WO2014200601A9

WO2014200601A9 - Engine exhaust manifold endothermic reactor, and associated systems and methods

Info

Publication number: WO2014200601A9
Application number: PCT/US2014/030593
Authority: WO
Inventors: Roy Edward Mcalister
Original assignee: Advanced Green Technologies, Llc
Priority date: 2013-03-15
Filing date: 2014-03-17
Publication date: 2015-09-24
Also published as: US20140260195A1; WO2014200601A3; WO2014200601A2

Abstract

Engine exhaust manifold endothermic reactors, and associated systems and methods are disclosed herein. A system in accordance with a particular embodiment of the technology includes an engine having a combustion region and an exhaust passage coupled to the engine to receive exhaust products from the combustion region. The exhaust passage can at least partially enclose a passage interior region. The system can further include a reactor having an external heat transfer surface positioned in the passage interior region, and a reaction zone positioned in a region enclosed by the external heat transfer surface. A hydrogen donor source can be coupled in fluid communication with the reaction zone of the reactor vessel via a donor passage, and a product passage can be coupled to the reaction zone to receive a reaction product from the reaction zone.

Description

ENGINE EXHAUST MANIFOLD ENDOTHERM IC REACTOR, AND

ASSOCIATED SYSTEMS AND METHODS

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Non-Provisional Patent Application No. 13/832,740, filed March 15, 2013, the disclosure of which is incorporated herein by reference in its entirety.

TECHNICAL FIELD

[0002] The present technology is directed generally to engine exhaust manifold endothermic reactors, and associated systems and methods. Such systems and methods can include endothermic reactors positioned within an exhaust manifold to receive heat for conducting endothermic reactions.

BACKGROUND

[0003] Renewable energy sources such as solar, wind, wave, falling water, and biomass-based sources have tremendous potential as significant energy sources, but currently suffer from a variety of problems that prohibit widespread adoption. For example, using renewable energy sources in the production of electricity is dependent on the availability of the sources, which can be intermittent. Solar energy is limited by the sun's availability (i.e., daytime only), wind energy is limited by the variability of wind, falling water energy is limited by droughts, and biomass energy is limited by seasonal variances, among other things. As a result of these and other factors, much of the energy from renewable sources, captured or not captured, tends to be wasted.

[0004] The foregoing inefficiencies associated with capturing and saving energy limit the growth of renewable energy sources into viable energy providers for many regions of the world, because they often lead to high costs of producing energy. Thus, the world continues to rely on oil and other fossil fuels as major energy sources because, at least in part, government subsidies and other programs supporting technology developments associated with fossil fuels make it deceptively convenient and seemingly inexpensive to use such fuels. At the same time, the replacement cost for the expended resources, and the costs of environment degradation, health impacts, and other by-products of fossil fuel use are not included in the purchase price of the energy resulting from these fuels.

[0005] In light of the foregoing and other drawbacks currently associated with sustainably producing renewable resources, there remains a need for improving the efficiencies and commercial viabilities of producing products and fuels with such resources.

BRIEF DESCRIPTION OF THE DRAWINGS

[0006] Figure 1 is a partially schematic, partially cross-sectional illustration of a reactor system that receives energy from a combustion engine in accordance with an embodiment of the presently disclosed technology.

[0007] Figure 2 is a partially schematic, partially cross-sectional illustration of a reactor system that receives energy from a combustion engine and returns reaction products to the engine in accordance with an embodiment of the presently disclosed technology.

[0008] Figure 3 is a partially schematic, partially cross-sectional illustration of a reactor system that includes a reactor vessel positioned within an exhaust manifold in accordance with another embodiment of the presently disclosed technology.

[0009] Figure 4A is a partially schematic, cross-sectional illustration of a representative reactor vessel suitable for positioning within an exhaust manifold in the manner shown in Figure 3.

[0010] Figure 4B is a partially schematic, cross-sectional illustration of another representative reactor vessel suitable for positioning within an exhaust manifold in the manner shown in Figure 3.

[0011] Figure 4C is a greatly magnified schematic illustration of a section of a separator assembly suitable for use with the reactor vessel shown in Figure 4B.

[0012] Figure 4D is a schematic illustration of a section of a separator assembly suitable for use with the reactor vessel shown in Figure 4B. [0013] Figure 4E is a schematic illustration of a section of a separator assembly suitable for use with the reactor vessel shown in Figure 4B.

[0014] Figure 4F is a schematic illustration of a section of a separator assembly suitable for use with the reactor vessel shown in Figure 4B.

[0015] Figure 5 is a partially schematic, cross-sectional illustration of a representative reactor vessel of the type shown in Figures 1 and 2.

[0016] Figure 6 is a partially schematic, cross-sectional illustration of a representative reactor vessel configured in accordance with another embodiment of the present technology.

[0017] Figure 7 is a partially schematic, cut-away illustration of a portion of a reactor having transmissive surfaces positioned annularly in accordance with an embodiment of the disclosed technology.

[0018] Figure 8 is a partially schematic, partially cross-sectional illustration of a system having a reactor with a re-radiation component in accordance with an embodiment of the presently disclosed technology.

[0019] Figure 9 illustrates absorption characteristics as a function of wavelength for a representative reactant and re-radiation material, in accordance with an embodiment of the presently disclosed technology.

[0020] Figure 10 is an enlarged, partially schematic illustration of a portion of the reactor shown in Figure 8 having a re-radiation component configured in accordance with a particular embodiment of the presently disclosed technology.

[0021] Figure 1 1 is a schematic cross-sectional view of a thermal transfer device configured in accordance with an embodiment of the present technology.

[0022] Figures 12A and 12B are schematic cross-sectional views of thermal transfer devices configured in accordance with other embodiments of the present technology.

[0023] Figure 13A is a schematic cross-sectional view of a thermal transfer device operating in a first direction in accordance with a further embodiment of the present technology, and Figure 13B is a schematic cross-sectional view of the thermal transfer device of Figure 13A operating in a second direction opposite the first direction.

[0024] Figure 14 is a partially schematic illustration of a heat pump suitable for transferring heat in accordance with an embodiment of the present technology.

[0025] Figure 15 is a partially schematic illustration of a system having a solar concentrator that directs heat to a reactor vessel in accordance with an embodiment of the disclosed technology.

[0026] Figure 16 is a partially schematic, enlarged illustration of a portion of a reactor vessel, including additional features for controlling the delivery of solar energy to the reaction zone in accordance with an embodiment of the disclosed technology.

[0027] Figure 17 is a partially schematic, cross-sectional illustration of an embodiment of a reactor vessel having annularly positioned product removal and reactant delivery systems in accordance with an embodiment of the disclosure.

[0028] Figure 18 is a partially schematic, partial cross-sectional illustration of a system having a solar concentrator configured in accordance with an embodiment of the present technology.

[0029] Figure 19 is a partially schematic, partial cross-sectional illustration of an embodiment of the system shown in Figure 1 with the solar concentrator configured to emit energy in a cooling process, in accordance with an embodiment of the disclosure.

[0030] Figure 20 is a partially schematic, partial cross-sectional illustration of a system having a movable solar concentrator dish in accordance with an embodiment of the disclosure.

[0031] Figure 21 is a partially schematic illustration of a system having a reactor with facing substrates for operation in a batch mode in accordance with an embodiment of the presently disclosed technology.

[0032] Figure 22 is a partially schematic, partially cross-sectional illustration of a reactor system that receives energy from a combustion engine and returns reaction products to the engine in accordance with an embodiment of the presently disclosed technology. [0033] Figure 23 is a partially schematic, cross-sectional illustration of a reactor having interacting endothermic and exothermic reaction zones in accordance with an embodiment of the disclosure.

DETAILED DESCRIPTION Overview

[0034] Several examples of devices, systems and methods for efficiently producing hydrogen fuels and structural materials are described below. The efficiencies can result from using waste heat produced by a combustion engine to heat the reactor, and by returning at least some reaction products to the engine for combustion or other purposes. The overall process can result in clean-burning fuel and re-purposed carbon and/or other constituents for use in durable goods, including polymers and carbon composites. Although the following description provides many specific details of the following examples in a manner sufficient to enable a person skilled in the relevant art to practice, make and use them, several of the details and advantages described below may not be necessary to practice certain examples of the technology. Additionally, the technology may include other examples that are within the scope of the claims but are not described here in detail.

[0035] References throughout this specification to "one example," "an example," "one embodiment" or "an embodiment" mean that a particular feature, structure, process or characteristic described in connection with the example is included in at least one example of the present technology. Thus, the occurrences of the phrases "in one example," "in an example," "one embodiment" or "an embodiment" in various places throughout this specification are not necessarily all referring to the same example. Furthermore, the particular features, structures, routines, steps or characteristics may be combined in any suitable manner in one or more examples of the technology. The headings provided herein are for convenience only and are not intended to limit or interpret the scope or meaning of the claimed technology.

[0036] Certain embodiments of the technology described below may take the form of computer-executable instructions, including routines executed by a programmable computer or controller. Those skilled in the relevant art will appreciate that the technology can be practiced on computer or controller systems other than those shown and described below. The technology can be embodied in a special-purpose computer, controller, or data processor that is specifically programmed, configured or constructed to perform one or more of the computer- executable instructions described below. Accordingly, the terms "computer" and "controller" as generally used herein refer to any data processor and can include internet appliances, hand-held devices, multi-processor systems, programmable consumer electronics, network computers, mini-computers, and the like. The technology can also be practiced in distributed environments where tasks or modules are performed by remote processing devices that are linked through a communications network. Aspects of the technology described below may be stored or distributed on computer-readable media, including magnetic or optically readable or removable computer discs as well as media distributed electronically over networks. In particular embodiments, data structures and transmissions of data particular to aspects of the technology are also encompassed within the scope of the present technology. The present technology encompasses both methods of programming computer-readable media to perform particular steps, as well as executing the steps.

[0037] A system in accordance with a particular embodiment of the technology includes an engine having a combustion region and an exhaust passage coupled to the engine to receive exhaust products from the combustion region. The exhaust passage can at least partially enclose a passage interior region. The system can further include a reactor having an external heat transfer surface positioned in the passage interior region, and a reaction zone positioned in a region enclosed by the external heat transfer surface. A hydrogen donor source can be coupled in fluid communication with the reaction zone of the reactor vessel via a donor passage, and a product passage can be coupled to the reaction zone to receive a reaction product from the reaction zone.

[0038] A system in accordance with another embodiment of the disclosed technology includes an engine having a combustion region, and an exhaust manifold coupled to the engine to receive exhaust products from the combustion region. The exhaust manifold can have a manifold external surface and a manifold internal surface at least partially enclosing an interior region, with insulation positioned around the external surface. The system can further include a reactor having a shell positioned in the interior region of the exhaust manifold, the shell having a shell external heat transfer surface, and a shell internal surface positioned around a reaction zone. A spiral heat transfer element is carried by the shell and projects into the passage interior region. A first wall is positioned annularly inwardly from the shell internal surface and is spaced radially apart from the shell internal surface to define a first annular passage. A second wall is positioned annularly inwardly from the first wall and spaced radially apart from the first wall to define a second annular passage positioned between the first and second walls, and a third passage positioned inwardly from the second wall. The second wall can include a porous medium that is transmissive to hydrogen but not transmissive to carbon compounds.

[0039] In still further embodiments, a representative system further includes an electrically-powered heater positioned in the second annular passage, and a galvanic circuit coupled across the second wall to pressurize the third passage. A hydrogen donor source is coupled to the first annular passage via a donor passage to direct a hydrogen donor to the reaction zone. A first product passage is coupled to the third passage to receive hydrogen, and a second product passage is coupled to the second annular passage to receive a carbon-bearing product. A liquid cooling system can be coupled to the engine to cool the engine, and can include a working fluid passage. A first heat exchanger can be coupled between the donor passage and the working fluid passage to transfer heat from the working fluid passage to the donor passage. The system can further include a second heat exchanger coupled between the donor passage and the exhaust manifold downstream of the reactor to transfer heat from the exhaust manifold to the donor passage. A third heat exchanger can be coupled between the donor passage and at least one of the first and second product passages to transfer heat from the at least one product passage to the donor passage. A turbine can be positioned downstream of the reactor and the spiral heat transfer element to extract energy from the flow that has passed around the reactor.

[0040] A method for operating an engine and a chemical reactor in accordance with a particular embodiment of the disclosed technology includes combusting a fuel in an engine to produce power and combustion products, directing the combustion products through an exhaust passage and around a reactor positioned within the exhaust passage, and transferring heat from the combustion products to a reaction zone within the reactor, via an external surface of the reactor. The method can further include directing a hydrogen donor into the reaction zone of the reactor, and dissociating the hydrogen donor into dissociation products in the reaction zone. The products can include a hydrogen-bearing constituent, and a non-hydrogen bearing constituent.

Representative Reactor Systems

[0041] Figures 1 and 2 illustrate representative reactor systems for producing hydrogen-based fuels and structural building blocks or architectural constructs in accordance with several embodiments of the technology. Figure 1 illustrates the general arrangement of a reactor that uses waste heat from a combustion process. Figure 2 illustrates further details of the reactor system, and illustrates mechanisms and arrangements by which the combustion engine and reactor can be coupled in a closed-loop fashion. Figures 3-6 illustrate further embodiments in which the reactor is positioned within an exhaust manifold.

[0042] Figure 1 is a partially schematic illustration of a representative system 100 that includes a reactor 1 10. The reactor 1 10 further includes a reactor vessel 1 1 1 that encloses or partially encloses a reaction zone 1 12. In at least some instances, the reactor vessel 1 1 1 has one or more transmissive surfaces positioned to facilitate the chemical reaction taking place within the reaction zone 1 12. Suitable transmissive surfaces are disclosed in co-pending U.S. Application No. 13/026,996, titled "REACTOR VESSELS WITH TRANSMISSIVE SURFACES FOR PRODUCING HYDROGEN-BASED FUELS AND STRUCTURAL ELEMENTS, AND ASSOCIATED SYSTEMS AND METHODS" (Attorney Docket No. 69545.8602US), filed on February 14, 201 1 , and incorporated herein by reference. To the extent of the foregoing reference and/or any other references incorporated herein by reference conflict with the present disclosure, the present disclosure controls. Various heat resources can produce a first heat quantity or heat flow, H-1 (e.g., from engine coolant), a second heat quantity or flow H-2 (e.g., from exhaust gases), and/or a third heat quantity or flow H-3 (e.g., from regenerative braking and/or suspension system generators). In other embodiments, other heat sources can produce other heat flows to enable endothermic reactions and processes. In a representative example, the reactor vessel 1 1 1 receives a hydrogen donor provided by a donor source 130 to a donor entry port 1 13. For example, the hydrogen donor can include methane or another hydrocarbon. A donor distributor or manifold 1 15 within the reactor vessel 1 1 1 disperses or distributes the hydrogen donor into the reaction zone 1 12. The reactor vessel 1 1 1 also receives steam from a steam/water source 140 via a steam entry port 1 14. A steam distributor 1 16 in the reactor vessel 1 1 1 distributes the steam into the reaction zone 1 12. The reactor vessel 1 1 1 can further include a heater 123 that supplies heat to the reaction zone 1 12 to facilitate endothermic reactions. The power for the heater (e.g., electrical power) can be provided by a renewable energy source 165. The renewable energy source 165 can include a solar, wind, water and/or other suitable sustainable sources. The reactions performed at the reaction zone 1 12 can include dissociating methane or another hydrocarbon into hydrogen or a hydrogen compound, and carbon or a carbon compound. In other embodiments, the reactor 1 10 can dissociate other hydrogen donors, e.g. nitrogenous hydrogen donors. Representative reactions are further described in co-pending U.S. Application No. 13/027,208 (referred to herein as the '208 Application) titled "CHEMICAL PROCESSES AND REACTORS FOR EFFICIENTLY PRODUCING HYDROGEN FUELS AND STRUCTURAL MATERIALS, AND ASSOCIATED SYSTEMS AND METHODS" (Attorney Docket No. 69545.8601 US), filed on February 14, 201 1 and incorporated herein by reference. The products of the reaction exit the reactor vessel 1 1 1 via an exit port

1 17 and are collected at a reaction product collector 1 17a.

