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  • B01J37/088—Decomposition of a metal salt

Definitions

• This invention relates to the field of photochemical reactions, and particularly to materials suitable for use in photochemical reaction apparatus.
• Photochemical reactions use light as a source of energy to promote chemical processes.
• Ultraviolet (UV) and visible light are widely used in chemical synthesis both in laboratories and in commercial manufacturing.
• Well known photochemical reactions include photodimerization, photopolymerization, photohalogenation, photoisomerization and photodegradation.
• cyclobutanetetracarboxylic dianhydride can be synthesized by photodimerization of maleic anhydride in a glass reactor using a mercury UV lamp (P. Boule et al., Tetrahedron Letters, Volume 11 , pages 865 to 868, (1976)).
• fluorine-containing compounds e.g., CF 3 CH 3
• HF hydrogen fluoride
• a suitable source e.g., an incandescent bulb or a UV lamp
• the portion of the reactor wall through which the light passes must have a suitable transmittance to allow light of a wavelength required for the photochlorination to enter the reactor.
• quartz or borosilicate glass like PyrexTM glass have been employed as transparent materials. Quartz is expensive, but has a low cut-off wavelength at about 160 nm; PyrexTM glass is less expensive, but has a relatively high cut-off wavelength at about 275 nm. Due to their reactivity, quartz and Pyrex are not appropriate materials of construction for chemical reactions involving base or HF. There is a need for additional materials which can be used for this purpose in photochemical reactions (e.g., photochlorinations).
• This invention provides an apparatus for photochemical reactions comprising a reactor and a light source situated so that light from the light source is directed through a portion of the reactor wall.
• the apparatus is characterized by said portion of the reaction wall comprising a functionalized copolymer of a terminally functionalized perfluoro(alkyl vinyl ether) wherein the functional group of the copolymer is selected from the group consisting of -SO 2 F, -SO 2 CI, - SO 3 H, -CO 2 R (where R is H or C 1 -C 3 alkyl), -PO 3 H 2 , and salts thereof.
• This invention also provides a photochemical reaction process wherein light from a light source is directed through a reactor wall to interact with reactants in said reactor.
• the process is characterized by the light directed through the reactor wall being directed through a functionalized copolymer of a terminally functionalized perfluoro(alkyl vinyl ether) wherein the functional group of the copolymer is selected from the group consisting Of -SO 2 F, -SO 2 CI, - SO 3 H, -CO 2 R (where R is H or C 1 -C 3 alkyl), -PO 3 H 2 , and salts thereof.
• copolymers of terminally functionalized perfluoro(alkyl vinyl ethers) are used as photochlorination reactor materials through which light is able to pass for the purpose of interacting with the reactants, thereby promoting the photochemical reaction.
• Suitable functionalized copolymers include copolymers of at least one perfluorinated alkylene monomer with a terminally functionalized perfluoro(alkyl vinyl ether).
• Nafion® thermoplastic resins are melt-processable perfluorinated copolymers of tetrafluoroethylene and perfluoro-3,6-dioxa-4- methyl-7-octenesulfonyl fluoride.
• the -SO 2 F end groups of a copolymer of a terminally functionalized perfluoro(alkyl vinyl ether) can be converted through hydrolysis to -SO 2 OH end groups.
• the -SO 2 OH end groups can be further treated with base to form salts.
• Suitable salt-forming cations include lithium, sodium, potassium, and ammonium.
• the acid, salt, and acid fluoride forms of these copolymers can be used in this invention as light transparent containers for photochemical reactions.
• copolymers having equivalent weights between 900 to 1200 e.g., copolymers having an equivalent weight between 950 to 1100.
• Equivalent weight is the ratio of the molecular weight of the copolymer to hydrogen in the acid form of the copolymer.
• the portion of the reactor wall fabricated from such polymeric materials may be limited to a fraction of the reactor wall (e.g., a window of the polymeric material positioned in a reactor principally fabricated from another material) or may constitute all or essentially all of the reactor wall (e.g., a tube reactor fabricated from the polymeric material).
