HK1187592B - Method for the synthesis of anhydrous hydrogen halide and anhydrous carbon dioxide - Google Patents

Description

Method for synthesizing anhydrous hydrogen halide and anhydrous carbon dioxide

Cross Reference to Related Applications

This application claims the benefit of U.S. provisional patent application No. 61/474,659 (filed 12/4/2011), which is incorporated herein by reference as if fully set forth herein.

Technical Field

The present invention relates to a process for the synthesis of anhydrous hydrogen halide and carbon dioxide. In the thermocatalytic reactor a, carbon dioxide is synthesized from carbon monoxide and water. In thermocatalytic reactor B, the hydrogen halide fluid is synthesized from an organic halide fluid, anhydrous hydrogen, and anhydrous carbon dioxide.

Background

The family of organic halides is very broad. The present invention relates to the family of refrigerant fluids and perfluorinated fluids. The chemical synthesis of appreciable amounts of organic halide fluids has been completed over the last 80 years, including most refrigerant fluids such as chlorofluorocarbons (hereinafter "CFCs"), hydrochlorofluorocarbons ("HCFCs"), halothane ("FCs"), hydrofluorocarbons ("HFCs"), and hydrofluoroolefins ("HFOs").

It has been determined that some fluids, particularly compounds used as refrigerants, have promoted ozone depletion and global warming in the atmosphere. International measures have been taken to phase out the use of these refrigerants and similar compounds. Currently, the scientific community is concerned with protecting the environment, particularly with respect to any chemical contamination, including the release of carbon dioxide into the atmosphere.

Current methods for treating and/or decomposing organic halide fluids (e.g., refrigerants) may include the use of extremely high temperatures. For example, certain processes for the decomposition of refrigerants include heating these compounds under reducing conditions to temperatures of about 1300 ℃ to 20000 ℃. Therefore, there is a need for a method for treating organic halide fluids under less severe conditions, i.e. temperatures below 1300 ℃.

Summary of The Invention

Accordingly, the present invention is directed to a method for synthesizing 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.

The illustrative embodiments provide a novel process for the synthesis of anhydrous hydrogen halide and carbon dioxide. In the thermocatalytic reactor a, carbon dioxide can be synthesized from carbon monoxide and water. In thermocatalytic reactor B, a hydrogen halide fluid is synthesized from an organic halide fluid, hydrogen gas, and anhydrous carbon dioxide.

In one exemplary embodiment, unit 1 has dual reactors a and B, wherein in a group of one or more dual reactors, one thermocatalytic reaction occurs in reactor a of a first heat sink vessel (heat sink vessel), one thermocatalytic reaction occurs in reactor B of a second heat sink vessel and a third heat sink vessel provides a means for balancing the heat in the first and second heat sink vessels.

In one aspect, the embodiments provide a method for the thermocatalytic synthesis of anhydrous hydrogen halide fluid and anhydrous carbon dioxide. In the thermocatalytic reactor a, carbon dioxide and hydrogen are formed from carbon monoxide and water. In thermocatalytic reactor B, a hydrogen halide fluid is synthesized from an organic halide fluid, hydrogen gas, and anhydrous carbon dioxide.

In another aspect, the embodiments provide a process using dual reactors a and B, wherein the reactants are carbon monoxide and water in reactor a, which reactor forms carbon dioxide and hydrogen in a low energy exothermic reaction at a pressure range from 1atm to 30atm and a temperature range from 300 ℃ to 900 ℃. In reactor B, the reactants are an organic halide fluid, anhydrous hydrogen and anhydrous carbon dioxide, the reactor forming a hydrogen halide fluid and carbon monoxide at a pressure ranging from 1atm to 30atm and at a temperature ranging from 600 ℃ to 900 ℃.

In another aspect, the embodiments provide a method having a hydrogen diffuser in which the hydrogen atom production is at least equal to the number of halogen atoms from the organohalide fluid.

In another aspect, the embodiments provide a method having a quality control device to adjust the flow rate of carbon dioxide molecules to be at least equal to the number of carbon atoms of the other reactants to form an anhydrous hydrogen halide fluid and carbon monoxide.

In another aspect, the embodiments provide a method for the thermocatalytic decomposition of organohalide fluids (e.g., refrigerant fluids and perfluorocarbon fluids).

In another aspect, the embodiments provide a method of using a thermocatalytic reactor for converting carbon monoxide and water to hydrogen and carbon dioxide.

In another aspect, the embodiments provide a method of using a thermocatalytic reactor for converting organic halides to anhydrous hydrogen halide and carbon monoxide.

In another aspect, the embodiments provide a method of using a thermocatalytic reaction (similar to a water-gas shift reaction) that uses a catalyst for converting carbon monoxide and water to hydrogen and carbon dioxide.

In another aspect, the embodiments provide a method of using a thermocatalytic reaction using a catalyst for the conversion of an organic halide to anhydrous hydrogen halide and carbon monoxide.

In another aspect, the embodiments provide a method for arranging dual reactors a and B, wherein no energy input is required to perform the reaction.

In another aspect, the embodiments provide a method for controlling the equilibrium between the halogen atoms and hydrogen atoms of the reactants to form only anhydrous hydrogen halide fluids.

In another aspect, the embodiments provide a method to control carbon dioxide (prevent the formation of any carbon (soot)) in reactor B and to form only carbon monoxide.

In another aspect, the embodiments provide a method of using a dual reactor. In reactor a, no organic halide, organic chloride compound or molecular chlorine is present, and in reactor B, no molecular oxygen is present, thereby preventing the formation of dioxins and furans.

In another aspect, the embodiments provide a process for the synthesis of hydrogen halide and carbon monoxide by conversion from hydrogen, carbon dioxide and organic halides (e.g., CFCs, HCFCs, FCs, and HFCs) as reactant fluids in the presence of a catalyst in the reaction zone of reactor B.

