WO2001036355A1 - Procede de production de 1,1,1,3,3-pentafluoropropane - Google Patents
Procede de production de 1,1,1,3,3-pentafluoropropane Download PDFInfo
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- WO2001036355A1 WO2001036355A1 PCT/JP2000/008002 JP0008002W WO0136355A1 WO 2001036355 A1 WO2001036355 A1 WO 2001036355A1 JP 0008002 W JP0008002 W JP 0008002W WO 0136355 A1 WO0136355 A1 WO 0136355A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
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- the present invention relates to 1,1,1,1,3,3-pentahalopropane (provided that at least one halogen is not F. The same applies hereinafter unless otherwise specified) and hydrogen fluoride (HF).
- HF hydrogen fluoride
- 1,1,1,3,3-Pentafluoropropane is a compound that can be used as an HFC (hydrofluorocarbon) foaming agent, refrigerant, and propellant without fear of destruction of the ozone layer. Since it is industrially important as a substitute for CFCs, its production method is urgently needed.
- HFC hydrofluorocarbon
- 1,1,1,3,3-pentahalopropane which is one of 1,1,1,3,3-pentahalopropane
- reaction effluent which exists as a liquid and a gas containing 1,1,1,1-trifluoro-3,3-dichloropropane, etc.
- reaction effluent or reaction mixture
- R-245fa is obtained by extracting the gaseous substance in a state and separating and purifying the extracted gaseous substance.
- the fluorination reaction as described above is usually performed in the presence of a catalyst in consideration of the yield of R-245fa.
- the catalyst used in this reaction is WQ 96/0 1 7 9 7 Discloses using a Lewis acid catalyst such as antimony pentahalide.
- the reaction temperature is generally an important factor in determining the reaction rate and, consequently, the size of the reactor, and must be selected appropriately.
- the fluorination reaction of 1,1,1,3,3-pentachloropropane is carried out at a relatively high temperature as described above in order to increase the reaction rate and to gasify the reaction effluent. Gasification of the reaction effluent is required for direct purification by distillation equipment attached to the reactor.
- the reaction temperature depends on the reaction pressure, but a temperature of 50 ° C or higher, generally 100 ° C or higher is selected.
- the reaction effluent containing at least R-245fa and unreacted HF generated by the above-mentioned fluorination reaction is withdrawn from the reactor in a gaseous state and separated and purified by distillation.
- R-245fa and HF form an azeotrope, it is difficult to simply and directly separate them by operations such as distillation.
- Japanese Patent Application Laid-Open No. H10-17501 filed by the present applicant discloses a method of extracting a mixture of R-245fa and HF by using an extraction method. It discloses a method for separating R—245fa with high efficiency. Disclosure of the invention
- a reactor made of a metal material having high thermal conductivity is used to heat a liquid reaction mixture (ie, a liquid reaction effluent) present in the reactor through the walls of the reactor.
- a liquid reaction mixture ie, a liquid reaction effluent
- the reaction solution is extremely corrosive, and the Severely corrodes the metal material of the vessel.
- the relatively high reaction temperatures used in conventional methods there is no long-term stable, non-corrosive metallic material for this reaction solution. Therefore, there is a problem that the life of the reactor is short and the production cost is high.
- WO99 / 26720 uses a double reactor including an outer container and a reactor arranged therein, and at least reacts. It is proposed to cover the inner surface of the container with resin.
- the above-mentioned method using a resin reactor is not a satisfactory method capable of addressing the problem of corrosion.
- the reason is that resin has a lower thermal conductivity than metal materials, so it is very difficult to sufficiently supply the amount of heat required to gasify the reaction mixture from the outside. This is because when a reactor having a large capacity is used, the above method is not suitable because the ratio of the heat transfer capacity (that is, the contact area between the reaction mixture and the reactor wall) and the amount of the reaction mixture decreases.
- An object of the present invention is to include a reaction step for fluorinating 1,1,1,1,3,3-pentahalopropane with HF in the presence of an antimony pentahalide catalyst 1,1,1,1,3,3. — To provide a process for the production of pentafluoropropane, which is economical and novel, with the above-mentioned problems of the prior art being improved;
- the method for producing 1,1,1,1,3,3-pentafluoropropane of the present invention comprises: 1,1,1,3,3-pentahalopropane (provided that at least one halogen is not F. That is, 5 At least one of the two halogen atoms is another halogen atom other than F.) is fluorinated with HF in the presence of an antimony pentahalide catalyst in a reactor to obtain at least 1, 1, 1, 1, Fluorination should be carried out at a reaction temperature of less than 50 ° C in the liquid phase reaction process to obtain a reaction mixture (or reaction effluent) containing 3,3-pentafluoropropane and antimony pentahalide catalyst. It is characterized by.
