WO2010095764A1 - Process for preparing fluorine-containing alkyne compound - Google Patents

Process for preparing fluorine-containing alkyne compound Download PDF

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Publication number
WO2010095764A1
WO2010095764A1 PCT/JP2010/053023 JP2010053023W WO2010095764A1 WO 2010095764 A1 WO2010095764 A1 WO 2010095764A1 JP 2010053023 W JP2010053023 W JP 2010053023W WO 2010095764 A1 WO2010095764 A1 WO 2010095764A1
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alkaline earth
fluorine
alkali metal
earth metal
group
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Tsuneo Yamashita
Masatoshi Nose
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Daikin Industries Ltd
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Daikin Industries Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B01J23/04—Alkali metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • B01J27/12—Fluorides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/618—Surface area more than 1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon

Definitions

  • the present invention relates to a process for preparing a fluorine -containing alkyne compound.
  • Muorine-containing alkyne compounds such as 3,3,3-trifluoropropyne are highly useful because the compounds are useful as materials or raw materials for refrigerants, etching agents, and aerosols, and can also be used as intermediates of various materials and monomer components of polymer compounds.
  • one known method for producing 3,3,3-trifruoropropyne uses 2,3-dibiOmo-l,l,l-trifluoropropene as a starting material and comprises performing the following production steps (see Non-Patent Literatures (NPLs) 1 to 3 listed below).
  • Another known method for producing 3,3,3-trifluoropropyne comprises preparing 3,3,3-trifruoropropyne from l,l,2-trichloro-3,3,3-trifluoropropene (see Non-Patent Literature 4).
  • this method entails a zinc waste disposal problem, because the method uses a zinc compound as a starting material.
  • Non-Patent Literature 5 a method comprising reacting l-iodo-3,3,3-trifluoropropene with potassium fluoride (KF) is also known (see Non-Patent Literature 5).
  • KF potassium fluoride
  • Non-Patent Literature (NPL) 6 listed below a method comprising reacting acetylenecarboxy ⁇ c acid (HC ⁇ CCOOH) with sulfur tetrafluoride (SF 4 ) is also reported (see Non-Patent Literature (NPL) 6 listed below).
  • NPL Non-Patent Literature 6 listed below.
  • this method is not industrially advantageous because acetylenecarboxylic acid used as a starting material is expensive and sulfur tetrafluoride is difficult to handle.
  • Patent Literature (PTL) l a method comprising reacting ( ⁇ )-l-halogeno-3,3,3-trifluoropiOpene as a starting material with a base in a liquid phase is also reported (see Patent Literature (PTL) l).
  • PTL Patent Literature
  • this method can be performed only when a ⁇ isomer is used as the starting material.
  • a large amount of alkaline waste is generated because a base is used for the reaction.
  • NPL l Journal of the American Chemical Society, 1951, 73, 1042-3.
  • NPL 2- Journal of the Chemical Society, 1951, 2495-504.
  • NPL 3 Journal of the Chemical Society, 1952, 3483-90.
  • NPL 4 Journal of Organic Chemistry, 1963, 28, 1139-40.
  • NPL 5 Journal of Fluorine Chemistry, 1978, 12(4), 321-4.
  • NPL 6 Journal of the American Chemical Society, 1959, 81,
  • a primary object of the invention is to provide a novel process for producing a fluorine-containing alkyne compound, such as
  • the present inventors conducted extensive research to achieve the above object, and found the following.
  • a specific fluorine-containing alkene compound is used as a starting material, and subjecting the starting material to a dehydrohalogenation reaction in a gas phase in the presence of at least one compound selected from the group consisting of alkali metal- or alkaline earth metal-containing halides; alkali metal- or alkaline earth metal-containing oxides; and alkali metal- or alkaline earth metal-containing hydroxides
  • the target fluorine -containing alkyne compound can be obtained with a high selectivity.
  • the compound can be produced with high efficiency, because this reaction can be conducted as a continuous reaction.
  • the present invention has been accomplished on the basis of this finding.
  • the present invention provides the following processes for producing a fluorine-containing alkyne compound.
