EP1968923A2 - Procede de fabrication de composes organiques fluores - Google Patents

Procede de fabrication de composes organiques fluores

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Publication number
EP1968923A2
EP1968923A2 EP07716234A EP07716234A EP1968923A2 EP 1968923 A2 EP1968923 A2 EP 1968923A2 EP 07716234 A EP07716234 A EP 07716234A EP 07716234 A EP07716234 A EP 07716234A EP 1968923 A2 EP1968923 A2 EP 1968923A2
Authority
EP
European Patent Office
Prior art keywords
compound
formula
catalyst
reaction
exposing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07716234A
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German (de)
English (en)
Inventor
Hsueh Sung Tung
Sudip Mukhopadhyay
Michael Van Der Puy
Jing Ji Ma
Daniel C. Merkel
Cheryl Bortz
Barbara Light
Steven D. Phillips
Kim M. Fleming
Susan Ferguson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell International Inc
Original Assignee
Honeywell International Inc
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Filing date
Publication date
Application filed by Honeywell International Inc filed Critical Honeywell International Inc
Publication of EP1968923A2 publication Critical patent/EP1968923A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/19—Halogenated dienes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
    • C07C17/087—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation

Definitions

  • This invention relates to novel methods for preparing fluorinated organic compounds.
  • Hydrofluorocarbons in particular hydrofluoroalkenes such tetrafluoropropenes (including 2,3,3 ,3-tetrafluoro-l-propene (HFO-1234yf) and 1,3,3,3-tetrafluoro-l-propene (HFO-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.
  • HFC's hydrofluoroalkenes
  • tetrafluoropropenes including 2,3,3 ,3-tetrafluoro-l-propene (HFO-1234yf) and 1,3,3,3-tetrafluoro-l-propene (HFO-1234ze)
  • HFO-1234ze 1,3,
  • HFCs 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.
  • CFCs chlorofluorocarbons
  • HCFCs hydrochlorofluorocarbons
  • Several methods of preparing hydrofluoroalkenes are known.
  • 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.
  • 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.
  • an oxygen-containing metal catalyst such as chromium oxyfluoride
  • Z is H.
  • 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).
  • 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):
  • CF 3 CF 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.
  • Z in such embodiments is H.
  • the compounds of Formula (I) contain at least four halogen substituents and even more preferably at least five halogen substituents.
  • the conversion step of the present invention comprises converting a compound of Formula (IA) wherein each X is F.
  • the compound of Formula (IA) is a penta-halogenated.
  • 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 l,l,l-trichloro-2,2- difluoropropane (HCFC-242bb), and 1,1,1,2,2-pentafluoropropane (HFC-245cb).
  • 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.
  • the step of converting a compound of Formula (I) comprises providing at least one trichlorodifluorpropane in accordance with Formula (IA), preferably CCI3CF2CH 3 (HCFC-242bb) and reacting same under conditions effective to produce at least one pentafluorpropane in accordance with Formula (IA), preferably
  • CF3CF2CH 3 (HFC-245cb), which in turn is preferably exposed to reaction conditions effective to produce at least one compound in accordance with Formula (II), preferably HFO-1234yf.
  • 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.
  • 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.
  • the converting step comprises exposing the compound of Formula (I), and preferably Formula (IA) 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%.
  • the conversion is at least about 95%, and more preferably at least about 97%.
  • 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.
  • C(X) 2 CClC(X) 3 (in) 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.
  • One beneficial aspect of the present invention is that it enables the production of desirable fluroolefins, 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.
  • the Formula (I) compound is exposed to reaction conditions effective to produce a reaction product containing one or more of the desired fluorolefms, preferably one or more compounds of Formula (II).
  • reaction conditions effective to produce a reaction product containing one or more of the desired fluorolefms, preferably one or more compounds of Formula (II).
  • 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.
  • 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 HFO-1234yf.
  • the catalyst does not include substantial amounts of oxygen containing catalyst.
  • 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.
  • the present converting step comprises first reacting said compound(s) by fiuorinating 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.
  • this reaction is at least partially catalyzed.
  • 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 SbCl 5 , SbF 5 , SbF 3 , TiCl 4 , SnCl 4 , FeCl 3 , AlCl 3 , AlF 3 , 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
  • this conversion step is carried out in a catalytic, continuous, gas-phase reaction mode using SbCVC 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%.
  • 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%.
  • at least one penta-fluorinated compound preferably HFC-245
  • 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.
  • 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.
  • the stream containing the compound of Formula (I), and preferably Formula (IA) is preheated to a temperature of from about 150 0 C to about 400 0 C, preferably about 300 0 C, and introduced into a reaction vessel (preferably a tube reactor), which is maintained at the desired temperature, preferably from about 40 0 C to about 200 0 C, more preferably from about 50 0 C to about 150 0 C, where it is preferably contacted with catalyst and fluorinating agent, such as HF.
  • a reaction vessel preferably a tube reactor
  • the vessel is comprised of materials which are resistant to corrosion as Hastelloy, Inconel, Monel and/or fluoropolymers linings.
  • 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.
  • 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.
  • 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.
  • 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 FeCb on carbon (designated herein as FeCVC for convenience), and combinations of these.
  • 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.
  • an inert diluent gas such as nitrogen, may be used in combination with the other reactor feed(s).
  • the stream containing the compound of formula (I), and preferably (IA) is preheated to a temperature of from about 150 0 C to about 400 0 C, preferably about 350 0 C, and introduced into a reaction vessel, which is maintained at the desired temperature, preferably from about 300 0 C to about 700 0 C, more preferably from about 45O°C to about 650 0 C.
