WO2012057367A1 - Process for producing 2,3,3,3-tetrafluoropropene - Google Patents

Process for producing 2,3,3,3-tetrafluoropropene Download PDF

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Publication number
WO2012057367A1
WO2012057367A1 PCT/JP2011/075365 JP2011075365W WO2012057367A1 WO 2012057367 A1 WO2012057367 A1 WO 2012057367A1 JP 2011075365 W JP2011075365 W JP 2011075365W WO 2012057367 A1 WO2012057367 A1 WO 2012057367A1
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Prior art keywords
reaction step
reaction
hydrogen fluoride
starting material
formula
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PCT/JP2011/075365
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French (fr)
Inventor
Kazuhiro Takahashi
Yuzo Komatsu
Akinori Ueda
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Daikin Industries, Ltd.
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Application filed by Daikin Industries, Ltd. filed Critical Daikin Industries, Ltd.
Priority to ES11802160T priority Critical patent/ES2551244T5/en
Priority to CN201180044988.6A priority patent/CN103108851B/en
Priority to US13/879,668 priority patent/US9040760B2/en
Priority to JP2013512043A priority patent/JP5679049B2/en
Priority to EP15176250.7A priority patent/EP2963005B1/en
Priority to EP11802160.9A priority patent/EP2632882B2/en
Publication of WO2012057367A1 publication Critical patent/WO2012057367A1/en
Priority to US14/695,116 priority patent/US9388099B2/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
    • C07C17/087—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated halogenated hydrocarbons
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Q—MEASURING OR TESTING PROCESSES INVOLVING ENZYMES, NUCLEIC ACIDS OR MICROORGANISMS; COMPOSITIONS OR TEST PAPERS THEREFOR; PROCESSES OF PREPARING SUCH COMPOSITIONS; CONDITION-RESPONSIVE CONTROL IN MICROBIOLOGICAL OR ENZYMOLOGICAL PROCESSES
    • C12Q1/00—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions
    • C12Q1/68—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions involving nucleic acids
    • C12Q1/6844—Nucleic acid amplification reactions
    • C12Q1/686—Polymerase chain reaction [PCR]
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6486—Measuring fluorescence of biological material, e.g. DNA, RNA, cells
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00—Features of devices classified in G01N21/00
    • G01N2201/06—Illumination; Optics
    • G01N2201/061—Sources
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present invention relates to a process for producing 2,3,3,3-tetrafluoropropene.
  • HFC-32 (CH 2 F 2 ) have been widely used as important replacements for CFC, HCFC, etc., which cause ozone layer depletion.
  • these alternative refrigerants are potent global warming
  • refrigerants would increase global warming. As a preventive measure, these refrigerants are recovered after use. However, complete recovery of the refrigerants is impossible. In addition, the diffusion of these refrigerants due to leakage, etc., cannot be ignored.
  • the use of C0 2 or hydrocarbon-based substances as alternative refrigerants has also been investigated. However, because C0 2 refrigerants have low efficiency and devices using such refrigerants inevitably become large, C0 2 refrigerants have many problems in terms of the overall reduction of greenhouse gas emissions, including energy to be consumed. Furthermore, hydrocarbon-based substances pose safety problems due to their high flammability.
  • HFO-1234yf used alone or in combination with other substances, such as hydrofluorocarbons , hydrofluoroolefins, and hydrochlorofluoroolefins, is expected to be useful as a refrigerant, and additionally as a blowing agent, propellant, extinguishing agent, or the like.
  • hydrohalopropane such as a hydrochloropropane or a hydrohalopropene such as a
  • hydrochloropropene used as a starting material, is fluorinated with hydrogen fluoride to ultimately prepare HFO-1234yf.
  • Patent Literature 1 listed below discloses a process in which HFO-1234yf is produced, via a
  • haloalkane or a haloalkene as a starting material to fluorination with HF, dehydrochlorination, etc.
  • Patent Literature 2 listed below discloses a process in which HFO-1234yf is produced, via a hydrochlorofluoroalkane, hydrochlorofluoroalkene, etc., by subjecting a hydrochloropropane, hydrochlorofluoropropane, etc., as a starting material to
  • Patent Literature 3 listed below discloses an integration process for preparing HFO-1234yf by using
  • 1,1,1,2,3-pentachloropropane (HCC-240db) as a starting material, fluorinating the starting material with HF to produce HCFO-1233xf , and then adding HF to the thus-obtained HCFO-1233xf to produce HCFC-244bb, followed by dehydrochlorination.
  • HFO- 1234yf 2,3,3,3-tetrafluoropropene
  • chloropropane compound or chloropropene compound represented by a specific general formula which is used as a starting material, is reacted with hydrogen fluoride in a gas phase in the absence of a catalyst while heating, and subsequently the product
  • the present invention has been accomplished based on this finding.
  • the present invention provides the following process for producing 2,3,3,3-tetrafluoropropene.
  • Item 1 A process for producing 2,3,3,3- tetrafluoropropene, the process comprising:
  • Item 2 The process according to Item 1, wherein the reaction temperature in the first reaction step is 250 to 600° C, and the reaction temperature in the second reaction step is 200 to 500° C.
  • Item 3 The process according to Item 1 or 2, wherein the amount of hydrogen fluoride in the first reaction step is 1 to 100 moles per mole of the chlorine-containing compound used as a starting material, and the amount of hydrogen fluoride in the second reaction step is 1 to 50 moles per mole of the chlorine- containing compound used as a starting material in the first reaction step.
  • the fluorination catalyst used in the second reaction step is at least one member selected from the group consisting of chromium oxides, chromium oxyfluorides , aluminium fluorides, aluminum oxyfluorides , and metal fluorides.
  • reaction product is used as a starting material in the second reaction step.
  • reaction product is used as a starting material in the second reaction step.
  • CZ 2 CC1CH 2 C1, wherein at least one of Z is F,
  • Item 9 The process according to any one of Items 1 to 8, wherein the first reaction step is conducted in a reactor made of an alloy containing 30% or more by weight of nickel.
  • Item 10 The process according to Item 9, wherein the alloy containing 30% or more by weight of nickel is at least one member selected from the group consisting of Hastelloy, Inconel, Monel, and Incolloy.
  • fluorination reaction is conducted in a single-stage reaction process .
  • CCIX 2 CHCICH 2 CI include CCI 3 CHCICH 2 CI (HCC-240db, bp. 179 e C/760 mmHg, 51-53° C/3 mmHg) , CFCl 2 CHClCH 2 Cl(HCFC-241db, bp. 157° C), CF 2 ClCHClCH 2 Cl(HCFC-242dc, bp. 113-114° C), and the like.
  • CCIX 2 CHCICH 2 CI include CCI 3 CHCICH 2 CI (HCC-240db, bp. 179 e C/760 mmHg, 51-53° C/3 mmHg) , CFCl 2 CHClCH 2 Cl(HCFC-241db, bp. 157° C), CF 2 ClCHClCH 2 Cl(HCFC-242dc, bp. 113-114° C), and the like.
  • HCC- 240db (CCI 3 CHCICH 2 CI(1,1,1,2, 3-pentachloropropane) )
  • the starting compounds can be used singly or in combination of two or more.
  • At least one of the above starting compounds is reacted with hydrogen fluoride in a gas phase in the absence of a catalyst while heating.
  • HCFO-1233xf that is an intermediate for 2,3,3,3- tetrafluoropropene (HFO-1234yf) .
  • the first reaction step requires the reaction of the starting compound with hydrogen fluoride in a gas phase in the absence of a catalyst.