  • Item 2 The process according to Item 1, wherein the catalyst is a fluoride of an alkali metal or an alkaline earth metal.
  • Item 3 The process according to Item 1 or 2, wherein the catalyst comprises a carrier and a catalyst component supported on the carrier, the catalyst component being at least one compound selected from the group consisting of alkali metal- or alkaline earth metal-containing halidesj alkali metal- or alkaline earth metal-containing oxides! and alkali metal- or alkaline earth metal-containing hydroxides.
  • Item 4 The process according to any one of Items 1 to 3, wherein Rf is a trifluoromethyl group.
  • Rf represents a fluorine-containing alkyl group, such as a perfluoroalkyl group having about 1 to about 10 carbon atoms, or a fluorinated alkyl group having about 1 to about 10 carbon atoms.
  • fluorine-containing alkyl group include trifluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nonafluoro-t-butyl group, and like groups.
  • One of X and Y is a halogen atom, and the other is a hydrogen atom.
  • the halogen atom include chlorine, fluorine, bromine, and iodine.
  • the fluorine-containing alkene compound can exist as Z(cis) or Ei ⁇ rans) isomers. Both the Z- and j ⁇ '-isomers can be used as the starting material in the present invention. This is an important distinction between the present invention and the method disclosed in the above Patent literature 1. According to the method of Patent literature 1, the reaction does not proceed when the j ⁇ '-isomer is used. Reaction process
  • This process can produce a fluorine-containing alkyne compound represented by formula"-
  • Rf is a fluorine-containing alkyl group, with a high selectivity.
  • alkali metal- or alkaline earth metal-containing halides examples include Na, K, Ii, Rb, and CsJ examples of alkaline earth metals include Ca, Mg, Sr, and BaJ and examples of halides include fluoride, chloride, iodide, and bromide.
  • halides of alkali metals or alkaline earth metals include fluorides such as NaF, KF, IiF, RbF, CsF, CaF 2 , MgF 2 , BaF 2 , and SrF 2 ; chlorides such as NaCl, KCl, IiCl, RbCl, CsCl, CaCl 2 , MgCl 2 , BaCl 2 , and SrCl 2 ; iodides such as NaI, KI, IiI, RbI, CsI, CaI 2 , MgI 2 , BaI 2 , and SrI 2 ; bromides such as NaBr, KBr, LiBr, RbBr, CsBr, CaBr 2 , MgBr 2 , BaBr 2 , and SrBr 2 .
  • fluorides such as NaF, KF, IiF, RbF, CsF, CaF 2 , MgF 2
  • Examples of oxides of alkali metals or alkaline earth metals include Na 2 O, K 2 O, Ii 2 O, Rb 2 O, Cs 2 O, CaO, MgO, BaO, and SrO.
  • Examples of hydroxides of alkali metals or alkaline earth metals include NaOH, KOH, IiOH, RbOH, CsOH, Ca(OH) 2 , Mg(OH) 2 , Ba(OH) 2 , and Sr(OH) 2 .
  • Such alkali metal- or alkaline earth metal-containing halides; alkali metal- or alkaline earth metal-containing oxides; and alkali metal- or alkaline earth metal-containing hydroxides can be used singly, or in a combination of two or more. Fluorides of alkali metals or alkaline earth metals are particularly preferable in the present invention.
  • the catalyst component that is at least one compound selected from the group consisting of alkali metal- or alkaline earth metal-containing halides; alkali metal- or alkaline earth metal-containing oxides; and alkali metal- or alkaline earth metal-containing hydroxides may be supported on a carrier.
  • Any carrier that is stable in the dehydrohalogenation reaction can be used.
  • the carrier can be appropriately selected from known carriers. For example, activated carbon, metallic aluminum, silica, alumina, zirconia, magnesia, titania, celite, zeolite, silicon carbide, diatomaceous earth, or the like can be preferably used as the carrier. Activated carbon is particularly preferable.
  • the carrier used to support the catalyst preferably has a large specific surface area of about 50 to about 1,500 m 2 /g, and more preferably about 300 to about 1,500 m 2 /g.
