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Overall permreactor-separator process designs and effective permreactor designs with increased mass and heat transfer, reactant conversion, product yield and optional recycling for processing methane, hydrocarbons, alcohols, carbon monoxide, natural gas, acidic natural gas, cool gas, biomass gas, an

Overall permreactor-separator process designs and effective permreactor designs with increased mass and heat transfer, reactant conversion, product yield and optional recycling for processing methane, hydrocarbons, alcohols, carbon monoxide, natural gas, acidic natural gas, cool gas, biomass gas, and mixtures of hydrocarbons with carbon dioxide, based on the reforming reactions of these feedstocks with steam and carbon dioxide and the dehydrogenation reactions of saturated hydrocarbons. Final exit streams from these gas phase processors contain pure hydrogen, hydrogen and carbon monoxide mixture, hydrogen and carbon dioxide mixture, and can be used as a direct feed in molten carbonate, solid oxide, proton exchange membrane, alkaline, phosphoric acid and other types of hydrogen driven fuel cells. Same final exit processed streams can be alternatively used for direct chemical synthesis such as methanol, for hydrogenations and hydrogen based reduction reactions such as those of unsaturated hydrocarbons to paraffins, and as feed in power generation systems such as gas turbines and gas engines.

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1. A process for conducting catalytic reforming of hydrocarbons and alcohols with steam and carbon dioxide for the production of pure hydrogen which includes the use of:a far outer impermeable hollow tubular cylinder nesting two more concentric permeable tubular cylinders, a next inner and a most in

1. A process for conducting catalytic reforming of hydrocarbons and alcohols with steam and carbon dioxide for the production of pure hydrogen which includes the use of:a far outer impermeable hollow tubular cylinder nesting two more concentric permeable tubular cylinders, a next inner and a most inner one, having the most inner permeable cylinder nested within the next inner permeable cylinder thus defining three different annular zones for the catalytic reforming reactions of said components, including next inner membrane and most inner membrane, with the most inner permeable cylinder filled with a reforming catalyst in pellet or particle from which comes in contact with the reactant hydrocarbons, alcohols, steam and carbon dioxide, and including gas heating tubes located along the most inner axis for heating the catalyst to the temperature of said reforming reaction, with the hydrogen product coming from the reforming reactions between hydrocarbons or alcohols with steam and carbon dioxide continuously removed via permeation along the most inner membrane, wherein most inner membrane is made from an inorganic or composite material, with the remaining reaction species partially permeating as well via the most inner membrane, with the permeated species diluted by an inert carrier gas flowing along the next inner annular zone, with hydrogen only continuously removed via permeation along the next inner membrane and continuously withdrawn as well out of the most inner catalytic zone causing for the continuous equilibrium shift of said catalytic reforming reactions evolving within this zone, with next inner membrane made from a metal or non-porous inorganic material permeable only to hydrogen, and with pure hydrogen permeating through the next inner membrane and withdrawn along the far outer cylindrical zone. 2. The process of claim 1 wherein the most inner membrane is made from one or more materials selected from the group consisting of alumina, silica, titania, yttria, zirconia, and the next inner membrane made from one or more materials selected from the group consisting of aluminum carbide and nitride, silicon carbide and nitride, titanium carbide and nitride, zirconium carbide and nitride, tantalum carbide and nitride, palladium, silver, copper, zinc, tantalum, vanadium, tungsten.3. The process of claim 1 wherein the feed hydrocarbon or alcohol is a single component or a mixture of components selected from the group consisting of methane, ethane, propane, n-butane, i-butane, methanol, ethanol, propanol, butanol, naphtha, gasoline, natural gas, coal gas containing methane, landfill gas containing methane, flue gas containing methane, biomass and sewage gas containing methane.4. The process of claim 1 wherein the combined feed hydrocarbon and carbon dioxide gas mixture is selected from the group consisting of a CH4 and CO2 mixture, acidic natural gas containing CH4 and CO2, coal gas containing CH4 and CO2 landfill gas containing CH4 and CO2, biomass and sewage gas containing CH4 and CO2, flue and waste gas mixture containing CH4 and CO2.5. The process of claim 1 wherein the reject exit stream from the most inner and next inner annular zones is subject to a condensation step which removes steam from the said reject exit stream, and subsequently passed through a membrane permeator wherein the hydrogen and carbon dioxide gases are separated by permeation via a polymer or composite membrane and the non permeated hydrocarbons, alcohols, and carbon monoxide exit from the non-permeate side of the permeator as a reject stream.6. The process of claim 5, wherein the reject stream from the permeator containing each one or a mixture of unreacted