In another aspect, the embodiments provide a method for recycling any hydrogen, carbon monoxide and/or carbon dioxide exiting from the hydrogen diffuser 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 obvious from the description, or may be learned by practice of the invention. These objects and other advantages of the present 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 method for synthesizing anhydrous hydrogen halide and carbon dioxide includes: reacting one or more organic halides with anhydrous hydrogen and anhydrous carbon dioxide to produce anhydrous carbon monoxide and one or more anhydrous hydrogen halides; and reacting this carbon monoxide with water to produce hydrogen and carbon dioxide.

In another aspect of the invention, a method for treating and/or decomposing an organohalide fluid without harmful environmental emissions comprises: reacting one or more organic halides, anhydrous hydrogen, and anhydrous carbon dioxide in a reactor B to produce carbon monoxide and one or more anhydrous hydrogen halides; collecting at least a portion of the anhydrous hydrogen halide; passing the carbon monoxide stream to a reactor A; reacting this carbon monoxide with water in reactor a to produce hydrogen and carbon dioxide; removing the water from the hydrogen and carbon dioxide to produce anhydrous hydrogen and anhydrous carbon dioxide; this hydrogen and anhydrous carbon dioxide are recycled to reactor B.

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 a flow chart arrangement for an apparatus 100 used in the present invention.

FIG. 2 is a schematic diagram of an embodiment of a dual reactor unit 1 of the plant 100 used according to the present invention.

Detailed description of the illustrated embodiments

Although the following detailed description contains many specific details for the purpose of illustration, it is to be 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 upon, the claimed method invention.

Fluids of organic halide compounds and/or refrigerants may include CFCs, HCFCs, FCs, HFCs, and HFOs (which include at least one fluid compound), such as refrigerant fluids including (but not limited to): r10 (carbon tetrachloride), R11 (trichlorofluoromethane), R12 (dichlorodifluoromethane), R13 (chlorotrifluoromethane), R14 (tetrafluoromethane), R21 (dichlorofluoromethane), R22 (chlorodifluoromethane), R23 (trifluoromethane), R30 (dichloromethane), 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-tetrafluoropropene), R1234ZE (1, 3, 3-tetrafluoropropene), R1243, 3-1243 ZF (1, 1-tetrafluoropropene), R ZF (1, 1-tetrafluoropropene), R141b (dichlorofluoroethane), R142b (chlorodifluoroethane), R143a (trifluoroethane), and the like. 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 processed according to the methods described herein. As used herein, a fluid is defined as any substance (liquid, or gas) that has low resistance to flow and tends to take the shape of its container. As used herein, organohalide refers to a molecule that includes both carbon and halogen, preferably carbon atoms among 1, 2,3, and 4 and at least one halogen atom per molecule. In certain embodiments, the organohalide and/or refrigerant includes at least one carbon atom and at least one fluorine atom.

One aspect of the present invention is a dual reactor unit in which two thermocatalytic reactions for the synthesis of anhydrous hydrogen halide and carbon dioxide can occur. Both reactions can occur in a plasma-free environment. In one exemplary embodiment, this dual reactor unit may include reactor a and reactor B. Both reactors a and B may be thermocatalytic reactor tubes. In reactor a, the thermally catalyzed reaction of carbon monoxide and water forms carbon dioxide and hydrogen. In reactor B, the thermally catalyzed reaction of the organic halide, hydrogen and carbon dioxide forms an anhydrous hydrogen halide product and a carbon monoxide recycle stream.

FIG. 1 is an illustration of an exemplary embodiment of a device or system 100. This exemplary embodiment includes a dual reactor unit 1, heat exchanger unit 2, hydrogen diffuser unit 3, a purification collector train (which 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. These 9 cells are all represented by a single digit. All accessories and/or components of each cell are represented by a two-digit number following the number representing this cell; i.e. the pipe connection of the gas inlet in the scrubber unit 9, is indicated by the numeral 902.

By following this numbering method, all elements of a unit can be described as follows. The heat transfer fluid 190 in the reactor unit 1 is brought to the operating temperature by the external heating means 126 of the heat-sink vessel 103. This heat transfer fluid 190 is circulated from the heat sink container 103 to the heat sink container 101 through the pipe joint 105 by the bi-directional flow circulator 104. Heat transfer fluid 190 may flow from heat sink 101 to bi-directional flow circulator 104 through pipe connections 110 and 109, and then on to heat sink 102 through pipe connections 108 and 107. The heat transfer fluid 190 may flow from the heat sink container 102, through the pipe connection 106, and back to the heat sink container 103. One means for thermally balancing the heat sink container 103 is through the inlet and outlet plumbing connections 120 and 121 and 122, 123 and the flow control valve 124. The dual reactor unit 1 can be filled or emptied of heat transfer fluid 190 via valve 137 and can be pressure protected via safety relief valve 138.

In our exemplary embodiment, once the operating temperature is reached, a stream 990 of carbon monoxide and water enters the reactor tubes 112 within the heat rejection vessel 101 through the pipe connection 125. This thermocatalytic reaction of carbon monoxide and water stream 990 takes place within reaction zone 111 with the aid of catalyst 180. Any excess heat of reaction may pass through the diathermic walls of the reactor tubes 112 and may be absorbed by the heat transfer fluid 190. This reaction forms a stream 191 of hydrogen and carbon dioxide, which may exit the reactor tube 112 through the pipe joint 115.

This stream 191 of hydrogen, unreacted carbon monoxide and carbon dioxide may enter this double pipe heat exchanger 210 via pipe connection 214 and exit via pipe connection 215 and flow to the hydrogen, unreacted carbon monoxide and carbon dioxide dryer unit 8 via pipe connection 802.

The dryer unit 8 may comprise a container 801 with an external heating device 806 for thermal regeneration of the drying agent 895. A stream 191 of hydrogen, unreacted carbon monoxide and carbon dioxide exits the dryer 801 through a pipe joint 804 in the form of a stream 191 of anhydrous hydrogen, anhydrous unreacted carbon monoxide and anhydrous carbon dioxide and then flows to a gas compressor 805.