  • the amount of catalyst component supported on the carrier is about 1 to about 60 wt.%, when the total weight of the catalyst component and the carrier is defined as 100 wt.%.
  • the efficiency of contact between the starting material and the catalyst component can be enhanced, so that the target fluorine-containing alkyne compound can be obtained with a high selectivity.
  • the dehydrohalogenation reaction can be performed by bringing a fluorine-containing alkene compound as the starting material in a gas phase into contact with the catalyst.
  • the dehydrohalogenation reaction can be performed by supplying a fluorine-containing alkene compound as a starting material in a gas phase to a reactor containing the catalyst.
  • the fluorine-containing alkene compound may be supplied to the reactor as is, or after dilution with an inert gas, such as nitrogen, helium, or argon.
  • the type of reactor is not particularly limited.
  • adiabatic reactors containing a catalyst multitubular reactors cooled using a heat-transmitting maximin, etc. can be used. It is preferable to use a reactor made of a material that is resistant to the corrosive action of hydrogen fluoride, such as Hastelloy, Inconel, Monel, or like reactors.
  • the dehydrohalogenation reaction temperature in the reactor is preferably about 200°C to about 650°C, and more preferably about 300°C to about 550°C. If the temperature is higher than this range, the selectivity will be low, whereas if the temperature is lower, the conversion of the starting material will be low, neither of which is desirable.
  • the pressure during the reaction is not particularly limited, and the reaction can be carried out under normal pressure or increased pressure. More specifically, the dehydrohalogenation reaction of the present invention can be carried out under atmospheric pressure (0.1 MPa), or under an increased pressure of up to about 1.0 MPa.
  • the reaction time is not particularly limited.
  • the contact time which is determined by WfFo, may typically be adjusted to a range of about 0.1 to 300 g-sec/cc, and preferably about 10 to about 180 g-sec/cc.
  • W/Fo is the ratio of a catalyst weight W (g) to a total flow rate Fo (flow rate at O 0 C and 0.1 MPa ⁇ cc/sec) of the starting material gas that is introduced to a reaction system.
  • the catalyst weight is defined as the total weight of the catalyst component and the carrier.
  • RfC ⁇ CH wherein Rf is a fluorine-containing alkyl group can be obtained.
  • the target fluorine-containing alkyne compound can be obtained with a high selectivity. Further, because it is a gas phase reaction, the reaction can be easily performed as a continuous reaction, and the target fluorine-containing alkyne compound can be efficiently produced. Furthermore, because both the Z- and ⁇ -isomers can be used as the starting material, the starting material can be selected from a wide range. Accordiiigly, the process of the present invention is highly useful as an industrial-scale production method for a fluorine-containing alkyne compound.
  • CsF cesium fluoride
  • purity: 99% cesium fluoride
  • 30.0 g of activated carbon (Calgon, BPL4xlO, specific surface area: 1,150 m 2 /g) that had been dried at 250 0 C for 4 hours under a stream of nitrogen and then cooled to room temperature was added to this solution. The mixture was gently stirred until no more air bubbles were generated under reduced pressure. After aging at room temperature for 5 hours, the mixture was dried in a nitrogen stream at 15O 0 C for 12 hours.
  • a tubular Hastelloy reactor having an inner diameter of 15 mm and a length of 1 m was charged with 30 g of Catalyst A.
  • the reactor was maintained at atmospheric pressure (0.1 MPa) at 300 0 C, and nitrogen (N2) was supplied to the reactor at a rate of 100 cc/r ⁇ in (flow rate at 0 0 C and 0.1 MPa) for 2 hours.
  • N2 nitrogen
  • 2-chloro-3,3,3-trifluoropropene (HCFC-1233xf, purity: 99.9 0 /0) was then supplied at a rate of 20 ce/min (flow rate at 0°C and 0.1 MPa), and the supply of nitrogen (N 2 ) was immediately stopped.
  • the reaction temperature was then adjusted to 350°C.
  • the contact time (WZF 0 ) was 90.0 g'sec/cc.
  • Example 3 The experiment was conducted under the same conditions as in Example 1, except that the reaction temperature was adjusted to 400°C.
