CA2635806C - Method for producing fluorinated organic compounds - Google Patents
Method for producing fluorinated organic compounds Download PDFInfo
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- CA2635806C CA2635806C CA2635806A CA2635806A CA2635806C CA 2635806 C CA2635806 C CA 2635806C CA 2635806 A CA2635806 A CA 2635806A CA 2635806 A CA2635806 A CA 2635806A CA 2635806 C CA2635806 C CA 2635806C
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
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- 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
- C07C21/19—Halogenated dienes
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
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- 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
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
Abstract
Disclosed is a process for producing fluorinated organic compounds, including hydrofluoropropenes, which preferably comprises converting at least one compound of Formula (I): C(X)3CF2C(X)3 (I) to at least one compound of Formula (II) CF3CF=CHZ (II) where each X and Z is independently H, F, Cl, I or Br, said process preferably not including any substantial amount of oxygen-containing catalyst in certain embodiments. Preferably Z is H.
Description
METHOD FOR PRODUCING FLUORINATED ORGANIC COMPOUNDS
BACKGROUND OF INVENTION
(1) Field of Invention:
This invention relates to novel methods for preparing fluorinated organic compounds.
BACKGROUND OF INVENTION
(1) Field of Invention:
This invention relates to novel methods for preparing fluorinated organic compounds.
(2) Description of Related Art:
Hydrofluorocarbons (HFC's), in particular hydrofluoroalkenes such tetrafluoropropenes (including 2,3,3,3-tetrafluoro-1-propene (HF0-1234yf) and 1,3,3,3-tetrafluoro-l-propene (HF0-1234ze)) have been disclosed to be effective refrigerants, fire extinguishants, heat transfer media, propellants, foaming agents, blowing agents, gaseous dielectrics, sterilant carriers, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, displacement drying agents and power cycle working fluids. Unlike chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), both of which potentially damage the Earth's ozone layer, HFCs do not contain chlorine and thus pose no threat to the ozone layer.
Several methods of preparing hydrofluoroalkenes are known. For example, U.S. Pat. No. 4,900,874 (Ihara et al) describes a method of making fluorine containing olefins by contacting hydrogen gas with fluorinated alcohols. Although this appears to be a relatively high-yield process, for commercial scale production the handling of hydrogen gas at high temperature raises difficult safety related questions.
Also, the cost of producing hydrogen gas, such as building an on-site hydrogen plant, can be in many situations prohibitive.
U.S. Pat. No. 2,931,840 (Marquis) describes a method of making fluorine containing olefins by pyrolysis of methyl chloride and tetrafluoroethylene or chlorodifluoromethane. This process is a relatively low yield process and a very large percentage of the organic starting material is converted in this process to unwanted and/or unimportant byproducts.
U.S. Pat. No. 2,996,555 (Rausch) describes a method for the vapor phase manufacture of fluorine containing olefins by a single step process in which an oxygen-containing metal catalyst, such as chromium oxyfluoride, is used to convert a compound of formula CX3CF2CH3 to 2,3,3,3-tetrafluoropropenen. This examples in this patent describe a process which produces a relatively low yield, that is, 60%.
The preparation of HF0-1234yf from trifluoroacetylacetone and sulfur tetrafluoride has been described. See Banks, et al., Journal of Fluorine Chemistry, Vol.
82, Iss. 2, p. 171-174 (1997). Also, U.S. Pat. No. 5,162,594 (Krespan) discloses a process wherein tetrafluoroethylene is reacted with another fluorinated ethylene in the liquid phase to produce a polyfluoroolefin product.
SUMMARY
Applicants have discovered a method for producing fluorinated organic compounds, including hydrofluoropropenes, which preferably comprises converting at least one compound of Formula (I):
C(X)3CF2C(X)3 (I) to at least one compound of Formula (II) CF3CF=CHZ (II) where each X and Z is independently H, F, Cl, I or Br, said process preferably not including any substantial amount of oxygen-containing catalyst in certain embodiments. Preferably Z is H. As used herein and throughout, unless specifically indicated otherwise, the term "converting" includes directly converting (for example, in a single reaction or under essentially one set of reaction conditions, and example of which is described hereinafter) and indirectly converting (for example, through two or more reactions or using more than a single set of reaction conditions). .
In certain preferred embodiments of the invention, the compound of Formula (I) comprises a compound wherein each X on one terminal carbon is H, wherein each X on the other terminal carbon is independently selected from F, Cl, I or Br.
Such preferred embodiments include converting at least one C3 alkane of Formula (IA):
C(X)3CF2CH3 (IA) to at least one compound of formula (II) CF3CF=CHZ (II) where each X is independently F, Cl, Br or I, said process preferably not including any substantial amount of oxygen-containing catalyst in certain embodiments..
Preferably Z in such embodiments is H.
Preferably the compounds of Formula (I) contain at least four halogen substituents and even more preferably at least five halogen substituents. In certainly highly preferred embodiments, the conversion step of the present invention comprises converting a compound of Formula (IA) wherein each X is F. Preferably the compound of Formula (IA) is a penta-halogenated. Even more preferably the penta-halogenated propane of Formula (IA) comprises a trichlorinated, difluorinated propane, penta-fluorinated propane, and combinations of these.
Hydrofluorocarbons (HFC's), in particular hydrofluoroalkenes such tetrafluoropropenes (including 2,3,3,3-tetrafluoro-1-propene (HF0-1234yf) and 1,3,3,3-tetrafluoro-l-propene (HF0-1234ze)) have been disclosed to be effective refrigerants, fire extinguishants, heat transfer media, propellants, foaming agents, blowing agents, gaseous dielectrics, sterilant carriers, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, displacement drying agents and power cycle working fluids. Unlike chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), both of which potentially damage the Earth's ozone layer, HFCs do not contain chlorine and thus pose no threat to the ozone layer.
Several methods of preparing hydrofluoroalkenes are known. For example, U.S. Pat. No. 4,900,874 (Ihara et al) describes a method of making fluorine containing olefins by contacting hydrogen gas with fluorinated alcohols. Although this appears to be a relatively high-yield process, for commercial scale production the handling of hydrogen gas at high temperature raises difficult safety related questions.
Also, the cost of producing hydrogen gas, such as building an on-site hydrogen plant, can be in many situations prohibitive.
U.S. Pat. No. 2,931,840 (Marquis) describes a method of making fluorine containing olefins by pyrolysis of methyl chloride and tetrafluoroethylene or chlorodifluoromethane. This process is a relatively low yield process and a very large percentage of the organic starting material is converted in this process to unwanted and/or unimportant byproducts.
U.S. Pat. No. 2,996,555 (Rausch) describes a method for the vapor phase manufacture of fluorine containing olefins by a single step process in which an oxygen-containing metal catalyst, such as chromium oxyfluoride, is used to convert a compound of formula CX3CF2CH3 to 2,3,3,3-tetrafluoropropenen. This examples in this patent describe a process which produces a relatively low yield, that is, 60%.
The preparation of HF0-1234yf from trifluoroacetylacetone and sulfur tetrafluoride has been described. See Banks, et al., Journal of Fluorine Chemistry, Vol.
82, Iss. 2, p. 171-174 (1997). Also, U.S. Pat. No. 5,162,594 (Krespan) discloses a process wherein tetrafluoroethylene is reacted with another fluorinated ethylene in the liquid phase to produce a polyfluoroolefin product.
SUMMARY
Applicants have discovered a method for producing fluorinated organic compounds, including hydrofluoropropenes, which preferably comprises converting at least one compound of Formula (I):
C(X)3CF2C(X)3 (I) to at least one compound of Formula (II) CF3CF=CHZ (II) where each X and Z is independently H, F, Cl, I or Br, said process preferably not including any substantial amount of oxygen-containing catalyst in certain embodiments. Preferably Z is H. As used herein and throughout, unless specifically indicated otherwise, the term "converting" includes directly converting (for example, in a single reaction or under essentially one set of reaction conditions, and example of which is described hereinafter) and indirectly converting (for example, through two or more reactions or using more than a single set of reaction conditions). .
In certain preferred embodiments of the invention, the compound of Formula (I) comprises a compound wherein each X on one terminal carbon is H, wherein each X on the other terminal carbon is independently selected from F, Cl, I or Br.
Such preferred embodiments include converting at least one C3 alkane of Formula (IA):
C(X)3CF2CH3 (IA) to at least one compound of formula (II) CF3CF=CHZ (II) where each X is independently F, Cl, Br or I, said process preferably not including any substantial amount of oxygen-containing catalyst in certain embodiments..
Preferably Z in such embodiments is H.
Preferably the compounds of Formula (I) contain at least four halogen substituents and even more preferably at least five halogen substituents. In certainly highly preferred embodiments, the conversion step of the present invention comprises converting a compound of Formula (IA) wherein each X is F. Preferably the compound of Formula (IA) is a penta-halogenated. Even more preferably the penta-halogenated propane of Formula (IA) comprises a trichlorinated, difluorinated propane, penta-fluorinated propane, and combinations of these.
Preferred compounds of Formula (IA) include 1,1,1-trichloro-2,2-difluoropropane (HCFC-242bb), and 1,1,1,2,2-pentafluoropropane (HFC-245cb).
In certain preferred embodiments, the step of converting a compound of Formula (I) to at least one compound of Formula (II) comprises directly converting a compound of Formula (I). In other embodiments, the step of converting a compound of Formula (I) to at least one compound of Formula (II) comprises indirectly converting a compound of Formula (I).