- reaction mixture refers to a mixture of liquids generated in the above-mentioned liquid phase reaction step, and the target substance 1,1,1,1,3,3-pentaflur And at least unreacted reactants (ie, 1,1,1,3,3-pentahalopropane and HF), containing at least o-propane (R-245fa) and the catalyst antimony 5-halide. Also includes intermediate fluorinated compounds.
- reaction temperature refers to the temperature of the reaction system in which the above-mentioned liquid phase reaction process proceeds, and specifically refers to the temperature in the reactor (more specifically, the temperature of the liquid phase in the reactor). Shall be.
- the present inventors have proposed a reaction for fluorinating 1,1,1,1,3,3-pentahalopropane with hydrogen fluoride in the presence of antimony pentahalide in a reactor (hereinafter simply referred to as “fluorine”). It has been found that by appropriately selecting the 1S reaction conditions, the reaction proceeds at a favorable reaction rate even at a low temperature of less than 50 ° C. Specifically, it was found that this could be achieved by increasing the HF concentration in the reaction system. In a preferred embodiment of the present invention, in the fluorination reaction step, HF is present in the reaction system in an amount of at least 5 times the molar amount of antimony pentahalide.
- the reaction mixture (or reaction effluent) is supplied to the extraction separation step, and the liquid-state reaction mixture and the liquid-state extractant are mixed by contact. Then, 1,1,1,3,3-pentafluopropane propane is separated from the reaction mixture by liquid-liquid extraction.
- the mixture of the reaction mixture contact-mixed with the extractant is separated into a liquid extractant phase and a liquid HF phase.
- the HF phase results from the fact that most of the unreacted HF contained in the reaction mixture is not extracted by the extractant, but forms a separate phase from the extractant phase.
- HF phase not only HF but also substantially all of the antimony pentahalide catalyst is distributed.
- the extractant phase has a higher distribution of 1,1,1,3,3-pentafluoropropane and a lower distribution of HF than the HF phase.
- 1,1,1,3,3-pentapenta-propane and intermediate fluorinated compounds other than R-245fa contained in the reaction mixture also showed the same behavior as R-245fa, and showed a higher behavior than the HF phase. Larger amounts are distributed to the extractant phase.
- the extractant phase is supplied to the distillation and separation step, and the HF remaining in the extractant phase is reduced to 1,1,1,3,3- ⁇ .
- the HF remaining in the extractant phase is reduced to 1,1,1,3,3- ⁇ .
- the extractant is separated from the fraction substantially free of 1,1,1,1,3,3-pentafluoropropane obtained in the above-mentioned distillation separation step.
- the residue may be recycled to the reactor. Further, the separated extractant may be recycled to the extraction separation step.
- 1,1,1,3,3-pentachloropropane is used as the extractant
- the 1,1,1,3,3-pentafluoropropane obtained in the above-mentioned distillation separation step is used. Since the fraction substantially free of propane only contains the starting material of the fluorination reaction and the intermediate fluorinated product, this fraction may be recycled to the reactor as it is, or a part may be returned to the reactor. And the remainder is extracted and separated.
- the present invention includes the following embodiments 1 to 12.
- 1,1,1,3,3-pentahalopropane (where at least one halogen is not F) is fluorinated with HF in the presence of an antimony pentahalide catalyst in a reactor.
- 1,1,1,3,3_pentane including a liquid phase reaction step to obtain a reaction mixture comprising at least 1,1,1,3,3-pentafluoropropane and an antimonypentahalide catalyst.
- the reaction mixture is supplied to the extraction separation step, and the reaction mixture and the extractant are contacted and mixed, and 1,1,1,1,3,3 ⁇ - ⁇ -n-taftanololopropane is extracted from the reaction mixture. Then, the extractant phase and the HF phase are separated, and the amount of 1,1,1,1,3,3-pentafluoropropane contained in the extractant phase is larger than the amount contained in the HF phase,
- the method according to any one of embodiments 1 to 3.
