Abstract:
An apparatus for the synthesis of anhydrous hydrogen halide fluids from organic halide fluids, such as perfluorocarbon fluids and refrigerant fluids, and anhydrous carbon dioxide for the environmentally safe disposition thereof.

Description:
CROSS REFERENCE TO RELATED APPLICATION 
     This application claims the benefit of U.S. Provisional Patent Application No. 61/474,657, filed on Apr. 12, 2011, which is hereby incorporated by reference as if fully set forth herein. 
    
    
     FIELD OF THE INVENTION 
     This invention relates to an apparatus for the synthesis of anhydrous hydrogen halide and carbon dioxide. In thermo-catalytic reactor A, carbon dioxide is synthesized from carbon monoxide and water. In thermo-catalytic reactor B, hydrogen halide fluids are synthesized from organic halide fluids, anhydrous hydrogen and anhydrous carbon dioxide. 
     BACKGROUND OF THE INVENTION 
     The organic halide family is very extensive. This invention is concerned with the family of refrigerant fluids and perfluoro fluids. The chemical synthesis of a significant number of organic halide fluids have been accomplished during the last 80 years, including the majority of refrigerant fluids such as chlorofluorocarbons (hereinafter “CFCs”), hydrochlorofluorocarbons (“HCFCs”), fluorocarbons (“FCs”) hydrofluorocarbons (“HFCs”) and hydrofluoroalkenes (“HFOs”). 
     It has been established that some fluids, particularly compounds used as refrigerants, have contributed to the depletion of ozone in the atmosphere and global warming. International action has been taken to phase out the use of these refrigerants and like compounds. Currently, the scientific community is concerned with protecting the environment, particularly with respect to any chemical contamination, including the release of carbon dioxide to the atmosphere. 
     Currently, the treatment and/or decomposition of organic halide fluids, such as refrigerants, require an apparatus that can include the use of extremely high temperatures. For example, certain apparatus for the decomposition of refrigerants can require heating the compounds to a temperature of about 1,300° C. to 20,000° C. under reducing conditions. Thus, there exists a need for an apparatus for the treatment of organic halide fluids under less severe conditions; i.e. temperatures less than 1,300° C. 
     SUMMARY OF THE INVENTION 
     Accordingly, the present invention is directed to a method for the synthesis of anhydrous hydrogen halide and anhydrous carbon dioxide that substantially obviates one or more of the problems due to limitations and disadvantages of the related art. 
     Exemplary embodiments provide a new apparatus for the synthesis of anhydrous hydrogen halide and carbon dioxide. In thermo-catalytic reactor A, carbon dioxide may be synthesized from carbon monoxide and water. In thermo-catalytic reactor B, hydrogen halide fluids may be synthesized from organic halide fluids, hydrogen and anhydrous carbon dioxide. 
     In an exemplary embodiment, dual reactors A and B of unit  1 , wherein a battery of one or more dual reactors a thermo-catalytic reaction takes place in reactor A of the first heat sink vessel, a thermo-catalytic reaction takes place in reactor B of the second heat sink vessel and the third heat sink vessel provides the means for balancing the heat in the first and second heat sink vessels. 
     In one aspect, the embodiments provide an apparatus for the thermo-catalytic synthesis of anhydrous hydrogen halide fluids and anhydrous carbon dioxide. In thermo-catalytic reactor A, carbon dioxide and hydrogen are synthesized from carbon monoxide and water. In thermo-catalytic reactor B, hydrogen halide fluids are synthesized from organic halide fluids, hydrogen and anhydrous carbon dioxide. 
     In another aspect, the embodiments provide an apparatus with dual reactors A and B, wherein reactor A, the reactants are carbon monoxide and water, which forms carbon dioxide and hydrogen with a low energy exothermic reaction in a pressure range from 1 atm to 30 atm and in a temperature range of 300° C. to 900° C. In reactor B the reactants are organic halide fluids, anhydrous hydrogen and anhydrous carbon dioxide, which forms hydrogen halide fluids and carbon monoxide, in a pressure range from 1 atm to 30 atm and in a temperature range of 600° C. to 900° C. 
     In another aspect, the embodiments provides an apparatus having a hydrogen diffuser where the hydrogen atom output is at least equal to the number of halide atoms from the organic halide fluid. 
     In another aspect, the embodiments provide an apparatus having a mass control device to regulate the flow of carbon dioxide molecules to be at least equal to the number of carbon atoms of the other reactants, forming the anhydrous hydrogen halide fluids and carbon monoxide. 
     In another aspect, the embodiments provide an apparatus for the thermal-catalytic decomposition of organic halide fluids such as refrigerant fluids and perfluorocarbon fluids. 
     In another aspect, the embodiments provide an apparatus with a thermo-catalytic reactor for the conversion of carbon monoxide and water to hydrogen and carbon dioxide. 
     In another aspect, the embodiments provide an apparatus with a thermo-catalytic reactor for the conversion of organic halide to anhydrous hydrogen halide and carbon monoxide. 
     In another aspect, the embodiments provide an apparatus with a thermo-catalytic reaction (similar to a water-gas shift reaction) utilizing a catalyst for the conversion of carbon monoxide and water to hydrogen and carbon dioxide. 
     In another aspect, the embodiments provide an apparatus with a thermo-catalytic reaction utilizing a catalyst for the conversion of organic halide to anhydrous hydrogen halide and carbon monoxide. 
     In another aspect, the embodiments provide an apparatus to arrange the dual reactors A and B wherein energy input is not required to run the reaction. 
     In another aspect, the embodiments provide an apparatus to control the balance between the halide atoms of the reactants and the hydrogen atoms to form only anhydrous hydrogen halide fluids. 
     In another aspect, the embodiments provide an apparatus to control the carbon dioxide in reactor B that prevents any formation of carbon (soot) and to form only carbon monoxide. 
     In another aspect, the embodiments provide an apparatus with dual reactors. In reactor A there are no organic halides, organic chloride compounds or molecular chlorine present and in reactor B there is no molecular oxygen present, thus preventing the formation of dioxins and furans. 
     In another aspect, the embodiments provide an apparatus for the synthesis of hydrogen halide and carbon monoxide from the conversion of hydrogen, carbon dioxide and organic halides, such as CFCs, HCFCs, FCs and HFCs, as the reactant fluids in the presence of a catalyst in the reaction zone of reactor B. 
     In another aspect, the embodiments provide an apparatus for any hydrogen, carbon monoxide and/or carbon dioxide exiting from the hydrogen diffuser to be recycled to the inlet of reactor A. 
     Additional features and advantages of the invention will be set forth in the description which follows, and in part will be apparent from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings. 
     To achieve these and other advantages and in accordance with the purpose of the present invention, as embodied and broadly described, a system for treatment and/or decomposition of organic halide fluids comprising: a dual reactor unit having a first reactor within a first heat sink vessel, a second reactor within a second heat sink vessel and a third heat sink balance vessel; wherein the first reactor and the second reactor are fluidly connected such that a product of a reaction that occurs in one reactor is fed into the other reactor. 
     In another aspect of the present invention, a dual reactor unit comprising: a first heat sink vessel including a first reactor, a second heat sink vessel including a second reactor, a third heat sink balance vessel; and a circulator; wherein the first heat sink vessel is fluidly connected to the second heat sink vessel, the third heat sink balance vessel and the circulator. 
     It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention as claimed. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  is one embodiment of the flow diagram arrangement of the apparatus  100  utilized by the present invention. 
         FIG. 2  is a diagram of one embodiment of a dual reactor unit  1  of the apparatus  100  utilized by the present invention. 
     
