WO2010013795A1 - Procédé de production du 2,3,3,3-tétrafluoropropène - Google Patents

Procédé de production du 2,3,3,3-tétrafluoropropène Download PDF

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WO2010013795A1
WO2010013795A1 PCT/JP2009/063628 JP2009063628W WO2010013795A1 WO 2010013795 A1 WO2010013795 A1 WO 2010013795A1 JP 2009063628 W JP2009063628 W JP 2009063628W WO 2010013795 A1 WO2010013795 A1 WO 2010013795A1
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halogenated
formula
represented
catalyst
tetrafluoropropane
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PCT/JP2009/063628
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English (en)
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Daisuke Karube
Takehiro Chaki
Yuko Shiotani
Akinari Sugiyama
Masatoshi Nose
Takashi Shibanuma
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Daikin Industries, Ltd.
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Priority to JP2011504258A priority Critical patent/JP5413451B2/ja
Publication of WO2010013795A1 publication Critical patent/WO2010013795A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
    • 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
    • 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
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
    • 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.
  • Patent Literature (PTL) 1 listed below discloses a process for producing
  • the HFO- 1234yf yield of this process is only about 5%, which is not satisfactory.
  • Patent Literature 2 listed below discloses the production Of CF 3 CF 2 CH 3 and HFO- 1234yf by reacting TFE and CH 3 F in the presence of SbF 5 supported on activated carbon. This reaction is costly because the CH 3 F used as a starting material is expensive. Further, this reaction uses SbFs, which is corrosive, and thus poses many problems for industrial purposes.
  • This process has a low yield and requires further improvement.
  • the starting material CF 3 CF 2 CHCl 2 is synthesized by the addition reaction of TFE and CFCl 3 , followed by reduction of the reaction product. Since CFCl 3 is a material derived from CCU, this process is rather costly.
  • HFO- 1234yf processes for producing HFO- 1234yf that have been reported include a process wherein chloromethyl tetrafluoropropanoate is reacted with an amine (Patent Literature 4); a process that involves thermal decomposition of l-trifluoromethyM,2,2-trifluorocyclobutane (Patent Literature 5); etc.
  • TFE is a material produced in large quantities on an industrial scale.
  • Various processes for increasing the carbon number by reacting TFE with Ci compounds have been reported. Examples of such processes include a process wherein TFE is reacted with (CH2 ⁇ ) n (Non-Patent Literature 2), a process wherein TFE is reacted with CHCI3, CCU, or the like (Patent Literature 6), and a process wherein TFE is reacted with CH2CIF.
  • CF2CICF2CH3 in the reduction reaction of CFC-214cb or HCFC"224ca is less than 60%.
  • Patent Literature PTL l U.S. Pat. No. 2,931,840
  • a principal object of the invention is to provide a novel process for producing 2,3,3,3-tetrafluoropropene (HFO- 1234yf) that is capable of producing HFO1234yf in a high yield, using inexpensive starting materials.
  • HFO1234yf 2,3,3,3-tetrafluoropropene
  • a specific halogenated fluoropropane that can be obtained from tetrafluoroethylene and a relatively inexpensive halogenated methane, such as chloroform, carbon tetrachloride, or the like! and by treating this starting material according to a specific reaction process.
  • the present invention was accomplished based on this finding.
  • the present invention provides a process for producing 2,3,3,3-tetrafluoropropene as summarized below. 1.
  • a process for producing 2,3,3,3-tetrafluoropropene comprising the following steps:
  • step (ii) contacting the 1-halogenated-l, 1,2,2-tetrafluoropropane obtained in step (i) with a catalyst in a gas phase to produce 2,3,3,3-tetrafluoropropene.
  • step (0 is performed by a method comprising reducing the halogenated fluoropropane represented by formula (l): ACF2CF2CHxF y Az with hydrogen in the presence of a catalyst.
  • step (i) is performed by a method comprising reducing the halogenated fluoropropane represented by formula (l): ACF2CF2CH ⁇ F y Az with hydrogen at 80 to 200 0 C in the presence of at least one catalyst selected from the group consisting of platinum, palladium, rhodium, ruthenium, nickel, rhenium, molybdenum, and zirconium.
  • step (ii) is performed by a method comprising contacting the l-halogenated-l,l,2,2-tetrafluoropropane with at least one catalyst selected from the group consisting of chromium oxides, fluorinated chromium oxides, and iron fluorides in a gas phase.
  • step ( ⁇ ) is performed by a method comprising contacting the l-halogenated-l,l,2,2-tetrafluoropropane with the catalyst in the presence of hydrogen fluoride and oxygen; the amount of the hydrogen fluoride being from 0.1 to 2 mol per 1 mol of the l-halogenated-l,l,2,2"tetrafluoropropane; and the amount of the oxygen being from 0.1 to 21 mol% based on the total amount of the l-halogenated-l,l,2,2-tetrafluoropropane, hydrogen fluoride, and oxygen. 7.
  • halogenated methane represented by formula (3) is a chloromethane represented by the formula CH n CU n, wherein n is an integer from 0 to 2.
  • x, y, and z is 3, with hydrogen at 80 to 200 0 C in the presence of at least one catalyst selected from the group consisting of platinum, palladium, rhodium, ruthenium, nickel, rhenium, molybdenum, and zirconium.