After exiting gas compressor 805, this stream 191 of hydrogen, unreacted carbon monoxide and carbon dioxide may then pass through conduit connection 706 to a carbon dioxide purifier/collector unit 7. This carbon dioxide purifier/collector unit 7 may comprise a column 702, a reflux condenser 703 with a cooling device inlet 720 and outlet 721, and a collector 701 with a heating device inlet 722 and outlet 723, wherein liquid carbon dioxide 790 may be collected. Liquid carbon dioxide 790 in accumulator 701 may be diverted to container fitting 707 through conduit fitting 708 and valve 726. After purifying and collecting the carbon dioxide stream 790, such carbon dioxide stream 790 exits the purifier/collector unit 701 through the pipe fitting 708.

In an exemplary embodiment, carbon dioxide stream 790 may then be flowed and enter double pipe heat exchanger 210 through pipe fitting 212 to flow through inner pipe 211. The wall of the inner tube 211 is a heat permeable wall and transfers heat from the outside of the inner tube 211 to the inside of the inner tube 211, thereby transferring heat to the carbon dioxide stream 790 in the inner tube 211. Carbon dioxide stream 790 exits through conduit coupling 213 and flows to reactor tube 114 through conduit couplings 120, 121, 122, 123, 119, 118, and 116 and flow control valve 124. The valve 226 in the line may be used as only one backup valve.

In one embodiment, this stream 791 of hydrogen, unreacted carbon monoxide, and trace carbon dioxide may exit the top of purifier/collector unit 7 through conduit coupling 714 and flow to gas compressor 705. Stream 791 exits gas compressor 705 and flows to hydrogen diffuser 301 through conduit fitting 303.

The hydrogen diffuser 301 may comprise an external heating device 310, a hydrogen inlet chamber 312 with a palladium wall 302 and a hydrogen collector 311. The hydrogen stream 390 may exit the hydrogen accumulator of this hydrogen diffuser 301 through the pipe connection 304. The flow of the purified hydrogen stream 390 may be adjusted by the mass flow controller 308 operating the flow control valves 306 and 309. In one embodiment, purified hydrogen stream 390 flows to reactor tube 114 via conduit fittings 119, 118, and 116. Any remaining hydrogen, carbon monoxide and carbon dioxide may exit the hydrogen diffuser 301 and may flow back to the reactor tube 112 as a humidified gas through line connections 129 and 125 via line connections 319 and 315, through the gas compressor 305, check valve 318, line connection 135 and 128 within the humidifier vessel 127 with valve 316 closed and 317 open. Optionally, when this hydrogen diffuser is in regeneration mode, any remaining hydrogen, carbon monoxide and carbon dioxide may pass through conduit fittings 319 and 315, valve 316 with valve 317 closed, and diffuser exhaust 307 exiting hydrogen diffuser 301 to atmosphere. The mass controller 308 also operates the flow control valve 124 to adjust the flow of the carbon dioxide stream 790 and operates the flow control valve 209 to adjust the flow of the organic halide 290.

In one embodiment, the flow of organohalide fluid stream 290 may be flowed through a double pipe heat exchanger 201 from a source to which it is connected to a gas compressor 205 and pipe connection 203, through heat exchanger 201 and out through pipe connection 206, and then through flow control valve 209 and pipe connections 118 and 116 to reactor tube 114.

The hydrogen gas flow 390, the carbon dioxide flow 790 and the organic halide fluid flow 290 are brought together, passed through the pipe joint 116 and into the reactor tube 114. A thermocatalytic reaction of carbon dioxide, hydrogen, and organic halide fluid may occur within reaction zone 113 (possibly with the aid of catalyst 181) to form a stream 192 of anhydrous hydrogen halide and anhydrous carbon monoxide. The flow of hydrogen halide and carbon monoxide stream 192 exits the reaction tube 114 through conduit connection 117 and conduit connection 207 into the inner tube 202 of the double pipe heat exchanger 201.

The wall of the inner tube 202 may be a diathermic wall and may transfer heat from the inside of the inner tube 202 to the outside of the inner tube 202, thereby transferring heat to the organohalide fluid stream 290 in the outer tube 201. The stream 192 of hydrogen halide and carbon monoxide exits the double pipe heat exchanger 201 through pipe connections 204 and 280. In this regard, the method of operation may have at least two modes: (1) the mode of recovering the hydrogen halide product (anhydrous hydrogen fluoride and/or anhydrous hydrogen bromide and/or anhydrous hydrogen chloride) can be by opening valve 281, closing valve 282, flowing through check valve 284 and into hydrogen fluoride purifier/collector unit 4 via conduit connection 406. (2) The mode of neutralizing the hydrogen halide product (anhydrous hydrogen fluoride and/or anhydrous hydrogen bromide and/or anhydrous hydrogen chloride) can be by opening valve 282, closing valve 281, flowing through check valve 283 to gas compressor 925 and through pipe fitting 902 into scrubber vessel 901, where the hydrogen halide is neutralized and the carbon monoxide is recycled into heat sink vessel 101.

The anhydrous hydrogen fluoride purifier/collector unit 4 may include a column 402, a reflux condenser 403 with a cooling device inlet 420 and outlet 421, a collector 401 in which liquid hydrogen fluoride 490 may be collected, and a flow control valve 426. The liquid hydrogen fluoride 490 in the accumulator 401 may be diverted through the pipe connection/dip tube 408 and the valve 426 to the container connection 407. At this point, hydrogen fluoride 490 present may be removed from the stream 192 of hydrogen halide and carbon monoxide. In the case where hydrogen fluoride 490 is the only hydrogen halide present in the stream 192 of hydrogen halide and carbon monoxide, the carbon monoxide stream 491 and any remaining hydrogen fluoride 490 may exit this hydrogen fluoride purifier/collector unit 4 via conduit coupling 414 and then flow through check valve 920 and conduit coupling 902 to the neutralization scrubber unit 9 via valves 416 and 516 (bypassing the hydrogen bromide purifier/collector unit 5 and the hydrogen chloride purifier/collector unit 6 by closing valves 413, 513 and 616).