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     Although the following detailed description of the apparatus contains many specific details for purposes of illustration, it is understood that one of ordinary skill in the art will appreciate that many examples, variations and alterations to the following details are within the scope and spirit of the invention. Accordingly, the exemplary embodiments of the invention described herein are set forth without any loss of generality to, and without imposing limitations thereon, the claimed process invention. 
     Organic halide compounds and/or refrigerants fluids can include CFCs, HCFCs, FCs, HFCs and HFOs, that include at least of one fluid compound, such as refrigerant fluids including, but not limited to: R10 (carbontetrachloride), R11 (trichlorofluoromethane), R12 (dichlorodifluoromethane), R13 (chlorotrifluoromethane), R14 (tetrafluoromethane), R21 (dichlorofluoromethane), R22 (chlorodifluoromethane), R23 (trifluoromethane), R30 (methylene chloride), R31 (chlorofluoromethane), R32 (dichloromethane), R40 (chloromethane), R41 (fluoromethane), R152a (difluoroethane), R110 (chloroethane), R112 (chlorodifluoroethane), R113 (trichlorotrifluoroethane), R114 (dichlorotetrafluoroethane), R115 (chloropentafluoroethane), R116 (hexafluoroethane), R123 (dichlorotrifluoroethane), R124 (chlorotetrafluoroethane), R125 (pentafluoroethane), R134a (tetrafluoroethane), R1234YF (2,3,3,3-Tetrafluoropropene), R1234ZE (1,3,3,3-Tetrafluoropropene), R1243ZF (1,1,1-Tetrafluoropropene), R141b (dichlorofluoroethane), R142b (chlorodifluoroethane), R143a (trifluoroethane), and like compounds. Similarly, brominated refrigerants, such as R12B (bromochlorodifluoromethane) and R13B (bromotrifluoromethane), and other related compounds having one or two carbon atoms and at least one bromine atom, can be treated according to the apparatus described herein. As used herein a fluid is defined as any substance, (liquid, or gas) that has a low resistance to flow and that tends to assume the shape of its container. As used herein, organic halide refers to molecules that include both carbon and a halogen, preferably including between 1, 2, 3 and 4 carbon atoms, and at least one halogen atom per molecule. In certain embodiments, the organic halide and/or refrigerant include at least one carbon atom and at least one fluorine atom. 
     One aspect of the present apparatus invention is a dual reactor unit wherein two thermo-catalytic reactions may take place for the synthesis of anhydrous hydrogen halide and carbon dioxide. Both reactions may take place in a plasma free environment. In an exemplary embodiment, the dual reactor unit may include a reactor A and reactor B. Both reactors A and B may be thermo-catalytic reactor tubes. In reactor A, the thermo-catalytic reaction of carbon monoxide and water forms carbon dioxide and hydrogen. In reactor B, the thermo-catalytic reaction of the organic halide, hydrogen and carbon dioxide forms anhydrous hydrogen halide products and carbon monoxide recycle fluid. 
       FIG. 1  is an exemplary embodiment of illustration of apparatus of system  100 . This exemplary embodiment includes a dual reactor unit  1 , heat exchangers unit  2 , hydrogen diffuser unit  3 , a series of purified collectors that may include anhydrous hydrogen fluoride purifier/collector unit  4 , hydrogen bromide purifier/collector unit  5 , hydrogen chloride purifier/collector unit  6 , a separate purifier/collector unit such as a carbon dioxide purifier/collector unit  7 , dryer unit  8  and hydrogen halide neutralization scrubber unit  9 . The nine units are represented with a single digit. All accessories and/or components of each unit are represented by two digits after the digit representing the unit; i.e. the pipe connection of the gas inlet in scrubber unit  9  is represented by the number  902 . 
     By following this numbering procedure, all the elements of the apparatus  100  can be described as follows. Heat transfer fluid  190  in reactor unit  1  is brought to the operating temperature via the external heating means  126  of heat sink vessel  103 . The heat transfer fluid  190  is circulated by means of bi-directional flow circulator  104  from heat sink vessel  103  via pipe connection  105  to heat sink vessel  101 . From heat sink vessel  101  heat transfer fluid  190  may flow via pipe connection  110  and  109  to bi-directional flow circulator  104  continuing via pipe connections  108  and  107  to heat sink vessel  102 . The heat transfer fluid  190  may flow from heat sink vessel  102 , via pipe connection  106 , back to heat sink vessel  103 . A means to heat balance heat sink vessel  103  is via inlet pipe connection  120  and  121  and outlet pipe connections  122 ,  123  and flow control valve  124 . Dual reactor unit  1  can be filled with or drained of heat transfer fluid  190  via valve  137  and may be pressure protected by safety relief valve  138 . 
     In an exemplary embodiment, once an operating temperature is reached, a flow of carbon monoxide and water stream  990  enters reactor tube  112  in heat sink vessel  101  via pipe connection  125 . The thermo-catalytic reaction of the carbon monoxide and water stream  990  takes place in reaction zone  111  assisted by catalyst  180 . Any excess heat of reaction passes through the diathermal wall of reactor tube  112  and may be absorbed by heat transfer fluid  190 . The reaction forms hydrogen, un-reacted carbon monoxide and carbon dioxide stream  191 , which may exit reactor tube  112  via pipe connection  115 . 
     The stream  191  enters the tube-in-tube heat exchanger  210  via pipe connection  214  and may exit via pipe connection  215  and flows to the dryer unit  8  via pipe connection  802 . 
     Dryer unit  8  may include vessel  801  with external heating means  806  for the thermo-regeneration of the drying agent  895 . Stream  191  exits dryer  801  as anhydrous hydrogen, anhydrous un-reacted carbon monoxide and anhydrous carbon dioxide stream  191  via pipe connection  804 , flowing to gas compressor  805 . 