• a suitable photochlorination apparatus includes a reactor in which light having a suitable wavelength (e.g., from about 250 nm to about 400 nm) can irradiate the reaction components for a time sufficient to convert at least a portion of the starting materials to one or more compounds having a higher chlorine content.
• the reactor may be, for example, a tubular reactor fabricated from functionalized perfluoro(alkyl vinyl ether) copolymer (e.g., either a coil or extended tube), or tank fabricated from fu nationalized perfluoro(alkyl vinyl ether) copolymer, or a tube or tank fabricated from an opaque material which has a window fabricated from functionalized perfluoro(alkyl vinyl ether) copolymer.
• the thickness of the functionalized perfluoro(alkyl vinyl ether) copolymer is sufficient to permit transmittance of the light of sufficient intensity to promote the reaction (e.g., 0.02 mm to 1 mm).
• a layer of reinforcing material fabricated from a highly transmitting material e.g., quartz
• a mesh of transmitting or opaque material may be used outside of the functionalized perfluoro(alkyl vinyl ether) copolymer layer.
• the apparatus also includes a light source.
• the light source may be any one of a number of arc or filament lamps known in the art.
• the light source is situated such that light having the desired wavelength may introduced into the reaction zone (e.g., a reactor wall or window fabricated from a functionalized perfluoro(alkyl vinyl ether) copolymer and suitably transparent to light having a wavelength of from about 250 nm to about 400 nm).
• the apparatus also includes a chlorine (Cb) source and a source of the material to be chlorinated.
• the chlorine source may be, for example, a cylinder containing chlorine gas or liquid, or equipment that produces chlorine (e.g., an electrochemical cell) that is connected to the reactor.
• the source of the material to be chlorinated may be, for example, a cylinder or pump fed from a tank containing the material, or a chemical process that produces the material to be chlorinated.
• processes in accordance with this invention for increasing the chlorine content of at least one compound selected from hydrocarbons and halohydrocarbons are processes in accordance with this invention for increasing the fluorine content of at least one compound selected from hydrocarbons and halohydrocarbons; and processes in accordance with this invention for producing at least one olefinic compound from a hydrocarbon or halohydrocarbon containing at least two carbon atoms and at least two hydrogen atoms.
• all of these processes involve reaction with chlorine in the presence of light.
• Included in this invention is a process for increasing the chlorine content of a halogenated hydrocarbon compound or a hydrocarbon compound by reacting said compound with chlorine (CI2) in the presence of light.
• Halogenated hydrocarbon compounds suitable as starting materials for the chlorination process of this invention may be saturated or unsaturated.
• Saturated halogenated hydrocarbon compounds suitable for the chlorination processes of this invention include those of the general formula C n HaB ⁇ CIcFd, wherein n is an integer from 1 to 4, a is an integer from 1 to 9, b is an integer from 0 to 4, c is an integer from 0 to 9, d is an integer from 0 to 9, the sum of b, c and d is at least 1 and the sum of a, b, c, and d is equal to 2n + 2.
• Saturated hydrocarbon compounds suitable for chlorination are those which have the formula CqH r where q is an integer from 1 to 4 and r is 2q + 2.
• Unsaturated halogenated hydrocarbon compounds suitable for the chlorination processes of this invention include those of the general formula CpH e BrfClgF n , wherein p is an integer from 2 to 4, e is an integer from 0 to 7, f is an integer from 0 to 2, g is an integer from 0 to 8, h is an integer from 0 to 8, the sum of f, g and h is at least 1 and the sum of e, f, g, and h is equal to 2p.
• Unsaturated hydrocarbon compounds suitable for chlorination are those which have the formula CjHj where i is an integer from 2 to 4 and j is 2i.
• the chlorine content of saturated compounds of the formula C n H 3 B ⁇ CI 0 Fd and CqH r and/or unsaturated compounds of the formula CpH e BrfClgFh and CjHj may be increased by reacting said compounds with CI2 in the vapor phase in the presence of light. Such a process is referred to herein as a photochlorination reaction.