- Each halogen of 1,1,1,3,3_pentahalopropane is F, C
- 1,1,1,3,3-pentahalopropane is 1,1,1,3,3-pentachloropropane and the reaction mixture is 1,1,1,3-tetrafluoro- 3- chloro 0 and emission mouth Purono ⁇ , 1, 1, 1-Torifunoreo port one 3, further comprising a 3-dichloro propane a method according to any of embodiments 1-4.
- Embodiment 10 The extractant is 1,1,1,3,3 ⁇ - ⁇ -chlorochloropropane, and after the distillation separation step, 1,1,1,3,3-pentafluoropropane is substantially removed.
- Embodiment 8 The method according to embodiment 7, wherein the fraction not containing is recycled to the reactor as it is.
- FIG. 1 is a process diagram illustrating one embodiment of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION
- intermediate fluorinated refers to a derivative of a starting material of 1,1,1,1,3,3-pentahalopropane in which halogens other than fluorine have been replaced by fluorine.
- fluorinated product refers to intermediate fluorinated compounds and the target substance 1,1,1,3,3-pentane Fluoropropane shall be referred to. 1. Fluorination reaction
- 1,1,1,1,3,3-pentahalopropane (where at least one halogen is not F) is fluorinated in a reactor with HF in the presence of an antimony pentahalide catalyst to form a reaction mixture.
- the reaction mixture is composed of a fluorinated product (1,1,1,3,3-pentafluoropropane and an intermediate fluorinated product), unreacted raw materials (1,1,1,1,3,3-pentahalopropane and HF), and antimony pentahalide.
- the fluorination reaction is performed at a reaction temperature of less than 50 ° C.
- the reaction temperature is lower than 50 ° C., the effect of suppressing the corrosion of the metal material used in the reactor can be obtained, but the reaction speed and the corrosion speed are taken into consideration in consideration of the balance.
- the optimal reaction temperature can be further selected within the range of less than 50 ° C.
- the reaction temperature should be as low as possible, for example, 30 ° C. or lower, preferably 25 ° C. or lower, more preferably 20 ° C. or lower.
- the reaction temperature is preferably higher than 110 ° C.
- the reaction temperature is preferably from 110 ° C to 50 ° C, more preferably from 110 ° C to 30 ° C, most preferably -10 ° C. C to 25 ° C, especially — 10 ° C to 20 ° C.
- the reaction temperature is preferably selected in consideration of the extraction / separation step.
- extraction must be performed at relatively low temperatures to achieve high extraction separation efficiencies and reduce mutual solubility.
- the extraction does not require temperature control of the reaction mixture by cooling or heating, or the reaction temperature is preset to a temperature suitable for extraction in order to minimize the load of cooling or heating. It is preferable to keep them close to each other. That is, it is preferable to set the temperature as low as possible so as to be suitable for extraction. On the other hand, setting the reaction temperature too low is not desirable because the reaction rate decreases. In consideration of these, it is preferable to set the reaction temperature in the range of 110 ° C to 30 ° C.
- the raw materials 1,1,1,1,3,3-pentahalopropane and HF may be supplied to the reactor in either a liquid phase or a gas phase, but the fluorination reaction proceeds in the liquid phase, Form a reaction mixture.
- This reaction mixture usually has a form of a solution (hereinafter, a liquid reaction mixture is also simply referred to as a “reaction solution”).
- the supply of 1,1,1,3,3_pentanopropropane or HF can be continuous or batch.
- the fluorination reaction produces HC1, which is released into the gas phase and can be easily separated from the reaction solution.
- the pressure in the reactor is not particularly limited, but is, for example, 0:! ⁇ 1. OMPa (absolute pressure).
- 1,1,1,3,3-pentahalopropane may be such that each halogen is selected from the group consisting of F, Cl, and Br.
- 1,1,1,3,3-pentahalopropane includes 1,1,1,3,3-pentachloropropane and its derivatives in which 1 to 4 chlorine atoms are substituted with fluorine, and Examples include 1,1,1-trihnoleo-1,3-dibromopropane and 1,1,3,3-tetrafluoro-1-bromopropane.