     Exiting gas compressor  805 , the stream  191  may enter the carbon dioxide purifier/collector unit  7  via pipe connection  706 . The carbon dioxide purifier/collector unit  7  may include column  702 , reflux condenser  703  with cooling mean inlet  720  and outlet  721  and collector  701  with heating means inlet  722  and outlet  723 , where the liquid carbon dioxide  790  can be collected. The liquid carbon dioxide  790  in collector  701  can be drained via pipe connection  708  and valve  726  to container connection  707 . After purification and collection of the carbon dioxide stream  790 , stream  790  exits purifier/collector unit  701  via pipe connection  708 . 
     In one exemplary embodiment, the carbon dioxide stream  790  may then be flowed to enter the tube-in-tube heat exchanger  210  via pipe connection  212 , flowing through inner tube  211 . The wall of the inner tube  211  is a diathermal wall and transfers heat from the outside of the inner tube  211  to the inside of the inner tube  211 , therefore passing heat to stream  790  in the inner tube  211 . Stream  790  exits via pipe connection  213  and flows via pipe connections  120 ,  121 ,  122 ,  123 ,  119 ,  118  and  116  and flow control valve  124  to reactor tube  114 . In line valve  226  may be used only as a servicing valve. 
     In one embodiment, the hydrogen, un-reacted carbon monoxide and traces of carbon dioxide stream  791  can exit from the top of purifier/collector unit  7  via pipe connection  714  and flows to gas compressor  705 . The stream  791  exits gas compressor  705  and flows to hydrogen diffuser  301  via pipe connection  303 . 
     Hydrogen diffuser  301  may include an external heating means  310 , hydrogen intake chamber  312  with palladium wall  302  and hydrogen collector  311 . The hydrogen stream  390  may exit the hydrogen collector of hydrogen diffuser  301  via pipe connection  304 . The purified hydrogen stream  390  flow may be regulated by mass flow controller  308  operating flow control valve  306  and  309 . In one embodiment, the purified hydrogen stream  390  flows via pipe connections  119 ,  118  and  116  to reactor tube  114 . Any remaining hydrogen, carbon monoxide and carbon dioxide can exit hydrogen diffuser  301  and may be recycled via pipe connection  319  and  315 , with valves  316  closed and  317  open, through gas compressor  305 , check valve  318 , pipe connection  135  and  128  in humidifier vessel  127  with the wet gas flowing back to reactor tube  112  via pipe connection  129  and  125 . Optionally, when the hydrogen diffuser is in the regeneration mode, any remaining hydrogen, carbon monoxide and carbon dioxide may exit hydrogen diffuser  301  via pipe connections  319  and  315 , valve  316 , with valve  317  closed, and diffuser exhaust  307  to atmosphere. The mass controller  308  also operates flow control valve  124  to regulate the flow of carbon dioxide stream  790  and operates flow control valve  209  to regulate the flow of organic halide  290 . 
     In one embodiment, the flow of the organic halide fluid stream  290  may be flowed through a tube-in-tube heat exchanger  201  from its connected source, to gas compressor  205  and pipe connection  203 , passing through heat exchanger  201  and exiting via pipe connection  206 , flowing via flow control valve  209  and pipe connections  118  and  116  to reactor tube  114 . 
     The hydrogen stream  390 , carbon dioxide stream  790  and organic halide fluid stream  290  come together, via pipe connection  116 , and flow into reactor tube  114 . The thermo-catalytic reaction of the carbon dioxide, hydrogen and organic halide fluid may take place in reaction zone  113 , may be assisted by catalyst  181 , forming anhydrous hydrogen halide and anhydrous carbon monoxide stream  192 . Stream  192  exits the reaction tube  114  via pipe connection  117  and pipe connection  207 , entering inner tube  202  of tube-in-tube heat exchanger  201 . 
     The wall of the inner tube  202  may be a diathermal wall and may transfer heat from the inside of the inner tube  202  to the outside of the inner tube  202 , therefore passing heat to the organic halide fluid stream  290  in the outer tube  201 . The hydrogen halide and carbon monoxide stream  192  exits tube-in-tube heat exchanger  201  via pipe connections  204  and  280 . The apparatus at this point may have at least two modes: (1) The mode of recovery of the hydrogen halide products (anhydrous hydrogen fluoride and/or anhydrous hydrogen bromide and/or anhydrous hydrogen chloride) may be by opening valve  281 , closing valve  282 , flowing through check valve  284  and entering the hydrogen fluoride purifier/collector unit  4  via pipe connection  406 . (2) The mode of neutralizing the hydrogen halide products (anhydrous hydrogen fluoride and/or anhydrous hydrogen bromide and/or anhydrous hydrogen chloride) may be by opening valve  282 , closing valve  281 , flowing through check valve  283 , to gas compressor  925  and entering scrubber vessel  901  via pipe connection  902 , wherein the hydrogen halides are neutralized and the carbon monoxide is recycled to heat sink vessel  101 . 
     The anhydrous hydrogen fluoride purifier/collector unit  4  may include column  402 , reflux condenser  403  with cooling means inlet  420  and outlet  421  and outlet  421 , collector  401  where the liquid hydrogen fluoride  490  can be collected and flow control valve  426 . The liquid hydrogen fluoride  490  in collector  401  can be drained via pipe connection/dip tube  408  and valve  426  to container connection  407 . The hydrogen fluoride  490  present may be removed from the hydrogen halide and carbon monoxide stream  192  at this point. In the event hydrogen fluoride  490  is the only hydrogen halide present in the hydrogen halide and carbon monoxide stream  192 , the carbon monoxide stream  491  and any remaining hydrogen fluoride  490  may exit the hydrogen fluoride purifier/collector unit  4  via pipe connection  414 , flowing through valve  416  and  516 , (bypassing hydrogen bromide purifier/collector unit  5  and hydrogen chloride purifier/collector unit  6  by closing valves  413 ,  513  and  616 ) to neutralizing scrubber unit  9  via check valve  920  and pipe connection  902 . 