  • the starting compound may be in a liquid form when supplied.
  • the starting compound is liquid at an ordinary temperature and ordinary pressure
  • the starting compound is vaporized using a vaporizer (vaporization region), passed through a preheating region, and then supplied to a mixing region wherein the starting compound is contacted with anhydrous hydrogen
  • reaction whereby the reaction can be conducted in a gas phase.
  • the reaction may also be carried out by supplying the starting compound in a liquid phase to a reactor, and vaporizing the compound when the compound enters a reaction temperature range to react with hydrogen fluoride.
  • vaporizing the starting compound There is no particular limitation to the methods for vaporizing the starting compound in the
  • the starting compound may be any organic compound having reaction temperature range.
  • the starting compound may be any organic compound having reaction temperature range.
  • the starting compound may be any organic compound having reaction temperature range.
  • vaporized into a gas phase by, for example, filling a reaction tube with a material that exhibits excellent thermal conductivity, exerts no catalytic activity in the reaction of the present invention, and is stable to hydrogen fluoride, such as metal pieces of corrosion-resistant materials including nickel beads, alumina beads, Hastelloy, Inconel, onel, Incolloy and the like. so as to homogenize the temperature distribution within the reaction tube; heating the reaction tube to not less than the vaporization temperature of the starting compound; and supplying the starting compound in a liquid phase thereinto.
  • a material that exhibits excellent thermal conductivity exerts no catalytic activity in the reaction of the present invention, and is stable to hydrogen fluoride, such as metal pieces of corrosion-resistant materials including nickel beads, alumina beads, Hastelloy, Inconel, onel, Incolloy and the like.
  • Hydrogen fluoride may generally be supplied to a reactor in a gas phase together with the starting compound.
  • the amount of the hydrogen fluoride supplied is generally about 1 to about 100 moles, preferably about 5 to about 50 moles, and more preferably about 15 to about 25 moles, per mol of the
  • HCFO-1233xf 2-chloro-3,3,3- trifluoropropene
  • HFO-1234yf 2,3,3,3-tetrafluoropropene
  • the starting compound may be supplied to the reactor as is or may be diluted with an inert gas such as nitrogen, helium, or argon and then supplied to the reactor.
  • an inert gas such as nitrogen, helium, or argon
  • the form of the reactor used in the first reaction step is not particularly limited.
  • examples of usable reactors include a fistulous adiabatic reactor, or an adiabatic reactor packed with a porous or nonporous metal or medium that improves the gas- phase mixing state between hydrogen fluoride and the starting material.
  • a multitubular reactor or the like in which a heating medium is used to cool the reactor and to homogenize the temperature distribution within the reactor.
  • the reactor is preferably made of an alloy containing 30% or more by weight of nickel. More specifically, a reactor formed of a material that is resistant to the corrosive action of hydrogen fluoride, such as Hastelloy, Inconel, Monel, and
  • Incolloy is preferably used.
  • the reaction temperature i.e., the temperature in the reactor, is about 250° C to about
  • reaction temperature 600° C, preferably about 300° C to about 500° C, and more preferably about 350° C to about 450° C. If the reaction temperature is higher than this range, the selectivity of components, such as HCFO- 1233xf, that can be intermediates for 2,3,3,3-tetrafluoropropene (HFO-1234yf) undesirably decreases. If the reaction temperature is lower than this range, the conversion of the starting compound undesirably decreases.
  • the pressure during the reaction is not particularly limited, as long as the starting compound and hydrogen fluoride can be present in the form of a gas phase, and the reaction may be conducted under ordinary pressure, increased pressure, or reduced pressure. More specifically, the first reaction step may be conducted under reduced pressure or atmospheric pressure (0.1 MPa) . This step also may be conducted under increased pressure at which the starting material does not turn into a liquid phase.
  • the reaction time is not particularly limited.
  • the residence time which is represented by V/Fo, may be
  • V/Fo is the ratio of the reaction space V (cc) in a gas phase to the total flow rate Fo (flow rate at 0 e C, 0.1 MPa: cc/sec) of the starting material gases (starting compound, hydrogen fluoride and inert gas) supplied to the reaction system.
  • the product obtained in the first reaction step is used as a starting material to be reacted with hydrogen fluoride in a gas phase in the presence of a fluorination catalyst while heating.
  • the reaction product also contains a chloropropane compound or a chloropropene compound, such as 1,2,3-trichloro- 1,1-difluoropropane (HCFC-242dc) and 2,3-dichloro-3,3- difluoropropene (HCFO-1232xf) .
  • a chloropropane compound or a chloropropene compound such as 1,2,3-trichloro- 1,1-difluoropropane (HCFC-242dc) and 2,3-dichloro-3,3- difluoropropene (HCFO-1232xf) .
  • At least one of HCFC-242dc and HCFO-1232xf is preferably used together with HCFO- 1233xf as the starting material in the second reaction step.
  • a fluorination catalyst used in the second reaction step a known catalyst having activity to fluorination reaction with hydrogen fluoride may be used.
  • metal oxides or metal oxyfluorides such as chromium oxides, chromium
  • metal fluorides such as MgF 2 , TaF 5 , and SbF 5 , also may be used.
  • the chromium oxides are not particularly limited.
  • chromium oxide represented by the composition formula: CrOm wherein preferably 1.5 ⁇ m ⁇ 3, more preferably 2 ⁇ m ⁇ 2.75, and even more preferably 2 ⁇ m ⁇ 2.3.
  • Any chromium oxide catalysts in the form of powder, pellets, etc., can be used, as long as they are suitable for the reaction. In particular, pellet-form catalysts are preferred.
  • the above chromium oxide catalysts can be produced, for example, by the process disclosed in Japanese Unexamined Patent Publication No. H5-146680.
  • the fluorinated chromium oxides can be prepared by the process disclosed in Japanese Unexamined Patent Publication No. H5-146680.
  • they can be prepared by fluorinating the chromium oxide obtained by the above-described process with hydrogen fluoride (HF treatment).
  • the degree of fluorination is not particularly limited.
  • a fluorinated chromium oxide having a fluorine content of about 10 to about 45 % by weight may be suitably used.
  • Japanese Unexamined Patent Publication No. Hll-171806 also may be used as a chromium oxide catalyst or fluorinated chrome oxide catalyst.
  • the chromium-based catalyst is in an amorphous state and comprises , as a main component , a chromium compound
  • the chromium in the chromium compound has an average valence number of not less than +3.5 and not more than +5.0.
  • the above-described fluorination catalyst may be used as supported on a carrier such as alumina and activated carbon.
  • Anhydrous hydrogen fluoride used as a starting material may be generally supplied to a reactor in the form of a gas phase together with the reaction product obtained in the first reaction step.
  • the amount of hydrogen fluoride supplied in the second reaction step may be determined based on the amount of said at least one chlorine-containing compound selected from the group consisting of a chloropropane represented by Formula ( 1 ) :
  • the amount of hydrogen fluoride is about 1 to about 50 moles, preferably about 5 to about 30 moles, and more preferably about 7 to about 15 moles, per mole of said at least one chlorine-containing compound.
  • the amount of hydrogen fluoride supplied in the second reaction step is preferably within the above-described range and smaller than the amount of hydrogen fluoride actually supplied in the first reaction step.
  • a fluorination reaction in the second reaction step can be conducted by using only the reaction product without adding further hydrogen fluoride.
  • the reaction product may be used as a starting material in the second reaction step after reducing the amount of hydrogen fluoride contained therein by a method such as distillation.