In the case where hydrogen bromide and/or hydrogen chloride is present in the stream of hydrogen halide and carbon monoxide 192, along with any remaining hydrogen fluoride 490, may exit the hydrogen fluoride purifier/collector unit 4 through conduit connection 414 and enter the hydrogen fluoride removal trap 410 through conduit connection 417, while valves 413 and 416 are closed and valve 415 is opened.

Any remaining hydrogen fluoride 490 is absorbed by the sodium fluoride 411 in the hydrogen fluoride removal trap 410. The hydrogen fluoride removal trap 410 has an external heating device 418 for desorbing the trapped hydrogen fluoride 490 and flowing the desorbed hydrogen fluoride 490 through conduit connection 412 (by simultaneously opening valve 413 and closing valves 415, 416, 513 and 616) through check valve 920 and conduit connection 902 to the neutralization scrubber unit 9 when required.

Where hydrogen bromide and/or hydrogen chloride are present in the stream 192 of hydrogen halide and carbon monoxide, they may be removed using an additional collector. In such an embodiment, the hydrogen fluoride removal trap 410 may allow hydrogen bromide and/or hydrogen chloride in the stream 192 of hydrogen halide and carbon monoxide to flow through valve 415 and gas compressor 505 to the hydrogen bromide purifier/collector unit 5 via piping connection 506. This anhydrous hydrogen bromide purifier/collector unit 5 consists of: column 502, reflux condenser 503 with cooling device inlet 520 and outlet 521, and collector 501 with heating device inlet 522, flow control valve 524, and outlet 523, where liquid hydrogen bromide 590 can be collected. Liquid hydrogen bromide 590 in the accumulator 501 may be diverted to the container junction 507 via the conduit junction 508 and the valve 526. At this point, hydrogen bromide 590 present will be removed from this stream 192 of hydrogen halide and carbon monoxide. In the case where hydrogen bromide 590 is the only hydrogen halide still present in the stream of hydrogen halide and carbon monoxide 192, this stream of hydrogen halide and carbon monoxide 192, along with any remaining hydrogen bromide 590, exits the hydrogen bromide purifier/collector unit 5 through conduit connection 514, passes through valves 513 and 516 (bypassing the hydrogen chloride purifier/collector unit 6 by closing valves 515 and 616) to the neutralization scrubber unit 9 through check valve 920 and conduit connection 902.

If hydrogen chloride is present in the stream 192 of hydrogen halide and carbon monoxide exiting from the hydrogen bromide purifier/collector unit 5 through conduit connection 514, valve 513 can be closed, with the flow passing through valve 515, gas compressor 605 and conduit connection 606. This anhydrous hydrogen chloride purifier/collector unit 6 consists of: a column 602, a reflux condenser 603 with a cooling device inlet 620 and outlet 621, and a collector 601 with a heating device inlet 622, flow control valve 624 and outlet 623, wherein liquid hydrogen chloride 690 can be collected. The liquid hydrogen chloride 690 in the accumulator 601 can be diverted to the container connection 607 via the pipe connection 608 and the valve 626. At this point, hydrogen chloride 690 will be removed from the stream 192 of hydrogen halide and carbon monoxide. The remaining stream 192 of hydrogen halide and carbon monoxide leaves the hydrogen chloride purifier/collector unit 6 through conduit connection 614, passes through valve 616, through check valve 920 and conduit connection 902 to the neutralization scrubber unit 9.

The neutralization scrubber unit 9 may include a vessel 901, piping joints 902, 908, 909, and 914, caustic solution 903, H-valves 904, 905, 906, and 907, a pump 910 for circulating, filling, and emptying the caustic solution 903 in the vessel 901, a ph meter 911, a temperature meter 912, a pressure meter 913, a gas compressor 915, and a valve 916. Carbon monoxide stream 491 and any remaining hydrogen halide fluid pass through pipe fitting 902 into neutralization scrubber unit 9, where the hydrogen halide fluid present is neutralized by caustic solution 903 circulated in vessel 901 by pump 910. The ph level of the caustic solution 903 is monitored by a ph meter 911 and the caustic solution 903 is replaced when needed by operating the H-valves 904, 905, 906, 907 and the pump 910. Carbon monoxide stream 491 leaves the neutralizer scrubber unit 9 via conduit coupling 914, then flows to the gas compressor 915 and (with valve 916 closed) to the humidifier vessel 127 via check valve 134 and conduit coupling 128.

The humidifier vessel 127 may contain water 130, may have a heating means 131, and a standard design of temperature and water level control. Carbon monoxide stream 491 may flow through water 130 in humidifier vessel 127, thereby adding water 130 to the gas stream. This carbon monoxide and water stream 990 exits humidifier vessel 127 through conduit fitting 129 and flows to reactor tube 112 through conduit fitting 125. This completes the flow chart of the apparatus 100 used in the method of the present invention.

This exemplary device 100 may include a plurality of interconnected parts, such as pipes, valves, sensors, etc., that may be constructed from: carbon steel, stainless steel, hastelloy, monel, inconel, nickel, or a similar material capable of operating at the temperatures and pressures contemplated herein. The apparatus 100 may be adapted for the thermal catalytic synthesis of anhydrous hydrogen halide fluid and carbon monoxide from organic halide fluid, anhydrous hydrogen and anhydrous carbon dioxide and for the hydrothermal catalytic synthesis of carbon dioxide from carbon monoxide and water.

FIG. 2 is a schematic representation of an exemplary two reactor unit 1 for use in the process of the present invention. This dual reactor may include the following components: a heat sink 101, a heat sink 102, a heat sink 103 for heat balancing, a thermocatalytic reactor tube 112 with a reaction zone 111 (containing catalyst 180) and a thermocatalytic reactor tube 114 with a reaction zone 113 (containing catalyst 181).