[0043] The system 100 can further include a source 150 of radiant energy (e.g., waste heat) and/or additional reactants, which provides constituents to a passage

1 18 within the reactor vessel 1 1 1 . For example, the heat/reactant source 150 can include a combustion chamber 151 that provides hot combustion/exhaust products 152 to the passage 1 18, as indicated by arrow A. The combustion products 152 and associated waste heat are produced by a process separate from the dissociation process (e.g., a power generation process). A combustion products collector 171 b collects combustion products exiting the reactor vessel 1 1 1 for further recycling and/or other uses. In a particular embodiment, the combustion products 152 can include hot carbon monoxide, water vapor, and/or other constituents. One or more transmissive surfaces 1 19 are positioned between the reaction zone 1 12 (which can be disposed annularly around the passage 1 18) and an interior region 120 of the passage 1 18. The transmissive surface 1 19 can accordingly allow radiant energy and/or a chemical constituent to pass radially outwardly from the passage 1 18 into the reaction zone 1 12, as indicated by arrows B. By delivering the radiant energy (e.g., heat) and/or chemical constituent(s) provided by the flow of combustion products 152, the system 100 can enhance the reaction taking place in the reaction zone 1 12, for example, by increasing the reaction zone temperature and/or pressure, and therefore the reaction rate, and/or the thermodynamic efficiency of the reaction. The foregoing process can accordingly recycle or reuse energy and/or constituents that would otherwise be wasted, in addition to facilitating the reaction at the reaction zone 1 12.

[0044] The composition and structure of the transmissive surface 1 19 can be selected to allow radiant energy to readily pass from the interior region 120 of the passage 1 18 to the reaction zone 1 12. Accordingly, the transmissive surface 1 19 can include glass, graphene, or a re-radiative component. Suitable re-radiative components are described further in co-pending U.S. Application No. 13/027,015, titled "CHEMICAL REACTORS WITH RE-RADIATING SURFACES AND ASSOCIATED SYSTEMS AND METHODS" (Attorney Docket No. 69545.8603US), filed on February 14, 201 1 and incorporated herein by reference.

[0045] As noted above, the combustion products 152 can include steam and/or other constituents that may serve as reactants in the reaction zone 1 12. Accordingly, the transmissive surface 1 19 can be manufactured to selectively allow such constituents into the reaction zone 1 12, in addition to or in lieu of admitting radiant energy into the reaction zone 1 12. In a particular embodiment, the transmissive surface 1 19 can be formed from a carbon crystal structure, for example, a layered graphene structure. The carbon-based crystal structure can include spacings (e.g., between parallel layers oriented transverse to the flow direction A) that are deliberately selected to allow water molecules to pass through. At the same time, the spacings can be selected to prevent useful reaction products produced in the reaction zone 1 12 from passing out of the reaction zone. In particular embodiments, the transmissive surface 1 19 can be formed by using the same type of architectural constructs produced or facilitated by the reactor 1 10. [0046] The system 100 can further include a controller 190 that receives input signals 191 (e.g., from sensors) and provides output signals 192 (e.g., control instructions) based at least in part on the inputs 191 . Accordingly, the controller 190 can include suitable processor, memory and I/O capabilities. The controller 190 can receive signals corresponding to measured or sensed pressures, temperatures, flow rates, chemical concentrations and/or other suitable parameters, and can issue instructions controlling reactant delivery rates, pressures and temperatures, heater activation, valve settings and/or other suitable actively controllable parameters. An operator can provide additional inputs to modify, adjust and/or override the instructions carried out autonomously by the controller 190.

[0047] Figure 2 is a partially schematic illustration of system 100 that includes a reactor 1 10 in combination with a radiant energy/reactant source 150 in accordance with another embodiment of the technology. In this embodiment, the radiant energy/reactant source 150 includes an engine 180, e.g., an internal combustion engine having a piston 182 that reciprocates within a cylinder 181 . In other embodiments, the engine 180 can have other configurations, for example, an external combustion configuration. In an embodiment shown in Figure 2, the engine 180 includes an intake port 184a that is opened and closed by an intake valve 183a to control air entering the cylinder 181 through an air filter 178. The air flow can be unthrottled in an embodiment shown in Figure 2, and can be throttled in other embodiments. A fuel injector 185 directs fuel into the combustion zone 179 where it mixes with the air and ignites to produce the combustion products 152. Additional fuel can be introduced by an injection valve 189a. The combustion products 152 exit the cylinder 181 via an exhaust port 184b controlled by an exhaust valve 183b. Further details of representative engines and ignition systems are disclosed in copending U.S. Application No. 12/653,085 (Attorney Docket No. 69545.8304US) filed on December 7, 2010, and incorporated herein by reference.

[0048] The engine 180 can include features specifically designed to integrate the operation of the engine with the operation of the reactor 1 10. For example, the engine 180 and the reactor 1 10 can share fuel from a common fuel source 130 which is described in further detail below. The fuel is provided to the fuel injector 185 via a regulator 186. The engine 180 can also receive end products from the reactor 1 10 via a first conduit or passage 177a, and water (e.g., liquid or steam) from the reactor 1 10 via a second conduit or passage 177b. Further aspects of these features are described in greater detail below, following a description of the other features of the overall system 100.

[0049] The system 100 shown in Figure 2 also includes heat exchangers and separators configured to transfer heat and segregate reaction products in accordance with the disclosed technology. In a particular aspect of this embodiment, the system 100 includes a steam/water source 140 that provides steam to the reactor vessel 1 1 1 to facilitate product formation. Steam from the steam/water source 140 can be provided to the reactor 1 10 via at least two channels. The first channel includes a first water path 141 a that passes through a first heat exchanger 170a and into the reactor vessel 1 1 1 via a first steam distributor 1 16a. Products removed from the reactor vessel 1 1 1 pass through a reactor product exit port 1 17 and along a products path 161 . The products path 161 passes through the first heat exchanger 170a in a counter-flow or counter-current manner to cool the products and heat the steam entering the reactor vessel 1 1 1 . The products continue to a reaction product separator 171 a that segregates useful end products (e.g., hydrogen and carbon or carbon compounds). At least some of the products are then directed back to the engine 180, and other products are then collected at a products collector 160a. A first valve 176a regulates the product flow. Water remaining in the products path 161 can be separated at the reaction product separator 171 a and returned to the steam/water source 140.

[0050] The second channel via which the steam/water source 140 provides steam to the reactor 1 10 includes a second water path 141 b that passes through a second heat exchanger 170b. Water proceeding along the second water path 141 b enters the reactor 1 10 in the form of steam via a second stream distributor 1 16b. This water is heated by combustion products that have exited the combustion zone 179 and passed through the transfer passage 1 18 (which can include a transmissive surface 1 19) along a combustion products path 154. The spent combustion products 152 are collected at a combustion products collector 160b and can include nitrogen compounds, phosphates, re-used illuminant additives (e.g., sources of sodium, magnesium and/or potassium), and/or other compositions that may be recycled or used for other purposes (e.g., agricultural purposes). The illuminant additives can be added to the combustion products 152 (and/or the fuel used by the engine 180) upstream of the reactor 1 10 to increase the amount of radiant energy available for transmission into the reaction zone 1 12.

[0051] In addition to heating water along the second water path 141 b and cooling the combustion products along the combustion products path 154, the second heat exchanger 170b can heat the hydrogen donor passing along a donor path 131 to a donor distributor 1 15 located within the reactor vessel 1 1 1 . The donor source 130 houses a hydrogen donor, e.g., a hydrocarbon such as methane, or a nitrogenous donor such as ammonia. The donor source 130 can include one or more heaters 132 (shown as first heater 132a and a second heater 132b) to vaporize and/or pressurize the hydrogen donor within. A three-way valve 133 and a regulator 134 control the amount of fluid and/or vapor that exits the donor source 130 and passes along the donor path 131 through the second heat exchanger 170b and into the reactor vessel 1 1 1 . As discussed above, the hydrogen donor can also serve as a fuel for the engine 180, in at least some embodiments, and can be delivered to the engine 180 via a third conduit or passage 177c.

[0052] In the reactor vessel 1 1 1 , the combustion products 152 pass through the combustion products passage 1 18 while delivering radiant energy and/or reactants through the transmissive surface 1 19 into the reaction zone 1 12. After passing through the second heat exchanger 170b, the combustion products 152 can enter a combustion products separator 171 b that separates water from the combustion products. The water returns to the steam/water source 140 and the remaining combustion products are collected at the combustion products collector 160b. In a particular embodiment, the separator 171 b can include a centrifugal separator that is driven by the kinetic energy of the combustion product stream. If the kinetic energy of the combustion product stream is insufficient to separate the water by centrifugal force, a motor/generator 172 can add energy to the separator 171 b to provide the necessary centrifugal force. If the kinetic energy of the combustion product stream is greater than is necessary to separate water, the motor/generator 172 can produce energy, e.g., to be used by other components of the system 100. The controller 190 receives inputs from the various elements of the system 100 and controls flow rates, pressures, temperatures, and/or other parameters.

[0053] The controller 190 can also control the return of reactor products to the engine 180. For example, the controller 190 can direct reaction products and/or recaptured water back to the engine 180 via a series of valves. In a particular embodiment, the controller 190 can direct the operation of the first valve 176a which directs hydrogen and carbon monoxide obtained from the first separator 171 a to the engine 180 via the first conduit 177a. These constituents can be burned in the combustion zone 179 to provide additional power from the engine 180. In some instances, it may be desirable to cool the combustion zone 179 and/or other elements of the engine 180 as shown. In such instances, the controller 190 can control a flow of water or steam to the engine 180 via second and third valves 176b, 176c and the corresponding second conduit 177b.

[0054] In some instances, it may be desirable to balance the energy provided to the reactor 1 10 with energy extracted from the engine 180 used for other proposes. Accordingly, the system 100 can included a proportioning valve 187 in the combustion products stream that can direct some combustion products 152 to a power extraction device 188, for example, a turbo-alternator, turbocharger or a supercharger. When the power extraction device 188 includes a supercharger, it operates to compress air entering the engine cylinder 181 via the intake port 184a. When the extraction device 188 includes a turbocharger, it can include an additional fuel injection valve 189b that directs fuel into the mixture of combustion products for further combustion to produce additional power. This power can supplement the power provided by the engine 180, or it can be provided separately, e.g., via a separate electrical generator.

[0055] As is evident from the forgoing discussion, one feature of the system 100 is that it is specifically configured to conserve and reuse energy from the combustion products 152. Accordingly, the system 100 can include additional features that are designed to reduce energy losses from the combustion products 152. Such features can include insulation positioned around the cylinder 181 , at the head of the piston 182, and/or at the ends of the valves 183a, 183b. Accordingly, the insulation prevents or at least restricts heat from being conveyed away from the engine 180 via any thermal channel other than the passage 1 18.

[0056] One feature of at least some of the foregoing embodiments is that the reactor system can include a reactor and an engine linked in an interdependent manner. In particular, the engine can provide waste heat that facilitates a dissociation process conducted at the reactor to produce a hydrogen-based fuel and a non-hydrogen based structural building block. The building block can include a molecule containing carbon, boron, nitrogen, silicon and/or sulfur, and can be used to form an architectural construct. Representative examples of architectural constructs, in addition to the polymers and composites described above are described in further detail in co-pending U.S. Application No. 13/027,214, titled "ARCHITECTURAL CONSTRUCT HAVING FOR EXAMPLE A PLURALITY OF ARCHITECTURAL CRYSTALS" (Attorney Docket No. 69545.8701 ) filed on February 14, 201 1 and incorporated herein by reference. An advantage of this arrangement is that it can provide a synergy between the engine and the reactor. For example, the energy inputs normally required by the reactor to conduct the dissociation processes described above can be reduced by virtue of the additional energy provided by the combustion product. The efficiency of the engine can be improved by adding clean- burning hydrogen to the combustion chamber, and/or by providing water (e.g., in steam or liquid form) for cooling the engine. Although both the steam and the hydrogen-based fuel are produced by the reactor, they can be delivered to the engine at different rates and/or can vary in accordance with different schedules and/or otherwise in different manners.

[0057] Figure 3 is a partially schematic, cross-sectional illustration of a system 200 that includes a reactor 210 having a reactor vessel 21 1 positioned in an engine exhaust manifold or passage 220. The exhaust manifold 220 can be coupled to an engine 180 having a reciprocating internal combustion configuration generally similar to that described above with reference to Figure 2. In other embodiments, the engine 180 can have other configurations, for example, a gas turbine configuration. In any of these embodiments, exhaust products from the engine 180 pass into the exhaust manifold 220 and around the reactor vessel 21 1 to provide heat to a reaction zone 212 located within the reactor vessel 21 1 . Further details of a representative manner in which the reactor 210 is integrated with other features of the system 200 are described below with continued reference to Figure 3. Further details of the reactor itself are described later with reference to Figures 4-6.

[0058] As shown in Figure 3, the exhaust manifold 220 can have an interior region 221 through which exhaust gases from the exhaust port 184b pass. The exhaust gases pass around the reactor vessel 21 1 as indicated by arrows E, and as they pass the reactor vessel 21 1 , transfer heat into the reactor vessel 21 1 . One or more heat transfer elements 213 can project into the interior region 221 of the exhaust manifold 220 to facilitate this heat transfer process. In particular embodiments, the reactor vessel 21 1 can also include an internal heater 214 that can, on an intermittent or continuous basis, supplement the heat provided to the reaction zone 212 by the exhaust gases passing through the manifold 220.