  • HFO- 1234yf 2,3,3,3-tetrafluoropropene
  • oxygen may be supplied to the reactor as entrained with the aforementioned starting material, especially in the second reaction step, in this case, the amount of oxygen to be supplied may be about 0.01 to about 0.3 mole per mole of the chlorine- containing compound supplied as a starting material in the first reaction step.
  • the form of the reactor used in the second reaction step is not particularly limited.
  • Examples of usable reactors include an adiabatic reactor packed with a catalyst and a
  • a reactor formed of a material that is resistant to the corrosive action of hydrogen fluoride such as Hastelloy, Inconel, and Monel, is preferably used.
  • the reaction temperature i.e., the temperature in the reactor, is about 200° C to about 500° C, preferably about 300" C to about 450° C, and more preferably about 350° C to about 400° C. If the reaction temperature is higher than this range, the selectivity of HFO-1234yf undesirably decreases. If the reaction temperature is lower than this range, the conversion of the starting compound undesirably decreases. In particular, the reaction temperature in the second reaction step is preferably within the above-described range and lower than that in the first reaction step.
  • the pressure during the reaction is not particularly limited, and the reaction may be conducted under ordinary
  • reaction in the present invention may be conducted under atmospheric pressure (0.1 MPa) , and may be also conducted under an increased pressure up to about 1.0 MPa.
  • the reaction time is not particularly limited.
  • the contact time which is represented by W/Fo, may be generally adjusted to a range of about 5 to about 20 g'sec/cc.
  • W/Fo is the ratio of the amount of packed catalyst W(g) to the total flow rate of the starting material gases supplied to the reactor in the second reaction step (total amount of product obtained in the first reaction step and HF) Fo (flow rate at 0°C, 1 atm: cc/sec).
  • the product obtained in the first reaction step may be supplied as is but is preferably supplied in the second reaction step after removing hydrogen chloride contained therein. Due to this, the effects of reducing energy loss caused by handling hydrogen chloride that is
  • Methods for removing hydrogen chloride from the product obtained in the first reaction step are not particularly limited.
  • hydrogen chloride can be easily removed as a column top product by distillation.
  • the product obtained in the first reaction step contains more than the amount of hydrogen fluoride required in the second reaction step, it may be supplied to the reactor in the second reaction step after removing
  • Methods for removing hydrogen fluoride are also not particularly limited. For example, according to a method for separating hydrogen fluoride by distillation or a method for extracting a phase substantially consisting of hydrogen fluoride by liquid- liquid separation, the amount of hydrogen fluoride contained in the product can be reduced by a simple method.
  • reaction product that contains the desired 2,3,3,3-tetrafluoropropene (HFO-1234yf) can be obtained with high selectivity at the reactor outlet in the second
  • the obtained HFO-1234yf can be purified and collected by distillation, etc.
  • the reaction product contains not only HFO-1234yf but also other components, such as hydrogen chloride, unreacted hydrogen
  • reaction product may contain a
  • HFO-1234yf CF 3 CHClCH 2 Cl(HCFC-243db) .
  • These compounds are produced as a precursor for HFO-1234yf according to the type of starting material used or reaction conditions, and can be reused as a starting material in the first reaction step or second reaction step.
  • the desired HFO-1234yf can be obtained with high selectivity.
  • Fig. 1 is a flowchart that shows one embodiment of the process of the present invention, which is a process comprising a step of producing HFO-1234yf according to the process of the present invention and a subsequent purification step.
  • 1,1,1,2,3- pentafluoropropane(HCC-240db) is used as a starting material and supplied to a reactor (1) together with hydrogen fluoride to conduct the reaction of the first reaction step in the absence of a catalyst.
  • the product obtained from the reactor (1) is sent to a distillation column ( 1 ) -1 to remove hydrogen chloride as a column top product.
  • other components are sent to a distillation column (l)-2 to remove excessive hydrogen fluoride as a column bottom product, and then the remainder is supplied to a reactor (2).
  • distillation column (l)-2 can be recycled by sending it to the reactor (1) and reused as a starting material.
  • the reaction of the product obtained from the first reaction step with hydrogen fluoride in the presence of a fluorination catalyst is conducted as the second reaction step.
  • the product obtained from the reactor (2) is sent to a distillation column (2) -2 to remove unreacted products and by-products, such as hydrogen fluoride, HCFO-1233xf. HCFC-242dc, and HCFO-1232xf, and other components are sent to a distillation column (2) -3.
  • the removed hydrogen fluoride, HCFO-1233xf , HCFC-242dc, HCFO-1232xf, etc . can be reused as a starting material for the reactor ( 2 ) .
  • the desired 2,3,3,3- tetrafluoropropene (HFO-1234yf) can be obtained by removing hydrogen fluoride as a column bottom product.
  • the hydrogen fluoride obtained in the distillation column (2) -3 can be sent to the reactor (1) and reused as a starting material.
  • the desired HFO-1234yf obtained in the distillation column (2) -3 can be further subjected to a crude purification step and a fine purification step to yield a final product.
  • Specific methods for the crude purification step and the fine purification step are not particularly limited. For example, water washing, dehydration (drying), distillation, liquid separation or other means can be applied to the steps.
  • 2,3,3,3- tetrafluoropropene (HFO-1234yf) can be obtained with high selectivity, and catalyst deterioration can be suppressed.
  • the process of the present invention is highly useful as a process for producing 2,3,3,3-tetrafluoropropene that is suitable for use on an industrial scale.
  • Fig. 1 is a flowchart showing one embodiment of the process of the present invention.
  • the temperature inside the reaction tube was set at 400° C and the pressure inside the reaction tube was set at
  • the molar ratio of HF to HCC-240db was 20, and the residence time (V/Fo), which is the ratio of the space volume (V) of the packed bed of nickel beads to the total flow rate (Fo) of HCC-240db and HF, was 8.0 sec.
  • Hydrogen chloride was removed from the product obtained in the first reaction step by distillation, and further,
  • a commonly used distillation column was used for distillation for removing the HC1.
  • the column had a theoretical plate number of 20, a column top pressure of 0.7 MPa, a column top temperature of -42° C, and a column bottom temperature of 62° C.
  • a distillation column used for reducing the amount of HF had a theoretical plate number of 30, an operating pressure of 0.2 MPa, a column top temperature of 47° C, and a column bottom temperature of 74° C. From the top of this distillation column, organic matter mainly including HF and HFO-1233xf was extracted. From the bottom of the column, organic matter mainly including HCFC-242dc was extracted. From the middle portion of the column, HF was extracted. The composition of column top products and column bottom products after distillation was analyzed by gas
  • a tubular reactor made of Hastelloy having an inner diameter of 15 mm and a length of 1 m was packed with 22 g of a fluorinated chromium oxide catalyst (fluorine content: about
  • the fluorinated chromium oxide catalyst was prepared by the following procedure. First, 114 g of 10% ammonia water was added to 765 g of a 5.7 % aqueous solution of chromium nitrate. After the resulting precipitate was filtered and washed, it was dried in air for 12 hours at 120° C to give a chromium hydroxide. The chromium hydroxide was formed into pellets having a diameter of 3.0 mm and a height of 3.0 mm and calcined in a nitrogen stream for two hours at 400° C.
  • a reactor made of Hastelloy C was filled with the obtained chromium oxide in the form of pellets. Increasing the temperature gradually from 200 to 360° C, the chromium oxide was heated and fluorinated with dilute HF in which hydrogen fluoride had been diluted to 20 vol% with nitrogen. After the temperature reached 360° C, the chromium oxide was further fluorinated with 100% HF to prepare the
  • the temperature inside the reaction tube was set at
  • the molar ratio of the HF to the starting material supplied to the reactor in the second reaction step was 9.3:1.