     In the event hydrogen bromide and/or hydrogen chloride are present in hydrogen halide and carbon monoxide stream  192 , the hydrogen halide and carbon monoxide stream  192 , along with any remaining hydrogen fluoride  490 , may exit hydrogen fluoride purifier/collector unit  4  via pipe connection  414  and enters hydrogen fluoride removal trap  410  via pipe connection  417 , simultaneously closing valves  413  and  416  and opening valve  415 . 
     Any remaining hydrogen fluoride  490  is absorbed by the sodium fluoride  411  in hydrogen fluoride removal trap  410 . Hydrogen fluoride removal trap  410  has an external heating means  418  which is used, when required, to desorb the trapped hydrogen fluoride  490  and flow the desorbed hydrogen fluoride  490  via pipe connection  412  (by simultaneously opening valve  413  and closing valves  415 ,  416 ,  513  and  616 ) to neutralizing scrubber unit  9  via check valve  920  and pipe connection  902 . 
     In the event there is hydrogen bromide and/or hydrogen chloride present in hydrogen halide and carbon monoxide stream  192  they may be removed using additional collectors. In such an embodiment, the hydrogen fluoride removal trap  410  may allow the hydrogen bromide and/or hydrogen chloride in hydrogen halide and carbon monoxide stream  192  to flow through valve  415  and gas compressor  505  to hydrogen bromide purifier/collector unit  5  via pipe connection  506 . The anhydrous hydrogen bromide purifier/collector unit  5  consists of column  502 , reflux condenser  503  with cooling means inlet  520  and outlet  521  and collector  501  with heating means inlet  522 , flow control valve  524  and outlet  523 , where the liquid hydrogen bromide  590  can be collected. The liquid hydrogen bromide  590  in collector  501  can be drained via pipe connection  508  and valve  526  to container connection  507 . The hydrogen bromide  590  present will be removed from the hydrogen halide and carbon monoxide stream  192  at this point. In the event hydrogen bromide  590  is the only hydrogen halide still present in the hydrogen halide and carbon monoxide stream  192 , the hydrogen halide and carbon monoxide stream  192 , with any remaining hydrogen bromide  590 , exits the hydrogen bromide purifier/collector unit  5  via pipe connection  514 , flowing through valves  513  and  516 , (bypassing hydrogen chloride purifier/collector unit  6  by closing valves  515  and  616 ) to neutralizing scrubber unit  9  via check valve  920  and pipe connection  902 . 
     If hydrogen chloride is present in the hydrogen halide and carbon monoxide stream  192  exiting from hydrogen bromide purifier/collector unit  5  via pipe connection  514 , valve  513  may be closed with the flow through valve  515 , gas compressor  605  and pipe connection  606 . The anhydrous hydrogen chloride purifier/collector unit  6  consists of column  602 , reflux condenser  603  with cooling means inlet  620  and outlet  621  and collector  601  with heating means inlet  622 , flow control valve  624  and outlet  623 , where the liquid hydrogen chloride  690  can be collected. The liquid hydrogen chloride  690  in collector  601  can be drained via pipe connection  608  and valve  626  to container connection  607 . The hydrogen chloride  690  will be removed from the hydrogen halide and carbon monoxide stream  192  at this point. The remaining hydrogen halide and carbon monoxide stream  192  exits the hydrogen chloride purifier/collector unit  6  via pipe connection  614 , flowing through valve  616 , to neutralizing scrubber unit  9  via check valve  920  and pipe connection  902 . 
     Neutralizing scrubber unit  9  may include vessel  901 , pipe connections  902 ,  908 ,  909  and  914 , caustic solution  903 , H pattern valves  904 ,  905 ,  906  and  907 , pump  910  for circulation, filling, and draining caustic solution  903  in vessel  901 , ph gauge  911 , temperature gauge  912 , pressure gauge  913 , gas compressor  915 , and valve  916 . The carbon monoxide stream  491  and any remaining hydrogen halide fluids enters neutralizing scrubber unit  9  via pipe connection  902  wherein the hydrogen halide fluids present are neutralized by caustic solution  903  circulating in vessel  901  by pump  910 . The ph level of caustic solution  903  is monitored by ph gauge  911  and caustic solution  903  is replaced when required via the operation of H pattern valves  904 ,  905 ,  906 ,  907  and pump  910 . Carbon monoxide stream  491  exits neutralizing scrubber unit  9  via pipe connection  914  flowing to gas compressor  915  and (with valve  916  closed) to humidifier vessel  127  via check valve  134  and pipe connection  128 . 
     Humidifier vessel  127  may contain water  130 , may have a heating means  131 , and a temperature and water level control of standard design. Carbon monoxide stream  491  may flow through water  130  in humidifier vessel  127 , adding water  130  to the gas flow. The carbon monoxide and water stream  990  exits humidifier vessel  127  via pipe connection  129  and flows to reactor tube  112  via pipe connection  125 . This completes the flow diagram of the apparatus  100 . 
     The exemplary apparatus  100  may include multiple interconnected pieces, such as piping, valves, sensors and the like, can be constructed of carbon steel, stainless steel, Hastelloy, Monel, Inconel, Nickel, or a like material capable of operating at the temperatures and pressures contemplated herein. Apparatus  100  may be suitable for the thermo-catalytic synthesis of anhydrous hydrogen halide fluids and carbon monoxide from organic halide fluids, anhydrous hydrogen and anhydrous carbon dioxide and the thermo-catalytic synthesis of carbon dioxide from carbon monoxide and water. 