- the catalyst may be prepared by the S bC 1 5 is reacted with HF, it may also be used S bC l 5 itself or S b F 5, Le. In general, they have a structure under HF atmosphere represented by HS b C 1 x F y + 1, the force X and y is considered to X ⁇ y der Ru is determined arbitrarily depending on the reaction conditions For example, it is preferable that 3 ⁇ X ⁇ 5.
- X and y are not limited to integers, 0 ⁇ x, y ⁇ 5 N x + y
- Sb C l x F catalyst is Ru represented by y can be a single compound represented by S b C 1 x F y, or may be a mixture of a plurality of types of compounds.
- SbC l x F y by mixing S b C 1 5 and S b F 5 at any ratio (by mole) as the catalyst.
- HF is a reaction system (a system (or atmosphere) in which the reaction proceeds and is present in the gas phase in the reactor) in an amount of 5 times or more mol of the antimony pentahalide.
- the amount of the substance is much smaller than the amount present in the liquid phase, so it may be considered that the substance is substantially in the liquid phase in the reactor). That is all.
- the amount of HF is preferably 100 times or less, more preferably 50 times or less, with respect to antimony pentahalide. If the amount of HF present in the reaction system is at least 5 times the mol of antimony pentahalide introduced as a catalyst, the reaction can proceed with good selectivity and reaction rate.
- HF is preferably present in an amount of at least 5 times, and more preferably at least 10 times, the mole of antimony pentahalide.
- the amount of HF introduced is, for 1,1,1,3,3_pentahalopropane, the amount theoretically necessary to produce the target substance R—245 5a (ie, 1, (The amount required assuming that 1,1,3,3-pentahalopropane is all R-245fa)). Less than twice the number of moles is advantageous for efficiency.
- a Ni-based corrosion-resistant material can be used as a material for the reactor. Specifically, materials such as Hastelloy, Monel, and Inconel are exemplified. If there is no need to heat from the outside, a resin with low thermal conductivity may be used as the reactor material or its lining material. Examples of the resin include a tetrafluoroethylene resin, a black trifluoroethylene resin, a vinylidene fluoride resin, and a PFA resin. 2. Extraction separation
- the reaction mixture is supplied to the extraction separation step.
- the reaction mixture and the extractant are contact-mixed, and 1,1,1,1,3,3-pentafluoropropane is extracted from the reaction mixture and separated into an extractant phase and an HF phase. Let me do it.
- 1,1,1,1,3,3-pentafluoropropane contains more, preferably most, of the extractant phase than the HF phase.
- the extractant phase additionally contains the unreacted 1,1,1,3,3-pentahalopropane and most of the intermediate fluorides and a small amount of HF.
- This extraction separation is a liquid-liquid extraction separation, in which a mixture of the reaction mixture and the extractant is separated into an HF phase and an extractant phase, and most of the unreacted HF is separated into the HF phase. It becomes possible to separate into.
- an extraction separation step it is possible to obtain a fraction containing 1,1,1,1,3,3-pentafluoropropane without substantially raising the reaction mixture to a relatively high temperature (gasification). Become.
- This extraction and separation step is very important in reducing the amount of heat to be supplied to the reactor.
- R-245fa and HF can be separated without the need to gasify the reaction mixture as described above, so there is no need to raise the reaction temperature, and rather a lower reaction temperature follows.
- the reaction temperature is set low and it is not necessary to supply heat from outside the reactor, the thermal conductivity of the reactor material does not need to be considered. Therefore, as described above, it is also possible to use a resin or the like as a material of the reactor or a lining material thereof.
- the extractant phase contains the fluorinated product (ie, the target substance, R-245fa and intermediate fluorinated product), unreacted 1,1,1,1,3,3-pentahalopropane, and a small amount of HF Is extracted.
- Intermediate fluorinated compounds generated by the fluorination reaction include, for example, 1,1,1,3,3-pentahalopropane as a starting material, which is free of fluorine and contains 1,1,1,1,3,3-pentahalopropane. Is simply referred to as “R — 240 fa”, the main component is “R—24 4” in which the halogen of 1,1,1,3,3_pentahalopropane is substituted with four Fs.
- the intermediate fluorinated compound will be 1,1,1,3-tetraethyl It is mainly composed of rafnoleol 3-chloropropane and 1,1,1-triphneoleol 3,3-dichloropropane, and slightly contains compounds in which more chlorine remains.