  • the ratio (W/Fo) of the amount of packed catalyst W(g) to the total flow rate of the starting material gases supplied to the reactor in the second reaction step (total amount of column top products in step (2) and HF) Fo (flow rate at 0°C, 0.1 MPa: cc/sec) was 9.9.
  • HFO-1234yf can be obtained with high selectivity.
  • Other components can be recycled as a starting material in the first or second reaction step.

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Abstract

This invention provides a process for producing 2,3,3,3-tetrafluoropropene, the process comprising: (1) a first reaction step of reacting hydrogen fluoride with at least one chlorine-containing compound selected from the group consisting of a chloropropane represented by Formula ( 1 ) : CC1X2CHC1CH2C1, wherein each X is the same or different and is CI or F, a chloropropene represented by Formula (2): CC1Y2CC1=CH2, wherein each Y is the same or different and is CI or F, and a chloropropene represented by Formula (3): CZ2=CC1CH2C1, wherein each Z is the same or different and is CI or F in a gas phase in the absence of a catalyst while heating; and (2) a second reaction step of reacting hydrogen fluoride with a reaction product obtained in the first reaction step in a gas phase in the presence of a fluorination catalyst while heating. According to the process of this invention, 2,3,3,3- tetrafluoropropene (HFO-1234yf) can be obtained with high selectivity, and catalyst deterioration can be suppressed.

Description

DESCRIPTION
Title of Invention: PROCESS FOR PRODUCING 2,3,3,
TETRAFLUOROPROPENE Technical Field
The present invention relates to a process for producing 2,3,3,3-tetrafluoropropene.
Background Art
Alternative refrigerants such as HFC-125 (C2HF5) and
HFC-32 (CH2F2) have been widely used as important replacements for CFC, HCFC, etc., which cause ozone layer depletion. However, these alternative refrigerants are potent global warming
substances, thus creating concern that diffusion of the
refrigerants would increase global warming. As a preventive measure, these refrigerants are recovered after use. However, complete recovery of the refrigerants is impossible. In addition, the diffusion of these refrigerants due to leakage, etc., cannot be ignored. The use of C02 or hydrocarbon-based substances as alternative refrigerants has also been investigated. However, because C02 refrigerants have low efficiency and devices using such refrigerants inevitably become large, C02 refrigerants have many problems in terms of the overall reduction of greenhouse gas emissions, including energy to be consumed. Furthermore, hydrocarbon-based substances pose safety problems due to their high flammability.
2,3, 3,3-tetrafluoropropene (HFO-1234yf, CF3CF=CH2) , which is an olefinic HFC having a low global warming potential, has recently been attracting attention as a material to solve the above problems. HFO-1234yf, used alone or in combination with other substances, such as hydrofluorocarbons , hydrofluoroolefins, and hydrochlorofluoroolefins, is expected to be useful as a refrigerant, and additionally as a blowing agent, propellant, extinguishing agent, or the like.
Some processes for producing HFO-1234yf have been disclosed. In most of these processes, a hydrohalopropane such as a hydrochloropropane or a hydrohalopropene such as a
hydrochloropropene, used as a starting material, is fluorinated with hydrogen fluoride to ultimately prepare HFO-1234yf.
For example. Patent Literature 1 listed below discloses a process in which HFO-1234yf is produced, via a
hydrochlorofluoroalkane or a hydrochlorofluoroalkene, by
subjecting a haloalkane or a haloalkene as a starting material to fluorination with HF, dehydrochlorination, etc.
Patent Literature 2 listed below discloses a process in which HFO-1234yf is produced, via a hydrochlorofluoroalkane, hydrochlorofluoroalkene, etc., by subjecting a hydrochloropropane, hydrochlorofluoropropane, etc., as a starting material to
fluorination with HF in the presence of a catalyst.
Furthermore, Patent Literature 3 listed below discloses an integration process for preparing HFO-1234yf by using
1,1,1,2,3-pentachloropropane (HCC-240db) as a starting material, fluorinating the starting material with HF to produce HCFO-1233xf , and then adding HF to the thus-obtained HCFO-1233xf to produce HCFC-244bb, followed by dehydrochlorination.
All of these processes use a hydrochlorocarbon as a starting material to prepare HFO-1234yf by a multiple-stage reaction process. However, each of the processes has a problem of a cost increase due to the use of a catalyst and also has a drawback of insufficient selectivity resulting from the formation of many products other than the desired product, i.e., HFO-1234yf. Further, the use of higher chlorinate as a starting material poses another problem in that catalyst activity is likely to deteriorate as reaction progresses.
Citation List
Patent Literature
PTL 1: WO2007/079431
PTL 2: WO2008/054781
PTL 3: Japanese Unexamined Patent Publication No. 2009-227675 Summary of Invention
Technical Problem
The present invention has been accomplished in view of the foregoing state of the art and its primary object is to provide a production process that is capable of producing
2,3,3,3-tetrafluoropropene (HFO-1234yf) in good yield, using a chloropropane compound or chloropropene compound as a starting material, and that is suitable for use on an industrial scale.
Solution to Problem
The present inventors conducted extensive
investigations to achieve the above object and found that
selectivity of the desired 2,3,3,3-tetrafluoropropene (HFO- 1234yf) can be improved, catalyst deterioration can be suppressed, and HFO-1234yf can be produced efficiently on an industrial scale according to a two-stage reaction process in which a
chloropropane compound or chloropropene compound represented by a specific general formula, which is used as a starting material, is reacted with hydrogen fluoride in a gas phase in the absence of a catalyst while heating, and subsequently the product
obtained by said reaction is reacted with hydrogen fluoride in a gas phase in the presence of a fluorination catalyst while
heating. The present invention has been accomplished based on this finding.
More specifically, the present invention provides the following process for producing 2,3,3,3-tetrafluoropropene.
Item 1. A process for producing 2,3,3,3- tetrafluoropropene, the process comprising:
(1) a first reaction step of reacting hydrogen fluoride with at least one chlorine-containing compound selected from the group consisting of a chloropropane represented by Formula ( 1 ) : CCIX2CHCICH2CI , wherein each X is the same or different and is CI or F, a chloropropene represented by Formula (2): CC1Y2CC1=CH2, wherein each Y is the same or different and is CI or F, and a chloropropene represented by Formula (3): CZ2=CC1CH2C1, wherein each Z is the same or different and is CI or F in a gas phase in the absence of a catalyst while heating; and
(2) a second reaction step of reacting a reaction product obtained in the first reaction step with hydrogen fluoride in a gas phase in the presence of a fluorination catalyst while heating.
Item 2. The process according to Item 1, wherein the reaction temperature in the first reaction step is 250 to 600° C, and the reaction temperature in the second reaction step is 200 to 500° C.
Item 3. The process according to Item 1 or 2, wherein the amount of hydrogen fluoride in the first reaction step is 1 to 100 moles per mole of the chlorine-containing compound used as a starting material, and the amount of hydrogen fluoride in the second reaction step is 1 to 50 moles per mole of the chlorine- containing compound used as a starting material in the first reaction step.
Item 4. The process according to any one of Items 1 to
3, wherein the fluorination catalyst used in the second reaction step is at least one member selected from the group consisting of chromium oxides, chromium oxyfluorides , aluminium fluorides, aluminum oxyfluorides , and metal fluorides.
Item 5. The process according to any one of Items 1 to
4, wherein after removing hydrogen chloride from the reaction product obtained in the first reaction step, the reaction product is used as a starting material in the second reaction step.