       FIG. 2  is an illustration of an exemplary dual reactor unit  1  used in this invention method. The dual reactor may include the following components: heat sink vessel  101 , heat sink vessel  102 , heat sink vessel  103  for balancing the heat, thermo-catalytic reactor tube  112  with reaction zone  111  containing catalyst  180  and thermo-catalytic reactor tube  114  with reaction zone  113  containing catalyst  181 . 
     An exemplary operation of dual reactor unit  1  may be as follows: The heat transfer fluid  190  in dual reactor unit  1  is brought to the operating temperature via external heating means  126  of heat sink vessel  103 . The heat transfer fluid  190  is circulated by means of bi-directional flow circulator  104  from heat sink vessel  103  via pipe connection  105  to heat sink vessel  101 . From heat sink vessel  101  the heat transfer fluid  190  flows via pipe connection  110  and  109  to bi-directional flow circulator  104  continuing via pipe connections  108  and  107  to heat sink vessel  102 . The heat transfer fluid  190  flows from heat sink vessel  102  via pipe connection  106  back to heat sink vessel  103 . A means to balance the heat transfer fluid  190  is via inlet pipe connection  120  and outlet pipe connection  122 . 
     Once operating temperature is reached, the process in heat sink vessel  101  may be as follows: A flow of carbon monoxide and water stream  990  enters reactor tube  112  in heat sink vessel  101  via pipe connection  125 . The thermo-catalytic reaction of the carbon monoxide and water stream  990  takes place in reaction zone  111  assisted by catalyst  180 . Any excess heat of reaction passes through the diathermal wall of reactor tube  112  and is absorbed by heat transfer fluid  190 . The reaction forms a hydrogen and carbon dioxide stream  191 , which exits reactor tube  112  via pipe connection  115 . 
     The process in heat sink vessel  102  may be as follows: The hydrogen stream  791 , carbon dioxide stream  790  and organic halide fluid stream  290  come together at pipe connection  116  and flow into reactor tube  114 . The thermo-catalytic reaction of the carbon dioxide, hydrogen and organic halide fluid takes place in reaction zone  113  assisted by catalyst  181 . Any excess heat of reaction passes through the diathermal wall of reactor tube  114  and is absorbed by heat transfer fluid  190 . The reaction forms anhydrous hydrogen halide and carbon monoxide stream  192 , which exits reactor tube  114  via pipe connection  117 . 
     Any impermeable metallic wall that can transfer heat through the metallic wall is a diathermal wall and is part of the diathermal wall in reactor tubes  112  and  114  of dual reactor unit  1 . Any impermeable metallic wall that is in contact with the reactant is part of the reaction zones in reactor tubes  112  and  114  of dual reactor unit  1 . The heat produced by the exothermic reaction of water and carbon monoxide in heat sink vessel  101  causes the temperature of the reaction zone to be increased to greater than the reaction temperature set point. The reaction zone may be maintained at a reaction zone temperature of between about 300° C. and 1000° C. 
     Anhydrous hydrogen fluoride collector unit  4 , anhydrous hydrogen bromide collector unit  5 , anhydrous hydrogen chloride collector unit  6 , anhydrous carbon dioxide collector unit  7 , dryer  8  and neutralizing scrubber  9  are of standard engineering design. Other operational requirements may not require any of the above or may require some of the above or may require additional components or may require any combination of the above and/or additional components. 
     In general, the reaction of carbon monoxide and water in the apparatus may be conducted at relatively low pressures. In certain embodiments, the reaction is carried out at pressures in the range of 1 atm to 30 atm, preferably at pressures in the range of 10 atm to 20 atm. In certain embodiments, the reaction is carried out at 15 atm. 
     In general, the reaction of the organic halide fluid, hydrogen and carbon dioxide in the apparatus may be conducted at relatively low pressures. In certain embodiments, the reaction is carried out at pressures in the range of 1 atm to 30 atm, preferably at pressures in the range of 10 atm to 20 atm. In certain embodiments, the reaction is carried out at 15 atm. 
     In certain embodiments, the flow of the anhydrous carbon dioxide and anhydrous hydrogen can be regulated by the apparatus depending upon the flow of the organic halide fluid being treated. For example, based upon the heat of reaction, the amount of anhydrous carbon dioxide and anhydrous hydrogen can be adjusted by the apparatus to operate the reactor at a level to reduce any external supply of heating or cooling. 
     One exemplary embodiment provides an apparatus for utilizing dual reactors; with reactor tube  114  containing a catalyst consisting of at least two metallic elements. The elements are selected from: atomic numbers 4, 5, 13, and 14, transition metals with atomic numbers from 21 to 29. 39 to 47, 57 to 71 and 72 to 79. In the presence of these catalysts the decomposition of the organic halide fluid is completed at a decreased temperature. 
     An alternative embodiment provides an apparatus for utilizing dual reactors; with reactor tube  112  containing a catalyst consisting of at least two metallic elements. The elements are selected from: atomic numbers 4, 5, 13, and 14, transition metals with atomic numbers from 21 to 29, 39 to 47, 57 to 71 and 72 to 79. In the presence of these catalysts the synthesis of hydrogen and carbon dioxide from carbon monoxide and water is obtained with the thermodynamic equilibrium being reached at lower temperatures and pressures. 
     A catalyst may be used to assist in the prevention of the formation of some hazardous compounds such as dioxins and furans, to accelerate the rate of reaction, to decrease the reaction temperature and/or to induce the reactions. Transition metals may be used as catalysts in either or both reactors. Exemplary metallic elements for the catalysts may be selected from the following: 
     