- the ratio of these fluorinated products depends on the reaction conditions such as the reaction temperature, the amount of the reaction solution, and the rate of charging the raw materials.
- a solvent selected from the group consisting of a chlorinated hydrocarbon compound, a solvent inert to a fluorination reaction for example, a fluorinated hydrocarbon compound, a fluorinated ether compound, and a fluorinated amine compound
- a fluorination reaction for example, a fluorinated hydrocarbon compound, a fluorinated ether compound, and a fluorinated amine compound
- chloride hydrocarbon compound 1, 1, 1, 3, 3-Pentaku Roropurono ⁇ 0 down, to Kisakuro port propene, trichlorethylene
- examples of the fluorinated hydrocarbon compounds include perfluoro-2-methinolepentane (sec—C 6 F 14 ), ⁇ 0 —funoleolone n—hexane (n—C 6 F 14 ), 43-10 mee (1, 1, 1, 2,2,3,4,5,5,5-decafluoropentane), 1H-perfluoro-2-pentene, ⁇ .
- fluorinated ester compounds include methyl-1,1,2,3,3,3-hexaphenole-propinoleate and ethynolee 1,1,2,3,3,3-hexafluoropropynoleatenole And propyl-1,1,2,3,3,3-hexafluoropropyl ether, 1-methoxy-nonafluorobutane, 1-ethoxy-nonafluorobutane and the like.
- fluorinated amine compound include perfluorotributylamine, perfluoropentylamine, perfluoro-N-methyl-morpholine and the like.
- the same conditions as in JP-A-10-17501 can be used.
- the temperature is kept in the range of 130 to 5 ° C, preferably 130 to 30 ° C, more preferably 130 to 0 ° C
- the pressure absolute pressure
- the extractant ratio S / F weight basis
- the extractant ratio S / F is usually in the range of 0.5 to 2.
- the extraction method can use any appropriate method, and is not particularly limited.
- a batch system, a countercurrent contact system, or the like is suitably used.
- the HF phase containing the antimony 5-halide catalyst obtained in the extraction separation step may be recycled to the fluorination reaction step after removing other impurities as necessary.
- the extractant phase is fed to the distillation and separation step.
- this extractant phase separated by extraction and separation a small amount of HF is distributed in addition to the 1,1,1,3,3-pentafluoroprop mouthpan.
- HF is distilled off in the form of an azeotrope with 1,1,1,3,3-pentafluoropropane, which is then substantially free of HF 1,1,1,1,3 , 3-Pentafluorop Distills fractions from mouth bread.
- the fraction containing the target substance 1,1,1,3,3-pentafluoropropane and the remaining 1,1,1,3,3-pentafluoropropane are substantially contained. No fractions are obtained. Therefore, the use of azeotropic distillation makes it possible to easily remove a relatively small amount of HF distributed to the extractant as an azeotrope with 1,1,1,1,3,3-pentafluoropropane.
- Separation of the fraction of 1,1,1,3,3-pentafluorolob mouth bread substantially free of HF from the extractant phase as described above may be carried out batchwise or continuously. Further, the distillation column for performing the distillation separation may be one column or may be divided into two columns.
- an azeotropic mixture of HF and R-245fa (1,1,1,3,3-pentafluoropropane) is first distilled off from the top of the column, and then By distilling a fraction of R-245fa substantially free of HF, R-245fa can be separated in a batch system.
- an azeotropic mixture of HF and R-245fa was distilled from the top of the first distillation column using two distillation columns, and the bottom formed in the first distillation column was distilled off.
- the liquid is fed to the second distillation column, and the R-245fa fraction, which is substantially free of HF, is distilled from the top of the second column to separate R-245fa in a continuous manner. can do.
- the azeotropic mixture flows out from the top of the column, and the R-245fa fraction substantially free of HF is distilled off from the middle stage of the distillation column to obtain R-245. fa can be separated in a continuous manner.
- the extractant phase contains a small amount of HF and the target substance, R-245fa, as well as intermediate fluorinated compounds and unreacted 1,1,1,3,3-pentahalopropane.
- Intermediate fluorides and 1,1,1,3,3-pentahalopropane are
- an azeotropic mixture of HF and 1,1,1,3,3-pentafluoropropane is withdrawn from the top of the column, and then substantially 1,1,1,3,3-pentafant substantially free of HF. It is possible to extract the chloropropane, while extracting the intermediate fluorinated product and the unreacted 1,1,1,3,3-pentahalopropane and the mixed solution of the extractant as the bottoms.