• the photochlorination of the present invention may be carried out in either the liquid or the vapor phase.
• initial contact of the starting materials with Cb may be a continuous process in which one or more starting materials are vaporized (optionally in the presence of an inert carrier gas, such as nitrogen, argon, or helium) and contacted with chlorine vapor in a reaction zone.
• a suitable photochlorination reaction zone is one in which light having a wavelength of from about 250 nm to about 400 nm can irradiate the reaction components for a time sufficient to convert at least a portion of the starting materials to one or more compounds having a higher chlorine content.
• the source of light may be any one of a number of arc or filament lamps known in the art. Light having the desired wavelength may introduced into the reaction zone by a number of means.
• the light may enter the reaction zone through a lamp well or window fabricated from a functionalized perfluoro(alkyl vinyl ether) copolymer suitably transparent to light having a wavelength of from about 250 nm to about 400 nm.
• the walls of the reaction zone may be fabricated from such a material so that at least a portion of the light used for the photochlorination can be transmitted through the walls.
• the process of the invention may be carried out in the liquid phase by feeding Cl 2 to a reactor containing the starting materials.
• Suitable liquid phase reactors include vessels fabricated from a functionalized perfluoro(alkyl vinyl ether) copolymer in which an external lamp is directed toward the reactor and metal, glass-lined metal or fluoropolymer-lined metal reactors having one or more wells or windows fabricated from a functionalized perfluoro(alkyl vinyl ether) copolymer for introducing light having a suitable wavelength.
• the reactor is provided with a condenser or other means of keeping the starting materials in the liquid state while permitting the hydrogen chloride (HCI) released during the chlorination to escape the reactor.
• HCI hydrogen chloride
• solvents suitable for step (a) include carbon tetrachloride, 1,1-dichlorotetrafluoroethane, 1,2-dichlorotetrafluoroethane, 1,1,2-trichlorotrifluoroethane, benzene, chlorobenzene, dichlorobenzene, fluorobenzene, and difluorobenzene.
• Suitable temperatures for the photochlorination of the starting materials of the formula are typically within the range of from about -2O 0 C to about 6O 0 C. Preferred temperatures are typically within the range of from about 0 0 C to about 40 0 C. In the liquid phase embodiment, it is convenient to control the reaction temperature so that starting material is primarily in the liquid phase; that is, at a temperature that is below the boiling point of the starting material(s) and product(s). .
• the pressure in a liquid phase process is not critical so long as the liquid phase is maintained. Unless controlled by means of a suitable pressure-regulating device, the pressure of the system increases as hydrogen chloride is formed by replacement of hydrogen substituents in the starting material by chlorine substituents. In a continuous or semi- batch process it is possible to set the pressure of the reactor in such a way that the HCI produced in the reaction is vented from the reactor (optionally through a packed column or condenser). Typical reactor pressures are from about 14.7 psig (101.3 kPa) to about 50 psig (344.6 kPa).
• the amount of chlorine (CI2) fed to the reactor is based on whether the starting material(s) to be chlorinated is(are) saturated or unsaturated, and the number of hydrogens in C n H a BrbCl c Fd, CqH r , CpH e BrfClgF n , and CjHj that are to be replaced by chlorine.
• One mole of CI2 is required to saturate a carbon-carbon double bond and a mole of CI2 is required for every hydrogen to be replaced by chlorine.
• a slight excess of chlorine over the stoichiometric amount may be necessary for practical reasons, but large excesses of chlorine will result in complete chlorination of the products.
• the ratio of CI2 to halogenated carbon compound is typically from about 1 :1 to about 10:1.