[0059] In a further aspect of an embodiment shown in Figure 3, the externally projecting heat transfer elements 213 can be arranged to impart a spiral or radial flow component to the exhaust gases. Accordingly, when the exhaust gases pass downstream to a turbine 288 or other energy extraction device, the turbine 288 can extract the rotational kinetic energy. The turbine 288 can be coupled to an electric generator 277 via a shaft 287. The generator 277 can in turn provide the electrical energy to an energy storage medium 206 e.g. a battery, a bank of capacitors and/or another suitable medium. The electrical energy can be retrieved from the energy storage medium 206 to power the reactor heater 214 and/or other components of the system 200.

[0060] Exhaust gases exiting the turbine 288 can proceed downstream along a flow axis F past a heat exchanger 240b which will be described later, and to an exhaust product separator 226. The exhaust product separator 226 can separate one or more constituents from the exhaust gas stream, and provide the constituents to an exhaust product collector 260c. Separated exhaust products can then be directed to any of a number of suitable uses, for example, sulfur applications, fertilizer applications, and/or others, depending upon the composition of the exhaust gas products. Any remaining exhaust gas exits the exhaust manifold or passage 220 at an exit 225.

[0061] At least some portions, and in particular embodiments, all portions, of the exhaust manifold or passage 220 can include insulation 224 that prevents or at least restricts heat from escaping the manifold 220. Instead, this heat is directed to the reaction zone 212. This is unlike most conventional exhaust gas manifolds, which typically facilitate heat transfer to the external environment for purposes of cooling.

[0062] The system 200 can include one or more reactant vessels 230 (e.g. donor sources) that supply one or more reactants (e.g., hydrogen donors) to the reaction zone 212. The reactant is gaseous in several embodiments, and can be liquid and/or solid, or any suitable combination of phases in others. In particular embodiments, the donor includes a hydrogen donor, e.g., methane or another hydrocarbon. Suitable hydrocarbons include ethane, propane or butane, along with cetane and/or octane rated compounds. In still further embodiments, the reactant can include a lower grade constituent, e.g., off-grade cetane or octane rated hydrocarbons, or wet alcohol. In at least some embodiments, the donor substance can include compounds other than hydrocarbon fuels (e.g., carbohydrates, fats, alcohols, esters, cellulose and/or others). In yet further embodiments, the hydrogen donor can include hydrogen atoms in combination with constituents other than carbon. For example, nitrogenous compounds (e.g., ammonia and/or urea) can serve a similar hydrogen donor function. Examples of other suitable hydrogen donors are described in the '208 Application, previously incorporated herein by reference.

[0063] In yet further embodiments, the donor substance can donate constituents other than hydrogen. For example, the reactor 210 can dissociate oxygen from C02 and/or another oxygen donor, or the reactor 210 can dissociate a halogen donor. In other embodiments, the donor can have other compositions and/or donate other constituents. In any of these embodiments, the donor is dissociated in the reaction zone 212 to produce two or more products. Accordingly, the system 200 can include multiple product collectors that collect the resulting products. In a particular embodiment shown in Figure 3, the product collectors include a first product collector 260a and a second product collector 260b. In particular embodiments, as was discussed above with reference to Figures 1 and 2, the reactant vessel 230 can supply a hydrocarbon to the reaction zone 212. In the reaction zone 212, the hydrocarbon can be dissociated into hydrogen or a hydrogen-bearing compound (directed to the first product collector 260a) and a carbon or carbon-bearing compound directed to the second product collector 260b. The hydrogen can be stored and/or delivered to the combustion zone 179 of the engine 180 via a product delivery passage 262 and the fuel injector 185. The hydrogen alone or in combination with other constituents can accordingly form a hydrogen-characterized fuel. An optional water source 275 can deliver water to the combustion zone 179. The system 200 can include a number of heat exchangers (e.g., counter-current or counter-flow heat exchangers) and/or other features that increase the overall efficiency of the reactor 210, as will be described in further detail below.

[0064] As shown in Figure 3, the reactant vessel 230 can perform multiple functions. For example, in addition to supplying a reactant to the reaction zone 212, the reactant vessel 230 can supply fuel to the engine 180. In particular, in a manner generally similar to that described above with reference to Figure 2, the reactant vessel 230 can provide fuel (e.g. a hydrocarbon fuel) to the engine 180 via the fuel injector 185, under the control of the regulator 186. The reactant vessel 230 can include features for preheating the fuel/reactant/donor prior to delivering the reactant to the fuel injector 185 and/or the reaction zone 212. For example, the reactant vessel 230 can include an internal heater 232. In a particular aspect of this embodiment, the internal heater 232 can be a resistive heater, which receives electrical current from the energy storage medium 206 described above. The reactant vessel 230 can receive heat from other sources, in addition to or in lieu of the heater 232. Such sources can include a burner 233 that burns a portion of the reactant contained within the reactant vessel 230 (and/or another suitable fuel) and provides the resultant heat to the reactant vessel 230 via a heat pipe 234 or other suitable thermal transfer device. The heat provided to the reactant vessel 230 can vaporize and/or pressurize the reactant therein. As described above, suitable reactants can include methane or methanol, optionally with water, which can operate as an oxidant.

[0065] The reactant or donor (both terms are used herein to refer to the compound delivered to the reactor 210) exits the reactant vessel 230 via a reactant passage 231 , which directs the reactant to the reaction zone 212 via one or more additional heat transfer arrangements that can further preheat the reactant before it arrives at the reaction zone 212. For example, the system 200 can include a first heat exchanger 240a having a first heat exchange passage 241 a and a second heat exchange passage 242a that are positioned in a counter-flow arrangement relative to each other. The reactant can pass through the first heat exchanger passage 241 a so as to receive heat from the second heat exchanger passage 242a. The second heat exchanger passage 242a can be coupled to an engine coolant circuit 276. The engine coolant circuit 276 can include antifreeze or another heat transfer working fluid that receives heat from the engine 180. In most conventional arrangements, this heat is rejected to the environment via a radiator. In the present embodiment, this heat is instead transferred to the reactant passing through the first heat exchanger passage 241 a. In a representative embodiment, the fluid in the second heat exchanger passage 242a can have a temperature of up to about 105°C, and in other embodiments, the temperature can have other suitable values.

[0066] The reactant passage 231 can further be coupled to a second heat exchanger 240b positioned at the exhaust manifold 220. The second heat exchanger 240b can include a heat exchange passage 241 b that is in direct thermal communication with the exhaust flow passing through the exhaust manifold 220, to further preheat the reactant in the reactant passage 231 . The temperature of the exhaust gas at this location (e.g., downstream of the turbine 288) can be up to about 600°C in a representative embodiment.

[0067] The system 200 can further include a third heat exchanger 240c that directs heat from products exiting the reactor 210 to the reactants entering the reactor 210. Accordingly, the third heat exchanger 240c can include a third heat exchanger passage 241 c having a counter-flow arrangement relative to one or more second heat exchanger passages 242c. In a particular embodiment shown in Figure 2, the third heat exchanger 240c includes two second heat exchanger passages 242c, one coupled between the reactor 210 and the first product collector 260a via a first product passage 261 a, and the other coupled between the reactor 210 and the second product collector 260b via a second product passage 261 b. Accordingly, both products exiting the reactor 210 can pre-heat the reactant. In other embodiments (e.g., for which more than two products are separated) the third heat exchanger 240c can include additional second heat exchanger passages 242c.

[0068] In at least some instances, the system 200 can further include a supplemental reactant vessel 230a coupled to the donor passage 231 . Accordingly, the system 200 can supply an additional reactant (in addition to the reactant provided by the reactant vessel 230) into the reaction zone 212. Suitable constituents carried by the supplemental reactor 230a can include but are not limited to methanol.

[0069] In a typical embodiment, the system 200 includes a vehicle 201 (e.g., a truck, a locomotive or another transportation medium) that carries the engine 180, the exhaust manifold 220 and the reactor 210. Accordingly, the system 200 includes one or more wheels 202, one of which is shown schematically in Figure 3. The wheel or wheels 202 can be coupled to a regenerative brake 203 that converts kinetic energy from the wheel to electrical energy during a braking operation, and directs the electrical energy to the energy storage medium 206. The energy storage medium 206 can in turn direct the electrical energy to the reactant vessel heater 232, the reactor heater 214 and/or other electrically powered subsystems to increase the overall efficiency of the vehicle-based system 200. Further embodiments of regenerative brakes and other vehicle-based energy capture techniques are disclosed in U.S. Application No. 13/584,786 (Attorney Docket No. 69545.8615US3) filed February 1 1 , 2013 and incorporated herein by reference.

[0070] When the vehicle 201 in not in use (or if the system 200 is fixed in place), the energy source 206 can be coupled to an electrical grid 204 via a power outlet 205 or other suitable arrangement. Accordingly, the energy source 206 can be recharged, e.g., during non-operational periods, so as to provide energy on an as- needed basis during operational periods. Power management tasks and other coordination tasks used to direct the operation of the reactor 210 and associated sub-systems can be controlled by a controller 290 that receives inputs 291 and provides appropriate outputs 292. The controller 290 can accordingly include one or more computer-readable media programmed with instruction that, when executed, carry out one or more of the tasks and operations described herein. Further details of the structure and operation of the reactor 210 are described below with reference to Figures 2A-5.

[0071] Figure 4A is a partially schematic, side cross-sectional illustration of an embodiment of the reactor 210 positioned within the exhaust manifold or passage 220. The manifold 220 can have a manifold internal surface 222 facing toward the reactor 210, and a manifold external surface 223 facing outwardly away from the reactor 210. As discussed above, the manifold 220 can be surrounded or at least partially surrounded with insulation 224 (e.g., a ceramic or other suitable material) that prevents or at least restricts heat from escaping via the manifold external surface 223. Instead, such heat is available for transfer by convection, conduction, and/or radiation to the manifold interior region 221 and the reactor 210. [0072] The reactor 210 can include a shell 215 having a shell internal surface 216a and a shell external surface 216b. The external surface 216b can include a highly thermally conductive, heat-resistant and oxidation-resistant material (e.g. a super alloy that includes nickel and/or cobalt, or another high temperature furnace alloy) to facilitate transferring heat from the exhaust gas to the reaction zone 212 within the reactor 210. Unlike the arrangement described above with reference to Figure 2, the shell 215 can prevent constituent transfers into the reactor 210 from the adjacent exhaust flow, while permitting heat transfer from the exhaust flow. As discussed above, the reactor 210 can further include one or more heat transfer elements 213 that project from the shell 215 into the interior region 221 of the manifold 220 to extract additional thermal energy from the exhaust gas and conduct that energy to the reaction zone 212 via the shell 215. In a particular embodiment, the heat transfer element 213 can have a generally spiral shape that, in addition to extracting heat from the passing exhaust flow, imparts a rotational motion to the exhaust flow, which can be extracted by the turbine 288 described above with reference to Figure 3. In one embodiment, the heat transfer element 213 can include a single screw-shaped annular element. In other embodiments, the heat transfer element 213 can have multiple components, e.g., multiple vanes, fins, or other surfaces that are at least partially inclined relative to the axial gas flow direction indicated by arrows E. Accordingly, any of these arrangements can generate the spiral flow pattern indicated by arrows S. The heat transfer elements can generally have a high surface area-to-volume ratio so as to increase the efficiency with which they collect and transmit heat.

[0073] The reactor 210 can have one or more annularly-positioned flow passages, defined by one or more corresponding walls. For example, the reactor vessel 21 1 can include a first wall 251 (e.g., in the form of a capped tube) positioned inwardly from the shell 215 to define, at least in part, a first passage 253a. The vessel 21 1 can further include a second wall 252 (e.g., in the form of a capped tube) positioned radially inwardly from the first wall 251 . Accordingly, the second wall 252 can define, at least in part, a second passage 253b positioned between the first wall 251 and the second wall 252, and a third passage 253c positioned inwardly from the second wall 252. The first wall 251 can be generally solid and thermally insulated or non-transmissive, so as to restrict or prevent the loss of heat generated by the reaction heater 214. Accordingly, a reactant flow provided by the reactant passage 231 can receive heat from the shell 215 as it travels axially along the annular first passage 253a, as indicated by arrows D. The first wall 251 can include openings or perforations 250 toward a distal end DE of the first passage 253a, allowing the reactant to pass inwardly into the second passage 253b. The reactant then travels back in a proximal direction through the second passage 253b toward a proximal end PE of the reactor 210.

[0074] As the reactant receives heat in both the first and second passages 253a, 253b, it begins to oxidize, partially oxidize, reform, and/or dissociate in a non- combustion, endothermic reaction process, forming one or more first products and one or more second products. These processes can be conducted in accordance with the parameters described in the '208 Application previously incorporated herein by reference. Representative reactions include:

Heat + CH4 + H20 -» CO + 3H2 Equation 1

Heat + CH4 C + 2H2 Equation 2

Heat + CH30H ^ CO + 2H2 Equation 3

Heat + CH30H + H20 -» C02 + 3H2 Equation 4

Heat + CH30H + "C"+ H20 -» 2CO + 3H2 Equation 5

Heat + CxHy + xH20 -» xCO +(0.5y +x)H2 Equation 6

Heat + 2NH3 -» N2 + 3H2 Equation 7

Heat + CO(NH2)2 -» CO + 2H2 + N2 Equation 8

Heat + CO(NH2)2 + H20 -» C02 + 3H2 + N2 Equation 9

CH4 + 0.5O2 -» CO + 3H2 + Heat Equation 10

HxCy + y/202 -» yCO +x/2H2 Equation 1 1

HxCy = yH20 -» yCO = (y+x/2)H2 Equation 12

[0075] In at least some cases, various carbon donors (identified as "C" in Equation 5) can contribute further carbon to the foregoing reactions. Suitable carbon donors can include coal, grain dust, food and/or farm wastes. In addition to or in lieu of such sources, optional surfactants can be added to improve emulsion stability, including surfactants that may also contribute carbon in the endothermic reaction. In at least some embodiments (e.g., as indicated by Equations 10-12), exothermic and/or partial oxidation reactions can contribute heat to the foregoing endothermic reactions.

[0076] In particular embodiments, the first products include hydrogen or hydrogen compounds, and the second products include carbon or carbon compounds. The second wall 252 can be constructed to separate these two products and direct each to a respective one of the first product collector 260a or the second product collector 260b described above with reference to Figure 3. In a particular embodiment, the second wall 252 can include a porous medium 254 having porous surfaces 255a and being selectively transmissive to hydrogen or selected hydrogen compounds, but is not transmissive to carbon or carbon compounds. Accordingly, hydrogen can pass into the third passage 253c as indicated by arrows H, and carbon or carbon compounds can remain in the second passage 253b, as indicated by arrows C. The hydrogen is then collected at the first product passage 261 a, and the carbon or carbon compounds are collected at the second product passage 261 b.