An example of such indirect conversion embodiments includes converting a first compound of Formula (I), for example HCFC-242bb, to a second compound of Formula (I), for example, HFC-245cb, and then converting the second Formula (I) compound to a Formula (II) compound. In certain more specific indirect conversion embodiments, the step of converting a compound of Formula (I) comprises providing at least one trichlorodiflumpropane in accordance with Formula (IA), preferably CCI3CF2CH3 (HCFC-242bb) and reacting same under conditions effective to produce at least one pentafluorpropane in accordance with Formula (IA), preferably CF3CF2CH3 (HFC-245cb), which in turn is preferably exposed to reaction conditions effective to produce at least one compound in accordance with Formula (II), preferably HF0-1234yf. In preferred embodiments said exposing step comprises conducting one or more of said reactions in a gas and/or liquid phase in the presence of a catalyst, preferably a metal-based catalyst. Examples of such preferred conversion steps are disclosed more fully hereinafter. Of course, it is contemplated that in the broad scope of the invention that any of the Formula (I) compounds may be converted, directly or indirectly, to a compound of Formula (II) in view of the teachings contained herein.
In certain preferred embodiments, the step of converting a compound of Formula (I) to at least one compound of Formula (II) comprises directly converting a compound of Formula (I). In other embodiments, the step of converting a compound of Formula (I) to at least one compound of Formula (II) comprises indirectly converting a compound of Formula (I).
An example of such indirect conversion embodiments includes converting a first compound of Formula (I), for example HCFC-242bb, to a second compound of Formula (I), for example, HFC-245cb, and then converting the second Formula (I) compound to a Formula (II) compound. In certain more specific indirect conversion embodiments, the step of converting a compound of Formula (I) comprises providing at least one trichlorodiflumpropane in accordance with Formula (IA), preferably CCI3CF2CH3 (HCFC-242bb) and reacting same under conditions effective to produce at least one pentafluorpropane in accordance with Formula (IA), preferably CF3CF2CH3 (HFC-245cb), which in turn is preferably exposed to reaction conditions effective to produce at least one compound in accordance with Formula (II), preferably HF0-1234yf. In preferred embodiments said exposing step comprises conducting one or more of said reactions in a gas and/or liquid phase in the presence of a catalyst, preferably a metal-based catalyst. Examples of such preferred conversion steps are disclosed more fully hereinafter. Of course, it is contemplated that in the broad scope of the invention that any of the Formula (I) compounds may be converted, directly or indirectly, to a compound of Formula (II) in view of the teachings contained herein.
In certain preferred embodiments the converting step comprises exposing the compound of Formula (I), and preferably Formula (1A) to one or more sets of reaction conditions effective to produce at least one compound in accordance with Formula (II).
The preferred conversion step of the present invention is preferably carried out under conditions, including the use of one or more reactions, effective to provide a Formula (I) conversion of at least about 50%, more preferably at least about 75%, and even more preferably at least about 90%. In certain preferred embodiments the conversion is at least about 95%, and more preferably at least about 97%.
Further in certain preferred embodiments, the step of converting the compound of Formula (I) to produce a compound of Formula (II) is conducted under conditions effective to provide a formula (II) selectivity of at least about 45%, more preferably at least about 55%, and more preferably at least about 75%. In certain preferred embodiments a selectivity of about 95% or greater may be achieved.
In other aspects of the present invention, a method is provided for producing the compound of Formula (I) by converting at least one compound of Formula (III):
C(X)2=CC1C(X)3 (III) to at least one compound of Formula (I), as described above, where each X is independently H, F, Cl, I or Br, provided at least one X is Cl, I or Br. In preferred embodiments, at least one X on the unsaturated carbon is Cl, I or Br, and even more preferably Cl. The details of exemplary conversion *steps in accordance with this aspect of the invention are provided in the examples.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
One beneficial aspect of the present invention is that it enables the production of desirable flurookfins, preferably C3. fluoroolefins, using relatively high conversion and high selectivity reactions. Furthermore, the present methods in certain preferred embodiments permit the production of the desirable fluoroolefins, either directly or indirectly, from relatively attractive starting materials.
Preferably the Formula (I) compound is exposed to reaction conditions effective to produce a reaction product containing one or more of the desired fluorolefins, preferably one or more compounds of Formula (II). Although it is contemplated that the exposure step in certain embodiments may effectively be carried out in a single reaction stage and/or under a single set of reaction conditions, as mentioned above, it is preferred in many embodiments that the conversion step comprise a series of reaction stages or conditions. In one preferred aspect of the present invention, the conversion step comprises: (a) reacting a first chlorinated compound of Formula (IA), in a gas and/or liquid phase reaction in the presence of at least a first catalyst to produce at least one compound of Formula (IA), preferably a compound of Formula (IA) which is penta-fluorinated, and even more preferably contains no other halogen substituents, such as HFC-245; (b) reacting the Formula (IA) compound, preferably the penta-fluorinated Formula (IA) compound, preferably in a gas phase and in the presence or absence of catalyst, which if present maybe the same or different than the first catalyst to produce at least one compound of Formula (II) and even more preferably HF0-1234yf. In certain embodiments, the catalyst does not include substantial amounts of oxygen containing catalyst. Each of the preferred reaction steps is described in detail below, with the headings being used for convenience but not necessarily by way of limitation.
I. FLUORINATION OF THE MULTI-HALOGENATED FORMULA I(A) One preferred reaction step in accordance may be described by those reactions in which the compound of Formula (IA) contains fluorine and at least one other halogen, and this compound is fluorinated to produce a compound of Formula (IA) which contains at least four, and preferably five, fluorine substituents, and even more preferably no other halogen substituents. In certain of such preferred embodiments, especially embodiments in which such compound comprises HCFC-242bb, the present converting step comprises first reacting said compound(s) by fluorinating said compound(s), preferably with HF in a gas and/or liquid phase, to produce an HFC, preferably an HFC that is at least tetrafluorinated, such as HFC-245.
Preferably this reaction, whether in the gas phase, the liquid phase, or both is at least partially catalyzed. In certain preferred embodiments, the compound of Formula (IA), such as HCFC-242bb is contacted with liquid HF in the presence of a catalyst including but not limited to SbC15, SbF5, SbF3, TiC14, SnC14, FeC13, AlC13, AlF3, and combinations of two or more of these, to synthesize a compound of Formula (IA) having an increased number of fluorine substituents, and preferably only fluorine substituents, such as CF3CF2CH3. SbC15 is found to be highly preferred in many desirable embodiments. In other preferred embodiments, this conversion step is carried out in a catalytic, continuous, gas-phase reaction mode using SbC15/C as the solid catalyst. The preferred fluorination of the compound of Formula (IA) is preferably carried out under conditions effective to provide a Formula (IA) conversion of at least about 50%, more preferably at least about 75%, and even more preferably at least about 90%. In certain preferred embodiments the conversion is at least about 95%, and more preferably at least about 97%. Further in certain preferred embodiments, the conversion of the compound of Formula (IA) comprises reacting such compound under conditions effective to produce at least one penta-fluorinated compound (preferably HFC-245) at a yield of at least about 70%, more preferably at least about 75%, and even more preferably at least about 80%.
In general, it is possible that the fluorination reaction step can be carried out in the liquid phase or in the gas phase, or in a combination of gas and liquid phases, and it is contemplated that the reaction can be carried out batch wise, continuous, or a combination of these.
In preferred gas phase fluorination of Formula (I) compounds, the reaction is at least partially a catalyzed reaction, and is preferably carried out on a continuous basis by introducing a stream containing the compound of Formula (I) into one or more reaction vessels, such as a tubular reactor. In certain preferred embodiments, the stream containing the compound of Formula (I), and preferably Formula (IA), is preheated to a temperature of from about 150 C to about 400 C, preferably about 300 C, and introduced into a reaction vessel (preferably a tube reactor), which is maintained at the desired temperature, preferably from about 40 C to about 200 C, more preferably from about 50 C to about 150 C, where it is preferably contacted with catalyst and fluorinating agent, such as BF.
Preferably the vessel is comprised of materials which are resistant to corrosion as Hastelloy, Inconel, Monel and/or fluoropolymers linings.
Preferably the vessel contains catalyst, for example a fixed or fluid catalyst bed, packed with a suitable fluorination catalyst, with suitable means to ensure that the reaction mixture is maintained with the desired reaction temperature range.
Thus, it is contemplated that the fluorination reaction step may be performed using a wide variety of process parameters and process conditions in view of the overall teachings contained herein. However, it is preferred in certain embodiments that this reaction step comprise a gas phase reaction, preferably in the presence of catalyst, and even more preferably a Sb-based and/or and Fe-based catalyst (such as FeC13 on carbon (designated herein as FeC13/C for convenience), and combinations of these.
In general it is also contemplated that a wide variety of reaction pressures may be used for the fluorination reaction, depending again on relevant factors such as the specific catalyst being used and the most desired reaction product. The reaction pressure can be, for example, superatmospheric, atmospheric or under vacuum, and in certain preferred embodiments is from about 1 to about 200 psia, and even more preferably from about 1 to about 120 psia.
In certain embodiments, an inert diluent gas, such as nitrogen, may be used in combination with the other reactor feed(s).
It is contemplated that the amount of catalyst use will vary depending on the particular parameters present in each embodiment.