Item 6. The process according to any one of Items 1 to
5, wherein after reducing the amount of hydrogen fluoride contained in the reaction product obtained in the first reaction step, the reaction product is used as a starting material in the second reaction step.
Item 7. The process according to any one of Items 1 to
6, wherein the second reaction step uses, as a starting material, at least one chlorine-containing compound selected from the group consisting of a chloropropane represented by Formula (4): CC1X2CHC1CH2C1, wherein at least one of X is F, a chloropropene represented by Formula (5): CC1Y2CC1=CH2, wherein at least one of Y is F, and a chloropropene represented by Formula (6):
CZ2=CC1CH2C1, wherein at least one of Z is F,
the chlorine-containing compound being contained in the reaction product obtained in the first reaction step.
Item 8. The process according to any one of Items 1 to 6, wherein the second reaction step uses, as a starting material, at least one chlorine-containing compound selected from the group consisting of CF2ClCHClCH2Cl(HCFC-242dc) and CF2C1CC1=CH2(HCF0- 1232xf),
the chlorine-containing compound being contained in the reaction product obtained in the first reaction step.
Item 9. The process according to any one of Items 1 to 8, wherein the first reaction step is conducted in a reactor made of an alloy containing 30% or more by weight of nickel.
Item 10. The process according to Item 9, wherein the alloy containing 30% or more by weight of nickel is at least one member selected from the group consisting of Hastelloy, Inconel, Monel, and Incolloy.
The process for producing 2,3,3,3-tetrafluoropropene of the present invention is described in detail below.
(1) Starting compound
In the present invention, at least one chlorine- containing compound selected from the group consisting of a chloropropane represented by Formula ( 1 ) : CC1X2CHC1CH2C1, wherein each X is the same or different and is CI or F, a chloropropene represented by Formula (2): CC1Y2CC1=CH2, wherein each Y is the same or different and is CI or F, and a chloropropene represented by Formula (3): CZ2=CC1CH2C1, wherein each Z is the same or different and is CI or F is used as a starting compound. When these chlorine-containing compounds are used as a starting material and reacted with hydrogen fluoride in a two-stage reaction process according to the conditions described below, the desired 2,3,3,3-tetrafluoropropene(HFO-1234yf) can be obtained with high selectivity as compared to the case in which
fluorination reaction is conducted in a single-stage reaction process .
Among the starting compounds, specific examples of the chloropropane represented by Formula ( 1 ) : CCIX2CHCICH2CI include CCI3CHCICH2CI (HCC-240db, bp. 179eC/760 mmHg, 51-53° C/3 mmHg) , CFCl2CHClCH2Cl(HCFC-241db, bp. 157° C), CF2ClCHClCH2Cl(HCFC-242dc, bp. 113-114° C), and the like. Specific examples of the
chloropropene represented by Formula ( 2 ) : CC1Y2CC1=CH2 include CC13CC1=CH2 (HCO-1230xf, bp. 128° C), CFCl2CCl=CH2(HCFO-1231xf, bp. 98.5-99° C), CF2C1CC1=CH2(HCF0-I232xf, bp. 57-58° C), and the like. Specific examples of the chloropropene represented by Formula (3): CZ2=CC1CH2C1 include CC12=CC1CH2C1(HCO-I230xa, bp. 138° C), CFC1=CC1CH2C1(HCF0-I231xb) , CF2=CC1CH2C1(HCF0-I232xc) , and the like.
Among these starting compounds, HCC- 240db (CCI3CHCICH2CI(1,1,1,2, 3-pentachloropropane) ) , HCO- 1230xf(CCl3CCl=CH2(2,3,3,3-tetrachloropropene) ) , and HCO-1230xa (CC12=CC1CH2C1 (1,1,2,3-tetrachloropropene) ) are particularly advantageous starting compounds in that they are readily
available and inexpensive.
In the present invention, the starting compounds can be used singly or in combination of two or more.
(2) Production process
In the present invention, it is necessary to adopt a two-stage reaction process comprising a first reaction step of reacting at least one of the aforementioned starting compounds with hydrogen fluoride in a gas phase in the absence of a catalyst while heating, and a second reaction step of reacting the reaction product obtained in the first reaction step with hydrogen fluoride in a gas phase in the presence of a
fluorination catalyst while heating. The use of such a two-stage reaction process enables the improvement of selectivity of the desired 2,3,3,3-tetrafluoropropene(HFO-1234yf) and further enables the suppression of deterioration of a catalyst used in the fluorination process.
Each reaction step will be described below in detail,
(i) First reaction step
In the first reaction step, at least one of the above starting compounds is reacted with hydrogen fluoride in a gas phase in the absence of a catalyst while heating.
In the first reaction step, the reaction of the starting compound with hydrogen fluoride under such conditions yields a product containing 2-chloro-3,3,3-trifluoropropene
(HCFO-1233xf) that is an intermediate for 2,3,3,3- tetrafluoropropene (HFO-1234yf) .
The first reaction step requires the reaction of the starting compound with hydrogen fluoride in a gas phase in the absence of a catalyst. As long as the starting compound and hydrogen fluoride come into contact with each other in a gas phase within the reaction temperature range descried below, the starting compound may be in a liquid form when supplied. For example, when the starting compound is liquid at an ordinary temperature and ordinary pressure, the starting compound is vaporized using a vaporizer (vaporization region), passed through a preheating region, and then supplied to a mixing region wherein the starting compound is contacted with anhydrous hydrogen
fluoride, whereby the reaction can be conducted in a gas phase. The reaction may also be carried out by supplying the starting compound in a liquid phase to a reactor, and vaporizing the compound when the compound enters a reaction temperature range to react with hydrogen fluoride. There is no particular limitation to the methods for vaporizing the starting compound in the
reaction temperature range. The starting compound may be
vaporized into a gas phase by, for example, filling a reaction tube with a material that exhibits excellent thermal conductivity, exerts no catalytic activity in the reaction of the present invention, and is stable to hydrogen fluoride, such as metal pieces of corrosion-resistant materials including nickel beads, alumina beads, Hastelloy, Inconel, onel, Incolloy and the like. so as to homogenize the temperature distribution within the reaction tube; heating the reaction tube to not less than the vaporization temperature of the starting compound; and supplying the starting compound in a liquid phase thereinto.
Hydrogen fluoride may generally be supplied to a reactor in a gas phase together with the starting compound. The amount of the hydrogen fluoride supplied is generally about 1 to about 100 moles, preferably about 5 to about 50 moles, and more preferably about 15 to about 25 moles, per mol of the
aforementioned starting compound. By setting the amount within such a range, the conversion of the starting compound and the selectivity of components, such as 2-chloro-3,3,3- trifluoropropene (HCFO-1233xf) , that can be intermediates for 2,3,3,3-tetrafluoropropene (HFO-1234yf) , can be maintained in a desirable range.
The starting compound may be supplied to the reactor as is or may be diluted with an inert gas such as nitrogen, helium, or argon and then supplied to the reactor.
The form of the reactor used in the first reaction step is not particularly limited. Examples of usable reactors include a fistulous adiabatic reactor, or an adiabatic reactor packed with a porous or nonporous metal or medium that improves the gas- phase mixing state between hydrogen fluoride and the starting material. Also usable is a multitubular reactor or the like in which a heating medium is used to cool the reactor and to homogenize the temperature distribution within the reactor. When fistulous reactors are used in the method using a reaction tube having a small inner diameter to improve the heat transfer efficiency, the relationship of the flow rate of the starting compound to the inner diameter of the reaction tube, for example, is preferably adjusted so as to achieve a high linear velocity and a large heating area.