       
         
               
               
               
               
             
           
               
                   
                   
               
               
                   
                 ATOMIC 
                   
                   
               
               
                   
                 NUMBER 
                 SYMBOL 
                 NAME 
               
               
                   
                   
               
             
             
               
                   
                  4 
                 Be 
                 Beryllium 
               
               
                   
                  5 
                 B 
                 Boron 
               
               
                   
                 13 
                 Al 
                 Aluminum 
               
               
                   
                 14 
                 Si 
                 Silicon 
               
               
                   
                 21 
                 Sc 
                 Scandium 
               
               
                   
                 22 
                 Ti 
                 Titanium 
               
               
                   
                 23 
                 V 
                 Vanadium 
               
               
                   
                 24 
                 Cr 
                 Chromium 
               
               
                   
                 26 
                 Fe 
                 Iron 
               
               
                   
                 27 
                 Co 
                 Cobalt 
               
               
                   
                 28 
                 Ni 
                 Nickel 
               
               
                   
                 29 
                 Cu 
                 Copper 
               
               
                   
                 39 
                 Y 
                 Yttrium 
               
               
                   
                 40 
                 Zr 
                 Zirconium 
               
               
                   
                 41 
                 Nb 
                 Niobium 
               
               
                   
                 42 
                 Mo 
                 Molybdenum 
               
               
                   
                 44 
                 Ru 
                 Ruthenium 
               
               
                   
                 45 
                 Rh 
                 Rhodium 
               
               
                   
                 46 
                 Pd 
                 Palladium 
               
               
                   
                 47 
                 Ag 
                 Silver 
               
               
                   
                 60 
                 Nd 
                 Neodymium 
               
               
                   
                 66 
                 Dy 
                 Dysprosium 
               
               
                   
                 74 
                 W 
                 Tungsten 
               
               
                   
                 77 
                 Ir 
                 Iridium 
               
               
                   
                 78 
                 Pt 
                 Platinum 
               
               
                   
                 79 
                 Au 
                 Gold 
               
               
                   
                   
               
             
          
         
       
     
     In one embodiment the catalysts may be prepared by using a mixture of metallic elements in the form of alloys. Each reactor may use one or more catalysts for the reaction. In the reactor for the synthesis of carbon dioxide and hydrogen the thermo-catalytic reaction of carbon monoxide and water (the water-gas shift reaction) may be enhanced by using a catalyst having two or more of the following elements: Al, Ni, Fe, Co, Pt, Ir, Cr, Mo, Cu, Pd, Rh, V and Au as the principal components of the alloy. In the reactor for the decomposition of organic halides, such as refrigerants and perfluorocarbon fluids, the thermo-catalytic reaction may be enhanced by using a catalyst having a blend of the following elements: Nd, Nb, Dy, Fe, B, Pt, Pd, Rh, Y, Co, Ni, Cr, Mo, Al, Ir and W as the principal components of the alloy. 
     The physical form of each of the alloys used in the blend can be produced in a variety of shapes, such as pellets, cylinders or flat sheets, with a preferable range of 0.5 mm to 5.0 mm in thickness, a preferable range of 10 mm2 to 100 mm2 in surface area per unit and a specific surface area in cm2/g. The alloys are very compact metallic materials with less porosity than catalyst oxide supports, where the typical specific surface area is measured in m2/g. In general the specific surface area for alloy is measured in cm2/g. 
     The majority of catalyst supports are mineral oxides and all mineral oxides react with hydrogen halides. Therefore, mineral oxide catalyst supports are not used in this invention. As an alternative, this invention may use sintered metallic alloy catalyst supports. Sintered metallic alloy catalysts and catalyst supports are resistant to corrosion by the hydrogen halide and high temperatures. Flat sheet particles of metallic alloys with a thickness of 0.5 mm to 5.0 mm, a unit surface area from 10 mm 2  to 100 mm 2  and a range of the specific surface area from 20 cm 2 /g to 80 cm 2 /g are used in the experimental unit however, a unit for an industrial plant would likely use a specific surface area in the range of 10 to 200 m 2 /g. 
     The catalysts prepared for the experimental work of this invention were selected from alloys as follows:
         Catalyst #1 consists of the elements Fe 50.0% wt, Ni 33.5% wt, Al 14.0% wt, Co 0.5% wt, Ti 0.5% wt, Si 1.125% wt and Rh/Pt 0.5% wt in an alloy form. True density of the alloy is in a range from 2.0 g/cm3 to 10 g/cm3 and the bulk density of the catalysts particles of the alloy is in a range from 0.25 to 0.5 g/cc.   Catalyst #2 consists of the elements Fe 63.0% wt, CR 18% wt, Mo 3% wt, Mn 2.0% wt, and Si 0.08% wt in an alloy form. True density of the alloy is in a range from 2.0 to 10 g/cm 3  and the bulk density of the catalysts is in a range from 0.25 to 0.5 g/cc. Other catalysts equivalent to alloy #2 are Hastelloy C, Inconel 600 and Stainless Steel 316   Catalyst #3 consists of the elements Fe 65.0% wt, Nd 29% wt, Dy 3.6% wt, Nb 0.5% wt, B 1.1% wt and Ir/Pt 0.08% wt in an alloy form. True density of the alloy is in a range from 2.0 to 10 g/cm 3  and the bulk density of the catalysts is in a range from 0.25 to 0.5 g/cc.   Catalyst #4 consists of the elements Pd 82.0% wt, Cu 17% wt and Pt/Rh 1.0% wt in an alloy form. True density of the alloy is in a range from 2.0 to 10 g/cm 3  and the bulk density of the catalysts are in a range from 0.25 to 0.5 g/cc.       

     The catalyst for the synthesis of anhydrous hydrogen halides, from the thermo-catalytic reaction of organic halides, hydrogen and carbon dioxide, is a blend of about 50% of alloy #2 and 50% of alloy #3. 
     A laboratory bench scale unit was set up for conditioning the catalysts of this invention and the results obtained from the subsequent test runs were at a maximum pressure of 4 atm. The tests were (1) the reaction of carbon monoxide and water and (2) the reaction of organic halide with carbon dioxide and hydrogen; with a comparison being made between the use of no catalyst or improvements over other catalysts. Four stainless steel 316 reactor tubes were prepared, each having dimensions of 19 mm OD, 16 mm ID and 900 mm (90 cm) in length. Each tube has a cross sectional flow area of 200 mm 2 , an internal wall surface of 45,000 mm 2  and an internal volume of about 180,000 mm 3  (180 cm 3 ). 
     In reactor tube #1, a stainless steel 316 sintered filter, having a 15 mm OD and 75 mm length, was inserted in one end. A 75 g blend of catalyst #1 and catalyst #2 was then added to reactor tube #1, followed by another stainless steel 316 sintered filter, having a 15 mm OD and 75 mm length, being inserted in the other end of reactor tube #1. The prepared reactor tube #1 was set in a high temperature heating oven and a passivation procedure was initiated. The passivation process was to flow 20 ml/minute of hydrogen fluoride for three hours at 1,000° C. to form a layer of metal fluoride in the active surface area of the catalyst. This was followed by a flow of 20 cc/minute of carbon dioxide for one hour at 900° C. and for one hour with the heater turned off. At this point, the flow of carbon dioxide was stopped and the reactor tube was opened to the atmosphere. 
     Reactor tube #2 is identical in construction and preparation to reactor tube #1; however the catalyst was changed by substituting a 75 g blend of catalyst #2 and catalyst #3. The passivation procedure was identical to reactor tube #1. 
     Reactor tube #3 is identical in construction to reactor tube #1, however it contained no filters or catalyst; i.e. an empty tube. There was no passivation procedure used with reactor tube #3. 
     Reactor tube #4 is identical in construction and preparation to reactor tube #1, however the catalyst was changed by substituting 75 g of catalyst #4. There was no passivation procedure used with reactor tube #4. 
     In another aspect, energy input may not be required for the apparatus arrangement of a battery of dual reactors. 
     EXAMPLES 
     The following reactions in the apparatus represent typical exothermic and endothermic reactions in which various illustrative organic halide fluids are thermo-catalytically formed into anhydrous hydrogen halide and carbon monoxide. The examples show the exothermic reactions having a higher energy value than the endothermic reactions with the benefit that the excess of energy of the exothermic reaction balances the heat sensible of the reactant component. Following is the heat of formation and heat capacity table used for the examples: 
     