hydrocarbons, alcohols, and carbon monoxide is fed in a consecutive steam reforming reaction zone for additional production of hydrogen and carbon dioxide gas products.7. The process of claim 5, wherein the reject stream from the permeator containing each one or a mixture of unreacted hydrocarbons, alcohols, and carbon monoxide is recycled into the initial catalytic most inner reforming zone for continuous reforming reaction.8. The process of claim 1, wherein the reject exit streams from the most inner and next inner annular zones have the contained steam required by condensation and subsequently passed through a cryogenic separator, wherein the contained in stream hydrogen and carbon monoxide are separated as gases, while the hydrocarbons, alcohols, and carbon dioxide are separated as condensed liquids and after heating are recycled back into the inlet of the preceding most inner catalytic reforming zone, wherein the separated hydrogen and carbon monoxide product mixture coming from the cryogenic separator is used in following listed consecutive applications; for fuel gas in solid oxide and molten carbonate fuel cells, for gas in gas turbines and gas engines.9. The process of claim 8 wherein the reactant hydrocarbon is methane and the reactant alcohol is methanol.10. The process of claim 8, wherein a part of the separated liquefied hydrocarbons, alcohols, and carbon dioxide components from the cryogenic separator are mixed with steam and fed into a subsequent reforming reaction zone for additional production of hydrogen and carbon monoxide.11. The process of claim 1, wherein the reject exit stream consists of hydrogen, carbon monoxide and unreacted steam and enters as a fuel gas feed into a solid oxide or molten carbonate fuel cell for continuous generation of electricity, wherein part or all of the permeate hydrogen coming out of the preceding membrane zone is fed as well in the fuel cell anode inlet providing for the supplementary hydrogen fuel feed.12. The process of claim 11 wherein the flue hot gas emitted by the fuel cell is used for at least partial heating of the preceding most inner catalytic reaction zone.13. The process of claim 16 wherein the flue hot gas emitted by the fuel cell comprises of steam and carbon dioxide and is recycled in the inlet of the preceding most inner catalytic zone for use as a reactant in the reforming reaction.14. The process of claim 1 wherein the permeate hydrogen from the membrane zone is used as fuel feed in a consecutive fuel cell for continuous generation of electricity, wherein the fuel cell is one of the listed types: solid oxide, molten carbonate, proton exchange membrane, phosphoric acid, alkaline.15. The process of claim 14 wherein the flue hot gas emitted by the fuel cell is used for at least partial heating of the preceding most inner catalytic zone.16. The process of claim 14 wherein the flue hot gas, emitted by the solid oxide and molten carbonate fuel cell, which contains steam and carbon dioxide, is recycled in the inlet of the preceding most inner catalytic zone for use as a reactant in the reforming reaction.17. The process of claim 14, wherein the fuel cell is of a cylindrical shape and its fuel anode encloses the cylindrical permeator by receiving and consuming directly the permeate hydrogen gas as fuel, wherein the flue hot gas emitted by the fuel cell is used for at least partial heating of the enclosed most inner catalytic reforming zone.18. The process of claim 1, wherein the reject exit stream rich in hydrogen and carbon monoxide after steam condensation is used as fuel feed in a gas engine or g gas turbine for continuous generation of electricity, wherein part or all of the permeate hydrogen coming out of the preceding membrane zone is fed as well in the engine or turbine providing for the supplementary hydrogen fuel.19. A process for conducting catalytic reforming of hydrocarbons and alcohols with steam and carbon dioxide for production of pure hydrogen which includes the use of:a far outer impermeable hollow tubular cylinder nesting two more concentric permeable tubular cylinders, a next-inner and a most-inner one, having the most inner permeable cylinder nested within the next inner permeable cylinder thus defining three different annular zones for the catalytic reforming reactions of said components, including next inner membrane and most inner membrane, with the annular space between the far outer and next-inner cylinders filled with a reforming catalyst in pellet or particle form which comes in contact with the reactant hydrocarbons, alcohols, steam and carbon dioxide, with the hydrogen product coming from the reforming reactions between hydrocarbons or alcohols with steam and carbon dioxide continuously removed via permeation along the next-inner membrane wherein next-inner membrane is made from an inorganic or composite material, with the remaining reaction species partially permeating as well via the next inner membrane, with the permeated species diluted by an inert carrier gas flowing along the next inner annular zone, with hydrogen only continuously removed via permeation along the most inner membrane causing for the continuous withdrawal of hydrogen out of the far outer catalytic zone and for the continuous equilibrium shift of said catalytic reforming reactions evolving within this zone, with said most inner membrane made from a metal or non-porous inorganic material permeable only to hydrogen, and with the permeated pure hydrogen withdrawn