The reactor is preferably made of an alloy containing 30% or more by weight of nickel. More specifically, a reactor formed of a material that is resistant to the corrosive action of hydrogen fluoride, such as Hastelloy, Inconel, Monel, and
Incolloy, is preferably used.
In the first reaction step, the reaction temperature, i.e., the temperature in the reactor, is about 250° C to about
600° C, preferably about 300° C to about 500° C, and more preferably about 350° C to about 450° C. If the reaction temperature is higher than this range, the selectivity of components, such as HCFO- 1233xf, that can be intermediates for 2,3,3,3-tetrafluoropropene (HFO-1234yf) undesirably decreases. If the reaction temperature is lower than this range, the conversion of the starting compound undesirably decreases.
The pressure during the reaction is not particularly limited, as long as the starting compound and hydrogen fluoride can be present in the form of a gas phase, and the reaction may be conducted under ordinary pressure, increased pressure, or reduced pressure. More specifically, the first reaction step may be conducted under reduced pressure or atmospheric pressure (0.1 MPa) . This step also may be conducted under increased pressure at which the starting material does not turn into a liquid phase.
The reaction time is not particularly limited. However, the residence time, which is represented by V/Fo, may be
generally adjusted to a range of about 1 to about 10 sec. V/Fo is the ratio of the reaction space V (cc) in a gas phase to the total flow rate Fo (flow rate at 0eC, 0.1 MPa: cc/sec) of the starting material gases (starting compound, hydrogen fluoride and inert gas) supplied to the reaction system.
Under the above reaction conditions, a reaction product that contains 2-chloro-3, 3, 3-trifluoropropene (HCFO-1233xf) can be obtained at the reactor outlet,
(ii) Second reaction step
In the second reaction step, the product obtained in the first reaction step is used as a starting material to be reacted with hydrogen fluoride in a gas phase in the presence of a fluorination catalyst while heating. The product obtained in the first reaction step contains 2- chloro-3, 3, 3-trifluoropropene (HCFO-1233xf) as a main component and also contains at least one chlorine-containing compound selected from the group consisting of a chloropropane represented by Formula ( ) : CC1X2CHC1CH2C1, wherein at least one of X is F , a chloropropene represented by Formula (5): CC1Y2CC1=CH2, wherein at least one of Y is F, and a chloropropene represented by Formula ( 6 ) : CZ2=CC1CH2C1, wherein at least one of Z is F. More
specifically, the reaction product also contains a chloropropane compound or a chloropropene compound, such as 1,2,3-trichloro- 1,1-difluoropropane (HCFC-242dc) and 2,3-dichloro-3,3- difluoropropene (HCFO-1232xf) . When the product containing the chloropropane compound, chloropropene compound, or the like is used as is as a starting material and reacted with hydrogen fluoride in the presence of a fluorination catalyst in the second reaction step, not only HCFO-1233xf but also the components contained in the product, such as HCFC-242dc and HCFO-1232xf, can be converted to 2, 3, 3, 3-tetrafluoropropene (HFO-1234yf) . As a result, the desired HFO-1234yf can be obtained with high
selectivity. Above all, in the present invention, at least one of HCFC-242dc and HCFO-1232xf is preferably used together with HCFO- 1233xf as the starting material in the second reaction step.
Moreover, since a fluorination catalyst is used only in the second reaction step, catalyst deterioration is significantly suppressed relative to the amount of produced HFO-1234yf , as compared to the case in which HFO-1234yf is produced by a single- stage fluorination reaction. This ensures an economically excellent production process.
In contrast, it is not favorable that only HCFO-1233xf is separated from the product obtained in the first reaction step and used in a reaction for synthesizing HFO-1234yf , while other components, such as a chloropropane compound and chloropropene compound, are recycled as the starting material in the first reaction step, because the selectivity of HCFO-1233xf in the first reaction step is unexpectedly decreased, resulting in the decrease in overall selectivity of HFO-1234yf.
As a fluorination catalyst used in the second reaction step, a known catalyst having activity to fluorination reaction with hydrogen fluoride may be used. For example, metal oxides or metal oxyfluorides, such as chromium oxides, chromium
oxyfluorides , aluminium fluorides, and aluminum oxyfluorides, may be used. In addition to these catalysts, metal fluorides, such as MgF2, TaF5, and SbF5, also may be used.
Among these catalysts, the chromium oxides, for instance, are not particularly limited. For example, it is preferable to use chromium oxide represented by the composition formula: CrOm, wherein preferably 1.5 < m < 3, more preferably 2 < m < 2.75, and even more preferably 2 < m < 2.3. Any chromium oxide catalysts in the form of powder, pellets, etc., can be used, as long as they are suitable for the reaction. In particular, pellet-form catalysts are preferred. The above chromium oxide catalysts can be produced, for example, by the process disclosed in Japanese Unexamined Patent Publication No. H5-146680.
In addition, the fluorinated chromium oxides can be prepared by the process disclosed in Japanese Unexamined Patent Publication No. H5-146680. For example, they can be prepared by fluorinating the chromium oxide obtained by the above-described process with hydrogen fluoride (HF treatment).
The degree of fluorination is not particularly limited. For example, a fluorinated chromium oxide having a fluorine content of about 10 to about 45 % by weight may be suitably used.
Further, the chromium-based catalyst disclosed in
Japanese Unexamined Patent Publication No. Hll-171806 also may be used as a chromium oxide catalyst or fluorinated chrome oxide catalyst. The chromium-based catalyst is in an amorphous state and comprises , as a main component , a chromium compound
containing at least one metallic element selected from the group consisting of indium, gallium, cobalt, nickel, zinc, and aluminum. The chromium in the chromium compound has an average valence number of not less than +3.5 and not more than +5.0.
The above-described fluorination catalyst may be used as supported on a carrier such as alumina and activated carbon.
Anhydrous hydrogen fluoride used as a starting material may be generally supplied to a reactor in the form of a gas phase together with the reaction product obtained in the first reaction step. The amount of hydrogen fluoride supplied in the second reaction step may be determined based on the amount of said at least one chlorine-containing compound selected from the group consisting of a chloropropane represented by Formula ( 1 ) :
CCIX2CHCICH2CI, a chloropropene represented by Formula ( 2 ) :
CC1Y2CC1=CH2, and a chloropropene represented by Formula ( 3) :
CZ2=CC1CH2C1, used as a starting material in the first reaction step. Specifically, the amount of hydrogen fluoride is about 1 to about 50 moles, preferably about 5 to about 30 moles, and more preferably about 7 to about 15 moles, per mole of said at least one chlorine-containing compound. The amount of hydrogen fluoride supplied in the second reaction step is preferably within the above-described range and smaller than the amount of hydrogen fluoride actually supplied in the first reaction step.
When the amount of hydrogen fluoride contained in the reaction product obtained in the first reaction step is within the aforementioned range, a fluorination reaction in the second reaction step can be conducted by using only the reaction product without adding further hydrogen fluoride. When the amount of hydrogen fluoride contained in the reaction product obtained in the first reaction step is larger than the aforementioned range, the reaction product may be used as a starting material in the second reaction step after reducing the amount of hydrogen fluoride contained therein by a method such as distillation.
The selectivity of 2,3,3,3-tetrafluoropropene (HFO- 1234yf) can be maintained in a desirable range by using anhydrous hydrogen fluoride within the above-described range in the presence of a fluorination catalyst.