  • the vessel is comprised of materials which are resistant to corrosion as Hastelloy, Inconel, Monel and/or fluoropolymers linings.
  • 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.
  • 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.
  • this reaction step may be preformed using a wide variety of process parameters and process conditions in view of the overall teachings contained herein.
  • 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.
  • 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.
  • reaction temperature for the step is from about 200 0 C to about 800 0 C, more preferably from about 400 0 C to about 800 0 C. In certain preferred embodiments, the reaction temperature is from about 300°C to about 600 0 C, and even more preferably in certain embodiments from about 500 0 C to about 600 0 C.
  • 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.
  • 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.
  • 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%.
  • the selectivity to compound of Formula (II), preferably HFO-1234yf is at least about 70%, more preferably at least about 80% and more preferably at least about 90%.
  • 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 0 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 N 2 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-fiow-meter.
  • the organic feed stream was also fed periodically as liquid at about 105 0 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 0 C by wrapping with constant temperature heat trace and electrical heating.
  • AU 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 6O 0 C to about 120 0 C.
  • the SbCl 5 /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 Cl 2 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% SbCls/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 N 2 . 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% SbCyC (SeI. 81%); from about 3 to about 6 wt% FeCyC (SeI. 52%); SbF 5 /C (SeI. 87%); 20 wt% SnCVC (SeI. 32%); 23 wt% TiCVC (SeI. 27%).
  • the catalyst temperatures o used ranged from about 60 0 C to about 120 0 C. SbCVC is believed to be a preferred catalyst for this gas-phase transformation.
  • 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 0 C by electrical heating.
  • HFC-245cb was fed from a cylinder kept at about 65 0 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 0 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 HFO-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 N 2 . The products were then substantial isolated by distillation. Results are tabulated in Table 1.
  • 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; CF 3 CF 2 CH 3 (245cb) line to the preheater about 50 0 C; Preheater, 350 0 C; N 2 - O seem.
  • 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 SbCU.
  • the contents were heated with stirring to about 100 0 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% CH 3 CF 2 CH 2 Cl, about 34.5% CH 3 CFCICH 2 Cl 5 21 % CH 3 CCI Z CH 2 CI, and about 1.8 % starting material. The conversion was about 97 %, while the combined yield of halopropanes was 76.7 %. Substantially pure CH 3 CF 2 CH 2 Cl was obtained by fractional distillation. The autoclave also contained about 77.8 grams of black residue.
  • Example 4A was repeated except that the reactants were heated to about 120 0 C for about 18 hours.
  • the crude organic layer so obtained consisted of about 58.8 % CH 3 CF 2 CH 2 Cl, about 28.3 % CH 3 CFCICH 2 Cl, and about 9.8 % CH 3 CCl 2 CH 2 Cl.
  • 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 % CH 3 CF 2 CH 2 Cl, about 25.9 % CH 3 CFCICH 2 Cl, and about 12.2 % CH 3 CCl 2 CH 2 Cl.
  • the combined yield of halopropanes was about 80%.
  • SbC15 catalyst was not effective in increasing the amount of the desired CH 3 CF 2 CH 2 Cl or increasing the total yield of useful products.
  • 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 0 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 (MgSO 4 ) and filtered to give about 1554 grams of the product mixture.
  • An autoclave was charged with about 100 grams of CH 3 CCI 2 CH 2 CI and about 44 grams of HF and the contents heated with stirring to about 130 0 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 % CH 3 CF 2 CH 2 Cl, about 23.1 % CH 3 CFCICH 2 Cl, and about 30.3 % CH 3 CCI 2 CH 2 CI.
  • the autoclave also contained about 1.9 grams of dark residue.
  • chlorinated antimony catalyst such as SbCIs
  • SbCIs chlorinated antimony catalyst
  • SnCl 4 may be preferred in embodiments in which CH 3 CF 2 CH 2 Cl is the desired product, since its use may allow a lower temperature to be used and result in a higher percentage of CH 3 CF 2 CH 2 Cl in the crude product.
  • 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 Na2SO3 to remove HCl and chlorine.
  • the reactor was charged with about 250.5 grams of CH 3 CF 2 CH 2 Cl of about
  • 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 ⁇ 0.5 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 % CH 3 CF 2 CH 2 Cl , about 50.9 %
  • a 450-W Hg lamp could also be used.
  • the ratios of CH 3 CF 2 CHCl 2 to CH 3 CF 2 CCl 3 VS. time were essentially the same as with a 100-watt lamp.
  • CH 3 CF 2 CHCl 2 (about 97.4 % pure, containing about 1.9 % CH 3 CF 2 CCl 3 ) was photochlorinated using a 100-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 % CH 3 CF 2 CHCl 2 and about 39.9 % CH 3 CF 2 CCl 3 . Thus the selectivity for CH 3 CF 2 CCl 3 was about 97 % at a CH 3 CF 2 CHCI 2 conversion of about 40 %.
  • Photochlorination of a mixture of CH 3 CF 2 CH2C1 and CH 3 CF 2 CHCl 2 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 CH 3 CF 2 CCl 3 (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.
  • CH 3 CF 2 CHCl 2 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 1OA. After an irradiation time of about 8.4 hours the conversion of CH 3 CF 2 CH 2 Cl exceeded about 90 %.
  • the composition of the crude product was about 6.9 wt% CH 3 CF 2 CH 2 Cl, 45.2 wt% CH 3 CF 2 CHCl 2 , and 43.5 wt% CH 3 CF 2 CCl 3 .
  • the amount of CH 3 CF 2 CHCl 2 initially increased with time, reaching a maximum of about 55 wt % after about 5 hours.
  • Example IQA About 65 cc of 50 weight% SbC15 on activated carbon support is provided at a temperature of about 95°C.
  • the catalyst was loaded into the Vi" OD x 36" L monel 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 0 C to ensure that the organic present in the bag was completely vaporized. GC/MS results showed the major product to be 1- 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%.
  • Example 2 was run similarly to Example 1OA 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 l-chloro-2,2-difluoropropane (262ca), about 29.3 area% for 1 ,2-dichloro-2-fluoropropane (261ba), about 4.7 area% for 263ca, about