along the most inner cylindrical zone. 20. The process of claim 19 wherein the next inner membrane is made from one or more materials selected from the group consisting of alumina, silica, titania, zirconia, yttria, and the most inner membrane made from one or more materials selected from the group consisting of aluminum carbide and nitride, silicon carbide and nitride, titanium carbide and nitride, zironcium carbide and nitride, tantalum carbide and nitride, palladium, silver copper, zinc, tantalum, vanadium, tungsten.21. The process of claim 19 wherein the feed hydrocarbon or alcohol is a single component or a mixture of components selected from the group consisting of methane, ethane, propane, n-butane, i-butane, methanol, ethanol, propanol, butanol, naphtha, gasoline, natural gas, coal gas containing methane, landfill gas containing methane, flue or waste gas containing methane, biomass and sewage gas containing methane.22. The process of claim 19 wherein the combined feed hydrocarbon and carbon dioxide gas mixture is selected from the group consisting of a CH4 and CO2 mixture, acidic natural gas containing CH4 and CO2, coal gas containing CH4 and CO2, landfill gas containing CH4 and CO2, biomass and sewage gas containing CH4 and CO2, flue and waste gas mixture containing CH4 and CO2.23. The process of claim 19, wherein the reject exit streams from the far outer and next inner annular zones have the contained steam removed by condensation, and subsequently passed through a membrane permeator, wherein the contained in stream hydrogen and carbon dioxide are separated by permeation via a polymer or composite membrane and the non permeated hydrocarbons, alcohols, and carbon monoxide exit from the non-permeate side of the permeator is a reject stream, wherein the separated hydrogen and carbon dioxide product mixture is used as a combined fuel-oxidant feed in a molten carbonic fact cell.24. The process of claim 23, wherein the reject stream from the permeator containing each one or a mixture of unreacted hydrocarbons, alcohols, and carbon monoxide is fed in a consecutive steam reforming reaction zone for additional production of hydrogen and carbon dioxide gas products.25. The process of claim 23, wherein the reject stream from the permeator containing each one or a mixture of unreacted hydrocarbons, alcohols, and carbon monoxide is recycled into the preceding catalytic far outer reforming zone for continuous reforming reaction.26. The process of claim 19, wherein the reject exit streams from the far outer and next inner annular zones have the contained steam removed by condensation and subsequently passed through a cryogenic separator wherein the contained in stream hydrogen and carbon monoxide are separated as gases while the hydrocarbons, alcohols, and carbon dioxide are separated as condensed liquids and after heating are recycled back into the inlet of the preceding for outer catalytic reforming zone, wherein the separated hydrogen and carbon monoxide product mixture containing from the cryogenic separator is used in the following listed consecutive applications: for fuel gas in solid oxide and molten carbonate fuel cells, for fuel gas in gas turbines and gas engines.27. The process of claim 26 wherein the reactant hydrocarbon is methane and the reactant alcohol is methanol.28. The process of claim 26, wherein part of the separated liquefied hydrocarbons, alcohols, and carbon dioxide components from the cryogenic separator is mixed with steam and fed into a consecutive reforming reaction zone for additional production of hydrogen and carbon monoxide which is used in the following listed consecutive applications: for fuel gas in solid oxide and molten carbonate fuel cells, for fuel gas in gas turbines and gas engines.29. The process of claim 19, wherein the reject exit stream consists of hydrogen, carbon monoxide, and unreacted steam and enters as a fuel gas feed into a solid oxide or molten carbonate fuel cell for continuous generation of electricity, wherein part or all of the permeate hydrogen coming out of the preceding membrane zone is fed as well in the fuel cell anode inlet providing for supplementary hydrogen fuel feed.30. The process of claim 29 wherein the flue hot gas emitted by the fuel cell is used for at least partial heating of the preceding far outer catalytic reaction zone.31. The process of claim 29 wherein the flue hot gas emitted by the fuel cell containing steam and carbon dioxide, is recycled in the inlet of the preceding far outer catalytic zone for use as a reactant in the reforming reaction.32. The process of claim 19 wherein the permeate hydrogen from the membrane zone is used as fuel feed in a consecutive fuel cell for continuous generation of electricity, wherein the fuel cell is one of the listed types: solid oxide, molten carbonate, proton exchange membrane, phosphoric acid alkaline.33. The process of claim 32 wherein the flue hot gas emitted by the fuel cell is used for at least partial heating of the preceding far outer catalytic zone.34. The process of claim 32 wherein the flue hot gas containing steam and carbon dioxide, emitted by the solid oxide and molten carbonate fuel cell, is recycled in the inlet of the preceding far outer catalytic zone for use as a reactant in the reforming reaction.35. The process of claim 32, wherein the fuel cell is of cylindrical shape and its fuel anode encloses the cylindrical permeator by receiving and consuming directly the permeate hydrogen