II. CONVERSION TO FORMULA (H) One preferred reaction step in accordance may be described by those reactions in which the compound of Formula (I), preferably Formula (IA) is converted to a compound of Formula (II). In certain preferred embodiments, the stream containing the compound of formula (I), and preferably (IA) is preheated to a temperature of from about 150 C to about 400 C, preferably about 350 C, and introduced into a reaction vessel, which is maintained at the desired temperature, preferably from about 300 C to about 700 C, more preferably from about 450 C to about 650 C.
Preferably the vessel is comprised of materials which are resistant to corrosion as Hastelloy, Inconel, Monel and/or fluoropolymers linings. Preferably the vessel contains catalyst, for example a fixed or fluid catalyst bed, packed with a suitable catalyst, with suitable means to heat the reaction mixture to the desired reaction temperature.
Thus, it is contemplated that this reaction step may be preformed using a wide variety of process parameters and process conditions in view of the overall teachings contained herein. However, it is preferred in certain embodiments that this reaction step comprise a gas phase reaction, preferably in the presence of catalyst, and even more preferably a carbon- and/or metal-based catalyst, preferably activated carbon, a nickel-based catalyst (such as Ni-mesh) and combinations of these. Other catalysts and catalyst supports may be used, including palladium on carbon, palladium-based catalyst (including palladium on aluminum oxides), and it is expected that many other catalysts may be used depending on the requirements of particular embodiments in view of the teachings contained herein. Of course, two or more any of these catalysts, or other catalysts not named here, may be used in combination.
While it is contemplated that a wide variety of reaction temperatures may be used, depending on relevant factors such as the catalyst being used and the most desired reaction product, it is generally preferred that the reaction temperature for the step is from about 200 C to about 800 C, more preferably from about 400 C to about 800 C. In certain preferred embodiments, the reaction temperature is from about 300 C to about 600 C, and even more preferably in certain embodiments from about 500 C to about 600 C.
In general it is also contemplated that a wide variety of reaction pressures may be used, depending again on relevant factors such as the specific catalyst being used and the most desired reaction product. The reaction pressure can be, for example, superatmospheric, atmospheric or under vacuum and in certain preferred embodiments is from about 1 to about 200 psia, and in certain embodiment from about 1 to about 120 psia.
In certain embodiments, an inert diluent gas, such as nitrogen, may be used in combination with the other reactor feed(s). It is contemplated that the amount of catalyst use will vary depending on the particular parameters present in each embodiment.
Preferably in such embodiments as described in this section, the conversion of the formula (I) compound is at least about 30%, more preferably at least about 50%, and even more preferably at least about 60%. Preferably in such embodiments, the 'selectivity to compound of Formula (II), preferably HF0-1234y1, is at least about 70%, more preferably at least about 80% and more preferably at least about 90%.
EXAMPLES
Additional features of the present invention are provided in the following examples, which should not be construed as limiting the claims in any way.
EXAMPLES lA
Liquid-phase catalytic fluorination of CC13CE2CH3 (242bb) with HE to CF3CF2CH3 (R245 cb) Example 1A
About 327 grams HF, about 50 grams CC13CF2CH3(242bb), and about 75 grams SbC15 were charged into a 1-L autoclave. The reaction mixture was stirred at 120 C for about 6 hours under about 760 psig of pressure. After the stipulated reaction time, the reactor was cooled up to about 0 C, and about 300 ml water was then added slowly into the autoclave over a period of about 45 minutes. After complete addition of water under stirring, the reactor was heated to about 70 C and then the overhead gases were transferred to another collecting cylinder. The yield of CF3CF2CH3 was about 82% at a 242bb conversion level of about 100%. The other major by-products were traces of CF3CFCICH3 and tarry material.
Example 1B
About 327 grams of HF, about 50 graqms of CC13CF2CH3(242bb), and about 75 grams of SbC15 were charged into a 1-L autoclave. The reaction mixture was stirred at about 100 C for about 6 hours under about 620 psig of pressure. After the reaction, the reactor was cooled to about 0 C, and about 300 ml water was then added slowly into the autoclave over a period of about 45 minutes. After complete addition of water under stirring, the reactor temperature was raised to 70 C and then the overhead gases were transferred to another collecting cylinder. The yield of CF3CF2CH3 was about 78% at a 242bb conversion level of about 86%. The other major by-products were traces of CF3CFC1CH3 and and other clorofluoropropanes.
Example 1C
About 327 grams HF, about 50 grams 1233xf, and about 75 grams SbC15 were charged into a 1-L autoclave. The reaction mixture was stirred at about 80 C
for about 6 hours under about 460 psig of pressure. After the reaction, the reactor was cooled to 0 C and 300 ml water was then added slowly into the autoclave over a period of about 45 minutes. After complete addition of water under stirring, the reactor was cooled to room temperature and then the overhead gases were transferred to another collecting cylinder. The yield of CF3CF2CH3 was about 67%. The only other major by-products includes products resulted from incomplete fluorination and trace of CF3CFCICH3.
Gas-phase catalytic fluorination of CC13CF2CH3 (242bb) with HF to CF3CF2CH3 (R245ch) A 22-inch (1/2-inch diameter) Monel pipe gas phase reactor was charged with 120 cc of 50wt% SbC15/C as the catalyst. The reactor was mounted inside a heater with three zones (top, middle and bottom). The reactor temperature was read by custom made 5-point thermocouples kept at the middle inside of the reactor. The inlet of the reactor was connected to a pre-heater, which was kept at about 300 C by electrical heating. The liquid-HF was fed from a cylinder into the pre-heater through a needle valve, liquid mass-flow meter, and a research control valve at a substantially constant flow of from about 1 to about 1000 grams per hour (g/h). The HF cylinder was kept at a constant pressure of 45 psig by applying anhydrous N2 gas pressure into the cylinder head space. A feed consisting of organic reactant (242bb) was fed at a rate ranging from about 10 to about 120 g/h as a gas from a cylinder kept at about 145 C
through a regulator, needle valve, and a gas mass-flow-meter. The organic feed stream was also fed periodically as liquid at about 105 C from a cylinder into the pre-heater through a needle valve, liquid mass-flow meter, and a research control valve at a substantially constant flow rate ranging from about 10 to about 150 g/h. The organic line from the cylinder to the pre-heater was kept at about 265 C by wrapping with constant temperature heat trace and electrical heating. All feed cylinders were mounted on scales to monitor their weight by difference. The reactions were run at a substantially constant reactor pressure of from about 0 to about 100 psig by controlling the flow of reactor exit gases by another research control valve. The exit gases coming out of the reactor were analyzed by on-line GC and GC/MS connected through a hotbox valve arrangements to prevent condensation. The reactor temperature was kept at from about 60 C to about 120 C. The SbC15/C catalyst was pretreated with about 50 g/h HF
at about the reaction temperature for about 8 hours under about 50 psig pressures. After HF pretreatment, the catalyst was further treated with about 20 seem of C12 and about 50 g/h of HF for an additional 4 hours. The pretreated catalyst was then contacted with organic in the presence of about 50 g/h HF. The conversion of 242bb was in the range of from about 60 to about 70% and the selectivity to 245cb was about 85% when the reaction was performed using 50 wt% SbC15/C as the catalyst at about 120 C
under about 30 psig pressure in the presence of about 50 g/h HF and about 20 g/h of 242bb.
The product was collected by flowing the reactor exit gases through a solution of from about 20wt% to about 60 wt% aqueous KOH scrubber solution and then trapping the exit gases from the scrubber into a cylinder kept in dry ice or liquid N2. The products were then isolated by distillation. The following catalysts were tested and found to have the selecetivity to HFC-245 as indicated in parenthesis: 30 wt% SbC15/C
(Sel.
81%); from about 3 to about 6 wt% FeC13/C (Sel. 52%); SbF5/C (Sel. 87%); 20 wt%
SnC14/C (Sel. 32%); 23 wt% TiC14/C (Sel. 27%). The catalyst temperatures o used ranged from about 60 C to about 120 C. SbC15/C is believed to be a preferred catalyst for this gas-phase transformation.
Catalytic conversion of CF3CF2CH3 to CF3CF=CH2 A 22-inch (1/2-inch diameter) Monel tube reactor was charged with about 120 cc of a catalyst. The reactor was mounted inside a heater with three zones (top, middle and bottom). The reactor temperature was read by custom made 5-point thermocouples kept at the middle inside of the reactor. The inlet of the reactor was connected to a pre-heater, which was kept at about 300 C by electrical heating. HFC-245cb was fed from a cylinder kept at about 65 C through a regulator, needle valve, and a gas mass-flow-meter. The line to the pre-heater was heat traced and kept at a substantially constant temperature of from about 65 C to about 70 C by electrical heating to avoid condensation. The feed cylinder was mounted on scales to monitor their weight by difference. The reactions were run at a substantially constant reactor pressure in the range of from about 0 to about 100 psig by controlling the flow of reactor exit gases by another research control valve. The gas mixture exiting the reactor was analyzed by on-line GC and= GC/MS connected through a hotbox valve arrangements to prevent condensation. The conversion of 245cb was in the range of from about 30% to about 70% and the selectivity to HF0-1234yf was in the range of from about 90% to about 100% depending on the reaction conditions. The products were collected by flowing the reactor exit gases through a 20-60-wt% of aqueous KOH scrubber solution and then trapping the exit gases from the scrubber into a cylinder kept in dry ice or liquid N2. The products were then substantial isolated by distillation. Results are tabulated in Table 1.