• photochlorination reactions of saturated halogenated hydrocarbon compounds of the general formula C n HaBr ⁇ CI 0 FcI and saturated hydrocarbon compounds of the general formula CqH 1 - which may be carried out in accordance with this invention include the conversion of C2H5 to a mixture containing CH2CICCI3, the conversion of CH2CICF3 to a mixture containing CHCI2CF3, the conversion of CCI3CH2CH2CI, CCI3CH2CHCI2, CCI 3 CHCICH 2 CI or CHCI2CCI2CH2CI to a mixture containing CCI3CCI2CCI3, the conversion of CH2FCF3 to a mixture containing CHCIFCF3 and CCI2FCF3, the conversion of CH3CHF2 to CCI3CCIF2, the conversion of CF3CHFCHF2 to a mixture containing CF3CCIFCHF2 and CF3CHFCCIF2, and the conversion of CF3CH2CHF2 to CF3CH2CCIF2.
• a catalytic process for producing a mixture containing 1 ,2,2-trichloro-1 , 1,3,3,3- pentafluoropropane i.e., CCIF2CCI2CF3 or CFC-215aa
• 1 ,2-dichloro- 1 ,1 ,1 ,3,3,3-hexafluoropropane i.e., CCIF2CCIFCF3 or CFC-216ba
• Contact times of from 0.1 to 60 seconds are typical; and contact times of from 1 to 30 seconds are often preferred.
• halogenated hydrocarbon compound or a hydrocarbon compound by reacting said compound with chlorine (Cl 2 ) in the presence of light as described above; and then reacting the halogenated hydrocarbon produced with hydrogen fluoride.
• Fluorination reactions are well known in the art. They can be conducted both in either the vapor phase or liquid phase using a variety of fluorination catalysts. See for example, Milos Hudlicky, Chemistry of Organic Fluorine Compounds 2 nd (Revised Edition), pages 91 to 135 and references cited therein (Ellis Harwood-Prentice Hall Publishers, 1992). Of note are vapor phase fluorinations in the presence of a fluorination catalyst.
• Preferred fluorination catalysts include chromium catalysts (e.g., Cr 2 O 3 by itself of with other metals such as magnesium halides or zinc halides on Cr 2 Os); chromium(lll) halides supported on carbon; mixtures of chromium and magnesium (including elemental metals, metal oxides, metal halides, and/or other metal salts) optionally on graphite; and mixtures of chromium and cobalt (including elemental metals, metal oxides, metal halides, and/or other metal salts) optionally on graphite, alumina, or aluminum halides such as aluminum fluoride.
• chromium catalysts e.g., Cr 2 O 3 by itself of with other metals such as magnesium halides or zinc halides on Cr 2 Os
• chromium(lll) halides supported on carbon mixtures of chromium and magnesium (including elemental metals, metal oxides, metal halides, and/or other metal salts) optional
• Fluorination catalysts comprising chromium are well known in the art (see e.g., U. S. Patent No. 5,036,036). Chromium supported on alumina can be prepared as described in U. S. Patent No. 3,541 ,834. Chromium supported on carbon can be prepared as described in U. S. Patent No. 3,632,834. Fluoridation catalysts comprising chromium and magnesium may be prepared as described in Canadian Patent No. 2,025,145. Other metals and magnesium optionally on graphite can be prepared in a similar manner to the latter patent.
• Preferred chromium fluorination catalysts comprise trivalent chromium.
• Cr 2 O 3 prepared by pyrolysis of (NH 4 ) 2 Cr 2 O 7 , Cr 2 O 3 having a surface area greater than about 200 m 2 /g, and Cr 2 O 3 prepared by pyrolysis of (NH 4 ) 2Cr 2 O 7 or having a surface area greater than about 200 m 2 /g some of which are commercially available.
• Halogenated hydrocarbon compounds suitable for the fluorination of this invention include saturated compounds of the general formula C m H w Br x ClyF z , wherein m is an integer from 1 to 4, w is an integer from 0 to 9, x is an integer from 0 to 4, y is an integer from 1 to 10, z is an integer from 0 to 9, and the sum of w, x, y, and z is equal to 2n + 2.