  • at least one catalyst selected from the group consisting of platinum, palladium, rhodium, ruthenium, nickel, rhenium, molybdenum, and zirconium.
  • the process of the invention is a process wherein a halogenated fluoropropane represented by formula (l) ACF2CF2CHxF y A z , wherein A is Cl, Br, or I; x is an integer from 0 to 2; y and z are each an integer from 0 to 3) and the total number of x, y, and z is 3, is used as a starting material, and 2,3,3,3-tetrafluoropropene
  • step (i) A step of dehydrofluorinating and fluorinating the l-halogenated-l,l,2,2-tetrafluoropropane obtained in step (i) to produce 2,3,3,3-tetrafluoropropene.
  • the desired product can be obtained with high selectivity in each step, and the ultimately desired 2,3,3,3-tetrafluoropropene can be produced with high selectivity and high yield.
  • the process of the invention is described in detail below,
  • a halogenated fluoropropane represented by formula (l): ACF2CF2CHxF y Az, wherein A is Cl, Br, or I; x is an integer from 0 to 2; y and z are each an integer from 0 to 31 and the total number of x, y, and z is 3, is used as a starting compound.
  • the halogenated fluoropropane is obtainable by, for example, a method that includes the addition reaction of tetrafluoroethylene and a halogenated methane represented by formula (3): CH x FyA z +i, wherein A, x, y, and z are as defined above.
  • a chloromethane represented by the formula CH n CUn is a starting material that is particularly advantageous because of its low cost.
  • Specific examples of these halogenated methanes include carbon tetrachloride (CCI4), chloroform (CHCI3), and the like.
  • the halogenated fluoropropane obtained by the addition reaction of the chloromethane represented by the formula CHnCU n , wherein n is an integer from 0 to 2, to tetrafluoroethylene, i.e., a compound represented by formula (l') : ClCF2CF2CH n Cl3n, wherein n is an integer from 0 to 2, is very advantageous for industrial purposes as an inexpensive starting material.
  • the addition reaction of the halogenated methane to tetrafluoroethylene may be performed by, for example, contacting tetrafluoroethylene with the halogenated methane represented by formula (3) in a solvent that is inert to the reaction or without a solvent in the presence of a Lewis acid catalyst.
  • the Lewis acid catalyst used in this reaction step is not limited, but may, for example, be a halide containing at least one element selected from the group consisting of B, Al, Ga, In, Fe, Ni, Co, Sb, Nb, Sn, Ti, Zr, W, and Ta.
  • halide containing at least one element selected from the group consisting of B, Al, Ga, In, Fe, Ni, Co, Sb, Nb, Sn, Ti, Zr, W, and Ta.
  • usable halides include BF 3 , BCl 3 , BBr 3 , AlF 3 , AlCl 3 , AlBr 3 , GaCl 3 , InCl 3 , FeCl 3 , NiCl 2 , C0CI2, SbF 5 , SbCl 5 , NbCl 5 , SnCl 2 , TiCk, ZrCl 4 , WCl 6 , TaCl 5 , etc.
  • Lewis acid catalysts particularly preferable is an aluminum halide represented by AIZ3, wherein the three Z are the same or different, each being F, Cl, or Br, provided that not all of the Z are F.
  • Particularly preferable is a fluorinated aluminum chloride with the average composition AlCl x Fy, wherein x is from about 0.05 to about 2.95; y is from about 0.05 to about 2.95; and the sum of x and y is 3.
  • the fluorinated aluminum chloride is typically a mixture of compounds with different compositions.
  • a particularly preferable catalyst is a mixture wherein y is from about 1.00 to about 2.95.
  • the production of the fluorinated aluminum chloride is detailed in U.S. Pat. No. 5, 162,594.
  • the catalyst represented by AlZ 3 wherein the three Z are the same or different, each being F, Cl, or Br, provided that not all of the Z are F, is used for the addition reaction in the reaction system, it changes to the above-mentioned particularly preferable catalyst.
  • the reaction of tetrafluoroethylene and the halogenated methane may be performed in the presence of aluminum chloride and a fluorine compound.
  • fluorine compounds used for activation are not limited as long as they are alkanes or alkenes with fluorine atom(s).
  • fluorine compound added is not limited, but the addition of a large amount of fluorine compound reduces the yield per batch and thus is not efficient.
  • the amount of the fluorine compound is preferably up to about 50 parts by weight based on 100 parts by weight of the halogenated methane represented by formula (3).
  • the amount of fluorine compound is more preferably from about 1 to about 30 parts by weight based on 100 parts by weight of the halogenated methane represented by formula (3).
  • the addition reaction of tetrafluoroethylene and the halogenated methane represented by formula (3) can be performed in a solvent such as perfluorooctane, perfluorobutyl tetrahydrofuran, or the like, which is inert to the addition reaction; however, the reaction is preferably performed without a solvent, in order to facilitate the purification.
  • a solvent such as perfluorooctane, perfluorobutyl tetrahydrofuran, or the like, which is inert to the addition reaction; however, the reaction is preferably performed without a solvent, in order to facilitate the purification.