- any appropriate method can be used for the distillation method and distillation conditions and is not particularly limited.
- the azeotropic mixture (including HF) obtained by the distillation separation process is subjected to fluorination reaction And may be recycled to the z or extraction separation step.
- the fraction (bottoms) substantially free of 1,1,1,1,3,3-pentafluoropropane can be recycled if necessary.
- the bottoms are mainly composed of intermediate fluorinated compounds (and unreacted 1,1,1,3,3-pentapentyl propane) and an extractant, which can be separated by a common separation operation such as distillation.
- the intermediate fluoride and the unreacted 1,1,1,3,3-pentahalopropane as the main components from which the extractant has been separated can be recycled as a starting material because they can be used as starting materials. it can.
- the extracted extractant can be recycled to the extraction separation process.
- 1,1,1,3,3-pentachloropropane When 1,1,1,3,3-pentachloropropane is used as the extractant, it does not substantially contain 1,1,1,1,3,3-pentafluoropropane obtained by the distillation separation process.
- the fraction (boiler effluent) may be recycled to the reactor as it is. This is because the extractant 1,1,1,1,3,3-pentachloropropane can be a starting material for the fluorination reaction.
- a portion of the fraction substantially free of 1,1,1,3,3_pentafluoropropane may be returned to the reactor and the remainder recycled to the extraction separation step.
- HF and 1,1,1,3,3-pentahalopropane (in the present embodiment, the above-described R-24Ofa are supplied through pipes 1 and 2, respectively.
- the temperature inside the reactor 10 is lower than 50 ° C, for example, 0 to 30 ° C.
- the supply of HF and R-240fa is in the liquid phase, but is not limited to this.
- the temperature in the reactor is maintained at the above temperature, the reaction temperature is set to less than 50 ° C, for example, 0 to 30 ° C, and HC1 generated during the fluorination reaction is reacted in a gaseous state. While carrying out the fluorination reaction.
- the fluorination reaction is sufficiently advanced to obtain a reaction solution (or a liquid reaction mixture) 3. Thereafter, the reaction solution 3 is sent to the extractor 20 through the pipe 11 to be mixed with the extractant by contact and separated into an HF phase 21 and an extractant phase 22.
- the extractant ratio SZF weight basis
- S b C 1 x F the extraction temperature is, for example, 130 to 30 ° C.
- the majority and substantially all of the 5 halogenated antimony unreacted HF (S b C 1 x F ) is distributed to the HF phase 2 1, fluorinated product containing R- 2 4 5 fa Most of the unreacted R—240 fa is distributed to the extractant phase 22.
- the HF phase 21 is recycled to the reactor 10 through the pipe 23, and the extractant phase 22 is sent to the first distillation column 30 through the pipe 24.
- the HF phase 21 is shown as the upper layer, and the extractant phase is shown as the lower phase. However, the opposite may occur depending on the extractant.
- the lowest azeotropic mixture consisting of R-245fa and HF is distilled off from the top of the column through the pipe 32 by azeotropic distillation, and is recycled to the reactor 10. I do.
- the distillation temperature is, for example, 13 to 50 ° C. (pressure; 0.1 to 0.5 MPa (absolute pressure)), and the R of the azeotrope at this time is R—2 45 fa
- the molar ratio of HF to HF is 1: 2 to; I: 1.
- R—245 f a which is substantially free of HF, which is the target substance, is distilled off from the top of the tower, and is obtained through a pipe 31.
- the pipes 31 and 32 are illustrated separately, but may be the same pipe.
- the residue obtained by distillation of H F and R—24 45 f a is sent to the second distillation column 40 through the pipe 33 as bottom liquid.
- This bottoms mainly contains the extractant and the intermediate fluorides R-244 and R-243.
- the intermediate fluorinated product is distilled off and separated from the top of the column, and recycled to the reactor 10 through the pipe 41.
- the bottom liquid mainly consisting of the extractant which is the residue after the separation, is sent to the pipe 11 through the pipe 42, and the extraction and separation process is performed using Lisa.
- 3,3_pentachloropropane is used, the bottoms from the second distillation column 40 are not only recycled through the pipe 11 to the extraction / separation step, but also a part thereof is recycled through the pipe 50. It is also possible to recycle to the reactor 10.