[0077] In one embodiment, the second wall 252 can be manufactured by winding selected filaments on a temporary forming mandrel sized to match or approximately match the inner diameter of this tube-shaped element. The fibers can be wound in a pattern that is selected or optimized for reinforcing a pressure- containing vessel. Filaments suitable for such purposes include polyacrylonitrile (PAN) including co-polymers and solutions with other compounds, pitch fiber, along with carbon fiber, silicon carbide and/or other suitable filament selections. The resulting matrix can then be heat treated and/or subjected to other furnace operations to convert the PAN to carbon. Additional carbon can be added to (e.g., deposited on) the matrix by one or more steps similar to the reaction identified above in Equation 2. The resulting structure can accordingly include a porous network that favors hydrogen (e.g., separates hydrogen) from feedstocks such as natural gas liquids and other reactants listed in Equations 1 -9, as well as from other products listed in Equations 1 -9 above.

[0078] In another embodiment, the tube forming the second wall 252 can be formed by compacting graphene, carbon, and/or other powders with one or more suitable organic polymers and/or binders, followed by heat treating to convert the organics and/or binders and densification to the degree desired for separation of hydrogen and/or carbon monoxide from other gases such as the reactants of Equations 1 -9. In particular, densifiying the matrix can include producing nanomaterials such as nanotubes, fibers, and whiskers by the technologies disclosed in U.S. Application Publication No. 2009/0186214, U.S. Patent No. 8, 158,217 and/or U.S. Patent No. 8,168,291 . Accordingly, the products formed at the reactor 210 can be used to form new structures for additional reactors. In particular, the carbon extracted from a hydrocarbon in one process can be used to form the porous medium that is used to separate additional carbon and hydrogen in a subsequent process.

[0079] In still further embodiments, the tube forming the second wall 252 can be repaired or repurposed after use in the reactor 210. For example, the initial use of the tube as a component of an exhaust manifold provides a highly purified, sterilized, and refined micro-porous electrode or filter matrix. After such use, the tube can have deposited on it a carbon fuzz so that the tube can function as a high value electrode for electro-dialysis or as a filter for fluids such as air, water, beer, whiskey, wine or pharmaceutical products.

[0080] The temperature of the reaction zone 212 may vary depending upon the operational state of the engine 180 (Figure 3). For example, during cold engine startup, the exhaust gases will have a relatively low temperature e.g., 120°C. As the engine warms up, the exhaust gas temperature will increase e.g., to 300°C for idle, coasting or lightly loaded operation. At maximum load conditions, the exhaust gas temperature can increase to 700°C. In any of these embodiments, the reactor heater 214 can supplement the energy provided to the reaction zone 212. The heater 214 can be an electrical resistance heater or induction heater that, under the control of the controller 290 (Figure 3) provides the requisite amount of heat. In some embodiments, the heater 214 is activated only during engine operational phases that result in relatively low exhaust gas temperatures. In other embodiments, the heater 214 is active at all times, but provides more heat during some operational phases than others. For example, a typical temperature for hydrogen dissociation is at least 650°C, and in several embodiments, it is desirable to conduct the reaction at higher temperatures (e.g., at least 700°C and in particular, from about 750°C to about 1600°C). Such elevated temperatures can produce product pressures high enough to support injecting the products (e.g., hydrogen) into a high compression ratio engine. In at least some instances, the heat transferred to the reactant via the engine coolant, the exhaust downstream of the turbine 288, and the exhaust upstream of the turbine 288 may be insufficient to elevate the reaction zone 212 to these temperatures. In such instances, the reactor heater 214 may operate at all times when the reactor 210 operates, but, as described above, its energy output can vary depending on the engine operational state and by extension reaction zone temperature. Temperature sensors, pressure sensors, and/or other feedback devices are used to determine the operational states and/or parameters of the system 200 to provide suitable information to the controller 290.

[0081] In another aspect of an embodiment shown in Figure 4A, the reaction vessel 21 1 can include one or more galvanic circuits 217, each of which can include one or more cathodes 218a and one or more anodes 218b. The galvanic circuit 217 can be coupled to the energy storage medium 206 (Figure 3) to provide a voltage across the second wall 252. When activated, the galvanic circuit 217 can pressurize the hydrogen collected in the third passage 253c, which can in turn facilitate the dissociation process conducted in the reaction zone 212 by reducing the hydrogen partial pressure in the reaction zone 212. In addition, hydrogen at elevated pressures within the third passage 253c can be used to facilitate high-pressure fuel injection at the injector 185 (Figure 3). Representative pressures include 200 Bar (gage) or higher.

[0082] Galvanic separation can facilitate the foregoing hydrogen separation and pressurization processes, e.g., by proton conduction. Composites and ceramics such as perovskite (SrCe03) oxide can provide suitable media for such processes, and can be used in addition to the porous medium described above. In particular, gas volumes at elevated temperatures, that include hydrogen, can be separated at increased rates by doped perovskite-type oxides. Such enhanced proton conductivity is provided with membranes such as doped SrCe03, CaZr03, BaCe03 and/or SrZr03. Suitable dopants include yttrium, ytterbium, europium, samarium, neodymium, and gadolinium.

[0083] Hydrogen separation by such oxide ceramics can be further enhanced by an increased pressure gradient and/or via a DC bias. In embodiments that apply a DC bias or galvanic drive in the hydrogen separation process, the hydrogen can permeate from a lower hydrogen pressure on one side of the membrane to a higher hydrogen partial pressure on the other side of the membrane, or vice versa. By contrast, in a non-galvanic hydrogen separation process in which a pressure difference exists across a separation membrane, transport is only from the high hydrogen partial pressure side to the low hydrogen partial pressure side of the membrane.

[0084] Catalysts may be utilized at a reaction surface to influence surface exchange reactions such as various steps or the processes of Equations 1 , 2, and/or 7 above, and the hydrogen permeation can be enhanced by coating the membrane with a surface catalyst to reduce the activation energy for the surface exchange reactions. In particular embodiments, the selected anode material is also a favorable catalyst. Representative anodes for galvanic hydrogen pumps include porous films of Ni, Ag, Pt, and Ni/BCY porous layer. In such hydrogen pumping processes, the gas mixture in the anode and cathode zones compartments can include steam or be humidified with water vapor to improve the proton conductivity of the electrolyte and suppress its electronic conductivity.

[0085] The hydrogen separation rate increases as the applied current is increased in accordance with Faraday's law. Depending upon factors such as reactant pressure and temperature, dopant selection, membrane thickness, and humidity, the applied galvanic voltage gradients can have values in a representative range of from about 0.2 VDC to about 20 VDC, which are sufficient to produce substantially higher pressure hydrogen. Such net galvanic voltage gradients may be produced by much higher voltage AC or DC electricity delivered to the reactor heater 214.

[0086] Thus various mixtures of reactants and products such as H2 along with CO, C02, H20, and/or N2 in the anode zone can be separated to provide pressurized H2 at the cathode zone. Such hydrogen pressurization driven by an applied external voltage can move hydrogen from a suitably pressurized gas mixture including reactants and products to higher pressure for delivery for denser storage and injection purposes. In particular embodiments, reactants are delivered to the anode 218b at 61 Bar (900PSI) and are reacted to produce hydrogen that is removed to improve the reaction yield and delivered by galvanic separation at voltage gradients of 0.2 to 20VD to the cathode 218a, at 122Bar (1800PSI).

[0087] As shown in Figure 4A, embodiments of the present technology include a coaxial flow circuit that heats the reactants in the first passage 253a via exhaust gases, and then directs the gases into the second passage 253b wherein the foregoing galvanic process facilitates hydrogen separation and pressurization. Accordingly, the exhaust gases can provide an initial quantity of heat alone or in combination with the heat received from heat transfer processes described above with reference to Figure 4A. Additional heat, e.g., obtained from a regenerative braking process, can be provided at higher and adaptively controlled temperatures to produce hydrogen at the desired rate and/or pressure needed to optimize or at least improve operation of the engine 180 (Figure 3).

[0088] Reactants delivered to the anode within the tube bore at 61 Bar (900PSI) can be reacted to produce hydrogen that is removed to improve the reaction yield and delivered by galvanic separation at voltage gradients of 0.2 to 20VD to the cathode at the outside zone of the separator tube at 122Bar (1800PSI). The pressurized hydrogen can be directly injected into the engine 180 (Figure 3).

[0089] In another embodiment, a system 200b is shown in Figure 4B for enabling endothermic hydrogen donor reactions such as depicted by representative Equations 1 -12 above. In the configuration of the system 200b, hydrogen is separated and pressurized to produce beneficial compressive loading of the second wall 252. This improves the fatigue endurance strength, reduces unwanted transmission of produced gases, and/or extends the useful life of the second wall 252. In operation, feed stock reactants enter the system 200b through the reactant passage 231 and travel through the first passage 253a to gain exhaust heat (H-2) that may be conductively and/or radiantly transferred into such reactants flowing through first passage 253a as shown. Hydrogen is produced by reactions (e.g., reactions 1 -12) upon receiving the second heat flow H-2, and/or hydrogen is produced upon receiving the third heat flow H-3 such as may be produced by the reactor heater 214. In particular embodiments, the reactor heater 214 can provide electric resistance heating and/or inductive heating. The reactions producing hydrogen can take place in the first passage 253a and/or third passage 253c. The reactants and/or the reaction products can travel into the third passage 253c from the first passage 253a via one or more openings located at distal end DE of the reactor 210. Hydrogen accumulated in third passage 253c is transferred from third passage 253c to second passage 253b.

[0090] Electricity for production of the third heat flow H-3 may be from any suitable source including spin-down or off-peak electrical energy in stationary applications. In mobile applications, electricity for production of the third heat flow H- 3 may be from any suitable source including regenerative deceleration of a vehicle and/or suspension system components such as linear generator springs and shock absorbers and may be applied directly or through an energy storage subsystem such as a battery and/or flywheel motor/generator.

[0091] The second wall 252, which may be a suitable filter or ion membrane material, provides transfer of hydrogen produced by the endothermic reactions facilitated by the second heat flow H-2 and/or the third heat flow H-3 from third passage 253c into second passage 253b. Other products (e.g., shown in Equations 1 -12) can remain in the third passage 253c and exit the reactor 210 via the second product passage 261 b. In certain embodiments, the second wall 252 may be a filter that passes hydrogen but not other products or unreacted feed stocks. In other embodiments the second wall 252 may include an ion permeable membrane, e.g., including mixed proton and electron conducting substances such as a selected perovskite type ceramic.

[0092] Certain embodiments provide the second wall 252 shown in Figure 4B can include an assembly that facilitates galvanic pressurization. For example, referring now to Figure 4C, the second wall 252 can include a separation assembly 278. The separation assembly 278 may provide galvanic pressurization of hydrogen with an inner electrode 280 that is hydrogen porous or permeable through first pores or passageways 282a, an outer electrode 286 that is hydrogen porous or permeable through second passageways 282b, and a hydrogen ion or proton conducting membrane 289 between the inner electrode 280 and the outer electrode 286. Upon application of suitable voltage between the inner electrodes 280 and the outer electrode 286, hydrogen ion delivery is accelerated and diatomic hydrogen delivered into the second passage 252b is pressurized. In such operations, the material of the membrane 289 may be perovskite-type ceramics, doped boron nitride, selected spinels, and/or functionalized silicon carbide, or graphene. Thus, the separation assemblies 278 (e.g., including electrically conductive electrodes 280, 286 that are separated by one or more hydrogen ion conducting membranes 289) provide separation and delivery of pressurized hydrogen.

[0093] In other embodiments, the inner and/or outer electrode 280, 286 is produced by deposition of graphene on a selected substrate (such as cobalt, iron, copper or nickel) that has been electroformed or otherwise shaped to form a suitable preform. Illustratively, a metal preform such as nickel can be utilized to host deposition of graphene from a suitable carbon donor such as methane, ethane, propane etc., and/or various paraffins, and/or petrolatum mixtures. This produces one or more layers of graphene and pores in or through the nickel preform. In instances that pores are produced, they may be made into passageways the 282a, 282b, which have dimensions suitable for serving as electrically conductive hydrogen passageways by etching the nickel with suitable chemicals such as ferric chloride and/or hydrochloric acid.

[0094] In another embodiment, the metal (such as a nickel preform) is dipped or sprayed with a mixture of petrolatum and a selected metal, such as cobalt nanoparticles, cobalt microparticles, or an iron donor (such as a ferrous organic compound, iron carbonyl, and/or urea particles), to provide distributed conversion catalysts upon thermal decomposition on and/or within co-deposited functionalized graphene. This provides distributed cobalt or iron catalysts for stimulating subsequent growth of multitudes of closely spaced single or multiwall nanotubes 284 that are produced by thermal decomposition of a suitable carbon donor such as a paraffinic gas, liquid or solid. A suitable outer electrode 286 is placed or grown on the surface formed by the nanotubes 284.

[0095] The configuration shown in Figure 4C can also include multiple layers 281 , 283, and/or the membrane layer 289 that conduct hydrogen ions or protons conducting, but are electron current insulating. Suitable substances of such layers include doped boron nitride or silicon nitride for proton conduction, and/or selected perovskite type ceramics such as SrCeC>3 modified by Yb additions for operation at temperatures above 600°C.

[0096] During operation as a galvanic hydrogen separation assembly, control of one or more suitable voltages applied by a conductive circuit including a voltage source 279 provide ionized hydrogen as electrons are stripped and transported to electrode 286. The stripped electrons are transported from the inner porous or permeable electrode 280 by impetus of the conductive circuit with the voltage source 279 to the outer electrode 286. Hydrogen molecules and/or atoms that may also be transported with hydrogen ions through the proton membrane layer 281 contribute additional electrons and are converted to ions upon passing through porous or permeable nanotubes 284 serving as an electrode.

[0097] The voltage source 279 provides suitably adjusted voltage to all electrodes, including adaptive occasional or cyclic reversal of polarity to improve the process efficiency for collecting and transporting electrons, particularly from the nanotubes 284 serving as electrodes for simultaneous or sequential electron deliveries to the outer electrode 286. The adaptive occasional or cyclic reversal of polarity helps to increase the Faraday efficiency of electron and ion currents and accelerates transport of hydrogen ions through the proton membrane layer 289 and through the nanotubes 284 serving as electrodes, where remaining hydrogen atoms or molecules contribute electrons that are similarly conducted to the outer electrode 286 as hydrogen ions pass through the layer 283 and through the electrode 286 as hydrogen ion pass through the proton membrane layer 283 and to and through the electrode 286 to regain stripped electrons and produce atomic and subsequently diatomic hydrogen that is galvanically pressurized to provide beneficial compressive loading of the second wall 252 shown in Figure 4B. In other embodiments, similar arrangements of multiple electrodes and hydrogen ion membrane components can be utilized to provide galvanic pressurization of the hydrogen separated, including the system shown in Figure 4A.

