Abstract:
A process is disclosed for the manufacture of 1,1,1,3,3,3-hexafluoropropane and 1,1,1,2,3,3-hexafluoropropane, hexafluoropropene and/or 1,1,1,2,3,3,3-heptafluoropropane. The process involves (a) reacting HF, Cl 2 , and at least one halopropene of the formula CX 3 CCI═CCIX (where each X is independently F or CI) to produce a product comprising CF 3 CCI 2 CF 3  and CF 3 CCIFCCIF 2 ; (b) reacting CF 3 CCI 2 CF 3  and CF 3 CCIFCCIF 2  produced in (a) with hydrogen, optionally in the presence of HF, to produce a product comprising CF 3 CH 2 CF 3  and at least one of CHF 2 CHFCF 3 , CF 3 CF═CF 2  and CF 3 CFHCF 3 ; and (c) recovering from the product produced in (b), CF 3 CH 2 CF 3  and at least one of CHF 2 CHFCF 3 , CF 3 CF═CF 2  and CF 3 CFHCF 3 . In (a), the CF 3 CCI 2 CF 3  and CF 3 CCIFCCIF 2  are produced in the presence of a chlorofluorination catalyst including (i) a crystalline alpha-chromium oxide where at least 0.05 atom % of the chromium atoms in the alpha-chromium oxide lattice are replaced by divalent copper, and/or (ii) a chromium-containing composition of (i) which has been treated with a fluorinating agent.

Description:
FIELD OF THE INVENTION 
       [0001]    This invention relates to the synthesis of 1,1,1,3,3,3-hexafluoropropane, 1,1,1,2,3,3-hexafluoropropane, hexafluoropropene and 1,1,1,2,3,3,3-heptafluoropropane. 
       BACKGROUND 
       [0002]    A number of chlorine-containing halocarbons are considered to be detrimental toward the Earth&#39;s ozone layer. There is a worldwide effort to develop materials having lower ozone depletion potential that can serve as effective replacements. For example, the hydrofluorocarbon, 1,1,1,2-tetrafluoroethane (HFC-134a) is being used as a replacement for dichlorodifluoromethane (CFC-12) in refrigeration systems. There is a need for manufacturing processes that provide halogenated hydrocarbons that contain less chlorine or no chlorine. The production of hydrofluorocarbons (i.e., compounds containing only carbon, hydrogen and fluorine), has been the subject of considerable interest to provide environmentally desirable products for use as solvents, blowing agents, refrigerants, cleaning agents, aerosol propellants, heat transfer media, dielectrics, fire extinguishants and power cycle working fluids. There is also interest in developing alternative processes for the manufacture of fluoroolefins from such hydrofluorocarbons. For example, 1,1,1,3,3,3-hexafluoropropane and 1,1,1,2,3,3,3-heptafluoropropane have utility as fire extinguishants and 1,1,1,2,3,3-hexafluoropropane has utility as a refrigerant. Further, they can also serve as suitable starting materials for the preparation of fluoroolefins. For example, hexafluoropropene is a useful monomer for preparation of fluoropolymers. 
       SUMMARY OF THE INVENTION 
       [0003]    This invention provides a process for the manufacture of 1,1,1,3,3,3-hexafluoropropane (HFC-236fa) and at least one compound selected from the group consisting of 1,1,1,2,3,3-hexafluoropropane (HFC-236ea), hexafluoropropene (HFP, CF 3 CF═CF 2 ) and 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea). The process comprises (a) reacting HF, Cl 2 , and at least one halopropene of the formula CX 3 CCl═CClX; wherein each X is independently selected from the group consisting of F and Cl, to produce a product comprising CF 3 CCl 2 CF 3  and CF 3 CClFCClF 2 , wherein said CF 3 CCl 2 CF 3  and CF 3 CClFCClF 2  are produced in the presence of a chlorofluorination catalyst comprising at least one chromium-containing component selected from (i) a crystalline alpha-chromium oxide where at least 0.05 atom % of the chromium atoms in the alpha-chromium oxide lattice are replaced by divalent copper, and (ii) a chromium-containing composition of (i) which has been treated with a fluorinating agent (e.g., anhydrous hydrogen fluoride); (b) reacting CF 3 CCl 2 CF 3  and CF 3 CClFCClF 2  produced in (a) with hydrogen, optionally in the presence of HF, to produce a product comprising CF 3 CH 2 CF 3  and at least one compound selected from the group consisting of CHF 2 CHFCF 3 , CF 3 CF═CF 2  and CF 3 CFHCF 3 ; and (c) recovering from the product produced in (b), CF 3 CH 2 CF 3  and at least one compound selected from the group consisting of CHF 2 CHFCF 3 , CF 3 CF═CF 2  and CF 3 CFHCF 3 . 
     