       
         
               
               
               
               
             
               
               
               
               
             
           
               
                   
                   
               
               
                   
                   
                   
                 Heat Capacity 
               
               
                   
                   
                 Heat of Formation 
                 Cal/mol ° C. @ constant 
               
               
                   
                 Symbol 
                 Kcal/mol ΔHf 25° C. 
                 pressure @ 500° C. average 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 CF 4   
                 −220.5 
                 14.56 
               
               
                   
                 CCl 2 F 2   
                 −114.2 
                 17.54 
               
               
                   
                 CHClF 2   
                 −113.0 
                 13.28 
               
               
                   
                 C 2 H 2 F 4   
                 206.7 
                 34.57 
               
               
                   
                 CO 
                 −26.4 
                 7.21 
               
               
                   
                 CO 2   
                 −94.0 
                 10.77 
               
               
                   
                 H 2   
                 0.0 
                 7.00 
               
               
                   
                 H 2 O 
                 −58.0 
                 8.54 
               
               
                   
                 HF 
                 −64.0 
                 6.94 
               
               
                   
                 HCl 
                 −22.0 
                 7.06 
               
               
                   
                   
               
             
          
         
       
     
     Example 1 
     Reactor tube #4 was heated to a temperature of 850° C. The CO flow meter was set for a 22 cc/minute flow through a water humidifier, where the CO joined with 18 mg/minute of H 2 O. The CO and H 2 O were flowed into the reaction zone contacting the catalyst blend and the reaction of the CO and H 2 O formed CO 2  and H 2 . During the nine minutes of collection, 390 cc of gaseous product with a cylinder pressure of 10 psig was collected in a sample cylinder having a 234 cc empty volume. The gaseous product was analyzed by a gas chromatograph with the only compounds detected being CO at 50% by mol, CO 2  at 25% by mol and H 2  at 25% by mol.
 
CO+H 2 O→C0 2 +H2+ΔH R  
 
−26.00−58.00→−94.00+0.00
 
ΔHr=84.00ΔHp=−94.00
 
ΔH R 25° C. =ΔHp−ΔHr=−94.00+84.00=−10Kcal/mol
 
CPr=+7.21=+8.54=+15.75Cal/mol×degrees C.
 
CPp=+10.77+7.00=+17.77Cal/mol×degrees C.
 
ΔCP=CPp−CPr=(17.75−15.75)=2×800=1600=1.6Kcal/mol
 
ΔH R 800° C. =−10.00Kcal/mol+1.60=−8.40Kcal/mol
 
     Exothermic Reaction 
     Example 2 
     Reactor tube #1 was heated to a temperature of 850° C. Three flow meters were calibrated for (1) carbon tetrafluoride at 22 cc/minute, (2) carbon dioxide at 22 cc/minute and (3) hydrogen at 44 cc/minute. The exhaust was checked with an electronic organic halide detector and no carbon tetrafluoride was detected. The product was collected for eight minutes into a sample cylinder at a pressure of 29 psig with the product being liquid anhydrous hydrogen fluoride. Partial pressure of anhydrous hydrogen fluoride was 22 psia and partial pressure of the carbon monoxide was 22 psia; the total pressure was 44 psia=29 psig. 
                                                                   GC-MS Analysis   FTIR Analysis                                        CF4   ND   HF (anhydrous    2/1           Dioxins   ND   vapor/liquid)/CO               Furans   ND                   Hydrogen   &lt;1%                   Carbon dioxide   &lt;5%                        CF 4 +2H2+C02+→2CO+4HF+ΔHR
 
−220.50+0.00−94.00→−26.40−64.00
 
ΔH r =−220.50−94.00=314.5
 
ΔH p =−2(26.40)−4×64.00=−308.8
 
ΔH R 25° C. =−308.8+314.50=+5.700Kcal/mol
 
CP r =+14.56+2(7.00)+10.77=+39.33Cal/mol×degrees C.
 
CP p =+2(7.21)+4(6.94)=+42.18Cal/mol×degrees C.
 
ΔCP=2.85×800=+2.28Kcal/mol
 
ΔH R 800° C. =+5.70+2.28=+7.98Kcal/mol
 
     Endothermic Reaction 
     Example 3 
     Reactor tube #1 was heated to a temperature of 850° C. Three flow meters were calibrated for (1) dichlorodifluoromethane at 22 cc/minute, (2) carbon dioxide at 22 cc/minute and (3) hydrogen at 44 cc/minute. The exhaust was checked with an electronic organic halide detector and no dichlorodifluoromethane was detected. The product was collected for eight minutes into a sample cylinder at a pressure of 54 psi+/−1 psi with the product being liquid anhydrous hydrogen fluoride and liquid anhydrous hydrogen chloride. 
                                           GC-MS Analysis                                    Dichlorodifluoromethane (R-12)   ND           Dioxins   ND           Furans   ND           Hydrogen   &lt;2%           Carbon dioxide   &lt;6%           Carbon monoxide   31%           Hydrogen fluoride   31%           Hydrogen chloride   31%                        CClF 2 + 2 H 2 +C0 2 +→ 2 CO+2HF+2HCl+ΔH R  
 
−114.20+0.00−94.00→−26.40−64.00−22.00
 
ΔH r =−114.20−94.00=−208.20
 
ΔH p =−2(112.40)=−224.8
 
ΔH R 25° C. =−224.8+208.20=−16.60Kcal/mol
 
CP r =+17.54+14.0+10.77=+42.31Cal/mol×degrees C.
 