[0098] In operation, voltage source 279 includes control by a computer that monitors the operating process parameters, including temperature and pressure measured by suitable sensors (not shown) in each electrode zone, for adaptive adjustment of the voltages applied to electrodes 280, 284, and 286 and improvement of the Faraday efficiency of ion and electron currents that are produced. This serves several purposes, including production of hydrogen pressure at electrode 286 to the desired magnitude for facilitating compact storage and/or to produce suitable pressure for direct injection before, at, and/or after TDC (including the use of such pressurized hydrogen to increase the pressure and/or temperature of fuel mixtures upon blending with other fuel selections). In addition, voltage source 279 provides adaptive adjustment of applied voltage magnitudes to each electrode, including cyclic reversal of polarity to electrodes 284 as may be needed to strip electrons from hydrogen atoms and/or molecules that arrive and thus increase the efficiency of the hydrogen separation and pressurization process. Accordingly, electrons that are stripped from hydrogen by electrodes 280 and/or 284 are delivered to electrode 286 to improve the process efficiency. Comparisons of the amperage conveyed by the respective circuits through voltage source 279 with the pressure produced as a result of such respective voltage magnitude adjustments and/or polarity reversals enables adaptive process efficiency improvement throughout a wide range of operating conditions.

[0099] Utilization of multiple layers of electrodes such as carbon nanotubes and/or functionalized graphene provides greater net hydrogen separation, proton conductivity, and hydrogen pressurization efficiency by enabling thinner layers of proton exchange membranes such as layers 281 , 289, and 283 with reduced ion impedance. Collateral advantages provided by developing such hydrogen pressurization include beneficial compressive loading of the assembly, greater fatigue endurance of the components, and reduction of gas transport through ion transport membranes and assured contact of interface surfaces to reduce impedance to hydrogen ion production and transport.

[00100] In another representative embodiment shown in Figure 4D, a separation assembly 278d may utilize one or more electrodes of parallel aligned single or multiwall nanotubes 284d on one or both sides of an elevated temperature ion exchange membrane 285. The elevated temperature ion exchange membrane 285 can be selected perovskite-type ceramics for proton conduction.

[00101] In another representative embodiment shown in Figure 4E, a separation assembly 278e utilizes one or more layers of functionalized graphene electrodes 286e on one or both sides of parallel aligned single and/or multiwall nanotubes 284n as electrodes on one or both sides elevated temperature ion exchange membrane 285. The elevated temperature ion exchange membrane can be selected Perovskite-type ceramics for proton conduction. [00102] In another representative embodiment shown in Figure 4F, a separation assembly 278f includes one or more layers of protective coatings 288. The protective coatings 288 can be doped or composited silicon carbide (SiC) or molybdenum disilicide (M0S12). The protective coatings 288 can contain or present various concentrations of conductive nanotubes or transition metals and/or platinum group metals that enhance the electrode performance. The coatings 288 can be included on functionalized graphene electrodes 286e (Figure 4E) and/or parallel aligned single and/or multiwall nanotubes 284n (as shown in Figure 4F) serving as electrodes on one or both sides of the elevated temperature ion exchange membrane 285. The elevated temperature ion exchange membrane 285 can be selected perovskite-type ceramics for proton conduction.

[00103] Figure 5 is an end cross-sectional illustration of a portion of the system 200 described above with reference to Figures 3 and 4. Figure 5 illustrates the manifold 220 attached to the engine 180 with an arrangement that, in addition to or in lieu of the insulation 224 reduces or prevents heat loss, so as to preserve the available heat for heating the reactor 210. For example, the system 200 can include a thermally insulating gasket 274 between the manifold 220 and the engine 180. The manifold 220 can be fastened to the engine 180 with thermally isolating or insulating elements. Such elements can include a thermally non-conductive bolt 269 and nut 271 , thermally insulating washers 272, a compression disk spring 270, and/or a fastener isolator tube 273, all of which reduce thermal losses. As a result, the efficiency with which the reaction carried out in the reactor 210 is conducted can be improved relative to the systems that do not include such insulating features.

[00104] Figure 6 is a partially schematic, cross-sectional illustration of a reactor 610 configured in accordance with another embodiment of the present technology, and disposed in the exhaust manifold 220 in a manner generally similar to that described above with reference to Figures 3-5. Accordingly, aspects of the reactor 610 shown in Figure 6 that are similar or generally similar to corresponding aspects of the reactor 210 described above are not described in detail below.

[00105] In a particular aspect of an embodiment shown in Figure 6, the reactor 610 includes a reactor vessel 61 1 that encloses an inwardly disposed, first wall 651 having a construction generally similar to the construction of the second wall 252 described above with reference to Figure 4A. Accordingly, the first wall 651 can include a hydrogen-selective porous medium. The first wall 651 can enclose a first passage 653a through which the hydrogen donor passes, as indicated by arrows D. Heat is provided to the first passage 653a via heat transfer from the exhaust gas flow (indicated by arrows E), supplemented in at least some operational phases with heat provided by the reactor heater 214. Accordingly, the first passage 653a forms a reaction zone 612. As the carbon donor dissociates in the reaction zone 612, the hydrogen passes outwardly through the first wall 651 into a second passage 653b as indicated by arrows H. The hydrogen passes out of the second passage 653b via a first product passage 261 a, and the remaining carbon and/or carbon compounds pass outwardly from the reactor 610 via a second product passage 261 b, as indicated by arrows C. The galvanic circuit 217 can include one or more cathodes 218a positioned in the second flow passage 653b, and one or more anodes 218b positioned in the first passage 253a. Accordingly, the pressure in the second passage 653b can be higher than the pressure in the first passage 653a, which can place a compressive force on the first wall 651 . As a result, the first wall 651 can be sized to withstand a radially compressive force, rather than a radially expansive force, which can reduce the thickness of the first wall 651 and/or increase the material options available for the first wall 651 .

[00106] In addition to producing hydrogen for fuel or other purposes, the reactor 210 can produce carbon and/or carbon compounds, which can have still further uses. For example representative carbon-based products from the reactor 210 include carbon, silicon carbide, halogenated hydrocarbons, graphite, and graphene. These products can be further processed, e.g., to form carbon films, ceramics, semiconductor devices, polymers and/or other structures. For example, the products can include carbon pipes, sheets, the second wall described above, and/or other suitable structures. Accordingly, the products of the reaction conducted in the reactor 210 can be architectural constructs or structural building blocks that can be used as is or after further processing. Other suitable products are described in the '208 Application.

[00107] One feature of several of the embodiments described with reference to Figures 3-6 is that the systems can include insulated exhaust manifolds, in combination with reactor surfaces that are highly thermally conductive. This combination can result in low thermal mass, low thermal inertia, and high thermal shock resistance. As a result, the efficiency of the dissociation reaction carried out at the reactor can be significantly greater than for systems that do not include these features.

[00108] Other features of the foregoing embodiments include the ability to use significantly less expensive fuels, including methane produced from sewage, garbage, farm wastes, and/or forest slash, in addition to or in lieu of natural gas, with considerably higher efficiencies than are available with conventional diesel engines. In addition to being less expensive, such fuels are generally more easily and quickly renewed than are conventional fuels. Engines converted to use such fuels can last longer than conventional engines, produce higher peak power, and/or reduce objectionable emissions. One feature that contributes to reduced emissions is not throttling the engine 180. The efficiency with which such fuels are generated is increased by using engine heat that is otherwise wasted. Excess energy can be readily stored at the energy storage medium 206.

[00109] Still further features include capturing heat and energy from the engine exhaust system, which has lower pressures and kinetic energy levels than other portions of the engine, and is therefore safer. In addition, the insulation provided around the exhaust manifold can provide a containment shell that further increases engine safety. Still further, the system is configured to absorb very large amounts of braking energy, via regenerative brakes, without generating unsafe heat levels.

[00110] In particular embodiments, the arrangement selected for a given reactor can depend on the power of the engine 180 to which it is coupled. For example, the arrangement shown in Figure 2 may be more suitable for larger engines (e.g., greater than 700 HP) for which high fuel use rates correspond to high radiant energy rates. The reactor 1 10 shown in Figure 2 is configured at least in part to make use of these elevated radiant energy levels. By contrast, the arrangement shown in Figures 3-6 may be more suitable for smaller engines (e.g., less than 700 HP) which do not generate as much radiant energy and which tend to be cheaper. In particular, many of the components used in the arrangements shown in Figures 3-6 can be formed from 310 stainless steel or other more reasonably priced materials. Further Representative Reactors

[00111] The following sections describe representative reactors and associated systems that may be used alone or in any of a variety of suitable combinations for carrying out one or more of the foregoing processes described above with reference to Figures 1 -6. In particular, any suitable component of the systems described in the following sections may replace or supplement a suitable component described in the foregoing sections.

[00112] In some embodiments, the reactants may be obtained on a local scale, the reactions may be conducted on a local scale, and the products may be used on a local scale to produce a localized result. In other embodiments, the reactants, reactions, products and overall effect of the process can have a much larger effect. For example, the technology can have continental and/or extra-continental scope. In particular embodiments, the technology can be deployed to preserve vast regions of permafrost, on a continental scale, and or preserve ecosystems located offshore from the preserved areas. In other embodiments, the technology can be deployed offshore to produce effects over large tracts of ocean waters. In still further, embodiments, the technology can be deployed on mobile systems that convey the benefits of the technology to a wide range of areas around the globe.

[00113] In general, the disclosed reactors dissociate, reform and/or respeciate a donor material (reactant) into multiple constituents (e.g., a first constituent and a second constituent). Particular aspects of the representative reactors described below are described in the context of specific reactants and products, e.g., a hydrogen and carbon bearing donor, a hydrogen-bearing product or constituent, and a carbon-bearing product or constituent. In certain other embodiments of the disclosed technology, the same or similar reactors may be used to process other reactants and/or form other products. For example, non-hydrogen feedstock materials (reactants) are used in at least some embodiments. In particular examples, sulfur dioxide can be processed in a non-combustion thermal reactor to produce sulfur and oxygen, and/or carbon dioxide can be processed to produce carbon and oxygen. In many of these embodiments, the resulting dissociation products can include a structural building block and/or a hydrogen-based fuel or other dissociated constituent. The structural building block includes compositions that may be further processed to produce architectural constructs. For example, the structural building blocks can include compounds or molecules resulting from the dissociation process and can include carbon, various organics (e.g. methyl, ethyl, or butyl groups or various alkenes), boron, nitrogen, oxygen, silicon, sulfur, halogens, and/or transition metals. In many applications the building block element does not include hydrogen. In a specific example, methane is dissociated to form hydrogen (or another hydrogen-bearing constituent) and carbon and/or carbon dioxide and/or carbon monoxide (structural building blocks). The carbon and/or carbon dioxide and/or carbon monoxide can be further processed to form polymers, graphene, carbon fiber, and/or another architectural construct. The architectural construct can include a self-organized structure (e.g., a crystal) formed from any of a variety of suitable elements, including the elements described above (carbon, nitrogen, boron, silicon, sulfur, and/or transition metals). In any of these embodiments, the architectural construct can form durable goods, e.g., graphene or carbon composites, and/or other structures.

Representative Reactors with Transmissive Surfaces

[00114] Figure 7 is a partially schematic, partially cut-away illustration of a reactor 1310 that includes a vessel 131 1 formed from three annularly (e.g., concentrically) positioned conduits 1322. Accordingly, the reactor 1310 can operate in a continuous flow manner. As used herein, "continuous flow" refers generally to a process in which reactants and products can be provided to and removed from the reactor vessel continuously without halting the reaction to reload the reaction zone with reactants. In other embodiments, the reactor 1310 can operate in a batch manner during which reactants are intermittently supplied to the reaction zone and products are intermittently removed from the reaction zone. The three conduits 1322 include a first or inner conduit 1322a, a second or intermediate conduit 1322b, and a third or outer conduit 1322c. The first conduit 1322a bounds a combustion products passage 1318 and accordingly has an interior region 1320 through which the combustion products 1 152 pass. The first conduit 1322a has a first transmissive surface 1319a through which radiant energy passes in a radially outward direction, as indicated by arrows B. In a particular aspect of this embodiment, the annular region between the first conduit 1322a and the second conduit 1322b houses a heater 1323, and the annular region between the second conduit 1322b and the third conduit 1322c houses a reaction zone 1312. The heater 1323 together with the radiant heat from the combustion products 1 152 provides heat to the reaction zone 1312. Accordingly, the second conduit 1322b can include a second transmissive surface 1319b that allows radiant energy from both the combustion products 1 152 and the heater 1323 to pass radially outwardly into the reaction zone 1312. In a particular aspect of this embodiment, the first transmissive surface 1319a and the second transmissive surface 1319b are not transmissible to chemical constituents of the combustion products 1 152, in order to avoid contact (e.g., corrosive or other damaging contact) between the combustion products 1 152 and the heater 1323. In another embodiment, the heater 1323 can be manufactured (e.g., with appropriate coatings, treatments, or other features) in a manner that protects it from chemical constituents passing through the first and second transmissive surfaces 1319a, 1319b. In still another embodiment, the heater 1323 can be positioned outwardly from the reaction zone 1312. In any of these embodiments, the heater 1323 can include an electrical resistance heater, an induction heater or another suitable device. In at least some instances, the heater 1323 is powered by combusting a portion of the hydrogen produced in the reaction zone 1312. In other embodiments, combustion is performed in the reactor itself, for example, with the second conduit 1322b serving as a gas mantle for radiating energy at frequencies selected to accelerate the desired reactions in reaction zone 1312.

[00115] In any of the forgoing embodiments, the reaction zone 1312 can house one or more steam distributors 1316 and one or more hydrogen donor distributors 1315. Each of the distributors 1315, 1316 can include pores 1324 and/or other apertures, openings or passages that allow chemical reactants to enter the reaction zone 1312. The donor distributors 1315, 1316 can include one or more spiral conduits, including, e.g., conduits arranged in a braided fashion to distribute reactants into the reaction zone uniformly in the axial, radial and circumferential directions. The reaction zone 1312 is bounded by the third conduit 1322c which can have an insulated reactor outer surface 1321 to conserve heat within the reaction zone 1312. During operation, the reaction taking place in the reaction zone 1312 can be controlled by adjusting the rate at which steam and the hydrogen donor enter the reaction zone 1312, the rate at which heat enters the reaction zone 1312 (via the combustion product passage 1318 and/or the heater 1323) and other variables, including the pressure at the reaction zone 1312. Appropriate sensors and control feedback loops carry out these processes autonomously, with optional controller intervention, as described above with reference to Figure 1 .