    
     DETAILED DESCRIPTION 
       [0004]    This invention provides a process for the preparation of CF 3 CH 2 CF 3  (HFC-236fa) and CF 3 CHFCHF 2  (HFC-236ea). This invention also provides a process for the preparation of HFC-236fa, HFC-236ea and CF 3 CF═CF 2  (HFP). Further this invention also provides a process for the preparation of HFC-236fa, HFC-236ea and HFC-227ea. 
         [0005]    In step (a) of the process of this invention, one or more halopropene compounds CX 3 CCl═CClX, wherein each X is independently selected from the group consisting of F and Cl, are reacted with chlorine (Cl 2 ) and hydrogen fluoride (HF) to produce a product mixture comprising CF 3 CCl 2 CF 3  (CFC-216aa) and CF 3 CClFCClF 2  (CFC-216ba). Accordingly, this invention provides a process for the preparation of mixtures of CF 3 CCl 2 CF 3  (CFC-216aa) and CF 3 CClFCClF 2  (CFC-216ba) from readily available starting materials. 
         [0006]    Suitable starting materials for the process of this invention include E- and Z—CF 3 CCl═CClF (CFC-1214xb), CF 3 CCl═CCl 2  (CFC-1213xa), CClF 2 CCl═CCl 2  (CFC-1212xa), CCl 2 FCCl═CCl 2  (CFC-1211xa), and CCl 3 CCl═CCl 2  (hexachloropropene or HCP) or mixtures thereof. 
         [0007]    Preferred starting materials for the process of this invention are CF 3 CCl═CCl 2  (CFC-1213xa) and CCl 3 CCl═CCl 2  (hexachloropropene, HCP) based on their ready accessibility. 
         [0008]    Preferably, the reaction of HF and Cl 2  with the halopropenes CX 3 CCl═CClX is carried out in the vapor phase in a heated tubular reactor. A number of reactor configurations are possible including horizontal or vertical orientation of the reactor and different modes of contacting the halopropene starting materials with HF and chlorine. Preferably the HF and chlorine are substantially anhydrous. 
         [0009]    In one embodiment of step (a) the halopropene starting material(s) are fed to the reactor containing the chlorofluorination catalyst. The halopropene starting material(s) may be initially vaporized and fed to the reactor as gas(es). 
         [0010]    In another embodiment of step (a), the halopropene starting material(s) may be contacted with HF in a pre-reactor. The pre-reactor may be empty (i.e., unpacked), but is preferably filled with a suitable packing such as Monel™ or Hastelloy™ nickel alloy turnings or wool, or other material inert to HCl and HF which allows efficient mixing of CX 3 CCl═CClX and HF vapor. 
         [0011]    When liquid feed of the halopropene starting material(s) to the pre-reactor is used, it is preferable for the pre-reactor to be oriented vertically with CX 3 CCl═CClX entering the top of the reactor and pre-heated HF vapor introduced at the bottom of the reactor. 
         [0012]    Suitable temperatures for the pre-reactor are within the range of from about 80° C. to about 250° C., preferably from about 100° C. to about 200° C. Under these conditions, for example, hexachloropropene is converted to a mixture containing predominantly CFC-1213xa. The starting material feed rate is determined by the length and diameter of the reactor, the temperature, and the degree of fluorination desired within the pre-reactor. Slower feed rates at a given temperature will increase contact time and tend to increase the amount of conversion of the starting material and increase the degree of fluorination of the products. 
         [0013]    The term “degree of fluorination” means the extent to which fluorine atoms replace chlorine substituents in the CX 3 CCl═CClX starting materials. For example, CF 3 CCl═CClF represents a higher degree of fluorination than CClF 2 CCl═CCl 2  and CF 3 CCl 2 CF 3  represents a higher degree of fluorination than CClF 2 CCl 2 CF 3 . 
         [0014]    The molar ratio of HF fed to the pre-reactor, or otherwise to the reaction zone of step (a), to halopropene starting material fed in step (a), is typically from about stoichiometric to about 50:1. The stoichiometric ratio depends on the average degree of fluorination of the halopropene starting material(s) and is typically based on formation of C 3 Cl 2 F 6 . For example, if the halopropene is HCP, the stoichiometric ratio of HF to HCP is 6:1; if the halopropene is CFC-1213xa, the stoichiometric ratio of HF to CFC-1213xa is 3:1. Preferably, the ratio of HF to halopropene starting material is from about twice the stoichiometric ratio of HF to halopropene (based on formation of C 3 Cl 2 F 6 ) to about 30:1. Higher ratios of HF to halopropene are not particularly beneficial; lower ratios result in reduced yields of C 3 Cl 2 F 6 . 
         [0015]    If the halopropene starting materials are contacted with HF in a pre-reactor, the effluent from the pre-reactor is contacted with chlorine in the reaction zone of step (a). 
         [0016]    In another embodiment of the invention, the halopropene starting material(s) may be contacted with Cl 2  and HF in a pre-reactor. The pre-reactor may be empty (i.e., unpacked), but is preferably filled with a suitable packing such as Monel™ or Hastelloy™ nickel alloy turnings or wool, activated carbon, or other material inert to HCl, HF, and Cl 2  which allows efficient mixing of CX 3 CCl═CClX, HF, and Cl 2 . 
         [0017]    Typically at least a portion of the halopropene starting material(s) react(s) with Cl 2  and HF in the pre-reactor by addition of Cl 2  to the olefinic bond to give a saturated halopropane as well as by substitution of at least a portion of the Cl substituents in the halopropropane and/or halopropene by F. Suitable temperatures for the pre-reactor in this embodiment of the invention are within the range of from about 80° C. to about 250° C., preferably from about 100° C. to about 200° C. Higher temperatures result in greater conversion of the halopropene(s) entering the reactor to saturated products and a greater degree of halogenation of the starting material. In the presence of HF, the degree of fluorination will also increase at higher pre-reactor temperatures. 
         [0018]    The term “degree of halogenation” means the extent to which hydrogen substituents in a halocarbon have been replaced by halogen and carbon-carbon double bonds have been saturated with halogen. For example, CF 3 CCl 2 CClF 2  has a higher degree of halogenation than CF 3 CCl═CCl 2 . Also, CF 3 CClFCF 3  has a higher degree of halogenation than CF 3 CHClCF 3 . 
         [0019]    The molar ratio of Cl 2  fed to the pre-reactor, or otherwise to the reaction zone of step (a), to halopropene starting material(s) fed in step (a), is typically from about 1:1 to about 10:1. Feeding Cl 2  at less than a 1:1 ratio will result in the presence of relatively large amounts of unsaturated materials and hydrogen-containing side products in the reactor effluent. 