- the second distillation column 4 is omitted, and all of the bottom liquid of the first distillation column 30 is passed through the pipe 51, a part of the pipe 42, and the pipe 50 to the reactor 10. May be recycled or withdrawn through line 51 A part of the bottom liquid may be returned to the reactor through the pipe 50, and the remainder may be recycled to the extraction / separation step through the pipe 11.
- 1,1,1,3,3,3 includes a reaction step of fluorinating 1,1,1,3,3-pentahalopropane with HF in the presence of an antimony pentahalide catalyst.
- R-245fa pentafluoropropane
- a simple manufacturing method is provided.
- the autoclave not only the liquid phase but also the gas phase exists, but the reactants contained in the gas phase (ie, 1,1,1,3,3-pentahalopropane and HF), fluorinated products and pentane
- the amount of antimony fluoride catalyst is negligible compared to the amount in the liquid phase. Therefore, substantially all of the reaction raw materials, the fluorinated products, and the antimony pentafluoride catalyst are contained in the liquid phase, and the liquid phase may be considered as a reaction system (the same applies to the following examples).
- Extractant Perfluoro-2-methylpentane Extraction temperature about 0 ° C
- Extractant ratio SZF about 1.5 (by weight)
- This mixture was subjected to a batch rectification operation using a 30-stage SUS Oldershaw distillation apparatus.
- 120 g of an azeotrope of R-245fa and HF was distilled off from the top of the apparatus to remove almost all HF.
- 280 g of R-245 a substantially free of HF could be extracted from the top of the column.
- Extractant Perfluoro-2-methylpentane Extraction temperature about 0 ° C
- Extractant ratio SZF about 1.5 (by weight)
- the extractant phase obtained as described above was analyzed and quantified in the same manner as in Example 1.
- the HF and organic substances contained in the extractant phase were as follows.
- Extractant 1,1,1,3,3-pentachloropropane Extraction temperature about 0 ° C
- R-243fa 0.65 g (0.004 mo 1) From the above results, extraction of R-245fa was possible even with 1,1,1,3,3-pentachloropropane as the extractant. It was found that R-245fa was produced with good selectivity.
- the extractant phase obtained in this example was also distilled in the same procedure as in Example 2. Also in this case, it was possible to obtain R-245fa (HF content 0.1% by weight or less) substantially containing no HF.
- An extractant phase rich in R-245fa was obtained in the same manner as in Example 1 except that perfluorohexane was used instead of perfluoro-2-methylpentane as the extractant.
- Extractant ratio SZF about 1.5 (by weight)
- the extractant phase obtained as described above was analyzed and quantified in the same manner as in Example 1.
- the HF and organic substances contained in the extractant phase were as follows.
- the extractant phase obtained in this example was distilled in the same procedure as in Example 2. Also in this case, it was possible to obtain R-245 ⁇ a (HF content: 0.1% by weight or less) substantially containing no HF.
- Extractant ratio SZF about 1.5 (by weight)
- the extractant phase obtained as described above was analyzed and quantified in the same manner as in Example 1.
- the HF and organic substances contained in the extractant phase were as follows.
- R-245fa could be extracted also in this example, and R-245fa was generated with high selectivity.
- the extractant phase obtained in this example was distilled in the same procedure as in Example 2. Also in this case, it was possible to obtain R-245fa (HF content 0.1% by weight or less) substantially containing no HF.
- Extractant Perfluoro-2-methylpentane Extraction temperature about ⁇ ° C
- Extractant ratio SZF about 1.5 (by weight)
- Corrosion tests were performed under conditions corresponding to the reaction solution to show that the invention can effectively reduce reactor corrosion.
- a test piece (1 OmmX 2 OmmX 1 mm) corresponding to the material of the reactor was placed in a pressure vessel lined with fluorocarbon resin at 1 mo 1 ° / mo. It was immersed 1 0 days in a solution of the S b F 5 / HF.
- the corrosion rate was determined based on the change in weight before and after immersion, varying the solution temperature and the material of the test piece.