Table 1: Transformation of CF3CF2CH3 to 1234yf # Cat T, = 112, CF3CF2CH3 (245cb) Conversion of 245cb 1234yf C sccm seem (Sel. %).
Reaction conditions: Pressure about 2.5 to about 5.3 psig; Catalyst, 100 cc"
: A is NORIT RFC 3; B is Shiro-Saga activated carbon; C is Aldrich activated carbon; D is Calgon activated carbon; E is 0.5 wt% Pd/C; F is 0.5 wt% Pt/C; G
is Ni-mesh; Organic cylinder temperature about 65 C; CF3CF2CH3 (245cb) line to the preheater about 50 C; Preheater, 350 C; N2 - 0 SCCM.
Preparation of CH3CF2CH2CI from 2,3-dichloropropene using HF/SbC15 Example 4A
A 2-gallon autoclave was charged with about 900 grams (8.1 mol) of 2,3-dichloropropene, about 405 grams (20.3 mol) of HF, and about 10 grams (0.033 mol) of SbC15. The contents were heated with stirring to about 100 C for about 19 hours.
The maximum pressure was about 285 psig. (approx. 2000 kPa). The contents were vented while hot into a fluoropolymer container containing ice, which was connected in sequence to a dry ice trap. The organic layer was separated and washed to remove residual acid, giving about 811.9 grams of crude product, which by GC analysis was comprised of about 41% CH3CF2CH2C1, about 34.5% CH3CFC1CH2C1, 21 %
CH3CC12CH2C1, and about 1.8 % starting material. The conversion was about 97 %, while the combined yield of halopropanes was 76.7 %. Substantially pure CH3CF2CH2C1 was obtained by fractional distillation. The autoclave also contained about 77.8 grams of black residue.
Example 4B
Example 4A was repeated except that the reactants were heated to about 120 C
for about 18 hours. The crude organic layer so obtained consisted of about 58.8 %
CH3CF2CH2C1, about 28.3 % CH3CFC1CH2C1, and about 9.8 % CH3CC12CH2C1. The combined yield of halopropanes was about 74 %.
Example 4C
Example 4A was repeated except that no catalyst was used. The crude organic layer so obtained consisted of about 58.7 % CH3CF2CH2C1, about 25.9 %
CH3CFC1CH2CI, and about 12.2 % CH3CC12CH2C1. The combined yield of halopropanes was about 80%. This example demonstrates that SbC15 catalyst was not effective in increasing the amount of the desired CH3CF2CH2CI or increasing the total yield of useful products.
Conversion of 2,3-diehloropropene to CH3CFCICH2C1 A two-gallon autoclave was evacuated and charged with about 1500 grams of 2,3-dichloropropene (about 13.4 mol). It was then cooled to about -5 C by means of internal cooling coils connected to a chiller. About 1500 grams (75 mol) was added, the chiller turned off, and the contents slowly heated to a temperature in the range of from about 20 to about 25 C with stirring. After approximately 18 hours, the contents were cooled to about 5 C before discharging into iced water. The organic phase was separated and washed with about 1 L of water, dried (MgSO4) and filtered to give about 1554 grams of the product mixture. GC analysis indicated that the crude product contained about 86.5 % CH3CFC1CH2C1, about 3.8 % CH3CF2CH2C1, and about 2.8 %
CH3CC12CH2C1. Similar results were obtained at a temperature of about 50 C, although the amount of CH3CFCICH2CI decreased slightly, while the amount of CH3CF2CH2C1 marginally increased.
Conversion of CH3CCI2CH2C1 to CH3CF2CH2C1 An autoclave was charged with about 100 grams of CH3CC12CH2C1 and about .
44 grams of HF and the contents heated with stirring to about 130 C for about 20.5 hours. The products were process substantially in accordance with the description in Example 1, which resulted in about 70 grams of crude product which was comprised, based on GC area %, about 43.8 % CH3CF2CH2C1, about 23.1 % CH3CFCICH2C1, and about 30.3 % CH3CC12CH2C1. The autoclave also contained about 1.9 grams of dark residue.
Conversion of a mixture of CH3CFCICH2CI and CH3CC12CH2C1 to A mixture of about 666 grams of CH3CFC1CH2C1, about 268 grams of CH3CC12CH2C1, about 474 grams of HF and about 11 grams of SnCI.4 were heated together with stirring to about 114 C for about 18 hours. The crude product was comprised of about 89 % CH3CF2CH2C1.
Based on the results of Examples 4 ¨ 7, the use of chlorinated antimony catalyst, such as. SbC15, may not be preferred in certain embodiments due to an added cost that may not provide the desired improvement in yield or conversion in some embodiments, and may produce considerable by-product residue. In certain embodiments, therefore, it is preferred to run the reaction without catalyst.
However, the use of SnC14 may be preferred in embodiments in which CH3CF2CH2CI is the desired product, since its use may allow a lower temperature to be used and result in a higher percentage of CH3CF2CH2C1 in the crude product.
EXAMPLES 8A ¨ 8C
Preparation of Cli3CF2CC13 The photochlorination of CH3CF2CH3 to CH3CF2CCI3 has been mentioned in JACS, 59 (1937) 2436 Example 8A - Photoehlorination of CIJACE&CH2C1 The photochlorination was done using a 100-W Hg lamp placed in a quartz jacket that was cooled with the use of a circulating cooling bath set at about -5 C. The quartz jacket was inserted into a glass reactor of about 400 mL capacity. The reactor was cooled externally by placing it in a glycol-water bath which was cooled with the use of cooling coils connected to a second circulating bath set at -8.5 C. The reactor was fitted with a thermocouple, stir bar, and a gas inlet tube for introducing chlorine gas from a cylinder via a calibrated flowmeter. Exiting gases passed through a water-cooled condenser, an air trap, and a scrubber containing NaOH and Na2S03 to remove HC1 and chlorine.
The reactor was charged with about 250.5 grams of CH3CF2CH2C1 of about 98.6 % purity and allowed to cool to a substantially constant temperature of about -5.5 C. The chlorine cylinder was then opened and the flow rate set at 23 g/h.
Immediately thereafter, the lamp was then turned on. After approximately 0.5 hours, the temperature of the reactor contents stabilized at about -3 10.5 C.
The photochlorination was continued for about 7 hours and a conversion of about 79.4% was achieved. The composition of the crude product, which amounted to about 309.3 grams, was about 19.2 % CH3CF2CH2C1 , about 50.9 %
CH3CF2CHC12 and about 24.8 % CH3CF2CC13. Substantially pure CH3CF2CC13 was obtained by fractional distillation.
A 450-W Hg lamp could also be used. The ratios of CH3CF2CHC12 to CH3CF2CCI3vs. time were essentially the same as with a 100-watt lamp.
Examole 88 -õPhotochlorination of CH3CF2C11C12 In a manner similar to that described in Example 8A, about 296.8 grams of CH3CF2CHC12 (about 97.4 % pure, containing about 1.9 % CH3CF2CC13) was photochlorinated using a l 00-W Hg lamp at a temperature of about -4 C and chlorine feed rate of about 22.3 g/h. After about 2.5 hours, the composition of the reactor contents was about 58.2 % CH3CF2CHC12 and about 39.9 % CH3CF2CC13. Thus the selectivity for CH3CF2CC13 was about 97 % at a CH3CF2CHC12 conversion of about %.
Photoehlorination of a mixture of CH3CF2CH2CI and CH3CF2CHC12 The selectivity found in Examples 8A and 8C is considered to be desirably for many embodiments of the invention. However, limiting the conversion achieved in those examples may be less than desired in certain applications. It is believed that the conversions may be limited in those example by two factors. One factor is the melting point of CH3CF2CC13 (53 C) and the other is lower selectivity at high conversion. The latter may be a problem in connection with certain commercial embodiments where such yield losses may be unacceptable. Therefore to keep selectivity high with relatively high conversion, it is advantageous in certain embodiments to run the photochlorination with less than 100 % conversion of CH3CF2CHC12 and recycle this material along with fresh CH3CF2CH2C1, preferably in the next batch. In preferred embodiments, the amount of CH3CF2CHC12 made is approximately equal to the amount added as recycled material.
A mixture of about 202.4 grams of CH3CF2CH2C1 and about 110.7 g of CH3CF2CHC12 was photochlorinated using a 100-watt Hg lamp at a temperature of about -4 C with a chlorine feed rate of about 22.2 g/h as described in Example 10A.
= After an irradiation time of about 8.4 hours the conversion of CH3CF2CH2C1 exceeded about 90 %. The composition of the crude product was about 6.9 wt%
CH3CF2CH2C1, 45.2 wt% CH3CF2CHC12, and 43.5 wt% CH3CF2CC13. The amount of CH3CF2CHC12 initially increased with time, reaching a maximum of about 55 wt % after about hours.
EXAMPLE 90A ¨ 90C
Conversion of 2,3-dichloropropene Example 10A
=
About 65 cc of 50 weight% SbC15 on activated carbon support is provided at a temperature of about 96 C. The catalyst was loaded into the 'A" OD x 36" L
mortal tube. 2,3-dichloropropene was used for the organic feed stock. After normal catalyst activation with HF and C12, the C12 flow was stopped and the HF feed was adjusted to a rate of about 47 g/hr. Shortly thereafter, the 2,3-dichloropropene feed was started at a rate of about 20 ¨.25 g/hr. The HF/organic mole ratio was 11.5/1. The pressure was about 20 psig. The contact time was about 6.73 sec. Reactor effluent samples were collected in Tedlar gas sample bags containing DI water to absorb the acid before analysis. The bags were then heated to about 60 C to ensure that the organic present in the bag was completely vaporized. GC/MS results showed the major product to be chloro-2,2-difluoropropane (262ca) with an area of about 93.3%. Also present are about 3.7 area% of 1,2,2-trifluoropropane (263ca) and about 3.4 area% of 272ca. The conversion of the 2,3-dichloropropene was about 100%.