         [0020]    In a preferred embodiment of step (a), the halopropene starting materials are vaporized, preferably in the presence of HF, and contacted with HF and Cl 2  in a pre-reactor and then contacted with the chlorofluorination catalyst. If the preferred amounts of HF and Cl 2  are fed in the pre-reactor, additional HF and Cl 2  are not required in the reaction zone. 
         [0021]    Suitable temperatures in the reaction zone(s) of step (a) are within the range of from about 230° C. to not more than 425° C., preferably from about 250° C. to about 400° C. Higher temperatures result in greater conversion of the CX 3 CCl═CClX starting materials, but also result in formation of overfluorinated products such as CF 3 CClFCF 3  and contribute to reduced catalyst life. As illustrated in the Examples, the preferred temperature range is somewhat dependent on the activity of the catalyst. Temperatures lower than about 250° C. result in low yields of CFC-216aa and CFC-216ba. Unconverted starting materials and products having a degree of fluorination lower than six may be recycled back to the reaction zone. 
         [0022]    Suitable reactor pressures for vapor phase embodiments of this invention may be in the range of from about 1 to about 30 atmospheres. Reactor pressures of about 5 atmospheres to about 20 atmospheres may be advantageously employed to facilitate separation of HCl from other reaction products. 
         [0023]    The chlorofluorination catalysts which are used in the process of the present invention are compositions comprising crystalline α-Cr 2 O 3  (α-chromium oxide) in which some of the chromium(III) ions have been substituted by copper(II) ions or compositions obtained by treatment of said compositions with a fluorinating agent. Of note are embodiments containing at least 1 atom % copper based on the total of the copper and chromium in the alpha-chromium oxide. The amount of copper relative to the total of chromium and copper in the alpha-chromium oxide of these compositions is preferably from about 1 atom % to about 5 atom %. Of particular note are embodiments containing from about 2 atom % to about 3 atom % copper based on the total of the copper and chromium in the alpha-chromium oxide. 
         [0024]    These compositions may be prepared, for example, by co-precipitation methods followed by calcination. 
         [0025]    In a typical co-precipitation procedure, an aqueous solution of copper and chromium(III) salts is prepared. The relative concentrations of the copper and chromium(III) salts in the aqueous solution is dictated by the bulk atom percent copper relative to chromium desired in the final catalyst. Therefore, the concentration of copper in the aqueous solution is preferably from about 1 atom % to about 5 atom % of the total concentration of copper and chromium in the solution. The concentration of chromium(III) in the aqueous solution is typically in the range of 0.3 to 3 moles per liter with 0.75-1.5 moles per liter being a preferred concentration. While different chromium(III) salts might be employed, chromium(III) nitrate or its hydrated forms such as [Cr(NO 3 ) 3 (H 2 O) 9 ], are the most preferred chromium(III) salts for preparation of said aqueous solution. 
         [0026]    While different copper salts might be employed for preparation of said aqueous solutions, preferred copper salts for preparation of catalysts for the process of this invention include copper(II) nitrate and its hydrated forms such as [Cu(NO 3 ) 2 (H 2 O) 2.5 ] and copper(II) chloride. 
         [0027]    The aqueous solution of the chromium(III) and copper salts may then be evaporated either under vacuum or at elevated temperature to give a solid which is then calcined. 
         [0028]    It is preferred to treat the aqueous solution of the chromium(III) and copper salts with a base such as ammonium hydroxide (aqueous ammonia) to precipitate the copper and chromium as the hydroxides. Bases containing alkali metals such as sodium or potassium hydroxide or the carbonates may be used but are not preferred. The addition of ammonium hydroxide to the aqueous solution of the chromium(III) and copper salts is typically carried out gradually over a period of 1 to 12 hours. The pH of the solution is monitored during the addition of base. The final pH is typically in the range of 6.0 to 11.0, preferably from about 7.5 to about 9.0, most preferably about 8.0 to about 8.7. The precipitation of the copper and chromium hydroxide mixture is typically carried out at a temperature of about 15° C. to about 60° C., preferably from about 20° C. to about 40° C. After the ammonium hydroxide is added, the mixture is typically stirred for up to 24 hours. The precipitated chromium and copper hydroxides serve as precursors to the catalysts of the invention 
         [0029]    After the precipitation of the copper and chromium hydroxide mixture is complete, the mixture is dried. This may be carried out by evaporation in an open pan on a hot plate or steam bath or in an oven or furnace at a suitable temperature. Suitable temperatures include temperatures from about 60° C. to about 130° C. (for example, about 100° C. to about 120° C.). Alternatively, the drying step may be carried out under vacuum using, for example, a rotary evaporator. 
         [0030]    Optionally, the precipitated copper and chromium hydroxide mixture may be collected and, if desired, washed with deionized water before drying. Preferably the precipitated copper and chromium hydroxide mixture is not washed prior to the drying step. 
         [0031]    After the copper and chromium hydroxide mixture has been dried, the nitrate salts are then decomposed by heating the solid from about 250° C. to about 350° C. The resulting solid is then calcined at temperatures of from about 400° C. to about 1000° C., preferably from about 400° C. to about 900° C. 
         [0032]    The copper-substituted alpha-chromium oxide compositions may also be prepared by a thermal method. In this method, a solution of the copper and chromium(III) salts is prepared as described for the co-precipitation technique. The mixed solution of the salts is then evaporated under atmospheric pressure or reduced pressure to give a solid. The solid is then placed in a furnace and the temperature raised gradually to decompose the salt. It is preferred to use the nitrate salts that decompose to the oxide. After decomposition of the nitrate salts is complete (about 350° C.), the increase in temperature is continued until the desired calcination temperature is reached. The desired calcination temperature is between about 450° C. to about 1000° C., a temperature of about 450° C. to about 900° C. being preferred. After the desired calcination temperature is reached, the solid is maintained at this temperature for an additional 8 to 24 hours, about 8 to about 12 hours being preferred. The decomposition and calcination is preferably carried out in the presence of oxygen, most preferably in the presence of air. 