An exemplary operation of the dual reactor unit 1 may be as follows: the heat transfer fluid 190 in the dual reactor unit 1 is brought to the operating temperature by the external heating device 126 of the heat-sink vessel 103. This heat transfer fluid 190 is circulated from the heat sink container 103 to the heat sink container 101 through the pipe joint 105 by the bi-directional flow circulator 104. Heat transfer fluid 190 may flow from heat sink 101 to bi-directional flow circulator 104 through pipe connections 110 and 109, and then on to heat sink 102 through pipe connections 108 and 107. The heat transfer fluid 190 flows from the heat sink container 102 back to the heat sink container 103 through the pipe connection 106. One means of balancing this heat transfer fluid 190 is through the inlet pipe fitting 120 and the outlet pipe fitting 122.

Once the operating temperature is reached, the process in the heat sink container 101 may be as follows: a stream 990 of carbon monoxide and water enters the reactor tubes 112 in the heat rejection vessel 101 through the pipe connections 125. This thermocatalytic reaction of carbon monoxide and water stream 990 takes place within reaction zone 111 with the aid of catalyst 180. Any excess heat of reaction may pass through the diathermic walls of the reactor tubes 112 and be absorbed by the heat transfer fluid 190. This reaction forms a stream 191 of hydrogen and carbon dioxide which exits the reactor tube 112 through the pipe connection 115.

The process in the heat sink container 102 may be as follows: the hydrogen gas stream 791, the carbon dioxide stream 790 and the organic halide fluid stream 290 join together at the conduit joint 116 and flow into the reactor tube 114. This thermally catalyzed reaction of carbon dioxide, hydrogen, and the organohalide fluid occurs in reaction zone 113 with the aid of catalyst 181. Any excess heat of reaction may pass through the diathermic walls of the reactor tubes 114 and be absorbed by the heat transfer fluid 190. This reaction forms a stream 192 of anhydrous hydrogen halide and carbon monoxide which exits the reactor tube 114 through the pipe joint 117.

Any impermeable metal wall through which heat can be transferred is a kind of diathermic wall and is part of the diathermic wall in the reactor tubes 112 and 114 of the dual reactor unit 1. Any impermeable metal wall in contact with the reactants is part of the reaction zone in the reactor tubes 112 and 114 of the dual reactor unit 1. The heat generated by the exothermic reaction of water and carbon monoxide within heat sink 101 raises the temperature of the reaction zone above the reaction temperature set point. The reaction zone may be maintained at a reaction zone temperature of between about 300 ℃ and 1000 ℃.

The anhydrous hydrogen fluoride collector unit 4, the anhydrous hydrogen bromide collector unit 5, the anhydrous hydrogen chloride collector unit 6, the anhydrous carbon dioxide collector unit 7, the dryer 8 and the neutralization scrubber 9 are all standard engineering designs. 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 with water can be carried out at relatively low pressures. In certain embodiments, this reaction is carried out at a pressure in the range of 1atm to 30atm, preferably in the range of 10atm to 20 atm. In certain embodiments, this reaction is carried out at 15 atm.

In general, the reaction of the organic halide fluid, hydrogen and carbon dioxide may be carried out at relatively low pressures. In certain embodiments, this reaction is carried out at a pressure in the range of 1atm to 30atm, preferably in the range of 10atm to 20 atm. In certain embodiments, this reaction is carried out at 15 atm.

In certain embodiments, the flow rates of anhydrous carbon dioxide and anhydrous hydrogen may be adjusted depending on the flow rate of the organohalide fluid being processed. For example, based on the heat of reaction, the amount of anhydrous carbon dioxide and anhydrous hydrogen may be adjusted to operate the reactor at a level that reduces any external heating or cooling supply.

One exemplary embodiment provides a method for using a dual reactor; wherein the reactor tube 114 contains a catalyst composed of at least two metal elements. These elements are selected from: transition metals of atomic numbers 4, 5, 13, and 14, having atomic numbers from 21 to 29, 39 to 47, 57 to 71, and 72 to 79. In the presence of these catalysts, decomposition of the organohalide fluid is accomplished at reduced temperatures.

An alternative embodiment provides a method for using dual reactors; wherein the reactor tube 112 contains a catalyst composed of at least two metal elements. These elements are selected from: transition metals of atomic numbers 4, 5, 13, and 14, having 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 achieved, wherein thermodynamic equilibrium is reached at lower temperatures and pressures.

A catalyst may be used to help prevent the formation of certain harmful compounds, such as dioxins and furans, in order to speed up the reaction, reduce the reaction temperature and/or initiate these reactions. The transition metal may be used as a catalyst in either or both reactors. Exemplary metal elements for these catalysts may be selected from:

atomic number	Symbol	Name (R)
			4	Be	Beryllium (beryllium)
5	B	Boron
			13	Al	Aluminium
14	Si	Silicon
			21	Sc	Scandium (Sc)
22	Ti	Titanium (IV)
			23	V	Vanadium oxide
24	Cr	Chromium (III)
			26	Fe	Iron

Atomic number	Symbol	Name (R)
			27	Co	Cobalt
28	Ni	Nickel (II)
			29	Cu	Copper (Cu)
39	Y	Yttrium salt
			40	Zr	Zirconium
41	Nb	Niobium (Nb)
			42	Mo	Molybdenum (Mo)
44	Ru	Ruthenium (II)
			45	Rh	Rhodium
46	Pd	Palladium (II)
			47	Ag	Silver (Ag)
60	Nd	Neodymium
			66	Dy	Dysprosium
74	W	Tungsten
			77	Ir	Iridium (III)
78	Pt	Platinum (II)
			79	Au	Gold (Au)

In one embodiment, these catalysts may be prepared by using a mixture of metallic elements in the form of an alloy. Each reactor may use one or more catalysts for the reaction. In a reactor for the synthesis of carbon dioxide and hydrogen, this thermo-catalytic reaction of carbon monoxide and water (water-gas shift reaction) can 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 main components of the alloy. In reactors for the decomposition of organic halides (e.g., refrigerants and perfluorocarbon fluids), this thermocatalytic reaction can be enhanced by using a catalyst having a blend of the following elements as the major component of the alloy: nd, Nb, Dy, Fe, B, Pt, Pd, Rh, Y, Co, Ni, Cr, Mo, Al, Ir, and W.