Ex pie 100 This example was run similarly to Example 10A but the reaction temperature was about 135 C. The contact time was about 6.07 sec. The GC,/MS results of the bag sample show about 72.8 area% for 1-chloro-2,2-difluoropropane (262ca), about 15.11 area% for 1,2-dichloro-2-fluoropropane (26 lba), about 4.8 area% for 263ca, about 4.1 area% for 2,2-difluoropropane (272ca) and about 2.6 area% for 1,1,1,2,2,3,3,4,4-nanofluorohexane.
Example 14)C
This Example was run similarly to Example 10A but the reaction temperature was about 195 C. The contact time was about 5.29 sec. The GC,/MS results of the bag sample show about 38.59 area% for 1-chloro-2,2-difluoropropane (262ca), about 29.3 area% for 1,2-dich1oro-2-fluompropane (261ba), about 4.7 area% for 263ca, about 20.12 area% for 272.ca and about 7.3 area% for 1,1,1,2,2,3,3,4,4-nanofluorohexane.
Having thus described a few particular embodiments of the invention, various alterations, modifications, and improvements will readily occur to those skilled in the art. Such alterations, modifications, and improvements are made obvious by this disclosure, and it will be understood that the scope of the claims will not be limited by any preferred embodiments or examples set forth, but should be given the broadest interpretation consistent with the description as a whole.
The preferred conversion step of the present invention is preferably carried out under conditions, including the use of one or more reactions, effective to provide a Formula (I) conversion of at least about 50%, more preferably at least about 75%, and even more preferably at least about 90%. In certain preferred embodiments the conversion is at least about 95%, and more preferably at least about 97%.
Further in certain preferred embodiments, the step of converting the compound of Formula (I) to produce a compound of Formula (II) is conducted under conditions effective to provide a formula (II) selectivity of at least about 45%, more preferably at least about 55%, and more preferably at least about 75%. In certain preferred embodiments a selectivity of about 95% or greater may be achieved.
In other aspects of the present invention, a method is provided for producing the compound of Formula (I) by converting at least one compound of Formula (III):
C(X)2=CC1C(X)3 (III) to at least one compound of Formula (I), as described above, where each X is independently H, F, Cl, I or Br, provided at least one X is Cl, I or Br. In preferred embodiments, at least one X on the unsaturated carbon is Cl, I or Br, and even more preferably Cl. The details of exemplary conversion *steps in accordance with this aspect of the invention are provided in the examples.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
One beneficial aspect of the present invention is that it enables the production of desirable flurookfins, preferably C3. fluoroolefins, using relatively high conversion and high selectivity reactions. Furthermore, the present methods in certain preferred embodiments permit the production of the desirable fluoroolefins, either directly or indirectly, from relatively attractive starting materials.
Preferably the Formula (I) compound is exposed to reaction conditions effective to produce a reaction product containing one or more of the desired fluorolefins, preferably one or more compounds of Formula (II). Although it is contemplated that the exposure step in certain embodiments may effectively be carried out in a single reaction stage and/or under a single set of reaction conditions, as mentioned above, it is preferred in many embodiments that the conversion step comprise a series of reaction stages or conditions. In one preferred aspect of the present invention, the conversion step comprises: (a) reacting a first chlorinated compound of Formula (IA), in a gas and/or liquid phase reaction in the presence of at least a first catalyst to produce at least one compound of Formula (IA), preferably a compound of Formula (IA) which is penta-fluorinated, and even more preferably contains no other halogen substituents, such as HFC-245; (b) reacting the Formula (IA) compound, preferably the penta-fluorinated Formula (IA) compound, preferably in a gas phase and in the presence or absence of catalyst, which if present maybe the same or different than the first catalyst to produce at least one compound of Formula (II) and even more preferably HF0-1234yf. In certain embodiments, the catalyst does not include substantial amounts of oxygen containing catalyst. Each of the preferred reaction steps is described in detail below, with the headings being used for convenience but not necessarily by way of limitation.
I. FLUORINATION OF THE MULTI-HALOGENATED FORMULA I(A) One preferred reaction step in accordance may be described by those reactions in which the compound of Formula (IA) contains fluorine and at least one other halogen, and this compound is fluorinated to produce a compound of Formula (IA) which contains at least four, and preferably five, fluorine substituents, and even more preferably no other halogen substituents. In certain of such preferred embodiments, especially embodiments in which such compound comprises HCFC-242bb, the present converting step comprises first reacting said compound(s) by fluorinating said compound(s), preferably with HF in a gas and/or liquid phase, to produce an HFC, preferably an HFC that is at least tetrafluorinated, such as HFC-245.
Preferably this reaction, whether in the gas phase, the liquid phase, or both is at least partially catalyzed. In certain preferred embodiments, the compound of Formula (IA), such as HCFC-242bb is contacted with liquid HF in the presence of a catalyst including but not limited to SbC15, SbF5, SbF3, TiC14, SnC14, FeC13, AlC13, AlF3, and combinations of two or more of these, to synthesize a compound of Formula (IA) having an increased number of fluorine substituents, and preferably only fluorine substituents, such as CF3CF2CH3. SbC15 is found to be highly preferred in many desirable embodiments. In other preferred embodiments, this conversion step is carried out in a catalytic, continuous, gas-phase reaction mode using SbC15/C as the solid catalyst. The preferred fluorination of the compound of Formula (IA) is preferably carried out under conditions effective to provide a Formula (IA) conversion of at least about 50%, more preferably at least about 75%, and even more preferably at least about 90%. In certain preferred embodiments the conversion is at least about 95%, and more preferably at least about 97%. Further in certain preferred embodiments, the conversion of the compound of Formula (IA) comprises reacting such compound under conditions effective to produce at least one penta-fluorinated compound (preferably HFC-245) at a yield of at least about 70%, more preferably at least about 75%, and even more preferably at least about 80%.
In general, it is possible that the fluorination reaction step can be carried out in the liquid phase or in the gas phase, or in a combination of gas and liquid phases, and it is contemplated that the reaction can be carried out batch wise, continuous, or a combination of these.
In preferred gas phase fluorination of Formula (I) compounds, the reaction is at least partially a catalyzed reaction, and is preferably carried out on a continuous basis by introducing a stream containing the compound of Formula (I) into one or more reaction vessels, such as a tubular reactor. In certain preferred embodiments, the stream containing the compound of Formula (I), and preferably Formula (IA), is preheated to a temperature of from about 150 C to about 400 C, preferably about 300 C, and introduced into a reaction vessel (preferably a tube reactor), which is maintained at the desired temperature, preferably from about 40 C to about 200 C, more preferably from about 50 C to about 150 C, where it is preferably contacted with catalyst and fluorinating agent, such as BF.
Preferably the vessel is comprised of materials which are resistant to corrosion as Hastelloy, Inconel, Monel and/or fluoropolymers linings.
Preferably the vessel contains catalyst, for example a fixed or fluid catalyst bed, packed with a suitable fluorination catalyst, with suitable means to ensure that the reaction mixture is maintained with the desired reaction temperature range.
Thus, it is contemplated that the fluorination reaction step may be performed using a wide variety of process parameters and process conditions in view of the overall teachings contained herein. However, it is preferred in certain embodiments that this reaction step comprise a gas phase reaction, preferably in the presence of catalyst, and even more preferably a Sb-based and/or and Fe-based catalyst (such as FeC13 on carbon (designated herein as FeC13/C for convenience), and combinations of these.
In general it is also contemplated that a wide variety of reaction pressures may be used for the fluorination reaction, depending again on relevant factors such as the specific catalyst being used and the most desired reaction product. The reaction pressure can be, for example, superatmospheric, atmospheric or under vacuum, and in certain preferred embodiments is from about 1 to about 200 psia, and even more preferably from about 1 to about 120 psia.
In certain embodiments, an inert diluent gas, such as nitrogen, may be used in combination with the other reactor feed(s).
It is contemplated that the amount of catalyst use will vary depending on the particular parameters present in each embodiment.
II. CONVERSION TO FORMULA (H) One preferred reaction step in accordance may be described by those reactions in which the compound of Formula (I), preferably Formula (IA) is converted to a compound of Formula (II). In certain preferred embodiments, the stream containing the compound of formula (I), and preferably (IA) is preheated to a temperature of from about 150 C to about 400 C, preferably about 350 C, and introduced into a reaction vessel, which is maintained at the desired temperature, preferably from about 300 C to about 700 C, more preferably from about 450 C to about 650 C.
Preferably the vessel is comprised of materials which are resistant to corrosion as Hastelloy, Inconel, Monel and/or fluoropolymers linings. Preferably the vessel contains catalyst, for example a fixed or fluid catalyst bed, packed with a suitable catalyst, with suitable means to heat the reaction mixture to the desired reaction temperature.