  • the amount of the Lewis acid catalyst used is preferably from about 0.1 to about 50 parts by weight, and more preferably from about 0.5 to about 10 parts by weight, based on 100 parts by weight of the total amount of the tetrafluoroethylene and the halogenated methane represented by formula (3).
  • the reaction temperature may typically be from about -40 to about 200 0 C, and preferably from about 10 to about 150°C.
  • the reaction pressure may be from an ordinary pressure to about 2 MPa, and particularly preferably from an ordinary pressure to about 1 MPa.
  • the reaction time may be typically from about 0.5 to about 12 hours.
  • the desired halogenated fluoropropane represented by formula (l): ACF2CF2CHxF y Az can be obtained with high conversion and good selectivity.
  • the halogenated fluoropropane represented by formula (l): ACF2CF2CH ⁇ F y Az obtained by the addition reaction of tetrafluoroethylene and a halogenated methane may be separated and purified, as required, according to a usual method, before being used as a starting material in the reduction step.
  • the l-halogenated-l,l,2,2-tetrafluoropropane represented by formula (2) can be obtained by reducing the halogenated fluoropropane represented by formula (l)- ACF2CF2CH x F y Az with hydrogen in the presence of a catalyst.
  • a catalyst for example, when l,l,l,3-tetrachloro-2,2,3,3-tetrafluoropropane
  • the catalyst used in the reduction reaction are noble metal catalysts such as platinum, palladium, rhodium, and ruthenium; and metal catalysts such as nickel, rhenium, molybdenum, and zirconium; with a noble metal catalyst being particularly preferable.
  • the form of the catalyst used is not limited, the catalyst is preferably supported on a carrier. Examples of suitable carrier include alumina, activated carbon, zeolite, etc.
  • a conventional method for preparing a noble metal catalyst can be applied to prepare such a supported catalyst.
  • the catalyst undergoes a hydrogen reduction treatment prior to use, in order to exhibit stable properties.
  • the reduction reaction in Reduction Step (0 can be performed in a liquid phase or gas phase.
  • the reaction may be performed, for example, by supplying hydrogen and the halogenated fluoropropane represented by formula (l): ACF2CF2CH x F y A z into a reactor charged with the above-mentioned catalyst in a gas phase.
  • the proportions of the hydrogen and the starting material can be substantially varied; however, in order to completely react hydrogen with the starting material and intermediate products such as l,3-dichloro-l,l,2,2-tetrafluoropropane (HCFC"234cb), it is preferred that hydrogen be used in an amount considerably larger than the stoichiometric quantity, such as, for example, in an amount of 2 mol or more based on 1 mol of the halogenated fluoropropane represented by formula (l). It is particularly preferred that hydrogen be used in an amount of about 2 to about 10 mol based on 1 mol of the halogenated fluoropropane represented by formula (l).
  • the reaction temperature in a gas-phase reaction may be from about 70 to about 350 0 C, and particularly preferably from about 80 to about 200 0 C, to prevent the production of C ⁇ byproduct compounds wherein starting materials are bound to each other.
  • the l-halogenated-l,l,2,2-tetrafluoropropane represented by formula (2) can be obtained with high conversion and high selectivity by suppressing the side reaction.
  • the contact time represented by the ratio of the catalyst weight W (g) relative to the total flow rate Fo (flow rate at O 0 C and 1 atm ⁇ cc/sec) of the starting gases (i.e., the halogenated fluoropropane and hydrogen) passed in the reaction system, i.e., W/Fo is preferably from about 0.1 to about 30 g -sec/cc.
  • the contact time is more preferably from about 1 to about 20 g -sec/cc, because if the contact time is too short, sufficient conversion of the starting material will not be obtained! whereas if the contact time is too long, the production of the Ce by-product compounds or the decomposition reaction to produce Ci or C2 compounds will take place.
  • the reaction can be performed using a solvent, e.g., ethanol, isopropyl alcohol, or a like alcohol, acetic acid, ethyl acetate, or pyridine, or can be performed without a solvent.
  • a solvent e.g., ethanol, isopropyl alcohol, or a like alcohol, acetic acid, ethyl acetate, or pyridine
  • the reaction temperature in the liquid-phase reaction is preferably from about room temperature to about 150 0 C
  • the reaction pressure is preferably from ordinary pressure to about 5 MPa.
  • the reaction time may be suitably selected according to the reactivity of the halogenated fluoropropane represented by formula (l) used, but may be typically from about 4 to about 72 hours.
  • the desired 2,3,3, 3-tetrafluoropropene can be obtained by contacting the l-halogenated-l,l,2,2-tetrafluoropropane represented by formula (2) obtained in the reduction step above with a catalyst in a gas phase.
  • the product obtained in the reduction step may be separated and purified, as required, according to a usual method, before being used as a starting material in this step. It is assumed that in this step, the HF is eliminated once, and the desired
  • catalysts usable in this reaction include halides, oxides, and the like containing at least one element selected from the group consisting of Al, Cr, Mg, Ca, Sr, Ba, Fe, Ni, Co, Mn, Sb, Nb, and Ta.