The physical form of each of the alloys used in such blends can be produced in a variety of shapes, such as pellets, cylinders, or plates, having a thickness in the preferred range of 0.5mm to 5.0mm, per unit of 10mm²To 100mm²Surface area of preferred range of (2) and specific surface area in cm²Expressed in terms of/g. These alloys are very compact metallic materials with specific catalytic propertiesLower porosity of the agent oxide support, wherein the typical specific surface area is m²Measured in the form of/g. In general, the specific surface area of the alloy is in cm²Measured in the form of/g.

Most catalyst supports are mineral oxides and all mineral oxides react with hydrogen halide. Thus, no mineral oxide catalyst support is used in the present invention. As an alternative, the present invention may use a sintered metal alloy catalyst support. The sintered metal alloy catalyst and catalyst support are resistant to hydrogen halide corrosion and high temperatures. Flat plate particles of a metal alloy with the following characteristics were used in this experimental unit: 0.5mm to 5.0mm thick, from 10mm²To 100mm²Per unit surface area and from 20cm²G to 80cm²Specific surface area range of/g, however, a plant unit would likely be used at 10m²G to 200m²Specific surface area in the range of/g.

The catalysts prepared for the experimental work of the present invention were selected from a variety of alloys:

catalyst #1, consisting of the following elements in an alloy form: fe50.0% 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. The true density of these alloys is from 2.0g/cm³To 10g/cm³And the bulk density of the catalyst particles of this alloy is in the range of from 0.25 to 0.5 g/cc.

Catalyst #2, which consists of the following elements in an alloy form: fe63.0% wt, CR 18% wt, Mo 3% wt, Mn 2.0% wt, and Si 0.08% wt. The true density of the alloy is from 2.0g/cm³To 10g/cm³And the bulk density of these catalysts is in the range of from 0.25 to 0.5 g/cc. Other catalysts equivalent to alloy #2 were hastelloy C, inconel 600, and stainless steel 316.

Catalyst #3, consisting ofAn alloy consisting of the following elements: fe65.0 wt%, Nd 29 wt%, Dy 3.6 wt%, Nb 0.5 wt%, B1.1 wt% and Ir/Pt 0.08 wt%. The true density of the alloy is from 2.0g/cm³To 10g/cm³And the bulk density of these catalysts is in the range of from 0.25 to 0.5 g/cc.

Catalyst #4, which consists of the following elements in an alloy form: pd82.0% wt, Cu 17% wt and Pt/Rh 1.0% wt. The true density of the alloy is from 2.0g/cm³To 10g/cm³And the bulk density of these catalysts is in the range of from 0.25 to 0.5 g/cc.

The catalyst used for the anhydrous hydrogen halide synthesis (synthesized from the thermocatalytic reaction of organic halide, hydrogen and carbon dioxide) is a blend of about 50% alloy #2 and 50% alloy # 3.

A bench scale unit was built for conditioning the catalysts of the invention and the results obtained from subsequent pilot runs were at a maximum pressure of 4 atm. These tests were (1) the reaction of carbon monoxide with water and (2) the reaction of organic halides with carbon dioxide and hydrogen; a comparison was made between the improvement without catalyst or over other catalysts. Four stainless steel 316 reactor tubes were prepared, each having the following dimensions: 19mm OD, 16mm ID and 900mm (90 cm) length. Each tube having a diameter of 200mm²Flow cross-sectional area of 45,000mm²And an inner wall surface of about 180,000mm³（180cm³) The internal volume of (a).

In reactor tube #1, a stainless steel 316 sintered filter (having 15mmOD and 75mm length) was inserted into one end. 75g of a blend of catalyst #1 and catalyst #2 was then added to reactor tube #1, after which another stainless steel 316 sintered filter (having a 15mm OD and a 75mm length) was inserted into the other end of reactor tube # 1. The prepared reactor tube #1 was placed in a high temperature furnace and a passivation procedure was initiated. The passivation process was to flow 20 ml/min of hydrogen fluoride at 1000 c for three hours to form a metal fluoride layer on the effective surface area of the catalyst. This was followed by 20 cc/min of carbon dioxide flowing at 900 ℃ for one hour and again with the heater turned off for one hour. At this point, the flow of carbon dioxide is stopped and the reactor tube is open to the atmosphere.

Reactor tube #2 is identical in construction and manufacture to reactor tube # 1; however, the catalyst was changed by replacement of 75g of the blend of catalyst #2 and catalyst # 3. This passivation procedure is identical to reactor tube # 1.

Reactor tube #3 is identical in construction to reactor tube # 1; however, it does not contain a filter or catalyst; i.e. an empty tube. No passivation procedure was used for reactor tube # 3.

Reactor tube #4 is identical in construction and manufacture to reactor tube # 1; however, the catalyst was changed by replacement of 75g of catalyst # 4. No passivation procedure was used for reactor tube # 4.

In another aspect, the process may employ a two reactor train equipment arrangement in which no energy input is required.

Examples of the invention

These reactions, in which various illustrative organic halide fluids are thermally catalyzed to form anhydrous hydrogen halide and carbon monoxide, represent typical exothermic and endothermic reactions. These examples show that these exothermic reactions (having higher energy values than the endothermic reactions) have the benefit that the excess energy of such exothermic reactions balances the heat sensitive reactant components. The following are the heat of formation and heat capacity tables for these examples:

example 1-reactor tube #4 was heated toA temperature of 850 ℃. The CO flow meter was set to flow 22 cc/min through a water humidifier in which CO was mixed with 18 mg/min H₂And O is converged. Reacting CO and H₂The O flows into the reaction zone to contact the catalyst blend and the reaction of the CO with H2O forms CO₂And H₂. Within a nine minute collection time, 390cc of gaseous product with a column pressure of 10psig was collected in one sample column (with an empty volume of 234 cc). The gaseous product was analyzed by a gas chromatograph, where the only compounds detected were 50% CO by moles, 25% CO2 by moles, and 25% H by moles₂。