Thus, it is contemplated that this reaction step may be preformed using a wide variety of process parameters and process conditions in view of the overall teachings contained herein. However, it is preferred in certain embodiments that this reaction step comprise a gas phase reaction, preferably in the presence of catalyst, and even more preferably a carbon- and/or metal-based catalyst, preferably activated carbon, a nickel-based catalyst (such as Ni-mesh) and combinations of these. Other catalysts and catalyst supports may be used, including palladium on carbon, palladium-based catalyst (including palladium on aluminum oxides), and it is expected that many other catalysts may be used depending on the requirements of particular embodiments in view of the teachings contained herein. Of course, two or more any of these catalysts, or other catalysts not named here, may be used in combination.
While it is contemplated that a wide variety of reaction temperatures may be used, depending on relevant factors such as the catalyst being used and the most desired reaction product, it is generally preferred that the reaction temperature for the step is from about 200 C to about 800 C, more preferably from about 400 C to about 800 C. In certain preferred embodiments, the reaction temperature is from about 300 C to about 600 C, and even more preferably in certain embodiments from about 500 C to about 600 C.
In general it is also contemplated that a wide variety of reaction pressures may be used, depending again on relevant factors such as the specific catalyst being used and the most desired reaction product. The reaction pressure can be, for example, superatmospheric, atmospheric or under vacuum and in certain preferred embodiments is from about 1 to about 200 psia, and in certain embodiment from about 1 to about 120 psia.
In certain embodiments, an inert diluent gas, such as nitrogen, may be used in combination with the other reactor feed(s). It is contemplated that the amount of catalyst use will vary depending on the particular parameters present in each embodiment.
Preferably in such embodiments as described in this section, the conversion of the formula (I) compound is at least about 30%, more preferably at least about 50%, and even more preferably at least about 60%. Preferably in such embodiments, the 'selectivity to compound of Formula (II), preferably HF0-1234y1, is at least about 70%, more preferably at least about 80% and more preferably at least about 90%.
EXAMPLES
Additional features of the present invention are provided in the following examples, which should not be construed as limiting the claims in any way.
EXAMPLES lA
Liquid-phase catalytic fluorination of CC13CE2CH3 (242bb) with HE to CF3CF2CH3 (R245 cb) Example 1A
About 327 grams HF, about 50 grams CC13CF2CH3(242bb), and about 75 grams SbC15 were charged into a 1-L autoclave. The reaction mixture was stirred at 120 C for about 6 hours under about 760 psig of pressure. After the stipulated reaction time, the reactor was cooled up to about 0 C, and about 300 ml water was then added slowly into the autoclave over a period of about 45 minutes. After complete addition of water under stirring, the reactor was heated to about 70 C and then the overhead gases were transferred to another collecting cylinder. The yield of CF3CF2CH3 was about 82% at a 242bb conversion level of about 100%. The other major by-products were traces of CF3CFCICH3 and tarry material.
Example 1B
About 327 grams of HF, about 50 graqms of CC13CF2CH3(242bb), and about 75 grams of SbC15 were charged into a 1-L autoclave. The reaction mixture was stirred at about 100 C for about 6 hours under about 620 psig of pressure. After the reaction, the reactor was cooled to about 0 C, and about 300 ml water was then added slowly into the autoclave over a period of about 45 minutes. After complete addition of water under stirring, the reactor temperature was raised to 70 C and then the overhead gases were transferred to another collecting cylinder. The yield of CF3CF2CH3 was about 78% at a 242bb conversion level of about 86%. The other major by-products were traces of CF3CFC1CH3 and and other clorofluoropropanes.
Example 1C
About 327 grams HF, about 50 grams 1233xf, and about 75 grams SbC15 were charged into a 1-L autoclave. The reaction mixture was stirred at about 80 C
for about 6 hours under about 460 psig of pressure. After the reaction, the reactor was cooled to 0 C and 300 ml water was then added slowly into the autoclave over a period of about 45 minutes. After complete addition of water under stirring, the reactor was cooled to room temperature and then the overhead gases were transferred to another collecting cylinder. The yield of CF3CF2CH3 was about 67%. The only other major by-products includes products resulted from incomplete fluorination and trace of CF3CFCICH3.
Gas-phase catalytic fluorination of CC13CF2CH3 (242bb) with HF to CF3CF2CH3 (R245ch) A 22-inch (1/2-inch diameter) Monel pipe gas phase reactor was charged with 120 cc of 50wt% SbC15/C as the catalyst. The reactor was mounted inside a heater with three zones (top, middle and bottom). The reactor temperature was read by custom made 5-point thermocouples kept at the middle inside of the reactor. The inlet of the reactor was connected to a pre-heater, which was kept at about 300 C by electrical heating. The liquid-HF was fed from a cylinder into the pre-heater through a needle valve, liquid mass-flow meter, and a research control valve at a substantially constant flow of from about 1 to about 1000 grams per hour (g/h). The HF cylinder was kept at a constant pressure of 45 psig by applying anhydrous N2 gas pressure into the cylinder head space. A feed consisting of organic reactant (242bb) was fed at a rate ranging from about 10 to about 120 g/h as a gas from a cylinder kept at about 145 C
through a regulator, needle valve, and a gas mass-flow-meter. The organic feed stream was also fed periodically as liquid at about 105 C from a cylinder into the pre-heater through a needle valve, liquid mass-flow meter, and a research control valve at a substantially constant flow rate ranging from about 10 to about 150 g/h. The organic line from the cylinder to the pre-heater was kept at about 265 C by wrapping with constant temperature heat trace and electrical heating. All feed cylinders were mounted on scales to monitor their weight by difference. The reactions were run at a substantially constant reactor pressure of from about 0 to about 100 psig by controlling the flow of reactor exit gases by another research control valve. The exit gases coming out of the reactor were analyzed by on-line GC and GC/MS connected through a hotbox valve arrangements to prevent condensation. The reactor temperature was kept at from about 60 C to about 120 C. The SbC15/C catalyst was pretreated with about 50 g/h HF
at about the reaction temperature for about 8 hours under about 50 psig pressures. After HF pretreatment, the catalyst was further treated with about 20 seem of C12 and about 50 g/h of HF for an additional 4 hours. The pretreated catalyst was then contacted with organic in the presence of about 50 g/h HF. The conversion of 242bb was in the range of from about 60 to about 70% and the selectivity to 245cb was about 85% when the reaction was performed using 50 wt% SbC15/C as the catalyst at about 120 C
under about 30 psig pressure in the presence of about 50 g/h HF and about 20 g/h of 242bb.
The product was collected by flowing the reactor exit gases through a solution of from about 20wt% to about 60 wt% aqueous KOH scrubber solution and then trapping the exit gases from the scrubber into a cylinder kept in dry ice or liquid N2. The products were then isolated by distillation. The following catalysts were tested and found to have the selecetivity to HFC-245 as indicated in parenthesis: 30 wt% SbC15/C
(Sel.
81%); from about 3 to about 6 wt% FeC13/C (Sel. 52%); SbF5/C (Sel. 87%); 20 wt%
SnC14/C (Sel. 32%); 23 wt% TiC14/C (Sel. 27%). The catalyst temperatures o used ranged from about 60 C to about 120 C. SbC15/C is believed to be a preferred catalyst for this gas-phase transformation.
Catalytic conversion of CF3CF2CH3 to CF3CF=CH2 A 22-inch (1/2-inch diameter) Monel tube reactor was charged with about 120 cc of a catalyst. The reactor was mounted inside a heater with three zones (top, middle and bottom). The reactor temperature was read by custom made 5-point thermocouples kept at the middle inside of the reactor. The inlet of the reactor was connected to a pre-heater, which was kept at about 300 C by electrical heating. HFC-245cb was fed from a cylinder kept at about 65 C through a regulator, needle valve, and a gas mass-flow-meter. The line to the pre-heater was heat traced and kept at a substantially constant temperature of from about 65 C to about 70 C by electrical heating to avoid condensation. The feed cylinder was mounted on scales to monitor their weight by difference. The reactions were run at a substantially constant reactor pressure in the range of from about 0 to about 100 psig by controlling the flow of reactor exit gases by another research control valve. The gas mixture exiting the reactor was analyzed by on-line GC and= GC/MS connected through a hotbox valve arrangements to prevent condensation. The conversion of 245cb was in the range of from about 30% to about 70% and the selectivity to HF0-1234yf was in the range of from about 90% to about 100% depending on the reaction conditions. The products were collected by flowing the reactor exit gases through a 20-60-wt% of aqueous KOH scrubber solution and then trapping the exit gases from the scrubber into a cylinder kept in dry ice or liquid N2. The products were then substantial isolated by distillation. Results are tabulated in Table 1.
Table 1: Transformation of CF3CF2CH3 to 1234yf # Cat T, = 112, CF3CF2CH3 (245cb) Conversion of 245cb 1234yf C sccm seem (Sel. %).
Reaction conditions: Pressure about 2.5 to about 5.3 psig; Catalyst, 100 cc"
: A is NORIT RFC 3; B is Shiro-Saga activated carbon; C is Aldrich activated carbon; D is Calgon activated carbon; E is 0.5 wt% Pd/C; F is 0.5 wt% Pt/C; G
is Ni-mesh; Organic cylinder temperature about 65 C; CF3CF2CH3 (245cb) line to the preheater about 50 C; Preheater, 350 C; N2 - 0 SCCM.