  • Such a catalyst can be prepared by any method that is capable of homogeneously dispersing a halide or an oxide containing at least one element selected from the above-mentioned elements. Examples of such methods include coprecipitation, kneading, ion exchange, vapor deposition, etc. Preferable methods include a method wherein a hydroxide is precipitated from an aqueous solution of a salt of the above-mentioned metal element; a method wherein a hydroxide cake is kneaded and ground using a ball mill, a homogenizer, or the like! etc.
  • the above-described catalyst may undergo a fluorination treatment for activation.
  • the fluorination treatment can be performed by contacting the catalyst with hydrogen fluoride, e.g., according to the method described in Japanese Unexamined Patent Publication No. 5-146680.
  • the reaction temperature in the fluorination treatment may be a temperature at which the water produced is not condensed (e.g., about 150 °C at 1 atm).
  • the fluorination temperature may be from about 100 to about 460°C.
  • the pressure during fluorination is not limited, but is preferably the pressure at which the catalytic reaction is performed.
  • At least one catalyst selected from the group consisting of chromium oxides, fluorinated chromium oxides, and iron fluorides be used.
  • the desired HFO- 1234yf can be obtained with good selectivity and high yield by using the above-mentioned catalyst, and employing the reaction conditions described below.
  • chromium oxides are, for example, those of the formula CrOm, wherein m is 1.5 ⁇ m ⁇ 3, preferably 2 ⁇ m ⁇ 2.75, and more preferably 2 ⁇ m ⁇ 2.3.
  • a method for preparing such a chromium oxide is as follows.
  • aqueous solution of a chromium salt (chromium nitrate, chromium chloride, chromium alum, chromium sulfate, or the like) is mixed with aqueous ammonia to produce a precipitate of chromium hydroxide.
  • the precipitate is then filtered, washed, and dried. Drying may be performed, for example, in air, at about 70 to about 200 0 C, and particularly at about 120 0 C, for about 1 to about 100 hours, and particularly for about 12 hours.
  • the product obtained at this stage is referred to as being in the state of chromium hydroxide.
  • This product is subsequently disintegrated into a powder.
  • the disintegrated chromium hydroxide powder is blended with graphite in an amount of about 3 wt% or less, as needed, and formed into pellets using a tableting machine.
  • the pellets may, for example, be about 3.0 mm in diameter and about 3.0 mm in height.
  • the molded pellets are calcined in an inert atmosphere, e.g., in a nitrogen stream, to produce an amorphous chromium oxide.
  • the calcined chromium oxide has a specific surface area of about 170 m 2 /g or more, preferably about 180 m 2 /g or more, and more preferably about 200 m 2 /g or more.
  • the upper limit of the specific surface area is about 240 m 2 /g, and preferably about 220 m 2 /g.
  • a specific surface area of 240 m 2 /g or more increases the activity, but also increases the degradation rate, whereas a specific surface area of less than 170 m 2 /g reduces the catalytic activity! thus, these ranges are undesired.
  • the specific surface area is herein measured according to the BET method.
  • a fluorinated chromium oxide can be prepared according to the method described in Japanese Unexamined Patent Publication No. 5- 146680.
  • a fluorinated chromium oxide can be obtained by, for example, fluorinating the chromium oxide obtained by the above-described method with hydrogen fluoride (HF treatment).
  • the pressure during fluorination is not limited, but is preferably a pressure at which the catalytic reaction is performed.
  • the fluorination temperature is, for example, from about 100 to about 460 0 C.
  • the fluorination treatment reduces the surface area of a catalyst; in general, however, the higher the specific surface area is, the higher the activity is.
  • the specific surface area of the fluorinated chromium oxide is preferably from about 25 to about 130 m 2 /g, and more preferably from about 40 to about 100 m 2 /g, but is not limited to this range.
  • the fluorination reaction of a chromium oxide may be performed, prior to carrying out the process of the invention described below, by supplying hydrogen fluoride to a reactor charged with the chromium oxide.
  • a fluorinated chromium oxide having a fluorine content of about 10 to about 30 wt% can be suitably used.
  • the chromium-based catalyst disclosed in Japanese Unexamined Patent Publication No. 11-171806 is usable as a chromium oxide catalyst or a fluorinated chromium oxide catalyst in the invention.
  • This chromium-based catalyst principally comprises a chromium compound containing at least one metal element selected from the group consisting of indium, gallium, cobalt, nickel, zinc, and aluminum, wherein the average valence of the chromium in the chromium compound is +3.5 or more and +5.0 or less, and the chromium-based catalyst is amorphous.
  • the iron fluoride used as a catalyst is not limited, but is preferably an iron fluoride represented by the formula FeF x , wherein x is from 2 to 3.
  • iron fluorides examples include commercially available products in the form of pellets, pellets produced from commercially available powdery products using a compacting machine or the like, etc.
  • the at least one catalyst selected from the group consisting of chromium oxides, fluorinated chromium oxides, and iron fluorides can be supported on a carrier such as alumina, activated carbon, or the like.
  • HF hydrogen fluoride
  • the l-halogenated-l,l,2,2-tetrafluoropropane can be used alone as a starting material! however, hydrogen fluoride may be additionally supplied.
  • hydrogen fluoride When hydrogen fluoride is supplied, the conversion of the 1-halogenated- 1, 1,2,2-tetrafluoropropane may decrease to some extent, but the selectivity to HFO- 1234yf can be improved.