CO+H₂O→C0₂+H₂+ΔHR

-26.00–58.00→-94.00+0.00

ΔH_r=84.00ΔH_p=-94.00

ΔH_R25℃=ΔH_p-ΔHr=-94.00+84.00=-10Kcal/mol

CP_r=+7.21=+8.54=+15.75Cal/mol X℃

CP_p=+10.77+7.00=+17.77Cal/mol X℃

ΔCP=CP_p–CP_r=(17.75-15.75)=2X800=1600=1.6Kcal/mol

ΔH_R800℃=-10.00Kcal/mol+1.60=-8.40Kcal/mol

Exothermic reaction

Example 2-reactor tube #1 was heated to a temperature of 850 ℃. Three flow meters were calibrated to (1) 22 cc/min carbon tetrafluoride, (2) 22 cc/min carbon dioxide and (3) 44 cc/min hydrogen. The exhaust gas was examined with an electronic organohalide detector and no carbon tetrafluoride was detected. The product, which was liquid anhydrous hydrogen fluoride, was collected into a sample cartridge at 29psig pressure for eight minutes. The partial pressure of anhydrous hydrogen fluoride is 22psia and the partial pressure of carbon monoxide is 22psia, the total pressure is 44psia =29 psig.

CF4+2H₂+C0₂+→2CO+4HF+ΔH_R

-220.50+0.00-94.00→-26.40–64.00

ΔH_r=-220.50-94.00=314.5

ΔH_p=-2(26.40)-4X64.00=-308.8

ΔH_R25℃=-308.8+314.50=+5.700Kcal/mol

CP_r=+14.56+2(7.00)+10.77=+39.33Cal/mol X℃

CP_p=+2(7.21)+4(6.94)=+42.18Cal/mol X℃

ΔCP=2.85X800=+2.28Kcal/mol

ΔH_R800℃=+5.70+2.28=+7.98Kcal/mol

Endothermic reaction

Example 3-reactor tube #1 was heated to a temperature of 850 ℃. The three flowmeters were calibrated to (1) dichlorodifluoromethane at 22 cc/min, (2) carbon dioxide at 22 cc/min and (3) hydrogen at 44 cc/min. The exhaust gas was checked with an electronic organic halide detector and dichlorodifluoromethane was not detected. The product, which was liquid anhydrous hydrogen fluoride and liquid anhydrous hydrogen chloride, was collected into a sample column at a pressure of 54psi +/-1psi for eight minutes.

CClF₂+2H₂+C0₂+→2CO+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_R25℃=-224.8+208.20=-16.60Kcal/mol

CP_r=+17.54+14.0+10.77=+42.31Cal/mol X℃

CP_p=+2(7.21+7.06+6.94)=+42.4Cal/mol X℃

ΔCP=(42.42–42.31)X800=+0.00Kcal/mol

ΔH_R800℃=-16.60Kcal/mol

Exothermic reaction

Example 4-reactor tube #2 was heated to a temperature of 850 ℃. The three flow meters were calibrated to (1) chlorodifluoromethane at 22 cc/min, (2) carbon dioxide at 22 cc/min and (3) hydrogen at 22 cc/min. The exhaust gas was checked with an electronic organic halide detector and no chlorodifluoromethane was detected. The product, which was liquid anhydrous hydrogen fluoride and liquid anhydrous hydrogen chloride, was collected into a sample column at a pressure of 53psi +/-1psi for eight minutes.

CHCl₂F₂+H₂+C0₂+→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_R25℃=-202.8+207.20=+4.20Kcal/mol

CP_r=+13.28+10.77+7.0=+31.05Cal/mol X℃

CP_p=+2(7.21)+2(6.94)+7.06=+35.36Cal/mol X℃

ΔCP=35.36–31.05=4.31X800=3,438.00Cal/mol

ΔCP=3,438.00Cal/mol/1000=3.44Kcal/mol

ΔH_R800℃=+4.20+3.45=+7.65Kcal/mol

Endothermic reaction

Example 5-reactor tube #2 was heated to a temperature of 850 ℃. The three flow meters were calibrated to (1) 22 cc/min tetrafluoroethane, (2) 44 cc/min carbon dioxide and (3) 22 cc/min hydrogen. The exhaust gas was checked with an electronic organic halide detector and no tetrafluoroethane was detected. The product, which is liquid anhydrous hydrogen fluoride, was collected into a sample column at a pressure of 64psi +/-2psi for eight minutes.

C₂H₂F₄+H₂+2C0₂+→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_R25℃=-361.60+394.70=+33.00Kcal/mol

CP_r=-(34.57+21.54+7.0)=-63.11Cal/mol X℃

CP_p=+4(7.21)+4(6.94)=+56.60Cal/mol X℃

ΔCP=-63.11–+56.60=-6.51X800=-5,208.00Kcal/mol

ΔCP=-5,208.00/1000=-5.21Kcal/mol

ΔH_R800℃=+33.00-5.20=27.80Kcal/mol

Endothermic reaction

Example 6-reactor tube #3, in the absence of catalyst, was heated to a temperature of 850 ℃. Three flow meters were calibrated to (1) 22 cc/min carbon tetrafluoride, (2) 22 cc/min carbon dioxide and (3) 44 cc/min hydrogen. The exhaust gas is examined with an electronic organohalide detector and carbon tetrafluoride is detected. The temperature was raised to 950 ℃, the exhaust gas was examined with an organic halide detector of this electron, and carbon tetrafluoride was detected. The temperature was raised to 1050 ℃, the exhaust gas was examined with an organic halide detector of this electron, and carbon tetrafluoride was detected. The temperature was raised to 1150 ℃, the exhaust gas was examined with an organic halide detector of this electron, and no carbon tetrafluoride was detected. Example 6 demonstrates that the catalyst of the invention reduces the temperature required for complete decomposition of perfluorocarbon (carbon tetrafluoride) by about 300 ℃.

The conclusion from the results of these examples is: (1) excess hydrogen and carbon dioxide do not affect the organic halide (e.g., CFC, HCFC, FC and HFC) decomposition reaction and are beneficial in preventing the generation of soot, (2) excess water does not have any negative effect on the water-gas shift reaction in the carbon monoxide and water reaction, (3) the exclusion of molecular oxygen in this process prevents the formation of unwanted compounds, especially when chloride or chlorine is present in the reaction zone, and (4) the temperature required for the catalyst of the present invention to completely decompose the organic halide is reduced by about 300 ℃.