         [0033]    Further information on the copper and chromium compositions useful for this invention is provided in U.S. Patent Application 60/706,159 filed Aug. 5, 2005, and hereby incorporated by reference herein in its entirety. 
         [0034]    The calcined copper-substituted alpha-chromium oxide compositions used in the present invention may be pressed into various shapes such as pellets for use in packing reactors. It may also be used in powder form. 
         [0035]    Typically, the calcined compositions will be pre-treated with a fluorinating agent prior to use as catalysts for changing the fluorine content of halogenated carbon compounds. Typically this fluorinating agent is HF though other materials may be used such as sulfur tetrafluoride, carbonyl fluoride, and fluorinated carbon compounds such as trichlorofluoromethane, dichlorodifluoromethane, chlorodifluoromethane, trifluoromethane, or 1,1,2-trichlorotrifluoroethane. This pretreatment can be accomplished, for example, by placing the catalyst in a suitable container which can be the reactor to be used to perform the process in the instant invention, and thereafter, passing HF over the dried, calcined catalyst so as to partially saturate the catalyst with HF. This is conveniently carried out by passing HF over the catalyst for a period of time, for example, about 0.1 to about 10 hours at a temperature of, for example, about 200° C. to about 450° C. Nevertheless, this pretreatment is not essential. 
         [0036]    Compounds that are produced in the chlorofluorination process in step (a) include the halopropanes CF 3 CCl 2 CF 3  (CFC-216aa) and CF 3 CClFCClF 2  (CFC-216ba). 
         [0037]    Halopropane by-products that have a higher degree of fluorination than CFC-216aa and CFC-216ba that may be produced in step (a) include CF 3 CClFCF 3  (CFC-217ba) and CF 3 CF 2 CF 3  (FC-218). 
         [0038]    Halopropane and halopropene by-products that may be formed in step (a) which have lower degrees of fluorination and/or halogenation than CFC-216aa and CFC-216ba include CF 3 CCl 2 CClF 2  (CFC-215aa), CF 3 CClFCCl 2 F (CFC-215bb), CF 3 CCl 2 CCl 2 F (CFC-214ab), and CF 3 CCl═CF 2  (CFC-1215xc). 
         [0039]    Prior to step (b), the CF 3 CCl 2 CF 3  and CF 3 CClFCClF 2 , (and optionally HF) in the effluent from the reaction zone in step (a), are typically separated from the low boiling components of the effluent (which typically comprise HCl, Cl 2 , HF, and over-fluorinated products such as CF 3 CClFCF 3 ) and the under-fluorinated components of the effluent (which typically comprise C 3 Cl 3 F 5  isomers, C 3 Cl 4 F 4  isomers, and/or under-halogenated components such as C 3 Cl 2 F 4  isomers and CF 3 CCl═CCl 2 ). The higher boiling components may be returned to step (a). 
         [0040]    In one embodiment of this invention, the under-fluorinated components CFC-215aa and CFC-215bb are converted to CF 3 CH 2 CHF 2  (HFC-245fa) and CF 3 CHFCH 2 F (HFC-245eb) as disclosed in U.S. Patent Application 60/706,162 filed Aug. 5, 2005. 
         [0041]    In another embodiment of this invention, the reactor effluent from step (a) is delivered to a distillation column in which HCl and any HCl azeotropes are removed from the top of the column while the higher boiling components are removed from the bottom of the column. The products recovered from the bottom of the first distillation column are then delivered to a second distillation column in which HF, Cl 2 , and any CFC-217ba are recovered at the top of the second distillation column and remaining HF and organic products, comprising CF 3 CCl 2 CF 3  and CF 3 CClFCClF 2 , are recovered at the bottom of the distillation column. The products recovered from the bottom of the second distillation column may be delivered to further distillation columns or may be delivered to a decanter controlled at a suitable temperature to permit separation of an organic-rich phase and an HF-rich phase. The HF-rich phase may be distilled to recover HF that is then recycled to step (a). The organic-rich phase may then be delivered to step (b). 
         [0042]    In step (b) of the process, CF 3 CCl 2 CF 3  and CF 3 CClFCClF 2  are contacted with hydrogen (H 2 ) in a second reaction zone. The CF 3 CCl 2 CF 3  and CF 3 CClFCClF 2  may be fed to the reactor zone at least in part as their azeotropes with HF. 
         [0043]    In one embodiment of step (b), a mixture comprising CF 3 CCl 2 CF 3  and CF 3 CClFCClF 2  is delivered in the vapor phase, along with hydrogen, to a reactor fabricated from nickel, iron, titanium, or their alloys, as described in U.S. Pat. No. 6,540,933; the teachings of this disclosure are incorporated herein by reference. A reaction vessel of these materials (e.g., a metal tube) optionally packed with the metal in suitable form may also be used. When reference is made to alloys, it is meant a nickel alloy containing form 1 to 99.9% (by weight) nickel, an iron alloy containing 0.2 to 99.8% (by weight) iron, and a titanium alloy containing 72-99.8% (by weight) titanium. Of note is use of an empty (unpacked) reaction vessel made of nickel or alloys of nickel such as those containing 40% to 80% nickel, e.g., Inconel™ 600 nickel alloy, Hastelloy™ C617 nickel alloy, or Hastelloy™ C276 nickel alloy. 
         [0044]    When used for packing, the metal or metal alloys may be particles or formed shapes such as perforated plates, rings, wire, screen, chips, pipe, shot, gauze, or wool. 
         [0045]    The temperature of the reaction in this embodiment of step (b) can be between about 350° C. to about 600° C., and is preferably at least about 450° C. Of note are processes wherein the reaction of (b) is conducted in a reaction zone at a temperature of from about 350° C. to about 600° C. which is unpacked or packed with a nickel alloy. 
         [0046]    The molar ratio of hydrogen to the CFC-216aa/CFC-216ba mixture fed to the reaction zone should be in the range of about 0.1 mole H 2  per mole of CFC-216 isomer to about 60 moles of H 2  per mole of CFC-216 isomer, more preferably from about 0.4 to 10 moles of H 2  per mole of CFC-216 isomer. 
         [0047]    The primary products from the above process are HFC-236fa, HFC-236ea and HFP. 