  • hydrogen fluoride when used, in general, it may be supplied into a reactor together with the 1-halogenated- 1, 1,2,2-tetrafluoropropane in a gas phase.
  • the amount of hydrogen fluoride is preferably from about 2 mol or less, and more preferably from about 1.5 mol or less, based on 1 mol of the
  • 1-halogenated- 1, 1,2,2-tetrafluoropropane is undesirable because the selectivity to HFO- 1234yf will not be significantly improved, and the conversion of the 1-halogenated- 1, 1,2,2-tetrafluoropropane may decrease.
  • the amount of hydrogen fluoride is small, the amount of 2-halogenated-3,3,3-trifluoropropene produced may increase, or the catalyst may degrade. It is thus preferred that 0.1 mol or more of hydrogen fluoride be used based on 1 mol of the l"halogenated-l,l,2,2-tetrafluoropropane represented by formula (2).
  • the starting material may be supplied as is into the reactor, or may be diluted with an inert gas such as nitrogen, helium, or argon.
  • the starting material may also be supplied to the reactor together with oxygen, in order to maintain the catalytic activity for an extended period of time.
  • the amount of oxygen is preferably from about 0.1 mol% or more, and more preferably from about 0.1 to about 21 mol%, based on the total amount of the l-halogenated-l,l,2,2-tetrafluoropropane represented by formula (2), hydrogen fluoride, and oxygen.
  • the type of the reactor used in this step is not limited; examples of usable reactors include an adiabatic reactor charged with the catalyst, a multitube reactor heated with a heating medium, etc.
  • the reactor used is preferably made of a material resistant to the corrosive action of hydrogen fluoride, such as Hastelloy, Inconel, Monel, or the like.
  • the reaction temperature in the reactor is preferably from about 200 to about 45O 0 C, and more preferably from about 250 to about 400 0 C. If the temperature is higher than this range, the catalytic activity will decrease, whereas if the temperature is lower, the conversion of the starting material will become low, which is undesirable.
  • the reaction can be performed at any pressure, e.g., at ordinary pressure or under increased pressure. More specifically, the reaction of the invention can be performed at atmospheric pressure (0.1 MPa), but may be performed at an increased pressure of up to about 1.0 MPa.
  • the reaction time is not limited, the contact time represented by the ratio of the catalyst weight W (g) relative to the total flow rate Fo (flow rate at O 0 C and 1 atm: cc/sec) of the starting gases (l-halogenated-l,l,2,2-tetrafluoropropane, hydrogen fluoride, and oxygen) passed in the reaction system, i.e., W/Fo, is from 5 to 100 g -sec/cc, and preferably from about 10 to about 40 g -sec/cc.
  • a reaction product containing HFO- 1234yf can be obtained at the outlet of the reactor.
  • the reaction product can be purified by distillation or the like and collected. Unreacted starting materials can be separated and purified, and then returned into the reactor and recycled. Because unreacted starting materials can be thus recycled, high productivity can be maintained even if the conversion of the starting material is low.
  • 2,3,3,3-tetrafluoropropene, 2,3,3, 3-tetrafluoropropene can be produced with good selectivity and high yield.
  • halogenated fluoropropane which is obtained by using an inexpensive starting material, i.e., a chloromethane represented by the formula CH n CUn and tetrafluoromethylene, is used as a starting material,
  • 2,3,3,3-tetrafluoropropene can be obtained with good selectivity and high yield using the inexpensive starting material.
  • the process of the invention is very advantageous as a process for producing 2,3,3,3-tetrafluoropropene on an industrial scale.
  • Example 1 (1) Production of Starting Compound (CFC”214cb) l,l,l,3-Tetrachloro-2,2,3,3-tetrafluoropropane (CFC”214cb) was produced according to the following reaction scheme '• CCl 4 + TFE ⁇ CFC-214cb A l L stainless steel autoclave was charged with anhydrous aluminum chloride (50 g, 0.37 mol), CCl 4 (1.0 kg, 6.50 mol), and CFC-214cb (200 g, 0.79 mol) and degassed under reduced pressure with stirring, after which tetrafluoroethylene (TFE) was supplied up to 0.05 MPa, and the autoclave was heated to 6O 0 C.
  • TFE tetrafluoroethylene
  • Tetrafluoroethylene (total- 0.33 kg, 3.30 mol) was subsequently supplied, with the pressure maintained at 0.4 MPa. After further stirring for 1 hour, the autoclave was cooled to room temperature, and the reaction solution was analyzed using gas chromatography. As a result, the conversion of CCl 4 was 50%, and the selectivity to
  • CFC-214cb was 91%. After filtering the reaction solution, the crude product was purified by distillation to obtain CFC-214cb (0.96 kg, 3.78 mol).
  • a gas-phase reactor including a cylindrical reaction tube (Hastelloy; diameter ⁇ 13 mm, length- 30 cm) equipped with an electric furnace was charged with activated carbon pellets (10 g) having palladium supported thereon in a proportion of
  • the reaction tube was heated to 15O 0 C while supplying hydrogen (83 mL/min, flow rate at O 0 C and 1 atm; this also applies to the Examples and Reference Examples shown below), and CFC-214cb (0.19 g/min, 17 mL/min in terms of gas volume) was subsequently supplied thereto.