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)

Abstract

L’invention concerne un procédé de fabrication de composés organiques fluorés, notamment d’hydrofluoropropènes, comprenant de préférence la transformation d’au moins un composé de formule (I) : C(X)3CF2C(X)3 (I) en au moins un composé de formule (II) CF3CF=CHZ (II) dans laquelle chaque X et chaque Z représentent indépendamment H, F, Cl, I ou Br, ledit procédé n’incluant de préférence pas de quantité substantielle de catalyseur contenant de l'oxygène dans certains modes de réalisation. Z représente de préférence H.
EP07716234A 2006-01-03 2007-01-03 Procede de fabrication de composes organiques fluores Withdrawn EP1968923A2 (fr)

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US75548606P 2006-01-03 2006-01-03
PCT/US2007/000064 WO2007079435A2 (fr) 2006-01-03 2007-01-03 Procede de fabrication de composes organiques fluores

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JP (2) JP5710103B2 (fr)
KR (1) KR101354492B1 (fr)
CN (2) CN103193584B (fr)
CA (1) CA2635806C (fr)
WO (1) WO2007079435A2 (fr)

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CN110128239A (zh) 2011-12-22 2019-08-16 蓝立方知识产权有限责任公司 生产四氯甲烷的方法
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CN104428273B (zh) 2012-07-10 2018-09-14 大金工业株式会社 用于制造含氟烯烃的方法
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JP6272878B2 (ja) 2012-09-30 2018-01-31 ブルー キューブ アイピー エルエルシー せきクエンチおよびそれを組み込んだ方法
JP6363610B2 (ja) 2012-10-26 2018-07-25 ブルー キューブ アイピー エルエルシー 混合器およびそれを組み込んだプロセス
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JP6251286B2 (ja) 2012-12-19 2017-12-20 ブルー キューブ アイピー エルエルシー 塩素化プロペン生成のための方法
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GB201615197D0 (en) 2016-09-07 2016-10-19 Mexichem Fluor Sa De Cv Catalyst and process using the catalyst
GB201615209D0 (en) 2016-09-07 2016-10-19 Mexichem Fluor Sa De Cv Catalyst and process using the catalyst
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WO2007079435A3 (fr) 2007-11-15
JP5710103B2 (ja) 2015-04-30
CN101395109A (zh) 2009-03-25
CA2635806A1 (fr) 2007-07-12
JP2014237681A (ja) 2014-12-18
CN101395109B (zh) 2013-09-18
CN103193584A (zh) 2013-07-10
JP2009522313A (ja) 2009-06-11
KR20080083041A (ko) 2008-09-12
WO2007079435A2 (fr) 2007-07-12
CN103193584B (zh) 2015-07-01
KR101354492B1 (ko) 2014-01-23
CA2635806C (fr) 2015-03-31

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