         [0048]    Alternatively, the contacting of hydrogen with the mixture of CFC-216aa and CFC-216ba, and optionally HF, is carried out in the presence of a hydrogenation catalyst. In this embodiment of step (b), said mixture is delivered in the vapor phase, along with hydrogen, to the reaction zone containing a hydrogenation catalyst. Hydrogenation catalysts suitable for use in this embodiment include catalysts comprising at least one metal selected from the group consisting of rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, and platinum. Said catalytic metal component is typically supported on a carrier such as carbon or graphite or a metal oxide, fluorinated metal oxide, or metal fluoride where the carrier metal is selected from the group consisting of magnesium, aluminum, titanium, vanadium, chromium, iron, and lanthanum. Preferred catalysts for the hydrogenolysis include palladium supported on carbon. The hydrogenolysis of saturated acyclic halofluorocarbons containing 3 or 4 carbon atoms using palladium supported on carbon is disclosed in U.S. Pat. No. 5,523,501, the teachings of which are incorporated herein by reference. 
         [0049]    The supported metal catalysts may be prepared by conventional methods known in the art such as by impregnation of the carrier with a soluble salt of the catalytic metal (e.g., palladium chloride or rhodium nitrate) as described by Satterfield on page 95 of  Heterogenous Catalysis in Industrial Practice,  2 nd  edition (McGraw-Hill, New York, 1991). The concentration of the catalytic metal(s) on the support is typically in the range of about 0.1% by weight of the catalyst to about 5% by weight. 
         [0050]    Suitable temperatures for the reaction zone containing said hydrogenation catalyst are in the range of from about 110° C. to about 400° C., preferably from about 125° C. to about 350° C. Higher temperatures typically result in greater conversion of CFC-216aa and CFC-216ba with fewer partially chlorinated intermediates such as C 3 HClF 6  isomers. At reaction zone temperatures in the range of 125° C. to 300° C. the primary products of the hydrodechlorination process are HFC-236fa and HFC-236ea. 
         [0051]    Temperatures above about 400° C. may cause hydrogenolysis of carbon-fluorine and carbon-carbon bonds; temperatures lower than about 125° C. will result in low conversion of the halopropanes and the formation of large amounts of partially chlorinated intermediates. 
         [0052]    The amount of hydrogen (H 2 ) fed to the reaction zone containing said hydrogenation catalyst is typically from about 1 mole of H 2  per mole of dichlorohexafluoropropane to about 20 moles of H 2  per mole of dichlorohexafluoropropane, preferably from about 2 moles of H 2  per mole of dichlorohexafluoropropane to about 10 moles of H 2  per mole of dichlorohexafluoropropane. 
         [0053]    The pressure used in the step (b) reaction zone is not critical and may be in the range of from about 1 to 30 atmospheres. A pressure of about 20 atmospheres may be advantageously employed to facilitate separation of HCl from other reaction products. 
         [0054]    To facilitate production of HFC-227ea in step (b), anhydrous hydrogen fluoride (HF) may be co-fed to the reaction zone containing a hydrogenation catalyst (e.g., palladium on alumina, fluorided alumina or aluminum fluoride). The amount of HF co-fed along with hydrogen to the reaction zone may be from about 0.2 mole HF per mole of CFC-216 isomer to about 4 moles of HF per mole of CFC-216 isomer. Under these conditions it is possible to obtain a mixture of products containing predominantly HFC-236fa and HFC-236ea or a mixture of products containing predominantly HFC-236fa and HFC-227ea by changing the temperature of the reaction zone. At temperatures in the reaction zone of 125° C. to about 250° C., the product mixture contains predominantly HFC-236fa and HFC-236ea. At temperatures in the reaction zone of about 275° C. to about 350° C., the product mixture contains predominantly HFC-236fa and HFC-227ea. Thus, the content of the product mixture is adjustable by manipulation of C 3 Cl 2 F 6 /HF/H 2  feed ratio and reaction zone temperature. 
         [0055]    The effluent from the step (b) reaction zone typically includes HCl, unreacted hydrogen, CF 3 CF═CF 2  (HFP), CF 3 CH 2 CF 3  (HFC-236fa), CF 3 CHFCHF 2  (HFC-236ea), and CF 3 CHFCF 3  (HFC-227ea), as well as any HF carried over from step (a) or step (b). In addition, small amounts of CF 3 CF 2 CH 2 F (HFC-236cb), CF 3 CCl═CF 2  (CFC-1215xc), and partially chlorinated by-products such as C 3 HClF 6  isomers including CF 3 CHClCF 3  (HCFC-226da), CF 3 CClFCHF 2  (HCFC-226ba), CF 3 CHFCClF 2  (HCFC-226ea), may be formed. 
         [0056]    In step (c), the desired products are recovered. The reactor effluent from step (b) may be delivered to a separation unit to recover CF 3 CH 2 CF 3 , CF 3 CHFCHF 2 , CF 3 CF═CF 2 , and/or CF 3 CFHCF 3  individually, as a mixture, or as their HF azeotropes. 
         [0057]    The partially chlorinated by-products, including any unconverted CFC-216ba and CFC-216aa, may be recovered and returned to step (a) or returned to the hydrogenation reactor in step (b). 
         [0058]    The reactor, distillation columns, and their associated feed lines, effluent lines, and associated units used in applying the process of this invention should be constructed of materials resistant to hydrogen fluoride and hydrogen chloride. Typical materials of construction, well-known to the fluorination art, include stainless steels, in particular of the austenitic type, the well-known high nickel alloys, such as Monel™ nickel-copper alloys, Hastelloy™ nickel-based alloys and, Inconel™ nickel-chromium alloys, and copper-clad steel. 
         [0059]    The following specific embodiments are to be construed as merely illustrative, and do not constrain the remainder of the disclosure in any way whatsoever. 
       EXAMPLES 
     Catalyst Preparations 
     Comparative Preparation Example 1 
     Preparation of 100% Chromium Catalyst 
       [0060]    A solution of 400 g Cr(NO 3 ) 3[ 9(H 2 O)] (1.0 mole) in 1000 mL of deionized water was treated dropwise with 477 mL of 7.4M aqueous ammonia raising the pH to about 8.5. The slurry was stirred at room temperature overnight. After re-adjusting the pH to 8.5 with ammonia, the mixture was poured into evaporating dishes and dried in air at 120° C. The dried solid was then calcined in air at 400° C.; the resulting solid weighed 61.15 g. The catalyst was pelletized (−12 to +20 mesh, 1.68 to 0.84 mm)) and 28.2 g (20 mL) was used in Comparative Example 1. 
       Preparation Example 1 
     Preparation of 99% Chromium/1% Copper Catalyst 
       [0061]    To a one liter beaker containing 261.0 g Cr(NO 3 ) 3[ 9(H 2 O)] (0.652 mole) and 1.46 g Cu(NO 3 ) 2[ 2.5 H 2 O] 0.0063 mole) was added 100 mL of deionized water. The slurry was placed on a stirring hot plate in a fume-hood and heated while stirring until oxides of nitrogen started to evolve. The beaker containing the paste-like material was placed in a furnace in the fume-hood after removing the stirrer. The temperature of the furnace was raised to 150° C. at the rate of 10 degrees/min and then to 550° C. at the rate of 1 degree/minute. It was held at 550° C. for an additional 10 hours. The resulting solid was pelletized (−12 to +20 mesh, 1.68 to 0.84 mm)) and 12.6 g (8.0 mL) was used in Example 1. 