  • the outlet gas from the reaction tube was washed with water through a washing column and dried through a calcium chloride column to remove the acid content and water content, and subsequently collected with a cold trap.
  • the collected liquid was analyzed using gas chromatography. As a result, the conversion of
  • CFC-214cb was 100%, and the product selectivities were as follows: HCFC-244cc: 82%; l,3-dichloro-l,l,2,2-tetrafluoropropane (HCFC"234cb): 4%, and
  • a gas-phase reactor including a cylindrical reaction tube (Hastelloyl diameter: 13 mm, length: 30 cm) equipped with an electric furnace was charged with 8.2 g of a catalyst obtained by fluorinating a chromium oxide represented by the formula Cr ⁇ 2 (cylindrical shape; diameter: 3 mm; height: 3 mm,' fluorine content: about 15 wt%).
  • This reaction tube was maintained at 300 0 C, and 60 mL/min of anhydrous hydrogen fluoride was supplied thereto and maintained for 1 hour.
  • the reaction tube was heated to 400 0 C while supplying nitrogen (100 mL/min), and maintained at 400 0 C for 1 hour.
  • HCFC-244cc the gas flowing from the reactor outlet was analyzed using gas chromatography.
  • the GC composition was as follows: HCFC-244cc: 55 %, HFO1234yf: 40 %, 3-chloro-2,3,3-trifluoropropene (HCFO- 1233yf): 2 %, 1,1,1,2,2-pentafluoropropane (HFC-245cb): 1 %, and others: 2 %; the HCFC-244cc conversion was 45%; and HFO- 1234yf was obtained at 92% selectivity.
  • a total of 255 g of HCFC"244cc (1.70 mol) was used for the reaction to yield 235 g of a crude product.
  • HFO"1234yf 68 g, 0.60 mol.
  • HCFC-244cc i.e., starting material
  • HCFO- 1233yf HCFO- 1233yf
  • HFC-245cb which were separated by rectification, can be reacted again under the conditions of this step for conversion to HFO"1234yf.
  • HCFO224ca Using the thus-obtained HCFO224ca as a starting material, l"chloro-l,l,2,2-tetrafluoropropane (HCFO244cc) was obtained by the method described below.
  • a gas phase reactor including a cylindrical reaction tube (HastelloyJ diameter: 25 mm, length: 30 cm) equipped with an electric furnace was charged with activated carbon pellets (15 g) having palladium supported thereon in a proportion of 3.0 wt%.
  • the reaction tube was heated to 200 0 C while supplying hydrogen (180 mL/min), and then HCFO224ca (0.44 g/min, 45 mL/min in terms of gas volume) was supplied thereto.
  • the outlet gas from the reaction tube was washed with water through a washing column and dried through a calcium chloride column to remove the acid content and water content, and subsequently collected with a cold trap.
  • the collected liquid was analyzed using gas chromatography. As a result, the conversion of
  • HCFC-224ca was 100%, and HCFO244cc and HCFO234cb were obtained at selectivities of 79% and 15%, respectively.
  • a total of 500 g of HCFO224ca (2.27 mol) was used for the reaction to yield 303 g of a crude product.
  • the resulting crude product was subjected to rectification distillation at atmospheric pressure using a 20-plate rectification column to yield HCFO244cc (255 g,
  • HCFO234cb separated by distillation can be reduced with hydrogen again for conversion to to HCFO244cc.
  • HFO- 1234yf 2,3,3,3-tetrafluoropropene
  • a gas phase reactor including a cylindrical reaction tube (Hastelloyl diameter: 13 mm, length: 30 cm) equipped with an electric furnace was charged with 8.2 g of a catalyst obtained by fluorinating a chromium oxide represented by the formula Cr ⁇ 2 (cylindrical shape! diameter: 3 mm; height: 3 mm! fluorine content: about 15 wt%).
  • This reaction tube was maintained at 300 0 C, and 60 mL/min of anhydrous hydrogen fluoride was supplied thereto and maintained for 1 hour.
  • the reaction tube was heated to 400 0 C while supplying nitrogen (100 mL/min), and maintained at 400 0 C for 1 hour.
  • the supply of the nitrogen gas was ceased, and HCFC-244cc (100 mL/min), anhydrous hydrogen fluoride (15 mL/min), and oxygen (3.9 mL/min, 8 vol% of the total gas flow) were subsequently supplied.
  • the outlet gas from the reaction tube was washed with water and dried with calcium chloride, and subsequently collected with a cold trap.
  • the gas flowing from the reactor outlet was analyzed using gas chromatography.
  • the GC composition was as follows- HCFC-244cc: 55 %, HFO-1234yf: 40 %, HCFO- 1233yf: 2 %, HFC-245cb: 1 % and others: 2 %; the
  • HCFC-244cc conversion was 45%; and HFO- 1234yf was obtained at 92% selectivity.
  • a total of 255 g of HCFC-244cc (1.70 mol) was used for the reaction to yield 235 g of a crude product.
  • HFO- 1234yf (68 g, 0.60 mol).