  • the contact time (W/Fo) was 90.0 g-sec/cc.
  • Example 3 The experiment was conducted under the same conditions as in
  • Example 1 except that the reaction temperature was adjusted to 500°C.
  • the contact time (W/Fo) was 90.0 gsedce.
  • a tubular Hastelloy reactor having an inner diameter of 20 mm and a length of 1 m was charged with 30 g of Catalyst B.
  • the reactor was maintained at atmospheric pressure (0.1 MPa) at 300°C, and nitrogen (Ns) was supplied to the reactor at a rate of 100 cc/miii (flow rate at 0°C and 0.1 MPa) for 2 hours.
  • Ns nitrogen
  • the reaction temperature was then adjusted to 400°C.
  • the contact time (W/Fo) was 60.0 g-sec/cc.

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Abstract

The present invention provides a process for producing a fluorine-containing alkyne compound represented by the formula: wherein Rf is a fluorine-containing alkyl group, the process including subjecting a fluorine-containing alkene compound represented by the formula: RfCX=CHY, wherein Rf is a fluorine-containing alkyl group, and one of X and Y is a halogen atom, and the other is a hydrogen atom, to a dehydrohalogenation reaction in a gas phase in the presence of at least one compound selected from the group consisting of alkali metal- or alkaline earth metal-containing halides; alkali metal- or alkaline earth metal-containing oxides; and alkali metal- or alkaline earth metal-containing hydroxides. This process can produce a fluorine-containing alkyne compound, such as 3,3,3-trifluoropropyne, with a high selectivity in a relatively simple manner.

Description

DESCRIPTION
Title of Invention: PROCESS FOR PREPARING FLUORINE-CONTAINING ALKYNE COMPOUND
Technical Field
The present invention relates to a process for preparing a fluorine -containing alkyne compound.
Background Art
Muorine-containing alkyne compounds such as 3,3,3-trifluoropropyne are highly useful because the compounds are useful as materials or raw materials for refrigerants, etching agents, and aerosols, and can also be used as intermediates of various materials and monomer components of polymer compounds. For example, one known method for producing 3,3,3-trifruoropropyne uses 2,3-dibiOmo-l,l,l-trifluoropropene as a starting material and comprises performing the following production steps (see Non-Patent Literatures (NPLs) 1 to 3 listed below).
CF3CH =CH2 -► CF3CHBrCH2Br ► CF3cBr = ^
CF3CBr2CH2Br ► CF3CBr = CHBr ► CF.C CH However, this method requires a multistep reaction, and is therefore very complicated. Furthermore, due to the use of highly corrosive bromine, the method is not suitable as an industrial-scale production method.
Another known method for producing 3,3,3-trifluoropropyne comprises preparing 3,3,3-trifruoropropyne from l,l,2-trichloro-3,3,3-trifluoropropene (see Non-Patent Literature 4). However, this method entails a zinc waste disposal problem, because the method uses a zinc compound as a starting material.
Further, a method comprising reacting l-iodo-3,3,3-trifluoropropene with potassium fluoride (KF) is also known (see Non-Patent Literature 5). However, this method uses an expensive starting material, and entails problems such as a very low yield and a large amount of by-products.
Further, a method comprising reacting acetylenecarboxyϋc acid (HC ≡ CCOOH) with sulfur tetrafluoride (SF4) is also reported (see Non-Patent Literature (NPL) 6 listed below). However, this method is not industrially advantageous because acetylenecarboxylic acid used as a starting material is expensive and sulfur tetrafluoride is difficult to handle.
Furthermore, a method comprising reacting (^)-l-halogeno-3,3,3-trifluoropiOpene as a starting material with a base in a liquid phase is also reported (see Patent Literature (PTL) l). However, this method can be performed only when a ^isomer is used as the starting material. Furthermore, a large amount of alkaline waste is generated because a base is used for the reaction. Citation list Patent Literature
PTL l: WO2008/132964 Al Non-Patent Literature
NPL l: Journal of the American Chemical Society, 1951, 73, 1042-3. NPL 2- Journal of the Chemical Society, 1951, 2495-504. NPL 3: Journal of the Chemical Society, 1952, 3483-90.