Preparation of CH3CF2CH2CI from 2,3-dichloropropene using HF/SbC15 Example 4A
A 2-gallon autoclave was charged with about 900 grams (8.1 mol) of 2,3-dichloropropene, about 405 grams (20.3 mol) of HF, and about 10 grams (0.033 mol) of SbC15. The contents were heated with stirring to about 100 C for about 19 hours.
The maximum pressure was about 285 psig. (approx. 2000 kPa). The contents were vented while hot into a fluoropolymer container containing ice, which was connected in sequence to a dry ice trap. The organic layer was separated and washed to remove residual acid, giving about 811.9 grams of crude product, which by GC analysis was comprised of about 41% CH3CF2CH2C1, about 34.5% CH3CFC1CH2C1, 21 %
CH3CC12CH2C1, and about 1.8 % starting material. The conversion was about 97 %, while the combined yield of halopropanes was 76.7 %. Substantially pure CH3CF2CH2C1 was obtained by fractional distillation. The autoclave also contained about 77.8 grams of black residue.
Example 4B
Example 4A was repeated except that the reactants were heated to about 120 C
for about 18 hours. The crude organic layer so obtained consisted of about 58.8 %
CH3CF2CH2C1, about 28.3 % CH3CFC1CH2C1, and about 9.8 % CH3CC12CH2C1. The combined yield of halopropanes was about 74 %.
Example 4C
Example 4A was repeated except that no catalyst was used. The crude organic layer so obtained consisted of about 58.7 % CH3CF2CH2C1, about 25.9 %
CH3CFC1CH2CI, and about 12.2 % CH3CC12CH2C1. The combined yield of halopropanes was about 80%. This example demonstrates that SbC15 catalyst was not effective in increasing the amount of the desired CH3CF2CH2CI or increasing the total yield of useful products.
Conversion of 2,3-diehloropropene to CH3CFCICH2C1 A two-gallon autoclave was evacuated and charged with about 1500 grams of 2,3-dichloropropene (about 13.4 mol). It was then cooled to about -5 C by means of internal cooling coils connected to a chiller. About 1500 grams (75 mol) was added, the chiller turned off, and the contents slowly heated to a temperature in the range of from about 20 to about 25 C with stirring. After approximately 18 hours, the contents were cooled to about 5 C before discharging into iced water. The organic phase was separated and washed with about 1 L of water, dried (MgSO4) and filtered to give about 1554 grams of the product mixture. GC analysis indicated that the crude product contained about 86.5 % CH3CFC1CH2C1, about 3.8 % CH3CF2CH2C1, and about 2.8 %
CH3CC12CH2C1. Similar results were obtained at a temperature of about 50 C, although the amount of CH3CFCICH2CI decreased slightly, while the amount of CH3CF2CH2C1 marginally increased.
Conversion of CH3CCI2CH2C1 to CH3CF2CH2C1 An autoclave was charged with about 100 grams of CH3CC12CH2C1 and about .
44 grams of HF and the contents heated with stirring to about 130 C for about 20.5 hours. The products were process substantially in accordance with the description in Example 1, which resulted in about 70 grams of crude product which was comprised, based on GC area %, about 43.8 % CH3CF2CH2C1, about 23.1 % CH3CFCICH2C1, and about 30.3 % CH3CC12CH2C1. The autoclave also contained about 1.9 grams of dark residue.
Conversion of a mixture of CH3CFCICH2CI and CH3CC12CH2C1 to A mixture of about 666 grams of CH3CFC1CH2C1, about 268 grams of CH3CC12CH2C1, about 474 grams of HF and about 11 grams of SnCI.4 were heated together with stirring to about 114 C for about 18 hours. The crude product was comprised of about 89 % CH3CF2CH2C1.
Based on the results of Examples 4 ¨ 7, the use of chlorinated antimony catalyst, such as. SbC15, may not be preferred in certain embodiments due to an added cost that may not provide the desired improvement in yield or conversion in some embodiments, and may produce considerable by-product residue. In certain embodiments, therefore, it is preferred to run the reaction without catalyst.
However, the use of SnC14 may be preferred in embodiments in which CH3CF2CH2CI is the desired product, since its use may allow a lower temperature to be used and result in a higher percentage of CH3CF2CH2C1 in the crude product.
EXAMPLES 8A ¨ 8C
Preparation of Cli3CF2CC13 The photochlorination of CH3CF2CH3 to CH3CF2CCI3 has been mentioned in JACS, 59 (1937) 2436 Example 8A - Photoehlorination of CIJACE&CH2C1 The photochlorination was done using a 100-W Hg lamp placed in a quartz jacket that was cooled with the use of a circulating cooling bath set at about -5 C. The quartz jacket was inserted into a glass reactor of about 400 mL capacity. The reactor was cooled externally by placing it in a glycol-water bath which was cooled with the use of cooling coils connected to a second circulating bath set at -8.5 C. The reactor was fitted with a thermocouple, stir bar, and a gas inlet tube for introducing chlorine gas from a cylinder via a calibrated flowmeter. Exiting gases passed through a water-cooled condenser, an air trap, and a scrubber containing NaOH and Na2S03 to remove HC1 and chlorine.
The reactor was charged with about 250.5 grams of CH3CF2CH2C1 of about 98.6 % purity and allowed to cool to a substantially constant temperature of about -5.5 C. The chlorine cylinder was then opened and the flow rate set at 23 g/h.
Immediately thereafter, the lamp was then turned on. After approximately 0.5 hours, the temperature of the reactor contents stabilized at about -3 10.5 C.
The photochlorination was continued for about 7 hours and a conversion of about 79.4% was achieved. The composition of the crude product, which amounted to about 309.3 grams, was about 19.2 % CH3CF2CH2C1 , about 50.9 %
CH3CF2CHC12 and about 24.8 % CH3CF2CC13. Substantially pure CH3CF2CC13 was obtained by fractional distillation.
A 450-W Hg lamp could also be used. The ratios of CH3CF2CHC12 to CH3CF2CCI3vs. time were essentially the same as with a 100-watt lamp.
Examole 88 -õPhotochlorination of CH3CF2C11C12 In a manner similar to that described in Example 8A, about 296.8 grams of CH3CF2CHC12 (about 97.4 % pure, containing about 1.9 % CH3CF2CC13) was photochlorinated using a l 00-W Hg lamp at a temperature of about -4 C and chlorine feed rate of about 22.3 g/h. After about 2.5 hours, the composition of the reactor contents was about 58.2 % CH3CF2CHC12 and about 39.9 % CH3CF2CC13. Thus the selectivity for CH3CF2CC13 was about 97 % at a CH3CF2CHC12 conversion of about %.
Photoehlorination of a mixture of CH3CF2CH2CI and CH3CF2CHC12 The selectivity found in Examples 8A and 8C is considered to be desirably for many embodiments of the invention. However, limiting the conversion achieved in those examples may be less than desired in certain applications. It is believed that the conversions may be limited in those example by two factors. One factor is the melting point of CH3CF2CC13 (53 C) and the other is lower selectivity at high conversion. The latter may be a problem in connection with certain commercial embodiments where such yield losses may be unacceptable. Therefore to keep selectivity high with relatively high conversion, it is advantageous in certain embodiments to run the photochlorination with less than 100 % conversion of CH3CF2CHC12 and recycle this material along with fresh CH3CF2CH2C1, preferably in the next batch. In preferred embodiments, the amount of CH3CF2CHC12 made is approximately equal to the amount added as recycled material.
A mixture of about 202.4 grams of CH3CF2CH2C1 and about 110.7 g of CH3CF2CHC12 was photochlorinated using a 100-watt Hg lamp at a temperature of about -4 C with a chlorine feed rate of about 22.2 g/h as described in Example 10A.
= After an irradiation time of about 8.4 hours the conversion of CH3CF2CH2C1 exceeded about 90 %. The composition of the crude product was about 6.9 wt%
CH3CF2CH2C1, 45.2 wt% CH3CF2CHC12, and 43.5 wt% CH3CF2CC13. The amount of CH3CF2CHC12 initially increased with time, reaching a maximum of about 55 wt % after about hours.
EXAMPLE 90A ¨ 90C
Conversion of 2,3-dichloropropene Example 10A
=
About 65 cc of 50 weight% SbC15 on activated carbon support is provided at a temperature of about 96 C. The catalyst was loaded into the 'A" OD x 36" L
mortal tube. 2,3-dichloropropene was used for the organic feed stock. After normal catalyst activation with HF and C12, the C12 flow was stopped and the HF feed was adjusted to a rate of about 47 g/hr. Shortly thereafter, the 2,3-dichloropropene feed was started at a rate of about 20 ¨.25 g/hr. The HF/organic mole ratio was 11.5/1. The pressure was about 20 psig. The contact time was about 6.73 sec. Reactor effluent samples were collected in Tedlar gas sample bags containing DI water to absorb the acid before analysis. The bags were then heated to about 60 C to ensure that the organic present in the bag was completely vaporized. GC/MS results showed the major product to be chloro-2,2-difluoropropane (262ca) with an area of about 93.3%. Also present are about 3.7 area% of 1,2,2-trifluoropropane (263ca) and about 3.4 area% of 272ca. The conversion of the 2,3-dichloropropene was about 100%.
Ex pie 100 This example was run similarly to Example 10A but the reaction temperature was about 135 C. The contact time was about 6.07 sec. The GC,/MS results of the bag sample show about 72.8 area% for 1-chloro-2,2-difluoropropane (262ca), about 15.11 area% for 1,2-dichloro-2-fluoropropane (26 lba), about 4.8 area% for 263ca, about 4.1 area% for 2,2-difluoropropane (272ca) and about 2.6 area% for 1,1,1,2,2,3,3,4,4-nanofluorohexane.