  • the CFC"244cc as a starting material, HCFO- 1233yf, and HFC-245cb, which were separated by rectification, can be reacted again under the conditions of this step for conversion to HFO-1234yf.
  • a gas-phase reactor including a cylindrical reaction tube (Hastelloy! diameter: 13 mm, length: 30 cm) equipped with an electric furnace was charged with activated carbon pellets (10 g) having palladium supported thereon in a proportion of 0.5 wt%, to prepare a reaction tube.
  • the reaction tube was heated to 150 0 C while supplying H2 gas (85 mL/min), and l,l,l,3-tetrachloro-2,2,3,3-tetrafluoropropane (CFC-214cb) (17 mL/min in terms of gas volume) was subsequently supplied thereto.
  • the molar ratio of H2 to CFC-214cb was 5, and the contact time (W/Fo) was 6.0 g-sec/cc.
  • the outlet gas from the reaction tube was washed with water through a heated washing column and dried through a calcium chloride column to remove the acid content and water content, and subsequently collected with a cold trap.
  • the resulting product was analyzed using gas chromatography.
  • the conversion of CFC-214cb was 99%, and the following products were obtained: HCFC"244cc at 84% selectivity! HCFC"234cb at 3.4% selectivity! HCFC-224ca at 4.0% selectivity! and other byproducts at 8.3% selectivity.
  • the reaction was performed in the same manner as Example 3, except that the H2 gas was supplied at 88 mL/min, and CFO214cb was supplied at 12 mL/min (in terms of gas volume).
  • the molar ratio of H2 to CFO214cb was 7, and W/Fo was 6.0 g -sec/cc.
  • the reaction was performed in the same manner as Example 3, except that the reaction tube was heated to 100 0 C.
  • the reaction was performed in the same manner as Example 4, except that the reaction tube was heated to 100 0 C.
  • the molar ratio of H2 to CFC-214cb was 7, and W/Fo was 6.0 g -sec/cc.
  • the resulting product was analyzed using gas chromatography. As a result, the conversion of CFC"214cb was 99%, and the following products were obtained:
  • HCFC-244cc at 84% selectivity! HCFC-234cb at 0.9% selectivity! HCFC-224ca at 5.1% selectivity! and other by-products at 9.6% selectivity.
  • the reaction was performed in the same manner as Example 4, except that the reaction tube was heated to 250 0 C.
  • the molar ratio of H2 to CFC-214cb was 7, and W/FQ was 6.0 g -sec/cc.
  • a tubular Hastelloy reactor with an inner diameter of 15 mm and a length of 1 m was charged with 30 g of a catalyst obtained by fluorinating a chromium oxide represented by the formula Cr ⁇ 2 (fluorine content: about 15 wt%).
  • the reactor was maintained at atmospheric pressure (l atm) and 300 0 C, and anhydrous hydrogen fluoride (HF) gas was supplied to the reactor at 60 cc/min for 1 hour.
  • CF2CICF2CH3 (HCFO244cc) gas was subsequently supplied at a rate of 30 cc/min, and the temperature of the reactor was changed to 320°C.
  • the experiment was conducted under the same conditions as Reference Example 1, except that the amount of the catalyst was changed to 25 g, and the flow rate of the anhydrous hydrogen fluoride (HF) gas was changed to 45 cc/min.
  • the molar ratio of HF to HCFC-244cc was 1.5, and the contact time (WfFo) was 20 g -sec/cc.
  • the analytical results are shown in Table 1.
  • the experiment was conducted under the same conditions as Reference Example 1, except that the amount of the catalyst was changed to 15 g, and the flow rate of the anhydrous hydrogen fluoride (HF) gas was changed to 15 cc/min.
  • the molar ratio of HF to HCFO244cc was 0.5, and the contact time (W/Fo) was 20 g -sec/cc.
  • the analytical results are shown in Table 1.
  • Reference Example 6 A tubular Hastelloy reactor with an inner diameter of 15 mm and a length of 1 m was charged with 20 g of the same catalyst as that used in Reference Example 1 (fluorine content: about 15 wt%).
  • the reactor was maintained at atmospheric pressure (l atm) and 300 0 C, and anhydrous hydrogen fluoride (HF) gas was supplied to the reactor at 60 cc/min for 1 hour.
  • HF hydrogen fluoride
  • the supply of HF was subsequently ceased, and then each of nitrogen (N 2 ) gas and CF2CICF2CH3 (HCFO244cc) gas was supplied at 30 cc/min, and the temperature of the reactor was changed to 350°C.
  • a tubular Hastelloy reactor with an inner diameter of 15 mm and a length of 1 m was charged with 16 g of the same catalyst as that used in Reference Example 1 (fluorine content: about 15 wt%).
  • the reactor was maintained at atmospheric pressure (l atm) and 300 0 C, and anhydrous hydrogen fluoride (HF) gas was supplied to the reactor at 60 cc/min for 1 hour.
  • HF hydrogen fluoride
  • N2 nitrogen
  • HCFC-244cc was 0, and the contact time (W/Fo) was 20 g -sec/cc.
  • the outlet gas from the reactor was analyzed using gas chromatography. The results are shown in Table 2.