• Examples of saturated compounds of the formula C m H w Br x ClyF z which may be reacted with HF in the presence of a catalyst include CH 2 CI 2 , CHCI 3 , CCI 4 , C 2 CI 6 , C 2 BrCI 5 , C 2 CI 5 F, C 2 CI 4 F 2 , C 2 CI 3 F 3 , C 2 CI 2 F 4 , C 2 CIF 5 , C 2 HCI 5 , C 2 HCI 4 F, C 2 HCI 3 F 2 , C 2 HCI 2 F 3 , C 2 HCIF 4 , C 2 HBrF 4 , C 2 H 2 CI 4 , C 2 H 2 CI 3 F, C 2 H 2 CI 2 F 2 , C 2 H 2 CIF 3 , C 2 H 3 CI 3 , C 2 H 3 CI 2 F, C 2 H 3 CIF 2 , C 2 H 4 CI 2 , C 2 H 4 CIF, C 3 CI 6 F 2 , C 3 CI 5
• HFC-125 may also be produced by the photochlorination of 1,1 ,2,2 tetrafluoroethane (i.e., CHF 2 CHF 2 or HFC-134) to produce 2-chloro-1, 1 ,2,2 tetrafluoroethane (i.e., CCI F 2 CHF 2 or HCFC-124a); and fluorination of the HCFC-124a to produce HFC-125.
• 1,1 ,2,2 tetrafluoroethane i.e., CHF 2 CHF 2 or HFC-134
• 2-chloro-1, 1 ,2,2 tetrafluoroethane i.e., CCI F 2 CHF 2 or HCFC-124a
• fluorination of the HCFC-124a to produce HFC-125.
• the photochlorination and further fluorination can be conducted in situ and the fluorinated product(s) recovered.
• the effluent from the photochlorination step may be fed to a second reactor for fluorination.
• the photochlorination product mixture can be fed to a fluorination reactor with or without prior separation of the products from the photochlorination reactor.
• HF can be fed together with chlorine and the other photochlorination starting materials to the photochlorination reactor and the effluent from the photochlorination reactor can be directed to a fluorination zone optionally containing a fluorination catalyst; and additional HF, if desired, can be fed to the fluorination zone.
• Producing Olefins Included in this invention is a process for producing an olefin from a halogenated hydrocarbon compound or a hydrocarbon compound by reacting said compound with chlorine (CI2) in the presence of light as described above; and then subjecting the halogenated hydrocarbon produced by the photochlorination to dehydrohalogenation. Dehydrohalogenation reactions are well known in the art.
• Suitable catalysts for dehydrohalogenation include carbon, metals (including elemental metals, metal oxides, metal halides, and/or other metal salts); alumina; fluorided alumina; aluminum fluoride; aluminum chlorofluoride; metals supported on alumina; metals supported on aluminum fluoride or chlorofluoride; magnesium fluoride supported on aluminum fluoride; metals supported on fluorided alumina; alumina supported on carbon; aluminum fluoride or chlorofluoride supported on carbon; fluorided alumina supported on carbon; metals supported on carbon; and mixtures of metals, aluminum fluoride or chlorofluoride, and graphite.
• metals including elemental metals, metal oxides, metal halides, and/or other metal salts
• alumina fluorided alumina
• aluminum fluoride aluminum chlorofluoride
• metals supported on alumina metals supported on aluminum fluoride or chlorofluoride
• Suitable metals for use on catalysts include chromium, iron, and lanthanum.
• the total metal content of the catalyst will be from about 0.1 to 20 percent by weight; typically from about 0.1 to 10 percent by weight.
• Preferred catalysts for dehydrohalogenation include carbon, alumina, and fluorided alumina.
• Halogenated hydrocarbon compounds suitable for the dehydrohalogenation of this invention include saturated compounds of the general formula C m H w Br x ClyF z , wherein m is an integer from 2 to 4, w is an integer from 1 to 9, x is an integer from 0 to 4, y is an integer from 1 to 9, z is an integer from 0 to 8, and the sum of w, x, y, and z is equal to 2n + 2.
• the compound photochlorinated to produce the compound subjected to dehydrohalogenation should contain at least two carbon atoms and two hydrogen atoms (e.g., for said compounds of the formulas C n H a BrbCl c Fd and CqH r w, n, a and q should be at least 2).