NPL 4: Journal of Organic Chemistry, 1963, 28, 1139-40. NPL 5: Journal of Fluorine Chemistry, 1978, 12(4), 321-4. NPL 6^ Journal of the American Chemical Society, 1959, 81,
3165-6.
Summary of Invention Technical Problem
The present invention has been accomplished in view of the problems of the prior art described above. A primary object of the invention is to provide a novel process for producing a fluorine-containing alkyne compound, such as
3,3,3-trifluoropropyne, with a high selectivity in a relatively simple manner. Solution to Problem
The present inventors conducted extensive research to achieve the above object, and found the following. When a specific fluorine-containing alkene compound is used as a starting material, and subjecting the starting material to a dehydrohalogenation reaction in a gas phase in the presence of at least one compound selected from the group consisting of alkali metal- or alkaline earth metal-containing halides; alkali metal- or alkaline earth metal-containing oxides; and alkali metal- or alkaline earth metal-containing hydroxides, the target fluorine -containing alkyne compound can be obtained with a high selectivity. Furthermore, the compound can be produced with high efficiency, because this reaction can be conducted as a continuous reaction. The present invention has been accomplished on the basis of this finding.
More specifically, the present invention provides the following processes for producing a fluorine-containing alkyne compound.
Item 1. A process for producing a fluorine-containing alkyne compound represented by the formula^
RfC≡CH wherein Rf is a fluorine-containing alkyl group, the process comprising subjecting a fluorine-containing alkene compound represented by the formula^ RfCX=CHY, wherein Rf is a fluorine-containing alkyl group, and one of X and Y is a halogen atom, and the other is a hydrogen atom, to a dehydrohalogenation reaction in a gas phase in the presence of at least one compound selected from the group consisting of alkali metal- or alkaline earth metal-containing halides; alkali metal- or alkaline earth metal-containing oxides; and alkali metal- or alkaline earth metal-containing hydroxides.
Item 2. The process according to Item 1, wherein the catalyst is a fluoride of an alkali metal or an alkaline earth metal.
Item 3. The process according to Item 1 or 2, wherein the catalyst comprises a carrier and a catalyst component supported on the carrier, the catalyst component being at least one compound selected from the group consisting of alkali metal- or alkaline earth metal-containing halidesj alkali metal- or alkaline earth metal-containing oxides! and alkali metal- or alkaline earth metal-containing hydroxides. Item 4. The process according to any one of Items 1 to 3, wherein Rf is a trifluoromethyl group.
The process for producing a fluorine-containing alkyne compound according to the present invention is described below in more detail. Starting compound
In the present invention, a fluorine-containing alkene compound represented by the formula '■ RfCX=CHY is used as a starting material.
In the formula, Rf represents a fluorine-containing alkyl group, such as a perfluoroalkyl group having about 1 to about 10 carbon atoms, or a fluorinated alkyl group having about 1 to about 10 carbon atoms. Specific examples of the fluorine-containing alkyl group include trifluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, nonafluoro-t-butyl group, and like groups.
One of X and Y is a halogen atom, and the other is a hydrogen atom. Examples of the halogen atom include chlorine, fluorine, bromine, and iodine.
When Y is a halogen atom, the fluorine-containing alkene compound can exist as Z(cis) or Eiύrans) isomers. Both the Z- and jδ'-isomers can be used as the starting material in the present invention. This is an important distinction between the present invention and the method disclosed in the above Patent literature 1. According to the method of Patent literature 1, the reaction does not proceed when the jδ'-isomer is used. Reaction process
The production process of the present invention comprises subjecting a fluorine-containing alkene compound represented by the formula^ RfCX=CHY, wherein Rf is a fluorine-containing alkyl group, and one of X and Y is a halogen atom, and the other is a hydrogen atom, to a dehydrohalogenation reaction in a gas phase in the presence of at least one compound selected from the group consisting of alkali metal- or alkaline earth metal-containing halidesj alkali metal- or alkaline earth metal-containing oxides; and alkali metal- or alkaline earth metal-containing hydroxides. This process can produce a fluorine-containing alkyne compound represented by formula"-
RfC≡CH
, wherein Rf is a fluorine-containing alkyl group, with a high selectivity.