       Preparation Example 2 
     Preparation of 99% Chromium/1% Copper Catalyst 
       [0062]    In a 2000 mL beaker was placed 400.2 g Cr(NO 3 ) 3[ 9(H 2 O)] (1.0 mole) and 1.64 g CuCl 2  (0.012 mole). To the solids was added 1000 mL deionized water. The mixture was stirred and when the dissolution was complete, the pH of the solution was raised from 2.0 to 8.0 by drop-wise addition of 8 molar aqueous ammonium hydroxide. The precipitated slurry was stirred for 24 hours at room temperature. It was then dried at 120-130° C. overnight and calcined at 450° C. for an additional 24 hours in air. The resulting solid was pelletized (−12 to +20 mesh, 1.68 to 0.84 mm)) and 11.0 g (8.0 mL) was used in Example 2. 
       Preparation Example 3 
     Preparation of 99% Chromium/1% Copper Catalyst 
       [0063]    In a 3000 mL beaker was placed 500.0 g Cr(NO 3 ) 3[ 9(H 2 O)] (1.25 moles) and 3.05 g Cu(NO 3 ) 2[ 2.5 H 2 O (0.013 mole). To the solids was added 1200 mL deionized water. The mixture was stirred and when the dissolution was complete, the pH of the solution was raised from 2.4 to 8.5 by drop-wise addition of 300 mL of 8 molar aqueous ammonium hydroxide. The precipitated slurry was stirred for 24 hours at room temperature. It was then dried at 110-120° C. overnight and calcined at 500° C. for an additional 24 hours in air. The resulting solid was pelletized (−12 to +20 mesh, 1.68 to 0.84 mm)) and 16.0 g (8.0 mL) was used in Example 3. 
       Preparation Example 4 
     Preparation of 98% Chromium/2% Copper Catalyst 
       [0064]    Preparation Example 1 was substantially repeated except that the amount of chromium(III) nitrate was 258.0 g (0.645 mole) and the amount of copper (II) nitrate was 2.9 g (0.0125 mole). The resulting solid was pelletized (−12 to +20 mesh, 1.68 to 0.84 mm)) and 12.6 g (8.0 mL) was used in Example 4. 
       Preparation Example 5 
     Preparation of 98% Chromium/2% Copper Catalyst 
       [0065]    Preparation Example 2 was substantially repeated with 400.2 g chromium(III) nitrate (1.0 mole) and 3.31 g (0.0246 mole) copper(II) chloride. The solid, calcined in air at 450° C. for 24 hours, was pelletized (−12 to +20 mesh, 1.68 to 0.84 mm)) and 10.9 g (8.0 mL) was used in Example 5. 
       Preparation Example 6 
     Preparation of 98% Chromium/2% Copper Catalyst 
       [0066]    In a 3000 mL beaker was placed 500.0 g Cr(No 3 ) 3[ 9(H 2 O)] (1.1.25 mole) and 6.1 g Cu(NO 3 ) 2[ 2.5 H 2 O] (0.0262 mole). To the solids was added 1200 mL deionized water. The mixture was stirred and when the dissolution was complete, the pH of the solution was raised from 2.4 to 8.2 by drop-wise addition of 300 mL 8 molar aqueous ammonium hydroxide. The precipitated slurry was stirred for 24 hours at room temperature. It was then dried at 110-120° C. overnight and calcined at 500° C. for an additional 24 hours in air. The resulting solid was pelletized (−12 to +20 mesh, 1.68 to 0.84 mm)) and 14.9 g (8.0 mL) was used in Example 6 as the catalyst. 
       Preparation Example 7 
     Preparation of 95% Chromium/5% Copper Catalyst 
       [0067]    Preparation Example 1 was substantially repeated except that the amount of chromium(III) nitrate was 250.0 g (0.625 mole) and the amount of copper(II) nitrate was 7.3 g (0.314 mole). The resulting solid was calcined at 550° C. overnight, pelletized (−12 to +20 mesh, 1.68 to 0.84 mm)) and 11.9 g (8.0 mL) was used in Example 7. 
       Preparation Examples 8-9 
     Preparation of 95% Chromium/5% Copper Catalyst 
       [0068]    Preparation Example 6 was substantially repeated except that the amounts of chromium(III) nitrate and copper(II) nitrate were adjusted to produce a catalyst having a ratio of chromium to copper of 95/5. The solid dried at 110-120° C. overnight was divided into two portions. One portion was calcined at 500° C. and another portion was calcined at 900° C. A 35.8 g (25.0 ml) portion, calcined at 500° C. and pelletized to −12 to +20 mesh, was used in Example 8. Similarly a 48.1 g (25.0 ml) portion, calcined at 900° C. and pelletized to −12 to +20 mesh (1.68 to 0.84 mm), was used in Example 9. 
       Examples 1-9 and Comparative Example 1 
     General Procedure for Chlorofluorination 
       [0069]    A weighed quantity of pelletized catalyst was placed in a ⅝ inch (1.58 cm) diameter Inconel™ nickel alloy reactor tube heated in a fluidized sand bath. The tube was heated from 50° C. to 175° C. in a flow of nitrogen (50 cc/min; 8.3(10) −7  m 3 /sec) over the course of about one hour. HF was then admitted to the reactor at a flow rate of 50 cc/min (8.3(10) −7  m 3 /sec). After 0.5 to 2 hours the nitrogen flow was decreased to 20 cc/min (3.3(10) −7  m 3 /sec) and the HF flow increased to 80 cc/min (1.3(10) −6  m 3 /sec); this flow was maintained for about 1 hour. The reactor temperature was then gradually increased to 400° C. over 3 to 5 hours. At the end of this period, the HF flow was stopped and the reactor cooled to 300° C. under 20 sccm (3.3(10) −7  m 3 /sec) nitrogen flow. CFC-1213xa was fed from a pump to a vaporizer maintained at about 118° C. It was combined with the appropriate molar ratios of HF and chlorine in a 0.5 inch (1.27 cm) diameter Monel™ nickel alloy tube packed with Monel™ turnings. The mixture of reactants then entered the reactor. The HF/1213xa/chlorine molar ratio was 20/1/4 for all runs and the contact time was 5 seconds for Examples 1-7, 30 seconds for Examples 8-9 and 20 seconds for Comparative Example 1. The reactions were conducted at a nominal pressure of one atmosphere. Analytical data for identified compounds is given in units of GC area %. Small quantities of other unidentified products were present. 
       General Procedure for Fluorocarbon Product Analysis 
       [0070]    The following general procedure is illustrative of the method used for analyzing the products of the chlorofluorination reactions. Part of the total reactor effluent was sampled on-line for organic product analysis using a gas chromatograph equipped a mass selective detector (GC-MS). The gas chromatography was accomplished with a 20 ft. (6.1 m) long×⅛ in. (0.32 cm) diameter tubing containing Krytox® perfluorinated polyether on an inert carbon support. The helium flow was 30 mL/min (5.0(10) −7  m 3 /sec). Gas chromatographic conditions were 60° C. for an initial hold period of three minutes followed by temperature programming to 200° C. at a rate of 6° C./minute. 
       Legend 
       [0071]      
         [0000]    
       