[00116] Still further embodiments of suitable reactors with transmissive surfaces are disclosed in pending U.S. Application No. 13/026,996, filed February 14, 201 1 , and incorporated herein by reference.

Representative Reactors with Re-Radiative Components

[00117] Figure 8 is a partially schematic illustration of a system 2100 that includes a reactor 21 10 having one or more selective (e.g., re-radiative) surfaces in accordance with embodiments of the disclosure. The reactor 21 10 further includes a reactor vessel 21 1 1 having an outer surface 2121 that encloses or partially encloses a reaction zone 21 12. In a representative example, the reactor vessel 21 1 1 receives a hydrogen donor provided by a donor source 2101 to a donor entry port 21 13. For example, the hydrogen donor can include methane or another hydrocarbon. A donor distributor or manifold 21 15 within the reactor vessel 21 1 1 disperses or distributes the hydrogen donor into the reaction zone 21 12. The reactor vessel 21 1 1 also receives steam from a steam/water source 2102 via a steam entry port 21 14. A steam distributor 21 16 in the reactor vessel 21 1 1 distributes the steam into the reaction zone 21 12. The reactor vessel 21 1 1 can still further include a heater 2123 that supplies heat to the reaction zone 21 12 to facilitate endothermic reactions. Such reactions can include dissociating methane or another hydrocarbon into hydrogen or a hydrogen compound, and carbon or a carbon compound. The products of the reaction (e.g., carbon and hydrogen) exit the reactor vessel 21 1 1 via an exit port 21 17 and are collected at a reaction product collector 2160a.

[00118] The system 2100 can further include a source 2103 of radiant energy and/or additional reactants, which provides constituents to a passage 21 18 within the reactor vessel 21 1 1 . For example, the radiant energy/reactant source 2103 can include a combustion chamber 2104 that provides hot combustion products 2105 to the passage 21 18, as indicated by arrow A. In a particular embodiment, the passage 21 18 is concentric relative to a passage centerline 2122. In other embodiments, the passage 21 18 can have other geometries. A combustion products collector 2160b collects combustion products exiting the reactor vessel 21 1 1 for recycling and/or other uses. In a particular embodiment, the combustion products 2105 can include carbon monoxide, water vapor, and other constituents.

[00119] One or more re-radiation components 2150 are positioned between the reaction zone 21 12 (which can be disposed annularly around the passage 21 18) and an interior region 2120 of the passage 21 18. The re-radiation component 2150 can accordingly absorb incident radiation R from the passage 21 18 and direct re-radiated energy RR into the reaction zone 21 12. The re-radiated energy RR can have a wavelength spectrum or distribution that more closely matches, approaches, overlaps and/or corresponds to the absorption spectrum of at least one of the reactants and/or at least one of the resulting products. By delivering the radiant energy at a favorably shifted wavelength, the system 2100 can enhance the reaction taking place in the reaction zone 21 12, for example, by increasing the efficiency with which energy is absorbed by the reactants, thus increasing the reaction zone temperature and/or pressure, and therefore the reaction rate, and/or the thermodynamic efficiency of the reaction. In a particular aspect of this embodiment, the combustion products 2105 and/or other constituents provided by the source 2103 can be waste products from another chemical process (e.g., an internal combustion process). Accordingly, the foregoing process can recycle or reuse energy and/or constituents that would otherwise be wasted, in addition to facilitating the reaction at the reaction zone 21 12.

[00120] In at least some embodiments, the re-radiation component 2150 can be used in conjunction with, and/or integrated with, a transmissive surface 21 19 that allows chemical constituents (e.g., reactants) to readily pass from the interior region 2120 of the passage 21 18 to the reaction zone 21 12. Further details of representative transmissive surfaces were discussed above under heading 3.1 . In other embodiments, the reactor 21 10 can include one or more re-radiation components 2150 without also including a transmissive surface 21 19. In any of these embodiments, the radiant energy present in the combustion product 2105 may be present as an inherent result of the combustion process. In other embodiments, an operator can introduce additives into the stream of combustion products 2105 (and/or the fuel that produces the combustion products) to increase the amount of energy extracted from the stream and delivered to the reaction zone 21 12 in the form of radiant energy. For example, the combustion products 2105 (and/or fuel) can be seeded with sources of sodium, potassium, and/or magnesium, which can absorb energy from the combustion products 2105 and radiate the energy outwardly into the reaction zone 21 12 at desirable frequencies. These illuminant additives can be used in addition to the re-radiation component 2150.

[00121] Figure 9 is a graph presenting absorption as a function of wavelength for a representative reactant (e.g., methane) and a representative re-radiation component. Figure 8 illustrates a reactant absorption spectrum 2130 that includes multiple reactant peak absorption ranges 2131 , three of which are highlighted in Figure 8 as first, second and third peak absorption ranges 2131 a, 2131 b, 2131 c. The peak absorption ranges 2131 represent wavelengths for which the reactant absorbs more energy than at other portions of the spectrum 2130. The spectrum 2130 can include a peak absorption wavelength 2132 within a particular range, e.g., the third peak absorption range 2131 c.

[00122] Figure 9 also illustrates a first radiant energy spectrum 2140a having a first peak wavelength range 2141 a. For example, the first radiant energy spectrum 2140a can be representative of the emission from the combustion products 2105 described above with reference to Figure 8. After the radiant energy has been absorbed and re-emitted by the re-radiation component 2150 described above, it can produce a second radiant energy spectrum 2140b having a second peak wavelength range 2141 b, which in turn includes a re-radiation peak value 2142. In general terms, the function of the re-radiation component 2150 is to shift the spectrum of the radiant energy from the first radiant energy spectrum 2140a and peak wavelength range 2141 a to the second radiant energy spectrum 2140b and peak wavelength range 2141 b, as indicated by arrow S. As a result of the shift, the second peak wavelength range 2141 b is closer to the third peak absorption range 2131 c of the reactant than is the first peak wavelength range 2141 a. For example, the second peak wavelength range 2141 b can overlap with the third peak absorption range 2131 c and in a particular embodiment, the re-radiation peak value 2142 can be at, or approximately at the same wavelength as the reactant peak absorption wavelength 2132. In this manner, the re-radiation component more closely aligns the spectrum of the radiant energy with the peaks at which the reactant efficiently absorbs energy. Representative structures for performing this function are described in further detail below with reference to Figures 9. [00123] Figure 10 is a partially schematic, enlarged cross-sectional illustration of a portion of the reactor 21 10 described above with reference to Figure 8, having a re-radiation component 2150 configured in accordance with a particular embodiment of the technology. The re-radiation component 2150 is positioned between the passage 21 18 (and the radiation energy R in the passage 21 18), and the reaction zone 21 12. The re-radiation component 2150 can include layers 2151 of material that form spaced-apart structures 2158, which in turn carry a re-radiative material 2152. For example, the layers 2151 can include graphene layers or other crystal or self-orienting layers made from suitable building block elements such as carbon, boron, nitrogen, silicon, transition metals, and/or sulfur. Carbon is a particularly suitable constituent because it is relatively inexpensive and readily available. In fact, it is a target output product of reactions that can be completed in the reaction zone 21 12. Further details of suitable structures are disclosed in co-pending U.S. Application No. 12/857,228 previously incorporated herein by reference. Each structure 2158 can be separated from its neighbor by a gap 2153. The gap 2153 can be maintained by spacers 2157 extending between neighboring structures 2158. In particular embodiments, the gaps 2153 between the structures 2158 can be from about 2.5 microns to about 25 microns wide. In other embodiments, the gap 2153 can have other values, depending, for example, on the wavelength of the incident radiative energy R. The spacers 2157 are positioned at spaced-apart locations both within and perpendicular to the plane of Figure 10 so as not to block the passage of radiation and/or chemical constituents through the component 2150.

[00124] The radiative energy R can include a first portion R1 that is generally aligned parallel with the spaced-apart layered structures 2158 and accordingly passes entirely through the re-radiation component 2150 via the gaps 2153 and enters the reaction zone 21 12 without contacting the re-radiative material 2152. The radiative energy R can also include a second portion R2 that impinges upon the re- radiative material 2152 and is accordingly re-radiated as a re-radiated portion RR into the reaction zone 21 12. The reaction zone 21 12 can accordingly include radiation having different energy spectra and/or different peak wavelength ranges, depending upon whether the incident radiation R impinged upon the re-radiative material 2152 or not. This combination of energies in the reaction zone 21 12 can be beneficial for at least some reactions. For example, the shorter wavelength, higher frequency (higher energy) portion of the radiative energy can facilitate the basic reaction taking place in the reaction zone 21 12, e.g., disassociating methane in the presence of steam to form carbon monoxide and hydrogen. The longer wavelength, lower frequency (lower energy) portion can prevent the reaction products from adhering to surfaces of the reactor 21 10, and/or can separate such products from the reactor surfaces. In particular embodiments, the radiative energy can be absorbed by methane in the reaction zone 21 12, and in other embodiments, the radiative energy can be absorbed by other reactants, for example, the steam in the reaction zone 21 12, or the products. In at least some cases, it is preferable to absorb the radiative energy with the steam. In this manner, the steam receives sufficient energy to be hot enough to complete the endothermic reaction within the reaction zone 21 12, without unnecessarily heating the carbon atoms, which may potentially create particulates or tar if they are not quickly oxygenated after dissociation.

[00125] The re-radiative material 2152 can include a variety of suitable constituents, including iron carbide, tungsten carbide, titanium carbide, boron carbide, and/or boron nitride. These materials, as well as the materials forming the spaced-apart structures 2158, can be selected on the basis of several properties including corrosion resistance and/or compressive loading. For example, loading a carbon structure with any of the foregoing carbides or nitrides can produce a compressive structure. An advantage of a compressive structure is that it is less subject to corrosion than is a structure that is under tensile forces. In addition, the inherent corrosion resistance of the constituents of the structure (e.g., the foregoing carbides and nitrides) can be enhanced because, under compression, the structure is less permeable to corrosive agents, including steam which may well be present as a reactant in the reaction zone 21 12 and as a constituent of the combustion products 2105 in the passage 21 18. The foregoing constituents can be used alone or in combination with phosphorus, calcium fluoride and/or another phosphorescent material so that the energy re-radiated by the re-radiative material 2152 may be delayed. This feature can smooth out at least some irregularities or intermittencies with which the radiant energy is supplied to the reaction zone 21 12.

[00126] Another suitable re-radiative material 2152 includes spinel or another composite of magnesium and/or aluminum oxides. Spinel can provide the compressive stresses described above and can shift absorbed radiation to the infrared so as to facilitate heating the reaction zone 21 12. For example, sodium or potassium can emit visible radiation (e.g., red/orange/yellow radiation) that can be shifted by spinel or another alumina-bearing material to the IR band. If both magnesium and aluminum oxides, including compositions with colorant additives such as magnesium, aluminum, titanium, chromium, nickel, copper and/or vanadium, are present in the re-radiative material 2152, the re-radiative material 2152 can emit radiation having multiple peaks, which can in turn allow multiple constituents within the reaction zone 21 12 to absorb the radiative energy.

[00127] The particular structure of the re-radiation component 2150 shown in Figure 9 includes gaps 2153 that can allow not only radiation to pass through, but can also allow constituents to pass through. Accordingly, the re-radiation component 2150 can also form the transmissive surface 21 19, which, as described above with reference to Figure 8, can further facilitate the reaction in the reaction zone 21 12 by admitting reactants.

[00128] Still further embodiments of suitable reactors with re-radiative components are disclosed in pending U.S. Application No. 13/027,015, filed February 14, 201 1 , and incorporated herein by reference.

Representative Reactors with Heat Pipes and Heat Pumps

[00129] Figure 1 1 is a schematic cross-sectional view of a thermal transfer device 3100 ("device 3100") configured in accordance with an embodiment of the present technology. As shown in Figure 1 1 , the device 3100 can include a conduit 3102 that has an input portion 3104, an output portion 3106 opposite the input portion 3104, and a sidewall 3120 between the input and output portions 3104 and 3106. The device 3100 can further include a first end cap 3108 at the input portion 3104 and a second end cap 31 10 at the output portion 3106. The device 3100 can enclose a working fluid 3122 (illustrated by arrows) that changes between a vapor phase 3122a and a liquid phase 3122b during a vaporization-condensation cycle.

[00130] In selected embodiments, the device 3100 can also include one or more architectural constructs 31 12. Architectural constructs 31 12 are synthetic matrix characterizations of crystals that are primarily comprised of graphene, graphite, boron nitride, and/or another suitable crystal. The configuration and the treatment of these crystals heavily influence the properties that the architectural construct 31 12 will exhibit when it experiences certain conditions. For example, as explained in further detail below, the device 3100 can utilize architectural constructs 31 12 for their thermal properties, capillary properties, sorbtive properties, catalytic properties, and electromagnetic, optical, and acoustic properties. As shown in Figure 10, the architectural construct 31 12 can be arranged as a plurality of substantially parallel layers 31 14 spaced apart from one another by a gap 31 16. In various embodiments, the layers 31 14 can be as thin as one atom. In other embodiments, the thickness of the individual layers 31 14 can be greater and/or less than one atom and the width of the gaps 31 16 between the layers 31 14 can vary. Methods of fabricating and configuring architectural constructs, such as the architectural constructs 31 12 shown in Figure 1 1 , are described in U.S. Patent Application No. 12/857,228 previously incorporated herein by reference.

[00131] As shown in Figure 1 1 , the first end cap 3108 can be installed proximate to a heat source (not shown) such that the first end cap 3108 serves as a hot interface that vaporizes the working fluid 3122. Accordingly, the first end cap 3108 can include a material with a high thermal conductivity and/or transmissivity to absorb or deliver heat from the heat source. In the embodiment illustrated in Figure 10, for example, the first end cap 3108 includes the architectural construct 31 12 made from a thermally conductive crystal (e.g., graphene). The architectural construct 31 12 can be arranged to increase its thermal conductively by configuring the layers 31 14 to have a high concentration of thermally conductive pathways (e.g., formed by the layers 31 14) substantially parallel to the influx of heat. For example, in the illustrated embodiment, the layers 31 14 generally align with the incoming heat flow such that heat enters the architectural construct 31 12 between the layers 31 14. This configuration exposes the greatest surface area of the layers 31 14 to the heat and thereby increases the heat absorbed by the architectural construct 31 12. Advantageously, despite having a much lower density than metal, the architectural construct 31 12 can conductively and/or radiatively transfer a greater amount of heat per unit area than solid silver, raw graphite, copper, or aluminum.

