフルオロプロペンの製造方法 | |
JP2015117184A (ja) | トリフルオロエチレンの製造方法 | |
JP2013227245A (ja) | 2,3,3,3−テトラフルオロプロペンおよび1,1−ジフルオロエチレンの製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201480036749.X Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14818121 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2015524016 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 14818121 Country of ref document: EP Kind code of ref document: A1 |