gas as fuel, wherein the flue hot gas emitted by the fuel cell is used for at least partial heating of the enclosed far outer catalytic reforming zone.36. The process of claim 32, wherein the reject exit stream rich in hydrogen and carbon monoxide after steam condensation is used as fuel feed in a gas engine or a gas turbine for continuous generation of electricity, wherein part or all of the permeate hydrogen coming out of the preceding membrane zone is fed as well in the engine or turbine providing for the supplementary hydrogen fuel.37. A process for conducting catalytic hydrocarbon reforming with carbon dioxide, for production of pure hydrogen and carbon dioxide which includes the use of:a far outer impermeable hollow tubular cylinder nesting two more concentric permeable tubular cylinders, a next-inner and a most-inner one, having the most inner permeable cylinder nested within the next inner permeable cylinder thus defining three different annular zones for the catalytic reforming reactions of said components including next inner membrane and most inner membrane, with the annular space between the far outer and next-inner cylinders filled with a reforming catalyst in pellet or particle form which comes in contact with the reactant hydrocarbons and carbon dioxide, with hydrogen and carbon dioxide coming from said reforming reactions continuously removed via permeation along the next-inner membrane wherein next-inner membrane is made from an inorganic or composite material, with the remaining reaction species partially permeating as well via the next inner membrane and with the permeated species diluted by an inert carrier gas flowing along the next inner annular zone, with said hydrogen and carbon dioxide species continuously removed via permeation along the most inner membrane, causing for the continuous withdrawal of hydrogen out of the far outer catalytic zone and for the continuous equilibrium shift of said catalytic reforming reactions evolving within this zone, with said most inner membrane made from a polymer or inorganic material which is permeable to both hydrogen and carbon dioxide species, with the permeated binary hydrogen-carbon dioxide mixture withdrawn by flowing along the most inner cylindrical zone. 38. The process of claim 37 wherein the next inner membrane is made from one or more materials selected from the group consisting of alumina, silica, titania, zirconia, yttria, and the most inner membrane made from one or more materials selected from the group consisting of alumina, silica, titania, zirconia, yttria, polyimides, polycarbonates, polybenziimidazoles, polyphospazenes, polysulfones.39. The process of claim 37 wherein the feed hydrocarbon or alcohol is a single component or a mixture of components selected from the group consisting of methane, ethane, propane, n-butane, i-butane, methanol, ethanol, propanol, butanol, naphtha, gasoline, natural gas, coal gas containing methane, landfill gas containing methane, flue and waste gas containing methane, biomass and sewage gas containing methane.40. The process of claim 37 wherein the combined feed hydrocarbon and carbon dioxide gas mixture is selected from the group consisting of a CH4 and CO2 mixture, acidic natural gas containing CH4 and CO2, coal gas containing CH4 and CO2, landfill gas containing CH4 and CO2, biomass and sewage gas containing CH4 and CO2, flue and waste gas mixtures containing CH4 and CO2.41. The process of claim 37 wherein the combined permeate from the membrane, hydrogen and carbon dioxide gas mixture is consumed as fuel-oxidant in a consecutive molten carbonate fuel cell.42. The process of claim 41 wherein the flue hot gas emitted by the molten carbonate fuel cell is used for at least partial heating of the preceding far outer catalytic reaction zone.43. The process of claim 41 wherein flue hot gas emitted by the molten carbonate fuel cell containing carbon dioxide, is recycled in the inlet of the preceding far outer catalytic zone for use as reactant in the reforming reaction.44. The process of claim 41, wherein the molten carbonate fuel cell is of a cylindrical shape and its fuel anode encloses the cylindrical permeator by receiving and consuming directly as fuel the permeate hydrogen-carbon dioxide mixture, wherein the flux hot gas emitted by the fuel cell is used for at least partial heating of the enclosed far outer catalytic reforming zone.45. The process of claim 37 wherein the reject exit-stream consisting of hydrogen and carbon monoxide enters as fuel gas feed in the anode of a consecutive solid oxide or molten carbonate fuel cell for continuous generation of electricity.46. The process of claim 45 wherein the flue hot gas emitted by the solid or molten carbonate fuel cell is used for at least partial heating of the preceding far outer catalytic zone.47. The process of claim 45 wherein the flue hot gas emitted by the solid oxide or molten carbonate fuel cell containing current dioxide, to be is recycled in the inlet of the preceding far outer catalytic zone for use as reactant in the reforming reaction.48. The process of claim 37, wherein the reject exit stream rich in hydrogen and carbon monoxide after stream condensation is used as fuel feed in a gas engine or a gas turbine for continuous generation of electricity, wherein part or all of the permeate hydrogen and carbon dioxide coming out of the preceding membrane zone is fed as well in the engine or turbine in order to provide for supplementary hydrogen fuel.