• a saturated compound of the formula C n HaB ⁇ CI 0 Fd or a saturated compound of the formula CqH 1 - as described above should contain at least two carbon atoms and two hydrogen atoms (e.g., for said compounds of the formulas C n H a BrbCl c Fd and CqH r w, n, a and q should be at least 2).
• the compound photochlorinated is a halogenated hydrocarbon that contains fluorine
• 1,1- difluoroethane i.e., CHF2CH3 or HFC-152a
• 1-chloro-1 ,1- difluoroethane i.e., CCIF2CH3 or HCFC-142b
• dehydrohalogenation of the HCFC-142b to produce 1 ,1-difluoroethylene.
• 1-chloro-1 ,1 ,2,3,3,3-hexafluoropropane i.e., CF3CHFCCIF2 or HCFC-226ea
• dehydrohalogenation of the HCFC-226ea to produce hexafluoropropylene.
• Photochlorination was carried out using a 110 volt/275 watt sunlamp placed (unless otherwise specified) at a distance of 0.5 inches (1.3 cm) from the outside of the first turn of the inlet end of a coil of fluoropolymer tubing material through which the materials to be chlorinated were passed.
• the fluoropolymer tubing used in the examples below was an 18 inch (45.7 cm) long Nafion® tube (0.065 inch (0.17 cm) OD X 0.055 inch (0.14 cm) ID) which was coiled to a diameter of 3 inches (7.6 cm) and contained suitable feed and exit ports.
• the organic feed material and chlorine were fed to the tubing using standard flow- measuring devices.
• CFC-114 is CCIF 2 CCIF 2 .
• CFC- 114a is CF 3 CCI 2 F.
• CFC-216ba is CF 3 CCIFCCIF 2 .
• HCFC-226ba is CF 3 CCIFCHF 2 .
• 1.0 seem standard cubic centimeter per minute is equal to about 1.7(1O) '8 cubic meters per second.
• Feed gases consisting of HFC-134a at a flow rate of 5.0 seem and chlorine gas at a flow rate of 2.5 seem were introduced into the Nafion® tubing. After exposure to light for one hour, the product was analyzed and found to contain 75.7 mole % of HFC-134a, 19.8 mole % of HCFC-124, 3.7 mole % of CFC-114a and 0.8 mole % of other unidentified compounds. The molar yield of CFC-114a compared to the total amount of CFC-114a and HCFC-124 was 15.7 %.
• Feed gases consisted of HFC-134 at a flow rate of 5.0 seem and chlorine gas at a flow rate of 2.5 seem. After exposure to light for one hour, the product was analyzed and found to contain 71.2 mole % of HFC-134, 27.4 mole % of HCFC-124a, 1.1 mole % of CFC-114 and 0.3 mole % of other unidentified compounds.
• Example 3
• Feed gases consisted of HFC-236ea at a flow rate of 5.0 seem and chlorine gas at a flow rate of 2.5 seem. After exposure to light for one hour, the product was analyzed and found to contain 61.1 mole % of HFC-236ea, 5.6 mole % of HCFC-226ba, 32.3 mole % of HCFC-226ea, 0.7 mole % of CFC-216ba and 0.3 mole % of other unidentified compounds.
• Feed gases consisted of HFC-236ea at a flow rate of 5.0 seem and chlorine gas at a flow rate of 7.5 seem. After exposure to light for one hour, the product was analyzed and found to contain 60.3 mole % of HFC-236ea, 5.7 mole % of HCFC-226ba, 33.0 mole % of HCFC-226ea, 0.7 mole % of CFC-216ba and 0.3 mole % of other unidentified compounds.
• HFC-245fa was analyzed prior to chlorination and found to have a purity of 99.8 %. Feed gases consisted of HFC-245fa at a flow rate of 3.5 seem and chlorine gas at a flow rate of 3.5 seem. After exposure to light for one hour, the product was analyzed and found to contain 67.1 mole % of HFC-245fa, 31.7 mole % of HCFC-235fa, and 1.2 mole % of other unidentified compounds.

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