To maintain catalyst activity for a long period of time, oxygen may be supplied to the reactor as entrained with the aforementioned starting material, especially in the second reaction step, in this case, the amount of oxygen to be supplied may be about 0.01 to about 0.3 mole per mole of the chlorine- containing compound supplied as a starting material in the first reaction step.
The form of the reactor used in the second reaction step is not particularly limited. Examples of usable reactors include an adiabatic reactor packed with a catalyst and a
multitubular reactor in which a heating medium is used to cool the reactor. As in the first reaction step, a reactor formed of a material that is resistant to the corrosive action of hydrogen fluoride, such as Hastelloy, Inconel, and Monel, is preferably used.
In the second reaction step, the reaction temperature, i.e., the temperature in the reactor, is about 200° C to about 500° C, preferably about 300" C to about 450° C, and more preferably about 350° C to about 400° C. If the reaction temperature is higher than this range, the selectivity of HFO-1234yf undesirably decreases. If the reaction temperature is lower than this range, the conversion of the starting compound undesirably decreases. In particular, the reaction temperature in the second reaction step is preferably within the above-described range and lower than that in the first reaction step.
The pressure during the reaction is not particularly limited, and the reaction may be conducted under ordinary
pressure or increased pressure. More specifically, the reaction in the present invention may be conducted under atmospheric pressure (0.1 MPa) , and may be also conducted under an increased pressure up to about 1.0 MPa.
The reaction time is not particularly limited. However, the contact time, which is represented by W/Fo, may be generally adjusted to a range of about 5 to about 20 g'sec/cc. W/Fo is the ratio of the amount of packed catalyst W(g) to the total flow rate of the starting material gases supplied to the reactor in the second reaction step (total amount of product obtained in the first reaction step and HF) Fo (flow rate at 0°C, 1 atm: cc/sec).
In the second reaction step, the product obtained in the first reaction step may be supplied as is but is preferably supplied in the second reaction step after removing hydrogen chloride contained therein. Due to this, the effects of reducing energy loss caused by handling hydrogen chloride that is
unnecessary in the second reaction step and improving the
selectivity of HFO-1234yf can be expected. Methods for removing hydrogen chloride from the product obtained in the first reaction step are not particularly limited. For example, hydrogen chloride can be easily removed as a column top product by distillation.
As described above, when the product obtained in the first reaction step contains more than the amount of hydrogen fluoride required in the second reaction step, it may be supplied to the reactor in the second reaction step after removing
excessive hydrogen fluoride from the product obtained in the first reaction step to reduce the content of hydrogen fluoride. Methods for removing hydrogen fluoride are also not particularly limited. For example, according to a method for separating hydrogen fluoride by distillation or a method for extracting a phase substantially consisting of hydrogen fluoride by liquid- liquid separation, the amount of hydrogen fluoride contained in the product can be reduced by a simple method.
(3) Reaction product:
According to the aforementioned process comprising two- stage reaction steps, a reaction product that contains the desired 2,3,3,3-tetrafluoropropene (HFO-1234yf) can be obtained with high selectivity at the reactor outlet in the second
reaction step. The obtained HFO-1234yf can be purified and collected by distillation, etc.
In the production process of the present invention, the reaction product contains not only HFO-1234yf but also other components, such as hydrogen chloride, unreacted hydrogen
fluoride, and CF3CCl=CH2(HCFO-1233xf) . In addition to these components, the reaction product may contain a
chlorofluoropropane compound, chlorofluoropropene compound, etc., such as CFCl2CHClCH2Cl(HCFC-241db) , CFCl2CCl=CH2(HCFO-1231xf) , CF2ClCHClCH2Cl(HCFC-242dc) , CF2C1CC1=CH2(HCF0-I232xf) , and
CF3CHClCH2Cl(HCFC-243db) . These compounds are produced as a precursor for HFO-1234yf according to the type of starting material used or reaction conditions, and can be reused as a starting material in the first reaction step or second reaction step. In particular, when HCFO-1233xf, HCFO-1232xf, or HCFC-242dc is reused as a starting material in the second reaction step, the desired HFO-1234yf can be obtained with high selectivity.
Fig. 1 is a flowchart that shows one embodiment of the process of the present invention, which is a process comprising a step of producing HFO-1234yf according to the process of the present invention and a subsequent purification step.
In the process shown in Figure 1, 1,1,1,2,3- pentafluoropropane(HCC-240db) is used as a starting material and supplied to a reactor (1) together with hydrogen fluoride to conduct the reaction of the first reaction step in the absence of a catalyst. The product obtained from the reactor (1) is sent to a distillation column ( 1 ) -1 to remove hydrogen chloride as a column top product. After that, other components are sent to a distillation column (l)-2 to remove excessive hydrogen fluoride as a column bottom product, and then the remainder is supplied to a reactor (2). The hydrogen fluoride separated in the
distillation column (l)-2 can be recycled by sending it to the reactor (1) and reused as a starting material.
In the reactor ( 2 ) , the reaction of the product obtained from the first reaction step with hydrogen fluoride in the presence of a fluorination catalyst is conducted as the second reaction step. After removing hydrogen chloride as a column top product in a distillation column (2)-l, the product obtained from the reactor (2) is sent to a distillation column (2) -2 to remove unreacted products and by-products, such as hydrogen fluoride, HCFO-1233xf. HCFC-242dc, and HCFO-1232xf, and other components are sent to a distillation column (2) -3. The removed hydrogen fluoride, HCFO-1233xf , HCFC-242dc, HCFO-1232xf, etc . , can be reused as a starting material for the reactor ( 2 ) .
In the distillation column (2) -3, the desired 2,3,3,3- tetrafluoropropene (HFO-1234yf) can be obtained by removing hydrogen fluoride as a column bottom product. The hydrogen fluoride obtained in the distillation column (2) -3 can be sent to the reactor (1) and reused as a starting material.
The desired HFO-1234yf obtained in the distillation column (2) -3 can be further subjected to a crude purification step and a fine purification step to yield a final product.
Specific methods for the crude purification step and the fine purification step are not particularly limited. For example, water washing, dehydration (drying), distillation, liquid separation or other means can be applied to the steps.
Advantageous Effects of Invention
According to the process for producing 2,3,3,3- tetrafluoropropene of the present invention, 2,3,3,3- tetrafluoropropene (HFO-1234yf) can be obtained with high selectivity, and catalyst deterioration can be suppressed.
Accordingly, the process of the present invention is highly useful as a process for producing 2,3,3,3-tetrafluoropropene that is suitable for use on an industrial scale.
Brief Description of Drawings
Fig. 1 is a flowchart showing one embodiment of the process of the present invention.
Description of Embodiments
An Example is given below to illustrate the present invention in more detail.
Example 1
(1) First reaction step A 1/2-inch pipe made of Inconel (inner diameter: 1.02 cm) equipped with a 1/8-inch thermometer protection tube made of Inconel (outer diameter: 0.32 cm) was used as a reaction tube and was packed with nickel beads (diameter: 3 mm) that were inactive to the reaction. The packed nickel bead bed length was 19.5 cm, and the space volume of the packed bed of nickel beads was 7.5 cm3.
To this reaction tube, 1, 1, 1,2,3-pentafluoropropane (HCC-240db) and anhydrous hydrogen fluoride were continuously supplied at a rate of 2.4 cc/min (flow rate at 0° C and 0.1 MPa) and at a rate of 47 cc/min (flow rate at 0° C and 0.1 MPa),
respectively. The temperature inside the reaction tube was set at 400° C and the pressure inside the reaction tube was set at
atmospheric pressure (0.1 MPa).