         
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                 214ab is CF 3 CCl 2 CCl 2 F 
                 215aa is CF 3 CCl 2 CClF 2   
               
               
                   
                 215bb is CCl 2 FCClFCF 3   
                 216aa is CF 3 CCl 2 CF 3   
               
               
                   
                 216ba is CClF 2 CClFCF 3   
                 216cb is CCl 2 FCF 2 CF 3   
               
               
                   
                 217ba is CF 3 CClFCF 3   
                 217ca is CF 3 CF 2 CClF 2   
               
               
                   
                 225da is CF 3 CHClCClF 2   
                 226ba is CF 3 CClFCHF 2   
               
               
                   
                 226da is CF 3 CHClCF 3   
                 226ea is CF 3 CHFCClF 2   
               
               
                   
                 1214 is C 3 Cl 2 F 4   
                 1215xc is CF 3 CCl═CF 2   
               
               
                   
                 HFP is CF 3 CF═CF 2   
               
               
                   
                   
               
             
          
         
       
     
       Chlorofluorination of 1213xa 
       [0072]    The chlorofluorination of CFC-1213xa was carried out at various temperatures using catalysts prepared according to Catalyst Preparation Examples 1-9. The analytical results shown in Table 1 are reported as GC area %. 
         [0000]    
       
         
               
               
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
               
                   
               
               
                 Ex.. 
                 Cat 
                 T 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 No. 
                 Prep. 
                 ° C. 
                 217ba 
                 217ca 
                 1215xc 
                 226da 
                 216aa 
                 216ba 
                 216cb 
                 215aa 
                 215bb 
                 214ab 
                 1214 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 1 
                 1 
                 280 
                 0.7 
                 ND 
                 0.9 
                 2.4 
                 14.4 
                 4.8 
                 0.6 
                 63.4 
                 8.5 
                 3.2 
                 0.3 
               
               
                   
                   
                 320 
                 3.4 
                 0.3 
                 1.0 
                 2.4 
                 36.3 
                 14.8 
                 1.2 
                 38.9 
                 1.4 
                 ND 
                 ND 
               
               
                   
                   
                 375 
                 5.8 
                 1.3 
                 0.3 
                 1.4 
                 60.2 
                 13.7 
                 0.4 
                 16.7 
                 ND 
                 ND 
                 ND 
               
               
                 2 
                 2 
                 280 
                 0.4 
                 ND 
                 0.4 
                 1.4 
                 13.2 
                 7.6 
                 0.8 
                 61.0 
                 13.8  
                 ND 
                 ND 
               
               
                   
                   
                 320 
                 1.4 
                 0.4 
                 0.2 
                 1.4 
                 31.1 
                 23.3 
                 1.0 
                 41.1 
                 0.1 
                 ND 
                 ND 
               
               
                   
                   
                 375 
                 3.2 
                 1.2 
                 0.1 
                 0.8 
                 59.3 
                 16.7 
                 0.2 
                 18.4 
                 0.1 
                 ND 
                 ND 
               
               
                 3 
                 3 
                 320 
                 2.4 
                 0.4 
                 0.3 
                 0.8 
                 32.8 
                 26.6 
                 2.0 
                 33.5 
                 1.1 
                 ND 
                 ND 
               
               
                   
                   
                 350 
                 2.9 
                 1.1 
                 0.3 
                 0.5 
                 42.3 
                 26.5 
                 1.4 
                 24.8 
                 ND 
                 ND 
                 ND 
               
               
                   
                   
                 375 
                 3.4 
                 1.6 
                 0.1 
                 0.5 
                 53.6 
                 21.8 
                 0.5 
                 18.5 
                 ND 
                 ND 
                 ND 
               
               
                 4 
                 4 
                 280 
                 0.2 
                 ND 
                 1.7 
                 0.4 
                 11.0 
                 2.3 
                 1.4 
                 26.5 
                 33.6  
                 18.2  
                 4.7 
               
               
                   
                   
                 320 
                 0.4 
                 ND 
                 0.9 
                 0.5 
                 21.0 
                 12.1 
                 1.9 
                 41.8 
                 20.4  
                 0.8 
                 0.1 
               
               
                   
                   
                 350 
                 0.5 
                 0.2 
                 0.6 
                 0.4 
                 28.1 
                 21.2 
                 2.5 
                 36.8 
                 9.4 
                 0.1 
                 ND 
               
               
                 5 
                 5 
                 350 
                 0.2 
                 0.2 
                 0.2 
                 0.2 
                 18.4 
                 28.8 
                 1.7 
                 45.5 
                 4.7 
                 ND 
                 ND 
               
               
                   
                   
                 375 
                 0.3 
                 0.5 
                 0.2 
                 0.1 
                 24.4 
                 30.6 
                 1.6 
                 41.4 
                 0.7 
                 ND 
                 ND 
               
               
                   
                   
                 400 
                 0.6 
                 0.9 
                 0.2 
                 0.1 
                 31.5 
                 28.5 
                 1.2 
                 36.7 
                 0.2 
                 ND 
                 ND 
               
               
                 6 
                 6 
                 320 
                 0.3 
                 0.2 
                 0.2 
                 0.2 
                 16.3 
                 27.7 
                 2.4 
                 41.7 
                 10.3  
                 ND 
                 ND 
               
               
                   
                   
                 350 
                 0.9 
                 0.8 
                 0.3 
                 0.2 
                 26.7 
                 33.1 
                 2.0 
                 33.9 
                 2.0 
                 ND 
                 ND 
               
               
                   
                   
                 375 
                 2.2 
                 1.8 
                 0.1 
                 0.1 
                 44.3 
                 28.4 
                 0.8 
                 21.8 
                 0.4 
                 ND 
                 ND 
               
               
                 7 
                 7 
                 320 
                 ND 
                 ND 
                 1.1 
                 0.1 
                 8.5 
                 4.3 
                 1.5 
                 39.6 
                 36.0  
                 7.8 
                 1.0 
               
               
                   
                   
                 350 
                 0.1 
                 0.1 
                 0.9 
                 0.1 
                 10.9 
                 10.4 
                 2.0 
                 42.9 
                 30.9  
                 1.6 
                 0.3 
               
               
                   
                   
                 400 
                 0.1 
                 0.1 
                 0.6 
                 ND 
                 12.4 
                 19.8 
                 1.9 
                 46.8 
                 17.9  
                 0.3 
                 0.1 
               