With respect to the compound used as a catalyst that is at least one compound selected from the group consisting of alkali metal- or alkaline earth metal-containing halides; alkali metal- or alkaline earth metal-containing oxides; and alkali metal- or alkaline earth metal-containing hydroxides, examples of alkali metals include Na, K, Ii, Rb, and CsJ examples of alkaline earth metals include Ca, Mg, Sr, and BaJ and examples of halides include fluoride, chloride, iodide, and bromide. Examples of halides of alkali metals or alkaline earth metals include fluorides such as NaF, KF, IiF, RbF, CsF, CaF2, MgF2, BaF2, and SrF2; chlorides such as NaCl, KCl, IiCl, RbCl, CsCl, CaCl2, MgCl2, BaCl2, and SrCl2; iodides such as NaI, KI, IiI, RbI, CsI, CaI2, MgI2, BaI2, and SrI2; bromides such as NaBr, KBr, LiBr, RbBr, CsBr, CaBr2, MgBr2, BaBr2, and SrBr2. Examples of oxides of alkali metals or alkaline earth metals include Na2O, K2O, Ii2O, Rb2O, Cs2O, CaO, MgO, BaO, and SrO. Examples of hydroxides of alkali metals or alkaline earth metals include NaOH, KOH, IiOH, RbOH, CsOH, Ca(OH)2, Mg(OH)2, Ba(OH)2, and Sr(OH)2. Such alkali metal- or alkaline earth metal-containing halides; alkali metal- or alkaline earth metal-containing oxides; and alkali metal- or alkaline earth metal-containing hydroxides can be used singly, or in a combination of two or more. Fluorides of alkali metals or alkaline earth metals are particularly preferable in the present invention.
The catalyst component that is at least one compound selected from the group consisting of alkali metal- or alkaline earth metal-containing halides; alkali metal- or alkaline earth metal-containing oxides; and alkali metal- or alkaline earth metal-containing hydroxides may be supported on a carrier. Any carrier that is stable in the dehydrohalogenation reaction can be used. The carrier can be appropriately selected from known carriers. For example, activated carbon, metallic aluminum, silica, alumina, zirconia, magnesia, titania, celite, zeolite, silicon carbide, diatomaceous earth, or the like can be preferably used as the carrier. Activated carbon is particularly preferable.
The carrier used to support the catalyst preferably has a large specific surface area of about 50 to about 1,500 m2/g, and more preferably about 300 to about 1,500 m2/g.
The amount of catalyst component supported on the carrier is about 1 to about 60 wt.%, when the total weight of the catalyst component and the carrier is defined as 100 wt.%.
By using a catalyst component supported on a carrier having a large specific surface area as described above, the efficiency of contact between the starting material and the catalyst component can be enhanced, so that the target fluorine-containing alkyne compound can be obtained with a high selectivity.
The dehydrohalogenation reaction can be performed by bringing a fluorine-containing alkene compound as the starting material in a gas phase into contact with the catalyst.
Usually, the dehydrohalogenation reaction can be performed by supplying a fluorine-containing alkene compound as a starting material in a gas phase to a reactor containing the catalyst. The fluorine-containing alkene compound may be supplied to the reactor as is, or after dilution with an inert gas, such as nitrogen, helium, or argon.
The type of reactor is not particularly limited. For example, adiabatic reactors containing a catalyst, multitubular reactors cooled using a heat-transmitting mediuin, etc. can be used. It is preferable to use a reactor made of a material that is resistant to the corrosive action of hydrogen fluoride, such as Hastelloy, Inconel, Monel, or like reactors.
The dehydrohalogenation reaction temperature in the reactor is preferably about 200°C to about 650°C, and more preferably about 300°C to about 550°C. If the temperature is higher than this range, the selectivity will be low, whereas if the temperature is lower, the conversion of the starting material will be low, neither of which is desirable.