Although the present invention has been described in detail, it should be understood that various changes, substitutions, and alterations can be made hereto without departing from the spirit and scope of the invention. Accordingly, the scope of the 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.

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 the 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 this invention pertains, except where these references contradict the statements made herein.

Claims (19)

1. A process for synthesizing anhydrous hydrogen halide and carbon dioxide, the process comprising:

reacting one or more organic halides with anhydrous hydrogen and anhydrous carbon dioxide to produce anhydrous carbon monoxide and one or more anhydrous hydrogen halides without producing carbon; and is

The carbon monoxide is reacted with water to produce hydrogen and carbon dioxide.

2. The process of claim 1, wherein reacting carbon monoxide with water is carried out in a first reactor and reacting the organic halide with hydrogen and carbon dioxide is carried out in a second reactor.

3. The method of claim 1, wherein reacting the one or more organic halides with anhydrous hydrogen and anhydrous carbon dioxide is performed in an environment free of molecular oxygen and with carbon dioxide as the only oxidant.

4. The method of claim 1, further comprising:

using a catalyst for the reaction of the one or more organic halides with anhydrous hydrogen and anhydrous carbon dioxide;

adding water to the anhydrous carbon monoxide by flowing the anhydrous carbon monoxide through a humidifier prior to reacting the carbon monoxide with water; and is

A catalyst is used for the reaction of the carbon monoxide with water.

5. The method of claim 1, further comprising flowing the hydrogen and carbon dioxide produced from the reaction of the carbon monoxide and water through a dryer to obtain anhydrous hydrogen and anhydrous carbon dioxide.

6. The method of claim 5, further comprising using anhydrous hydrogen and anhydrous carbon dioxide from the dryer as reactants in the step of reacting one or more organic halides with anhydrous hydrogen and anhydrous carbon dioxide to produce anhydrous carbon monoxide and one or more anhydrous hydrogen halides.

7. The method of claim 5, further comprising separating the anhydrous hydrogen from the anhydrous carbon dioxide and flowing the separated anhydrous hydrogen through a diffuser to produce pure hydrogen.

8. The method of claim 7, wherein the separating anhydrous hydrogen from anhydrous carbon dioxide is performed using a collector unit.

9. The method of claim 8, further comprising the step of contacting the anhydrous hydrogen from the diffuser with the anhydrous carbon dioxide from the collector unit and with the one or more organic halides for reacting one or more organic halides with anhydrous hydrogen and anhydrous carbon dioxide to produce anhydrous carbon monoxide and one or more anhydrous hydrogen halides.

10. The method of claim 1, further comprising flowing the hydrogen produced from the reaction of water and carbon monoxide through a diffuser membrane.

11. The method of claim 10, further comprising contacting the hydrogen gas that does not flow through the diffuser membrane with the carbon monoxide and water to produce hydrogen and carbon dioxide when reacting the carbon monoxide and water.

12. The method of claim 1, wherein reacting the carbon monoxide with water to produce hydrogen and carbon dioxide is performed at a temperature range of 300 ℃ to 1000 ℃ and a pressure range of 1 to 30 atm.

13. The method of claim 1, further comprising:

separating the hydrogen from the carbon dioxide using a first collector unit that collects the carbon dioxide; and is

Separating the anhydrous hydrogen halide using a series of second collector units, wherein the series of second collector units comprises one or more collector units, each collector unit for collecting one type of hydrogen halide.

14. The method of claim 13, further comprising:

flowing the hydrogen and carbon dioxide through a dryer to produce anhydrous hydrogen and anhydrous carbon dioxide prior to separating the hydrogen from the carbon dioxide; and is

After separating the hydrogen from the carbon dioxide, the anhydrous hydrogen is flowed into a hydrogen diffuser along with trace amounts of other impurities.

15. The method of claim 13, wherein the one or more anhydrous hydrogen halides comprise one or more selected from the group consisting of anhydrous hydrogen fluoride, anhydrous hydrogen bromide, and anhydrous hydrogen chloride; and is

Wherein the second series of collector units comprises a collector unit for each type of anhydrous hydrogen halide included in the one or more anhydrous hydrogen halides.

16. The method of claim 1, further comprising neutralizing the one or more anhydrous hydrogen halides by flowing the one or more anhydrous hydrogen halides through a caustic solution.

17. The method of claim 1, further comprising:

performing the two reaction steps in a dual reactor unit comprising a first thermocatalytic reactor tube and a second thermocatalytic reactor tube, wherein the carbon monoxide is produced in the second thermocatalytic reactor tube, and wherein the carbon dioxide and hydrogen are produced in the first thermocatalytic reactor tube;

recycling the carbon monoxide produced in the second thermocatalytic reactor tube into the first thermocatalytic reactor tube as reactants for producing the carbon dioxide and hydrogen; and is

Recycling at least a portion of the carbon dioxide and hydrogen from the first thermocatalytic reactor tube into the second thermocatalytic reactor tube to react with the one or more organic halides.

18. A method for treating and/or decomposing an organohalide fluid without harmful environmental emissions, the method comprising:

reacting one or more organic halides, anhydrous hydrogen, and anhydrous carbon dioxide in a reactor B to produce carbon monoxide and one or more anhydrous hydrogen halides without producing carbon;

collecting at least a portion of the anhydrous hydrogen halide;

flowing the carbon monoxide into a reactor a;

reacting the carbon monoxide with water in reactor a to produce hydrogen and carbon dioxide;

removing water from the hydrogen and carbon dioxide to produce anhydrous hydrogen and anhydrous carbon dioxide;

the anhydrous hydrogen and anhydrous carbon dioxide are recycled into reactor B.

19. The method of claim 18, further comprising collecting at least some of the anhydrous carbon dioxide prior to recycling the anhydrous carbon dioxide into the reactor B.