- Tables 1 and 2 show that the corrosion rate is very low at low temperatures below 50 ° C. Therefore, it is apparent that by performing the fluorination reaction in the presence of antimony pentahalide at a low temperature of less than 50 ° C. as in the present invention, the corrosion of the reactor is suppressed.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00974969A EP1231195A4 (en) | 1999-11-15 | 2000-11-14 | PROCESS FOR THE PRODUCTION OF 1,1,1,3,3-PENTAFLUOROPROPANE |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11/323971 | 1999-11-15 | ||
JP32397199 | 1999-11-15 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10130116 A-371-Of-International | 2002-05-15 | ||
US10/775,167 Division US6846963B2 (en) | 1999-11-15 | 2004-02-11 | Process for producing 1,1,1,3,3-pentafluoropropane |
Publications (1)
Publication Number | Publication Date |
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WO2001036355A1 true WO2001036355A1 (fr) | 2001-05-25 |
Family
ID=18160689
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2000/008002 WO2001036355A1 (fr) | 1999-11-15 | 2000-11-14 | Procede de production de 1,1,1,3,3-pentafluoropropane |
Country Status (2)
Country | Link |
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EP (1) | EP1231195A4 (ja) |
WO (1) | WO2001036355A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004507515A (ja) * | 2000-09-02 | 2004-03-11 | イネオス フラウアー ホールデイングス リミテッド | ハイドロフルオロアルカンの製造 |
US8912369B2 (en) | 2012-06-29 | 2014-12-16 | Central Glass Company, Limited | Method for production of 1-chloro-3,3,3-trifluoropropene |
US9174897B2 (en) | 2012-06-28 | 2015-11-03 | Central Glass Company, Limited | Method for purifying trans-1,3,3,3-tetrafluoropropene |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8648221B2 (en) | 2011-01-19 | 2014-02-11 | Honeywell International Inc. | Integrated process to co-produce trans-1-chloro-3,3,3-trifluoropropene, trans-1,3,3,3-tetrafluoropropene, and 1,1,1,3,3-pentafluoropropane |
US8889924B2 (en) | 2012-02-14 | 2014-11-18 | Honeywell International Inc. | Process for the production of 1,3,3,3-tetrafluoropropene |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0729932A1 (en) * | 1995-03-03 | 1996-09-04 | Central Glass Company, Limited | Method of producing halopropane |
JPH09268141A (ja) * | 1996-04-03 | 1997-10-14 | Central Glass Co Ltd | 1,1,1,3,3−ペンタフルオロプロパンの製造方法 |
JPH10101594A (ja) * | 1996-09-25 | 1998-04-21 | Asahi Glass Co Ltd | 1,1,1,3,3−ペンタフルオロプロパンの製造法 |
EP0921109A1 (en) * | 1996-06-27 | 1999-06-09 | Daikin Industries, Limited | Method for purifying 1,1,1,3,3-pentafluoropropane |
-
2000
- 2000-11-14 EP EP00974969A patent/EP1231195A4/en not_active Withdrawn
- 2000-11-14 WO PCT/JP2000/008002 patent/WO2001036355A1/ja not_active Application Discontinuation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0729932A1 (en) * | 1995-03-03 | 1996-09-04 | Central Glass Company, Limited | Method of producing halopropane |
JPH09268141A (ja) * | 1996-04-03 | 1997-10-14 | Central Glass Co Ltd | 1,1,1,3,3−ペンタフルオロプロパンの製造方法 |
EP0921109A1 (en) * | 1996-06-27 | 1999-06-09 | Daikin Industries, Limited | Method for purifying 1,1,1,3,3-pentafluoropropane |
JPH10101594A (ja) * | 1996-09-25 | 1998-04-21 | Asahi Glass Co Ltd | 1,1,1,3,3−ペンタフルオロプロパンの製造法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1231195A4 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004507515A (ja) * | 2000-09-02 | 2004-03-11 | イネオス フラウアー ホールデイングス リミテッド | ハイドロフルオロアルカンの製造 |
US9174897B2 (en) | 2012-06-28 | 2015-11-03 | Central Glass Company, Limited | Method for purifying trans-1,3,3,3-tetrafluoropropene |
US8912369B2 (en) | 2012-06-29 | 2014-12-16 | Central Glass Company, Limited | Method for production of 1-chloro-3,3,3-trifluoropropene |
Also Published As
Publication number | Publication date |
---|---|
EP1231195A4 (en) | 2004-09-29 |
EP1231195A1 (en) | 2002-08-14 |
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