The pressure during the reaction is not particularly limited, and the reaction can be carried out under normal pressure or increased pressure. More specifically, the dehydrohalogenation reaction of the present invention can be carried out under atmospheric pressure (0.1 MPa), or under an increased pressure of up to about 1.0 MPa.
The reaction time is not particularly limited. However, the contact time, which is determined by WfFo, may typically be adjusted to a range of about 0.1 to 300 g-sec/cc, and preferably about 10 to about 180 g-sec/cc. W/Fo is the ratio of a catalyst weight W (g) to a total flow rate Fo (flow rate at O0C and 0.1 MPa^ cc/sec) of the starting material gas that is introduced to a reaction system. When a catalyst component supported on a carrier is used, the catalyst weight is defined as the total weight of the catalyst component and the carrier.
According to the above process, hydrogen halide represented by XY is eliminated from a fluorine-containing alkene compound represented by the chemical formula^ RfCX=CHY wherein Rf is a fluorine-containing alkyl group, one of X and Y is a halogen atom, and the other is a hydrogen atom, so that a fluorine-containing alkyne compound represented by the chemical formula
RfC≡CH wherein Rf is a fluorine-containing alkyl group can be obtained.
Advantageous Effects of Invention According to the process of the present invention, the target fluorine-containing alkyne compound can be obtained with a high selectivity. Further, because it is a gas phase reaction, the reaction can be easily performed as a continuous reaction, and the target fluorine-containing alkyne compound can be efficiently produced. Furthermore, because both the Z- and ^-isomers can be used as the starting material, the starting material can be selected from a wide range. Accordiiigly, the process of the present invention is highly useful as an industrial-scale production method for a fluorine-containing alkyne compound.
Description of Embodiments The present invention will be described below in more detail with reference to Preparation Examples for catalysts used in the present invention, and Examples of the process of the present invention. Preparation Example 1
25.0 g of cesium fluoride (CsF, purity: 99%) that had been dried in a nitrogen stream at 400°C for 4 hours and then allowed to cool to room temperature was dissolved in 150 ml of pure water. 30.0 g of activated carbon (Calgon, BPL4xlO, specific surface area: 1,150 m2/g) that had been dried at 2500C for 4 hours under a stream of nitrogen and then cooled to room temperature was added to this solution. The mixture was gently stirred until no more air bubbles were generated under reduced pressure. After aging at room temperature for 5 hours, the mixture was dried in a nitrogen stream at 15O0C for 12 hours. The resulting solid was calcined in a nitrogen stream at 400°C for 3 hours to yield 53.9 g of a solid. This solid was designated Catalyst A. Preparation Example 2 5.0 g of potassium fluoride (KF, purity: 99%) that had been dried in a nitrogen stream at 4000C for 4 hours and then allowed to cool to room temperature was dissolved in 200 ml of pure water. 45.2 g of activated carbon (Granular Shirasagi, C2X4/6-2; specific surface area: 1,050 m2/g) that had been dried in a nitrogen stream at 250°C for 4 hours and cooled to room temperature was added to this solution. The mixture was gently stirred until no more air bubbles were generated under reduced pressure. After aging at room temperature for 5 hours, the mixture was dried in a nitrogen stream at 1200C for 15 hours. The resulting solid was calcined in a nitrogen stream at 4000C for 3 hours to yield 49.8 g of a solid. This solid was designated Catalyst B. Example 1
A tubular Hastelloy reactor having an inner diameter of 15 mm and a length of 1 m was charged with 30 g of Catalyst A.
The reactor was maintained at atmospheric pressure (0.1 MPa) at 3000C, and nitrogen (N2) was supplied to the reactor at a rate of 100 cc/rαin (flow rate at 00C and 0.1 MPa) for 2 hours. As a starting material, 2-chloro-3,3,3-trifluoropropene (HCFC-1233xf, purity: 99.90/0) was then supplied at a rate of 20 ce/min (flow rate at 0°C and 0.1 MPa), and the supply of nitrogen (N2) was immediately stopped. The reaction temperature was then adjusted to 350°C. The contact time (WZF0) was 90.0 g'sec/cc. One hour and a half after the target reaction temperature was reached, the outlet gas from the reactor was analyzed using gas chromatography. Table 1 shows the results.