               
                 8 
                 8 
                 280 
                 ND 
                 ND 
                 0.8 
                 ND 
                 3.5 
                 0.9 
                 0.5 
                 26.7 
                 36.0  
                 26.5  
                 4.6 
               
               
                   
                   
                 320 
                 ND 
                 ND 
                 1.9 
                 ND 
                 6.7 
                 11.8 
                 0.8 
                 49.8 
                 27.2  
                 0.7 
                 0.3 
               
               
                   
                   
                 425 
                 ND 
                 ND 
                 0.9 
                 0.2 
                 5.5 
                 25.7 
                 0.7 
                 59.1 
                 5.9 
                 0.1 
                 0.2 
               
               
                 9 
                 9 
                 280 
                 ND 
                 ND 
                 0.3 
                 ND 
                 2.9 
                 0.4 
                 0.6 
                 20.2 
                 47.3  
                 25.9  
                 1.9 
               
               
                   
                   
                 320 
                 ND 
                 ND 
                 0.3 
                 ND 
                 3.8 
                 1.4 
                 1.0 
                 29.3 
                 48.4  
                 14.3  
                 1.1 
               
               
                   
                   
                 425 
                 ND 
                 ND 
                 0.3 
                 ND 
                 5.1 
                 12.8 
                 1.4 
                 50.8 
                 28.1  
                 0.6 
                 0.2 
               
               
                 Comp. 
                   
                 320 
                 12.4  
                 ND 
                 0.2 
                 2.4 
                 30.3 
                 18.0 
                 ND 
                 34.5 
                 ND 
                 ND 
                 ND 
               
               
                 Ex 1 
               
               
                   
               
               
                 ND = Not Detected 
               
             
          
         
       
     
         [0073]    Examination of the data in the chlorofluorination examples above show that the fluorine content of the starting CFC-1213xa is increased to produce CFC-216aa and CFC-216ba as well as other useful products containing a higher fluorine content than the starting material by using the catalysts of this invention. The CF 3 CCl 2 CF 3  and CF 3 CClFCClF 2  may be hydrogenated over palladium on carbon in accordance with the teachings of U.S. Pat. No. 5,523,501 to provide a mixture of CF 3 CH 2 CF 3  and CHF 2 CHFCF 3 . Alternatively, the CF 3 CCl 2 CF 3  and CF 3 CClFCClF 2  may be hydrogenated in a reaction zone at a temperature of from 450° C. to 600° C. which, is unpacked or packed with nickel alloy to produce a mixture of CF 3 CH 2 CF 3  and at least one of CHF 2 CHFCF 3  and CF 3 CF═CF 2 . Alternatively, the CF 3 CCl 2 CF 3  and CF 3 CClFCClF 2  may be hydrogenated in the presence of HF over a catalyst of palladium on flourided alumina to produce CF 3 CH 2 CF 3  and CF 3 CHFCF 3 . The CF 3 CH 2 CF 3  and at least one compound selected from the group consisting of CHF 2 CHFCF 3 , CF 3 CF═CF 2  and CF 3 CFHCF 3  may then be recovered using procedures well known to the art. 
       Example 10 
     Hydrodechlorination of a 1:1 CF 3 CCl 2 CF 3 /CF 3 CClFCClF 2  Mixture 
       [0074]    A 1% Pd on fluorided aluminum oxide catalyst was prepared by impregnating a sample of Harshaw 3945 aluminum oxide (100.0 g) suspended in 80 g of deionized water with a 5.05 g aliquot of a solution of aqueous PdCl 2  (19.8% Pd). The mixture stood at room temperature for about one hour with occasional agitation and was then evaporated to dryness at 120° C. for 18 hours. The catalyst was reduced under a flow of 1:1 hydrogen/helium (200 sccm, 3.3(10) −6  m 3 /sec) at 300° C. for 8 hours. 
         [0075]    A sample of the catalyst (10.02 g, 15 cc), pre-conditioned by use in hydrodefluorination reactions, was placed in a ⅝ inch (1.58 cm) diameter Inconel™ nickel alloy reactor tube heated in a fluidized sand bath. The catalyst was activated by heating from 250° C. to 400° C. in a flow of air (20 cc/min; 3.3(10) −7  m 3 /sec) over the course of about 3.5 hours. At the end of this period, the catalyst was cooled to 150° C. and hydrogen was passed through the catalyst bed (25 cc/min; 4.2(10) −7  m 3 /sec). The temperature was increased to 200° C. over the course of an hour and then held at 200° C. for 1.5 hours. The catalyst was then purged with nitrogen at 20 cc/min (3.3(10) −7  m 3 /sec) at 200° C. for 16 hours. HF (50 cc/min (8.3(10) −7  m 3 /sec) and nitrogen (20 cc/min (3.3(10) −7  m 3 /sec) were then co-fed to the reactor at 200° C. After about 0.5 hour, the HF flow was increased to 80 cc/min (1.3(10) −6  m 3 /sec) and the temperature was gradually increased to 400° C. over 3 hours. At the end of this period, the HF flow was stopped and the reactor cooled to 250° C. under 20 sccm (3.3(10) −7  m 3 /sec) nitrogen flow. 
         [0076]    Hydrogen and a mixture of CFC-216aa and CFC-216ba (1:1) were co-fed to the reactor in a molar ratio was 2/1; the contact time was 30 seconds. The reactions were conducted at a nominal pressure of one atmosphere. Analytical data for identified compounds is given in units of GC area %. Small quantities of other unidentified products were present. The results are shown in Table 2. 
         [0000]    
       
         
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 2 
               
               
                   
               
               
                 Ex. No.. 
                 T ° C. 
                 C3H8 
                 HFP 
                 236ea 
                 236fa 
                 226ba 
                 226ea 
                 226da 
                 216aa 
                 216ba 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 10 
                 125 
                 ND 
                 0.2 
                 0.8 
                 13.8 
                 0.1 
                 1.5 
                 36.9 
                 ND 
                 46.4 
               
               
                   
                 200 
                 0.7 
                 0.3 
                 19.9 
                 33.9 
                 1.3 
                 12.0 
                 20.2 
                 ND 
                 10.5 
               
               
                   
                 250 
                 1.7 
                 2.0 
                 31.9 
                 42.2 
                 1.4 
                 6.0 
                 10.0 
                 ND 
                 2.6 
               
               
                   
               
               
                 ND = Not Detected