[00132] As further shown in Figure 1 1 , the second end cap 31 10 can expel heat from the device 3100 to a heat sink (not shown) such that the second end cap 31 10 serves as a cold interface that condenses the working fluid 3122. The second end cap 31 10, like the first end cap 3108, can include a material with a high thermal conductivity (e.g., copper, aluminum) and/or transmissivity to absorb and/or transmit latent heat from the working fluid 3122. Accordingly, like the first end cap 3108, the second end cap 31 10 can include the architectural construct 31 12. However, rather than bringing heat into the device 3100 like the first end cap 3108, the second end cap 31 10 can convey latent heat out of the device 3100. In various embodiments, the architectural constructs 31 12 of the first and second end caps 3108 and 31 10 can be made from the similar materials and/or arranged to have substantially similar thermal conductivities. In other embodiments, the architectural constructs 31 12 can include different materials, can be arranged in differing directions, and/or otherwise configured to provide differing thermal conveyance capabilities including desired conductivities and transmissivities. In further embodiments, neither the first end cap 3108 nor the second end cap 31 10 includes the architectural construct 31 12.

[00133] In selected embodiments, the first end cap 3108 and/or the second end cap 31 10 can include portions with varying thermal conductivities. For example, a portion of the first end cap 3108 proximate to the conduit 3102 can include a highly thermally conductive material (e.g., the architectural construct 31 12 configured to promote thermal conductivity, copper, etc.) such that it absorbs heat from the heat source and vaporizes the working fluid 3122. Another portion of the first end cap 3108 spaced apart from the conduit 3102 can include a less thermally conductive material to insulate the high conductivity portion. In certain embodiments, for example, the insulative portion can include ceramic fibers, sealed dead air space, and/or other materials or structures with high radiant absorptivities and/or low thermal conductivities. In other embodiments, the insulative portion of the first end cap 3108 can include the architectural construct 31 12 arranged to include a low concentration of thermally conductive pathways (e.g., the layers 31 14 are spaced apart by large gaps 31 16) such that it has a low availability for conductively transferring heat.

[00134] In other embodiments, the configurations of the architectural constructs 31 12 may vary from those shown in Figure 1 1 based on the dimensions of the device 3100, the temperature differential between the heat source and the heat sink, the desired heat transfer, the working fluid 3122, and/or other suitable thermal transfer characteristics. For example, architectural constructs 31 12 having smaller surface areas may be suited for microscopic applications of the device 3100 and/or high temperature differentials, whereas architectural constructs 31 12 having higher surface areas may be better suited for macroscopic applications of the device 3100 and/or higher rates of heat transfer. The thermal conductivities of the architectural constructs 31 12 can also be altered by coating the layers 31 14 with dark colored coatings to increase heat absorption and with light colored coatings to reflect heat away and thereby decrease heat absorption.

[00135] Referring still to Figure 1 1 , the device 3100 can return the liquid phase 3122b of the working fluid 3122 to the input portion 3104 by capillary action. The sidewall 3120 of the conduit 3102 can thus include a wick structure that exerts a capillary pressure on the liquid phase 3122b to drive it toward a desired location (e.g., the input portion 3104). For example, the sidewall 3120 can include cellulose, ceramic wicking materials, sintered or glued metal powder, nanofibers, and/or other suitable wick structures or materials that provide capillary action.

[00136] In the embodiment shown in Figure 1 1 , the architectural construct 31 12 is aligned with the longitudinal axis 31 18 of the conduit 3102 and configured to exert the necessary capillary pressure to direct the liquid phase 3122b of the working fluid 3122 to the input portion 3104. The composition, dopants, spacing, and/or thicknesses of the layers 31 14 can be selected based on the surface tension required to provide capillary action for the working fluid 3122. Advantageously, the architectural construct 31 12 can apply sufficient capillary pressure on the liquid phase 3122b to drive the working fluid 3122 short and long distances (e.g., millimeters to kilometers). Additionally, in selected embodiments, the surface tension of the layers 31 14 can be manipulated such that the architectural construct 31 12 rejects a preselected fluid. For example, the architectural construct 31 12 can be configured to have a surface tension that rejects any liquid other than the liquid phase 3122b of the working fluid 3122. In such an embodiment, the architectural construct 31 12 can function as a filter that prevents any fluid other than the working fluid 3122 (e.g., fluids tainted by impurities that diffused into the conduit 3102) from interfering with the vaporization-condensation cycle.

[00137] In other embodiments, the selective capillary action of the architectural construct 31 12 separates substances at far lower temperatures than conventional distillation technologies. The faster separation of substances by the architectural construct 31 12 can reduce or eliminates substance degradation caused if the substance reaches higher temperatures within the device 3100. For example, a potentially harmful substance can be removed from the working fluid 3122 by the selective capillary action of the architectural construct 31 12 before the working fluid 3122 reaches the higher temperatures proximate to the input portion 3104.

[00138] The conduit 3102 and the first and second end caps 3108 and 31 10 can be sealed together using suitable fasteners able to withstand the temperature differentials of the device 3100. In other embodiments, the device 3100 is formed integrally. For example, the device 3100 can be molded using one or more materials. A vacuum can be used to remove any air within the conduit 3102, and then the conduit 3102 can be filled with a small volume of the working fluid 3122 chosen to match the operating temperatures.

[00139] In operation, the device 3100 utilizes a vaporization-condensation cycle of the working fluid 3122 to transfer heat. More specifically, the first end cap 3108 can absorb heat from the heat source, and the working fluid 3122 can in turn absorb the heat from the first end cap 3108 to produce the vapor phase 3122a. The pressure differential caused by the phase change of the working fluid 3122 can drive the vapor phase 3122a of the working fluid 3122 to fill the space available and thus deliver the working fluid 3122 through the conduit 3102 to the output portion 3104. At the output portion 3104, the second end cap 31 10 can absorb heat from the working fluid 3122 to change the working fluid 3122 to the liquid phase 3122b. The latent heat from the condensation of the working fluid 3122 can be transferred out of the device 3100 via the second end cap 31 10. In general, the heat influx to the first end cap 3108 substantially equals the heat removed by the second end cap 31 10. As further shown in Figure 1 1 , capillary action provided by the architectural construct 31 12 or other wick structure can return the liquid phase 3122b of the working fluid 3122 to the input portion 3104. In selected embodiments, the termini of the layers 31 14 can be staggered or angled toward the conduit 3102 to facilitate entry of the liquid phase 3122b between the layers 31 14 and/or to facilitate conversion of the liquid phase 3122b to the vapor phase 3122b at the input portion 3104. At the input portion 3104, the working fluid 3122 can again vaporize and continue to circulate through the conduit 3102 by means of the vaporization-condensation cycle. [00140] The device 3100 can also operate the vaporization-condensation cycle described above in the reverse direction. For example, when the heat source and heat sink are reversed, the first end cap 3108 can serve as the cold interface and the second end cap 31 10 can serve as the hot interface. Accordingly, the input and output portions 3104 and 3106 are inverted such that the working fluid 3122 vaporizes proximate to the second end cap 31 10, condenses proximate to the first end cap 3108, and returns to the second end cap 31 10 using the capillary action provided by the sidewall 3120. The reversibility of the device 3100 allows the device 3100 to be installed irrespective of the positions of the heat source and heat sink. Additionally, the device 3100 can accommodate environments in which the locations of the heat source and the heat sink may reverse. For example, as described further below, the device 3100 can operate in one direction during the summer to utilize solar energy and the device 3100 can reverse direction during the winter to utilize heat stored during the previous summer.

[00141] Embodiments of the device 3100 including the architectural construct 31 12 at the first end cap 3108 and/or second end cap 31 10 have higher thermal conductivity per unit area than conventional conductors. This increased thermal conductivity can increase process rate and the temperature differential between the first and second end caps 3108 and 31 10 to produce greater and more efficient heat transfer. Additionally, embodiments including the architectural construct 31 12 at the first and/or second end caps 3108 and 31 10 require less surface area to absorb the heat necessary to effectuate the vaporization-condensation cycle. Thus, the device 3100 can be more compact than a conventional heat pipe that transfers an equivalent amount of heat and provide considerable cost reduction.

[00142] Referring still to Figure 1 1 , in various embodiments, the device 3100 can further include a liquid reservoir 3124 in fluid communication with the conduit 3102 such that the liquid reservoir 3124 can collect and store at least a portion of the working fluid 3122. As shown in Figure 1 1 , the liquid reservoir 3124 can be coupled to the input portion 3104 of the conduit 3102 via a pipe or other suitable tubular shaped structure. The liquid phase 3122b can thus flow from the sidewall 3120 (e.g., the architectural construct 31 12, wick structure, etc.) into the liquid reservoir 3124. In other embodiments, the liquid reservoir 3124 is in fluid communication with another portion of the conduit 3102 (e.g., the output portion 3106) such that the liquid reservoir 3124 collects the working fluid 3122 in the vapor phase 3122a or in mixed phases.

[00143] The liquid reservoir 3124 allows the device 3100 to operate in at least two modes: a heat accumulation mode and a heat transfer mode. During the heat accumulation mode, the vaporization-condensation cycle of the working fluid 3122 can be slowed or halted by funneling the working fluid 3122 from the conduit 3102 to the liquid reservoir 3124. The first end cap 3108 can then function as a thermal accumulator that absorbs heat without the vaporization-condensation cycle dissipating the accumulated heat. After the first end cap 3108 accumulates a desired amount of heat and/or the heat source (e.g., the sun) no longer supplies heat, the device 3100 can change to the heat transfer mode by funneling the working fluid 3122 into the conduit 3102. The heat stored in first end cap 3108 can vaporize the incoming working fluid 3122 and the pressure differential can drive the vapor phase 3122a toward the output portion 3106 of the conduit 3102 to restart the vaporization-condensation cycle described above. In certain embodiments, the restart of the vaporization-condensation cycle can be monitored to analyze characteristics (e.g., composition, vapor pressure, latent heat, efficiency) of the working fluid 3122.

[00144] As shown in Figure 1 1 , a controller 3126 can be operably coupled to the liquid reservoir 3124 to modulate the rate at which the working fluid 3122 enters the conduit 3102 and/or adjust the volume of the working fluid 3122 flowing into or out of the conduit 3102. The controller 3126 can thereby change the pressure within the conduit 3102 such that the device 3100 can operate at varying temperature differentials between the heat source and sink. Thus, the device 3100 can provide a constant heat flux despite a degrading heat source (e.g., first end cap 3108) or intermittent vaporization-condensation cycles.

[00145] Figures 12A and 12B are schematic cross-sectional views of thermal transfer devices 3200a, 3200b ("devices 3200") in accordance with other embodiments of the present technology. Several features of the devices 3200 are generally similar to the features of the device 3100 shown in Figure 1 1 . For example, each device 3200 can include the conduit 3102, the sidewall 3120, and the first and second end caps 3108 and 31 10. The device 3200 also transfers heat from a heat source to a heat sink utilizing a vaporization-condensation cycle of the working fluid 3122 generally similar to that described with reference to Figure 10. Additionally, as shown in Figures 12A and 12B, the device 3200 can further include the liquid reservoir 3124 and the controller 3126 such that the device 3200 can operate in the heat accumulation mode and the heat transfer mode.

[00146] The devices 3200 shown in Figures 12A and 12B can utilize gravity, rather than the capillary action described in Figure 10, to return the liquid phase 3122b of the working fluid 3122 to the input portion 3104. Thus, as shown in Figures 12A and 12B, the heat inflow is below the heat output such that gravity can drive the liquid phase 3122b down the sidewall 3120 to the input portion 3104. Thus, as shown in Figure 12A, the sidewall 3120 need only include an impermeable membrane 3228, rather than a wick structure necessary for capillary action, to seal the working fluid 3122 within the conduit 3102. The impermeable membrane 3228 can be made from a polymer such as polyethylene, a metal or metal alloy such as copper and stainless steel, and/or other suitable impermeable materials. In other embodiments, the devices 3200 can utilize other sources of acceleration (e.g., centrifugal force, capillary action) to return the liquid phase 3122b to the input portion 3104 such that the positions of the input and output portions 3104 and 3106 are not gravitationally dependent.

[00147] As shown in Figure 12B, in other embodiments, the sidewall 3120 can further include the architectural construct 31 12. For example, the architectural construct 31 12 can be arranged such that the layers 31 14 are oriented orthogonal to the longitudinal axis 31 18 of the conduit 3102 to form thermally conductive passageways that transfer heat away from the conduit 3102. Thus, as the liquid phase 3122b flows along the sidewall 3120, the architectural construct 31 12 can draw heat from the liquid phase 3122b, along the layers 31 14, and away from the sidewall 3120 of the device 3200. This can increase the temperature differential between the input and output portions 3104 and 3106 to increase the rate of heat transfer and/or facilitate the vaporization-condensation cycle when the temperature gradient would otherwise be insufficient. In other embodiments, the layers 31 14 can be oriented at a different angle with respect to the longitudinal axis 31 18 to transfer heat in a different direction. In certain embodiments, the architectural construct 31 12 can be positioned radially outward of the impermeable membrane 3228. In other embodiments, the impermeable membrane 3228 can be radially outward of architectural construct 31 12 or the architectural construct 31 12 itself can provide a sufficiently impervious wall to seal the working fluid 3122 within the conduit 3102.

[00148] The first and second end caps 3108 and 31 10 shown in Figures 12A and 12B can also include the architectural construct 31 12. As shown in Figures 12A and 12B, the layers 31 14 of the architectural constructs 31 12 are generally aligned with the direction heat input and heat output to provide thermally conductive passageways that efficiently transfer heat. Additionally, the architectural constructs 31 12 of the first and/or second end caps 3108 and 31 10 can be configured to apply a capillary pressure for a particular substance entering or exiting the conduit. For example, the composition, spacing, dopants, and/or thicknesses of the layers 31 14 of the architectural constructs 31 12 can be modulated to selectively draw a particular substance between the layers 31 14. In selected embodiments, the architectural construct 31 12 can include a first zone of layers 31 14 that are configured for a first substance and a second zone of layers 31 14 that are configured for a second substance to selectively remove and/or add two or more desired substances from the conduit 3102.

[00149] In further embodiments, the second end cap 31 10 can utilize the sorbtive properties of the architectural constructs 31 12 to selectively load a desired constituent of the working fluid 3122 between the layers 31 14. The construction of the architectural construct 31 12 can be manipulated to obtain the requisite surface tension to load almost any element or soluble. For example, the layers 31 14 can be preloaded with predetermined dopants or materials to adjust the surface tension of adsorption along these surfaces. In certain embodiments, the layers 31 14 can be preloaded with C0₂ such that the architectural construct 31 12 can selectively mine C0₂ from the working fluid 3122 as heat releases through the second end cap 31 10. In other embodiments, the layers 31 14 can be spaced apart from one another by a predetermined distance, include a certain coating, and/or otherwise be arranged to selectively load the desired constituent. In some embodiments, the desired constituent adsorbs onto the surfaces of individual layers 31 14, while in other embodiments the desired constituent absorbs into zones between the layers 31 14. In further embodiments, substances can be purposefully fed into the conduit 3102 from the input portion 3104 (e.g., through the first end cap 3108) such that the added substance can combine or react with the working fluid 3122 to produce the desired constituent. Thus, the architectural construct 31 12 at the second end cap 31 10 can facilitate selective mining of constituents. Additionally, the architectural construct 31 12 can remove impurities and/or other undesirable solubles that may have entered the conduit 3102 and potentially interfere with the efficiency of the device 3200.