The chemical formulas of the resulting products are as follows. CF3C≡CH (3,3,3-Trifiuoropropyne) CF3CF=CH2 (HFC-1234yf) CF3CH=CHCl (CS)-HCFC- 1233zd + tø -HCFC- 1233zd) CF3CH=CHF (Cδ)-HFC-1234ze + tø-HFC-1234ze) CF3CH=CH2 (HFC-1243z£) Example 2
The experiment was conducted under the same conditions as in Example 1, except that the reaction temperature was adjusted to 400°C. The contact time (W/Fo) was 90.0 g-sec/cc. One hour and a hah0 after the target reaction temperature was reached, the outlet gas from the reactor was analyzed using gas chromatography. Table 1 shows the results. Example 3 The experiment was conducted under the same conditions as in
Example 1, except that the reaction temperature was adjusted to 500°C. The contact time (W/Fo) was 90.0 gsedce. One hour and a half after the target reaction temperature was reached, the outlet gas from the reactor was analyzed using gas chromatography. Table 1 shows the results.
Table 1
Figure imgf000010_0001
Example 4
A tubular Hastelloy reactor having an inner diameter of 20 mm and a length of 1 m was charged with 30 g of Catalyst B.
The reactor was maintained at atmospheric pressure (0.1 MPa) at 300°C, and nitrogen (Ns) was supplied to the reactor at a rate of 100 cc/miii (flow rate at 0°C and 0.1 MPa) for 2 hours. As a starting material, (^■l-chloro-3,3,3-trifiuoropropene (U)ΗCFC-1233zd; purity: 99.9%) was then supplied at a rate of 20 cc/min (flow rate at 0°C and 0.1 MPa), and the supply of nitrogen (N2) was immediately stopped. The reaction temperature was then adjusted to 400°C. The contact time (W/Fo) was 60.0 g-sec/cc. Two hours after the target reaction temperature was reached, the outlet gas from the reactor was analyzed using gas chromatography. Table 2 shows the results. Although (^■lxhloro-3,3,3-trifiuoropropene, which is an isomer of
(^-l-chloro-3,3,3-trifluoropropene used as the starting material in the above reaction, was also produced, the (i^-lxhloro-3,3,3-trifluoropropene was regarded as part of the starting material, and thus excluded from the starting material conversion (%) calculations shown in Table 2. Example 5
The experiment was conducted under the same conditions as in Example 4, except that the reaction temperature was adjusted to 500°C. The contact time (W/Fo) was 60.0 g-sec/cc. One hour and a half after the target reaction temperature was reached, the outlet gas from the reactor was analyzed using gas chromatography. Table 2 shows the results.
Table 2
Figure imgf000011_0001

Claims

[Claim l] A process for producing a fluorine-containing alkyne compound represented by the formula^
RfC≡CH wherein Rf is a fluorinexontaining alkyl group, the process comprising subjecting a fluorine -containing alkene compound represented by the formula : RfCX=CHY, wherein Rf is a fluorme-containing alkyl group, and one of X and Y is a halogen atom, and the other is a hydrogen atom, to a dehydrohalogenation reaction in a gas phase in the presence of at least one compound selected from the group consisting of alkali metal- or alkaline earth metal-containing halideS)' alkali metal- or alkaline earth metal-containing oxides; and alkali metal- or alkaline earth metal-containing hydroxides.
[Claim 2] The process according to claim 1, wherein the catalyst is a fluoride of an alkali metal or an alkaline earth metal.
[Claim 3] The process according to claim 1 or 2, wherein the catalyst comprises a carrier and a catalyst component supported on the carrier, the catalyst component being at least one compound selected from the group consisting of alkali metal- or alkaline earth metal-containing halidesJ alkali metal- or alkaline earth metal-containing oxides; and alkali metal- or alkaline earth metal-containing hydroxides.
[Claim 4] The process according to any one of claims 1 to 3, wherein Rf is a trifluoromethyl group.
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