  • Reference Example 8 A Tubular Hastelloy straight reactor (diameter: 2.54 cm) equipped with an electric furnace was charged with 82 g of the same fluorinated chromium oxide catalyst as that of Reference Example 1. The reactor was heated to 400 0 C while passing nitrogen (N2) gas to dry the catalyst, and the temperature was held at 400 0 C for 1 hour. The supply of the nitrogen gas was ceased, and oxygen (O2) gas was introduced at a flow rate of 2.2 cc/min (8 vol% of the total gas flow) and CF2CICF2CH3
  • a Tubular Hastelloy straight reactor (diameter: 2.54 cm) equipped with an electric furnace was charged with 8.2 g of the same fluorinated chromium oxide catalyst as that of Reference Example 1.
  • the reactor was heated to 400 0 C while passing nitrogen (N2) gas to dry the catalyst, and the temperature was held at 400 0 C for 1 hour.
  • a commercially available iron fluoride powder represented by the formula FeF ⁇ was formed into cylindrical pellets with a diameter of about 2 mm and a height of about 5 mm, using a compacting machine.
  • a Tubular Hastelloy straight reactor with a diameter of 2.54 cm was charged with 10 g of the iron fluoride catalyst pellets to prepare a reactor.
  • the reactor was heated to 400 0 C while passing nitrogen (N2) gas to dry the catalyst, and the temperature was held at 400 0 C.
  • the supply of the nitrogen gas was subsequently ceased, and a mixed gas of 18 cc/min CF2CICF2CH3 (HCFC"244cc) gas and 1.6 cc/min oxygen was introduced via the reactor inlet.

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Abstract

La présente invention porte sur un procédé de production du 2,3,3,3-tétrafluoropropène comprenant les étapes de réaction suivantes : (i) la réduction d'un fluoropropane halogéné représenté par la formule (1) : ACF2CF2CH2FyAz, dans laquelle A représente Cl, Br ou I ; x est un entier de 0 à 2 ; y et z sont chacun un entier de 0 à 3 ; et le nombre total de x, y et z est de 3, pour produire un 1,1,2,2-tétrafluoropropane halogéné en 1 représenté par la formule (2) : ACF2CF2CH3 ; et (ii) la mise en contact du 1,1,2,2-tétrafluoropropane halogéné en position 1 obtenu à l'étape (i) avec un catalyseur dans une phase gazeuse pour produire du 2,3,3,3-tétrafluoropropène. Conformément à l'invention, le 2,3,3,3-tétrafluoropropène (HFO-1234yf) peut être produit avec un haut rendement, à l'aide de matières de départ bon marché.
PCT/JP2009/063628 2008-07-30 2009-07-24 Procédé de production du 2,3,3,3-tétrafluoropropène WO2010013795A1 (fr)

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WO2011099604A3 (fr) * 2010-02-12 2011-10-13 Daikin Industries, Ltd. Procédé de production d'un alcène contenant du fluor
WO2011130108A1 (fr) * 2010-04-14 2011-10-20 Arkema Inc. Procédé de fabrication de tétrafluorooléfines
CN102442880A (zh) * 2011-10-22 2012-05-09 山东东岳高分子材料有限公司 一种2,3,3,3-四氟丙烯的制备方法
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CN109111339A (zh) * 2018-10-29 2019-01-01 中国科学院上海有机化学研究所 一种2,3,3,3-四氟丙烯的制备方法及装置
US10301236B2 (en) 2015-05-21 2019-05-28 The Chemours Company Fc, Llc Hydrofluorination of a halogenated olefin with SbF5 in the liquid phase
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JP2019156732A (ja) * 2018-03-08 2019-09-19 ダイキン工業株式会社 ＨＣＦＣ−２２４ｃａ及び／又はＣＦＯ−１２１３ｙａの精製方法、ＨＣＦＣ−２２４ｃａの製造方法、並びにＣＦＯ−１２１３ｙａの製造方法

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WO2011099604A3 (fr) * 2010-02-12 2011-10-13 Daikin Industries, Ltd. Procédé de production d'un alcène contenant du fluor
US20120302802A1 (en) * 2010-02-12 2012-11-29 Yuzo Komatsu Process for producing fluorine-containing alkene
WO2011130108A1 (fr) * 2010-04-14 2011-10-20 Arkema Inc. Procédé de fabrication de tétrafluorooléfines
CN106146246A (zh) * 2011-02-04 2016-11-23 旭硝子株式会社 2,3,3,3‑四氟丙烯的纯化方法
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CN102442880B (zh) * 2011-10-22 2014-05-21 山东东岳高分子材料有限公司 一种2,3,3,3-四氟丙烯的制备方法
CN102442880A (zh) * 2011-10-22 2012-05-09 山东东岳高分子材料有限公司 一种2,3,3,3-四氟丙烯的制备方法
US10301236B2 (en) 2015-05-21 2019-05-28 The Chemours Company Fc, Llc Hydrofluorination of a halogenated olefin with SbF5 in the liquid phase
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CN109111339A (zh) * 2018-10-29 2019-01-01 中国科学院上海有机化学研究所 一种2,3,3,3-四氟丙烯的制备方法及装置
CN109111339B (zh) * 2018-10-29 2021-06-08 中国科学院上海有机化学研究所 一种2,3,3,3-四氟丙烯的制备方法及装置
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