The molar ratio of HF to HCC-240db was 20, and the residence time (V/Fo), which is the ratio of the space volume (V) of the packed bed of nickel beads to the total flow rate (Fo) of HCC-240db and HF, was 8.0 sec.
Effluents obtained from the reactor 65 hours after the start of reaction were analyzed by gas chromatography. The conversion of HCC-240db was 100%. Table 1 below shows the
selectivity of each component.
[Table 1]
Figure imgf000019_0001
(2) Treatment for removing hydrogen chloride and hydrogen
fluoride
Hydrogen chloride was removed from the product obtained in the first reaction step by distillation, and further,
distillation was conducted to reduce the amount of hydrogen T/JP2011/075365
-18- fluoride. A commonly used distillation column was used for distillation for removing the HC1. The column had a theoretical plate number of 20, a column top pressure of 0.7 MPa, a column top temperature of -42° C, and a column bottom temperature of 62° C. A distillation column used for reducing the amount of HF had a theoretical plate number of 30, an operating pressure of 0.2 MPa, a column top temperature of 47° C, and a column bottom temperature of 74° C. From the top of this distillation column, organic matter mainly including HF and HFO-1233xf was extracted. From the bottom of the column, organic matter mainly including HCFC-242dc was extracted. From the middle portion of the column, HF was extracted. The composition of column top products and column bottom products after distillation was analyzed by gas
chromatography and by titration with NaOH aqueous solution. The results are shown in Table 2 below.
[Table 2]
Distillation column material balance (mol/hr)
Figure imgf000020_0001
(3) Second reaction step
A tubular reactor made of Hastelloy having an inner diameter of 15 mm and a length of 1 m was packed with 22 g of a fluorinated chromium oxide catalyst (fluorine content: about
15.0%) that had been obtained by subjecting chromium oxide to fluorination treatment. The fluorinated chromium oxide catalyst was prepared by the following procedure. First, 114 g of 10% ammonia water was added to 765 g of a 5.7 % aqueous solution of chromium nitrate. After the resulting precipitate was filtered and washed, it was dried in air for 12 hours at 120° C to give a chromium hydroxide. The chromium hydroxide was formed into pellets having a diameter of 3.0 mm and a height of 3.0 mm and calcined in a nitrogen stream for two hours at 400° C. A reactor made of Hastelloy C was filled with the obtained chromium oxide in the form of pellets. Increasing the temperature gradually from 200 to 360° C, the chromium oxide was heated and fluorinated with dilute HF in which hydrogen fluoride had been diluted to 20 vol% with nitrogen. After the temperature reached 360° C, the chromium oxide was further fluorinated with 100% HF to prepare the
fluorinated chromium oxide catalyst.
The temperature inside the reaction tube was set at
365° C, and the pressure inside the reaction tube was set at atmospheric pressure (0.1 MPa) . Anhydrous hydrogen fluoride (HF) gas was supplied to the reactor at a flow rate of 118 cc/min (flow rate at 0°C, 0.1 MPa; the same applies hereinafter), oxygen gas was fed to the reactor at a flow rate of 2.2 cc/min, and these reaction conditions were maintained for one hour. After that, the mixture of the compounds obtained as column top and column bottom products in the treatment for removing hydrogen fluoride described above (molar ratio of HCFO-1233xf:HCFC- 242dc:HCFO-1232xf is 89:8.1:2.9) was supplied to the reactor at a flow rate of 12.7 cc/min.
At that point, the molar ratio of the HF to the starting material supplied to the reactor in the second reaction step was 9.3:1. The ratio (W/Fo) of the amount of packed catalyst W(g) to the total flow rate of the starting material gases supplied to the reactor in the second reaction step (total amount of column top products in step (2) and HF) Fo (flow rate at 0°C, 0.1 MPa: cc/sec) was 9.9.
Effluents obtained from the reactor 28 hours after the start of reaction were analyzed by gas chromatography. The conversion of HCFO-1233xf supplied to the reactor in the second reaction step was 24%, and the conversion of HCFC-242dc and HCFO- 1232xf supplied to the reactor in the second reaction step was 100%. Table 3 below shows the composition of the organic matter obtained at the reactor outlet. [ able 3]
Figure imgf000022_0001
From the above results, it was confirmed that according to the production process of the present invention, HFO-1234yf can be obtained with high selectivity. Other components can be recycled as a starting material in the first or second reaction step.

Claims

[Claim 1]
A process for producing 2,3,3,3-tetrafluoropropene, the process comprising:
(1) a first reaction step of reacting hydrogen fluoride with at least one chlorine-containing compound selected from the group consisting of a chloropropane represented by Formula ( 1 ) : CC1X2CHC1CH2C1, wherein each X is the same or different and is CI or F, a chloropropene represented by Formula (2) : CC1Y2CC1=CH2, wherein each Y is the same or different and is CI or F, and a chloropropene represented by Formula ( 3 ) : CZ2=CC1CH2C1, wherein each Z is the same or different and is CI or F in a gas phase in the absence of a catalyst while heating; and
(2) a second reaction step of reacting a reaction product obtained in the first reaction step with hydrogen fluoride in a gas phase in the presence of a fluorination catalyst while heating.
[Claim 2]
The process according to Claim 1, wherein the reaction temperature in the first reaction step is 250 to 600° C, and the reaction temperature in the second reaction step is 200 to 500° C.
[Claim 3]
The process according to Claim 1 or 2, wherein the amount of hydrogen fluoride in the first reaction step is 1 to 100 moles per mole of the chlorine-containing compound used as a starting material, and the amount of hydrogen fluoride in the second reaction step is 1 to 50 moles per mole of the chlorine- containing compound used as a starting material in the first reaction step.
[Claim 4]
The process according to any one of Claims 1 to 3, wherein the fluorination catalyst used in the second reaction step is at least one member selected from the group consisting of chromium oxides, chromium oxyfluorides , aluminium fluorides, aluminum oxyfluorides , and metal fluorides.
[Claim 5]
The process according to any one of Claims 1 to 4, wherein after removing hydrogen chloride from the reaction product obtained in the first reaction step, the reaction product is used as a starting material in the second reaction step.
[Claim 6]
The process according to any one of Claims 1 to 5, wherein after reducing the amount of hydrogen fluoride contained in the reaction product obtained in the first reaction step, the reaction product is used as a starting material in the second reaction step.
[Claim 7]
The process according to any one of Claims 1 to 6, wherein the second reaction step uses, as a starting material, at least one chlorine-containing compound selected from the group consisting of a chloropropane represented by Formula ( 4 ) :
CC1X2CHC1CH2C1, wherein at least one of X is F, a chloropropene represented by Formula (5): CC1Y2CC1=CH2, wherein at least one of Y is F, and a chloropropene represented by Formula (6):
CZ2=CC1CH2C1, wherein at least one of Z is F,
the chlorine-containing compound being contained in the reaction product obtained in the first reaction step.
[Claim 8]
The process according to any one of Claims 1 to 6, wherein the second reaction step uses, as a starting material, at least one chlorine-containing compound selected from the group consisting of CF2ClCHClCH2Cl(HCFC-242dc) and CF2C1CC1=CH2(HCFO- 1232xf), the chlorine-containing compound being contained in the reaction product obtained in the first reaction step.
[Claim 9]
The process according to any one of Claims 1 to 8, wherein the first reaction step is conducted in a reactor made of an alloy containing 30% or more by weight of nickel.
[Claim 10]
The process according to Claim 9, wherein the alloy containing 30% or more by weight of nickel is at least one member selected from the group consisting of Hastelloy, Inconel, Monel, and Incolloy.
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