CP p =+2(7.21+7.06+6.94)=+42.4Cal/mol×degrees C.
 
ΔCP=(42.42−42.31)×800=+0.00Kcal/mol
 
ΔH R 800° C. =−16.60Kcal/mol
 
     Exothermic Reaction 
     Example 4 
     Reactor tube #2 was heated to a temperature of 850° C. Three flow meters were calibrated for (1) chlorodifluoromethane at 22 cc/minute, (2) carbon dioxide at 22 cc/minute and (3) hydrogen at 22 cc/minute. The exhaust was checked with an electronic organic halide detector and no chlorodifluoromethane was detected. The product was collected for eight minutes into a sample cylinder at a pressure of 53 psi+/−1 psi with the product being liquid anhydrous hydrogen fluoride and liquid anhydrous hydrogen chloride. 
                                           GC-MS Analysis                                    Chlorodifluoromethane (R-22)   ND           Dioxins   ND           Furans   ND           Hydrogen   &lt;1%           Carbon dioxide   &lt;4%           Carbon monoxide   38%           Hydrogen fluoride   40%           Hydrogen chloride   20%                        CHCl 2 F 2 +H 2 +C0 2 +→2CO+2HF+HCl+ΔH R  
 
−113.00+0.00−94.00→−26.40−64.00−22.00
 
ΔH r =−113.00−94.00=−207.00
 
ΔH p =−2(26.40)−2(64.00)−22=−202.8
 
ΔH R 25° C. =−202.8+207.20=+4.20Kcal/mol
 
CP r =+13.28+10.77+7.0=+31.05Cal/mol×degrees C.
 
CP p =+2(7.21)+2(6.94)+7.06=+35.36Cal/mol×degrees C.
 
ΔCP=35.36−31.05=4.31×800=3,438.00Cal/mol
 
ΔCP=3,438.00Cal/mol/1000=3.44Kcal/mol
 
ΔH R 800° C. =+4.20+3.45=+7.65Kcal/mol
 
     Endothermic Reaction 
     Example 5 
     Reactor tube #2 was heated to a temperature of 850° C. Three flow meters were calibrated for (1) tetrafluoroethane at 22 cc/minute, (2) carbon dioxide at 44 cc/minute and (3) hydrogen at 22 cc/minute. The exhaust was checked with an electronic organic halide detector and no tetrafluoroethane was detected. The product was collected for eight minutes into a sample cylinder at a pressure of 64 psi+/−2 psi with the product being liquid anhydrous hydrogen fluoride. 
                                           GC-MS Analysis                                    Tetrafluoroethane (R-134a)   ND           Dioxins   ND           Furans   ND           Hydrogen   &lt;2%           Carbon dioxide   &lt;4%           Carbon monoxide   48%           Hydrogen fluoride   48%                        C 2 H 2 F 4 +H 2 +2C0 2 +→4CO+4HF+ΔH R  
 
−206.70+0.00−94.00→−26.40−64.00
 
ΔH r =−(206.70+188.00)=−394.70
 
ΔH p =−4(90.40)−2(64.00)=−361.60
 
ΔH R 25° C. =−361.60+394.70=+33.00Kcal/mol
 
CP r =−(34.57+21.54+7.0)=−63.11Cal/mol×degrees C.
 
CP p =+4(7.21)+4(6.94)=+56.60Cal/mol×degrees C.
 
ΔCP=−63.11−+56.60=−6.51×800=−5,208.00Kcal/mol
 
ΔCP=−5,208.00/1000=−5.21Kcal/mol
 
ΔH R 800° C. =+33.00−5.20=27.80Kcal/mol
 
     Endothermic Reaction 
     Example 6 
     Reactor tube #3, with no catalyst present, was heated to a temperature of 850° C. Three flow meters were calibrated for (1) carbon tetrafluoride at 22 cc/minute, (2) carbon dioxide at 22 cc/minute and (3) hydrogen at 44 cc/minute. The exhaust was checked with an electronic organic halide detector and carbon tetrafluoride was detected. The temperature was increased to 950° C., the exhaust was checked with the electronic organic halide detector and carbon tetrafluoride was detected. The temperature was increased to 1050° C., the exhaust was checked with the electronic organic halide detector and carbon tetrafluoride was detected. The temperature was increased to 1150° C., the exhaust was checked with the electronic organic halide detector and no carbon tetrafluoride was detected. Example 6 proves that the catalyst of this invention decreases the temperature required for the complete decomposition of the perfluorocarbon (carbon tetrafluoride) by about 300° C. 
     Conclusions from the results of the examples are: (1) The excess of hydrogen and carbon dioxide in the reaction of the decomposition of organic halides, such as CFCs, HCFCs, FCs and HFCs does not affect the reaction and is beneficial in preventing the generation of soot, (2) the excess of water in the reaction of carbon monoxide with water in the water-gas shift reaction does not create any negative effect, (3) the exclusion of molecular oxygen in the process prevents the formation of unwanted compounds, such as dioxins and furans, especially when chloride or chlorine is present in the reaction zone and (4) the catalysts of the invention decreases the temperature required for the complete decomposition of the organic halide by about 300° C. 
     Although the present apparatus invention has been described in detail, it should be understood that various changes, substitutions, and alterations can be made hereupon without departing from the principle and scope of the invention. Accordingly, the scope of the present invention should be determined by the following claims and their appropriate legal equivalents. 
     The singular forms “a”, “an” and “the” include plural referents, unless the context clearly dictates otherwise. 
     Optional or optionally means that the subsequently described event or circumstances may or may not occur. The description includes instances where the event or circumstance occurs and instances where it does not occur. 
     Ranges may be expressed herein as from about one particular value, and/or to about another particular value. When such a range is expressed, it is to be understood that another embodiment is from the one particular value and/or to the other particular value, along with all combinations within said range. 
     Throughout this application, where patents or publications are referenced, the disclosures of these references in their entireties are intended to be incorporated by reference into this application, in order to more fully describe the state of the art to which the invention pertains, except when these reference contradict the statements made herein.