Example 14)C
This Example was run similarly to Example 10A but the reaction temperature was about 195 C. The contact time was about 5.29 sec. The GC,/MS results of the bag sample show about 38.59 area% for 1-chloro-2,2-difluoropropane (262ca), about 29.3 area% for 1,2-dich1oro-2-fluompropane (261ba), about 4.7 area% for 263ca, about 20.12 area% for 272.ca and about 7.3 area% for 1,1,1,2,2,3,3,4,4-nanofluorohexane.
Having thus described a few particular embodiments of the invention, various alterations, modifications, and improvements will readily occur to those skilled in the art. Such alterations, modifications, and improvements are made obvious by this disclosure, and it will be understood that the scope of the claims will not be limited by any preferred embodiments or examples set forth, but should be given the broadest interpretation consistent with the description as a whole.
Claims (17)
1. A method for producing fluorinated organic compounds comprising:
fluorinating at least a first compound of Formula IA to form a second compound of Formula IA
C(X)3CF2CH3 (IA) wherein in the first compound X is independently H, F, CI, I or Br and at least one X
is a chlorine, wherein said second compound of Formula (IA) is pentafluorinated; and dehydrofluorinating the second compound of Formula IA to form a compound of Formula II
CF3CF=CHZ (II) where Z is independently H, F, Cl, I or Br, wherein said dehydrofluorinating step is carried out in the substantial absence of oxygen-containing metal catalyst.
fluorinating at least a first compound of Formula IA to form a second compound of Formula IA
C(X)3CF2CH3 (IA) wherein in the first compound X is independently H, F, CI, I or Br and at least one X
is a chlorine, wherein said second compound of Formula (IA) is pentafluorinated; and dehydrofluorinating the second compound of Formula IA to form a compound of Formula II
CF3CF=CHZ (II) where Z is independently H, F, Cl, I or Br, wherein said dehydrofluorinating step is carried out in the substantial absence of oxygen-containing metal catalyst.
2. The method of claim 1 wherein Z in said compound of Formula (II) is H.
3. The method of claim 1 wherein said first compound of Formula (IA) comprises trichlorinated, difluorinated propane.
4. The method of claim 1 wherein said first compound of Formula (IA) is 1,1,1-trichloro-2,2-difluoropropane (HCFC-242bb).
5. The method of claim 1 wherein said first compound of Formula (IA) comprises 1,1,1-trichloro-2,2-difluoropropane (HCFC-242bb) and said second compound of Formula (IA) comprises 1,1,1,2,2-pentafluoropropane (HFC- 245cb).
6. The method of claim 1 further comprising the step of providing said first compound of Formula (IA) by converting at least one compound of Formula (III):
C(X)2=CClC(X)3 (III) to at least one first compound of Formula (IA), where each X in Formula III is independently H, F, Cl, I or Br, provided at least one X in Formula III is Cl, I or Br.
C(X)2=CClC(X)3 (III) to at least one first compound of Formula (IA), where each X in Formula III is independently H, F, Cl, I or Br, provided at least one X in Formula III is Cl, I or Br.
7. The method of claim 6 wherein at least one X on the unsaturated carbon of Formula (III) is Cl, I or Br.
8 The method of claim 7 wherein at least one X on the unsaturated carbon of Formula (III) is Cl.
9. A method for producing fluorinated organic compounds comprising fluorinating at least a first compound of Formula IA to form a second compound of Formula IA
C(X)3CF2CH3 (IA) wherein in the first compound X is independently H, F, or Cl and at least one X is Cl, wherein said second compound of Formula (IA) is pentafluorinated, and wherein said fluorinating step comprises reacting the first compound of formula IA with HF
to form the second compound of Formula (IA); and dehydrofluorinating the second compound of Formula IA to form a compound of Formula II
CF3CF=CHZ (II) where Z is independently H or F said dehydrohalogenating step is in the presence of a carbon-based catalyst, metal-based catalyst, or both, that does not include an oxygen atom.
C(X)3CF2CH3 (IA) wherein in the first compound X is independently H, F, or Cl and at least one X is Cl, wherein said second compound of Formula (IA) is pentafluorinated, and wherein said fluorinating step comprises reacting the first compound of formula IA with HF
to form the second compound of Formula (IA); and dehydrofluorinating the second compound of Formula IA to form a compound of Formula II
CF3CF=CHZ (II) where Z is independently H or F said dehydrohalogenating step is in the presence of a carbon-based catalyst, metal-based catalyst, or both, that does not include an oxygen atom.
10. The method of claim 9 wherein said fluorinating step contains at least a first fluorination catalyst and said dehydrofluorinating step contains at least a second catalyst, which comprises a carbon-based catalyst, metal-based catalyst, or both, that does not include an oxygen atom.
11. The method of claim 10 wherein said first fluorination catalyst comprises a Sb- based catalyst.
12. The method of claim 10 wherein said first fluorination catalyst comprises a Fe- based catalyst.
13. The method of claim 10 wherein said second catalyst comprises a metal-based catalyst that does not include an oxygen atom.
14. The method of claim 13 wherein said second catalyst comprises a nickel-based catalyst.
15. The method of claim 10 wherein said second catalyst comprises a carbon-based catalyst.
16. The method of claim 10 wherein said second compound is pentafluoropropane.
17. The method of claim 16 wherein said compound of Formula (II) comprises 2,3,3,3-tetrafluoropropene.
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| PCT/US2007/000064 WO2007079435A2 (en) | 2006-01-03 | 2007-01-03 | Method for producing fluorinated organic compounds |
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| CN103193584B (en) * | 2006-01-03 | 2015-07-01 | 霍尼韦尔国际公司 | Method for producing fluorinated organic compounds |
| PT2546224T (en) * | 2006-01-03 | 2019-01-10 | Honeywell Int Inc | Method for producing fluorinated organic compounds |
| JP5416587B2 (en) | 2006-10-03 | 2014-02-12 | メキシケム、アマンコ、ホールディング、ソシエダッド、アノニマ、デ、カピタル、バリアブレ | process |
| GB0625214D0 (en) | 2006-12-19 | 2007-01-24 | Ineos Fluor Holdings Ltd | Process |
| US9035111B2 (en) * | 2007-08-22 | 2015-05-19 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
| CN102076643B (en) * | 2008-06-26 | 2014-08-06 | 阿科玛股份有限公司 | Catalytic gas phase fluorination of 1230xa to 1234yf |
| KR20110086037A (en) | 2008-10-13 | 2011-07-27 | 다우 글로벌 테크놀로지스 엘엘씨 | Process for the production of chlorinated and/or fluorinated propens |
| US8288598B2 (en) * | 2009-01-16 | 2012-10-16 | Honeywell International Inc. | Isomerization of 1,1,3,3-tetrafluoropropene |
| KR20120093857A (en) | 2009-10-09 | 2012-08-23 | 다우 글로벌 테크놀로지스 엘엘씨 | Process for the production of chlorinated and/or fluorinated propenes |
| WO2011044536A1 (en) | 2009-10-09 | 2011-04-14 | Dow Global Technologies, Inc | Process for the production of chlorinated and/or fluorinated propenes and higher alkenes |
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| ES2567178T5 (en) | 2010-02-12 | 2023-04-28 | Daikin Ind Ltd | Procedure for producing a fluorine-containing alkene |
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| CA2836493A1 (en) | 2011-05-31 | 2012-12-06 | Max Markus Tirtowidjojo | Process for the production of chlorinated propenes |
| ES2721451T3 (en) | 2011-06-08 | 2019-07-31 | Dow Agrosciences Llc | Procedure for the production of chlorinated and / or fluorinated propenes |
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| CN104024187B (en) | 2011-12-02 | 2017-04-12 | 蓝立方知识产权有限责任公司 | Process for the production of chlorinated alkanes |
| CA2856545A1 (en) | 2011-12-02 | 2013-06-06 | Dow Global Technologies Llc | Process for the production of chlorinated alkanes |
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| CN104159874B (en) | 2011-12-23 | 2016-08-24 | 陶氏环球技术有限责任公司 | Produce alkene and/or the method for aromatic compounds |
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| CN104755448A (en) | 2012-09-20 | 2015-07-01 | 陶氏环球技术有限公司 | Process for the production of chlorinated propenes |
| US9321707B2 (en) | 2012-09-20 | 2016-04-26 | Blue Cube Ip Llc | Process for the production of chlorinated propenes |
| IN2015DN03119A (en) | 2012-09-30 | 2015-10-02 | Dow Global Technologies Llc | |
| WO2014066083A1 (en) | 2012-10-26 | 2014-05-01 | Dow Global Technologies, Llc | Mixer and reactor and process incorporating the same |
| CA2893841C (en) | 2012-12-18 | 2018-07-24 | Dow Global Technologies Llc | Process for the production of chlorinated propenes |
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| CA2635806A1 (en) | 2007-07-12 |
| JP2009522313A (en) | 2009-06-11 |
| CN101395109B (en) | 2013-09-18 |
| KR20080083041A (en) | 2008-09-12 |
| JP2014237681A (en) | 2014-12-18 |
| KR101354492B1 (en) | 2014-01-23 |
| WO2007079435A3 (en) | 2007-11-15 |
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| EP1968923A2 (en) | 2008-09-17 |
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