[00150] Similarly, in selected embodiments, the architectural construct 31 12 at the first end cap 31 10 can also selectively load desired compounds and/or elements to prevent them from ever entering the conduit 3102. For example, the architectural construct 31 12 can filter out paraffins that can impede or otherwise interfere with the heat transfer of the device 3200. In other embodiments, the devices 3200 can include other filters that may be used to prevent certain materials from entering the conduit 3102.

[00151] Moreover, similar to selective loading of compounds and elements, the architectural construct 31 12 at the first and second end caps 3108 and 31 10 may also be configured to absorb radiant energy of a desired wavelength. For example, the layers 31 14 can have a certain thickness, composition, spacing to absorb a particular wavelength of radiant energy. In selected embodiments, the architectural construct 31 12 absorbs radiant energy of a first wavelength and converts it into radiant energy of a second wavelength, retransmitting at least some of the absorbed energy. For example, the layers 31 14 may be configured to absorb ultraviolet radiation and convert the ultraviolet radiation into infrared radiation.

[00152] Additionally, the layers 31 14 can also catalyze a reaction by transferring heat to a zone where the reaction is to occur. In other implementations, the layers 31 14 catalyze a reaction by transferring heat away from a zone where a reaction is to occur. For example, heat may be conductively transferred into the layers 31 14 (e.g., as discussed in U.S. Patent Application No. 12/857,515, filed August 16, 2010, entitled "APPARATUSES AND METHODS FOR STORING AND/OR FILTERING A SUBSTANCE" which is incorporated by reference herein in its entirety) to supply heat to an endothermic reaction within a support tube of the layers 31 14. In some implementations, the layers 31 14 catalyze a reaction by removing a product of the reaction from the zone where the reaction is to occur. For example, the layers 31 14 may absorb alcohol from a biochemical reaction within a central support tube in which alcohol is a byproduct, thereby expelling the alcohol on outer edges of the layers 31 14, and prolonging the life of a microbe involved in the biochemical reaction.

[00153] Figure 13A is schematic cross-sectional view of a thermal transfer device 3300 ("device 3300") operating in a first direction in accordance with a further embodiment of the present technology, and Figure 13B is a schematic cross- sectional view of the device 3300 of Figure 13A operating in a second direction opposite the first direction. Several features of the device 3300 are generally similar to the features of the devices 3100 and 3200 shown in Figures 1 1 -13B. For example, the device 3300 can include the conduit 3102, the first and second end caps 3108 and 31 10, and the architectural construct 31 12. As shown in Figures 13A and 13B, the sidewall 3120 of the device 3300 can include two architectural constructs 31 12: a first architectural construct 31 12a having layers 31 14 oriented parallel to the longitudinal axis 31 18 of the conduit 3102 and a second architectural construct 31 12b radially inward from the first architectural construct 31 12a and having layers 31 14 oriented perpendicular to the longitudinal axis 31 18. The layers 31 14 of the first architectural construct 31 12a can perform a capillary action, and the layers 31 14 of the second architectural construct 31 12b can form thermally conductive passageways that transfer heat away from the side of the conduit 3102 and thereby increase the temperature differential between the input and output portions 3104 and 3106.

[00154] Similar to the device 3100 shown in Figure 1 1 , the device 3300 can also operate when the direction of heat flow changes and the input and output portions 3104 and 3106 are inverted. As shown in Figure 13A, for example, the device 3300 can absorb heat at the first end cap 3108 to vaporize the working fluid 3122 at the input portion 3104, transfer the heat via the vapor phase 3122a of the working fluid 3122 through the conduit 3102, and expel heat from the second end cap 31 10 to condense the working fluid 3122 at the output portion 3106. As further shown in Figure 13A, the liquid phase 3122b of the working fluid 3122 can move between the layers 31 14 of the first architectural construct 31 12b by capillary action as described above with reference to Figure 1 1 . In other embodiments, the sidewall 3120 can include a different capillary structure (e.g., cellulose) that can drive the liquid phase 3122b from the output portion 3106 to the input portion 3104. As shown in Figure 13B, the conditions can be reversed such that heat enters the device 3300 proximate to the second end cap 31 10 and exits the device 3300 proximate to the first end cap 3108. Advantageously, as discussed above, the dual-direction vapor-condensation cycle of the working fluid 3122 accommodates environments in which the locations of the heat source and the heat sink reverse.

[00155] In at least some embodiments, a heat pump can be used to transfer heat, in addition to or in lieu of a heat pipe, and the transferred heat can be used to enhance the efficiency and/or performance of a reactor to which the heat pump is coupled. In particular embodiments, the heat is extracted from a permafrost, geothermal, ocean and/or other source. Figure 14 is a partially schematic illustration of a reversible heat pump 3150 positioned to receive heat from a source 3202 (e.g., a geothermal source), as indicated by arrow H1 , and deliver the heat at a higher temperature than that of the source, as indicated by arrow H2. The heat pump 3150 transfers heat via a working fluid that can operate in a closed loop refrigeration cycle. Accordingly, the heat pump 3150 can include a compressor 3154, an expansion valve 3162, supply and return conduits 3156, 3160, and first and second heat exchangers 3152, 3158. In operation, the working fluid receives heat from the source 3202 via the second heat exchanger 3158. The working fluid passes through the supply conduit 3156 to the compressor 3154 where it is compressed, and delivers heat (e.g., to a non-combustion reactor) at the first heat exchanger 3152. The working fluid then expands through the expansion valve 3162 and returns to the second heat exchanger 3158 via the return conduit 3160.

[00156] The working fluid can be selected based at least in part on the temperature of the source 3202 and the required delivery temperature. For example, the working fluid can be a relatively inert fluid such as Freon, ammonia, or carbon dioxide. Such fluids are compatible with various polymer and metal components. These components can include tube liner polymers such as fluorinated ethylene- propylene, perfluoroalkoxy, polyvinylidene fluoride, tetraflouroethylene, an ethylene- propylene dimer, and/or many other materials that may be reinforced with fibers such as graphite, E-glass, S-glass, glass-ceramic or various organic filaments to form the conduits 3156, 3160. The heat exchangers 3158 can be made from metal alloys, e.g., Type 304 or other "300" series austenitic stainless steels, aluminum alloys, brass or bronze selections. The compressor 3154 can be a positive displacement or turbine type compressor depending upon factors that include the scale of the application. The expansion valve 3162 can be selected to meet the pressure drop and flow requirements of a particular application.

[00157] In a representative embodiment for which the source 3202 is at a moderate temperature (e.g., 125°F (52°C)), the working fluid can include carbon dioxide that is expanded through the valve 3162 to a reduced temperature (e.g., 1 15°F (46°C)). The working fluid receives heat at the source 3202 to achieve a representative temperature of 120°F (49°C). At the compressor 3154, the temperature of the working fluid is elevated to a representative value of 325°F (163°C) or higher. In particular embodiments, one or more additional heat pump cycles (not shown) can be used to further elevate the delivery temperature. It can be particularly advantageous to use heat pump cycles to deliver heat at a higher temperature than the source 3202 because such cycles typically deliver two to ten times more heat energy compared to the energy required for operation of the compressor 3154.

[00158] In a generally similar manner, it can be advantageous to use one or more heat pump cycles in reverse to cool a working fluid to a temperature below the ambient temperature and thus "refrigerate" the substance being cooled. For example, permafrost or methane hydrates in lake bottoms or ocean deposits can be cooled to a temperature far below the ambient temperature of the air or surrounding water in such applications.

[00159] Still further embodiments of suitable reactors with transmissive surfaces are disclosed in pending U.S. Application No. 13/027,244, filed February 14, 201 1 , and incorporated herein by reference.

Representative Reactors with Solar Conveyors

[00160] Figure 15 is a partially schematic illustration of a system 4100 including a reactor vessel 41 10 having a reaction zone 41 1 1 . The system 4100 further includes a solar collector 4101 that directs solar energy 4103 to the reaction zone 41 1 1 . The solar collector 4101 can include a dish, trough, heliostat arrangement, fresnel lens and/or other radiation-focusing element. The reactor vessel 41 10 and the solar collector 4101 can be mounted to a pedestal 4102 that allows the solar collector 4101 to rotate about at least two orthogonal axes in order to continue efficiently focusing the solar energy 4103 as the earth rotates. The system 4100 can further include multiple reactant/product vessels 4170, including first and second reactant vessels 4170a, 4170b, and first and second product vessels, 4170c, 4170d. In particular embodiments, the first reactant vessel 4170a can provide a reactant that contains hydrogen and carbon, such as methane, which is processed at the reaction zone 41 1 1 in an endothermic reaction to produce hydrogen and carbon which is provided to the first and second product vessels 4170c, 4170d, respectively. In other embodiments, other reactants, for example, municipal solid waste streams, biomass reactants, and/or other waste streams can be provided at a hopper 4171 forming a portion of the second reactant vessel 4170b. In any of these embodiments, an internal reactant delivery system and product removal system provide the reactants to the reaction zone 41 1 1 and remove the products from the reaction zone 41 1 1 , as will be described in further detail later with reference to Figure 17.

[00161] The system 4100 can further include a supplemental heat source 4180 that provides heat to the reaction zone 41 1 1 when the available solar energy 4103 is insufficient to sustain the endothermic reaction at the reaction zone 41 1 1 . In a particular embodiment, the supplemental heat source 4180 can include an inductive heater 4181 that is positioned away from the reaction zone 41 1 1 during the day to allow the concentrated solar energy 4103 to enter the reaction zone 41 1 1 , and can slide over the reaction zone 41 1 1 at night to provide heat to the reaction zone 41 1 1 . The inductive heater 4181 can be powered by a renewable clean energy source, for example, hydrogen produced by the reactor vessel 41 10 during the day, or falling water, geothermal energy, wind energy, or other suitable sources.

[00162] In any of the foregoing embodiments, the system 4100 can further include a controller 4190 that receives input signals 4191 and directs the operation of the devices making up the system 4100 via control signals or other outputs 4192. For example, the controller 4190 can receive a signal from a radiation sensor 4193 indicating when the incident solar radiation is insufficient to sustain the reaction at the reaction zone 41 1 1 . In response, the controller 4190 can issue a command to activate the supplemental heat source 4180. The controller 4190 can also direct the reactant delivery and product removal systems, described further below with reference to Figure 17.

[00163] Figure 16 is a partially schematic illustration of an embodiment of the reactor vessel 41 10 shown in Figure 15, illustrating a transmissive component 41 12 positioned to allow the incident solar energy 4103 to enter the reaction zone 41 1 1 . In a particular embodiment, the transmissive component 41 12 can include a glass or other suitably transparent, high temperature material that is easily transmissible to solar radiation, and configured to withstand the high temperatures in the reaction zone 41 1 1 . For example, temperatures at the reaction zone 41 1 1 are in some embodiments expected to reach 44000°F, and can be higher for the reactants and/or products.

[00164] In other embodiments, the transmissive component 41 12 can include one or more elements that absorb radiation at one wavelength and re-radiate it at another. For example, the transmissive component 41 12 can include a first surface 41 13a that receives incident solar energy at one wavelength and a second surface 41 13b that re-radiates the energy at another wavelength into the reaction zone 41 1 1 . In this manner, the energy provided to the reaction zone 41 1 1 can be specifically tailored to match or approximate the absorption characteristics of the reactants and/or products placed within the reaction zone 41 1 1 . Further details of representative re-radiation devices were described above.

[00165] In other embodiments, the reactor vessel 41 10 can include other structures that perform related functions. For example, the reactor vessel 41 10 can include a Venetian blind arrangement 41 14 having first and second surfaces 41 13a, 41 13b that can be pivoted to present one surface or the other depending upon external conditions, e.g., the level of incident solar energy 4103. In a particular aspect of this embodiment, the first surface 41 13a can have a relatively high absorptivity and a relatively low emissivity. This surface can accordingly readily absorb radiation during the day. The second surface 41 13b can have a relatively low absorptivity and a relatively high emissivity and can accordingly operate to cool the reaction zone 41 1 1 (or another component of the reactor 41 10), e.g., at night. A representative application of this arrangement is a reactor that conducts both endothermic and exothermic reactions, as is described further in Section 3.8 below. Further details of other arrangements for operating the solar collector 4101 (Figure 14) in a cooling mode are described in Section 3.5 below.

[00166] In still further embodiments, the reactor 41 10 can include features that redirect radiation that "spills" (e.g., is not precisely focused on the transmissive component 41 12) due to collector surface aberrations, environmental defects, non- parallel radiation, wind and/or other disturbances or distortions. These features can include additional Venetian blinds 41 14a that can be positioned and/or adjusted to redirect radiation (with or without wavelength shifting) into the reaction zone 41 1 1 .

[00167] Figure 17 is a partially schematic, cross-sectional illustration of a portion of a reactor vessel 41 10 configured in accordance with an embodiment of the present disclosure. In one aspect of this embodiment, the reactor 41 10 includes a reactant delivery system 4130 that is positioned within a generally cylindrical, barrel- shaped reactor vessel 41 10, and a product removal system 4140 positioned annularly inwardly from the reactant delivery system 4130. For example, the reactant delivery system 4130 can include an outer screw 4131 , which in turn includes an outer screw shaft 4132 and outwardly extending outer screw threads 4133. The outer screw 4131 has an axially extending first axial opening 4135 in which the product removal system 4140 is positioned. The outer screw 4131 rotates about a central rotation axis 41 15, as indicated by arrow O. As it does so, it carries at least one reactant 4134 (e.g., a gaseous, liquid, and/or solid reactant) upwardly and to the right as shown in Figure 17, toward the reaction zone 41 1 1 . As the reactant 4134 is carried within the outer screw threads 4133, it is also compacted, potentially releasing gases and/or liquids, which can escape through louvers and/or other openings 41 18 located annularly outwardly from the outer screw 4131 . As the reactant 4134 becomes compacted in the outer screw threads 4133, it forms a seal against an inner wall 41 19 of the vessel 41 10. This arrangement can prevent losing the reactant 4134, and can instead force the reactant 4134 to move toward the reaction zone 41 1 1 . The reactant delivery system 4130 can include other features, in addition to the outer screw threads 4133, to force the reactant 4134 toward the reaction zone 41 1 1 . For example, the inner wall 41 19 of the reactor vessel 41 10 can include one or more spiral rifle grooves 41 16 that tend to force the reactant 4134 axially as the outer screw 4131 rotates. In addition to, or in lieu of this feature, the entire outer screw 4131 can reciprocate back and forth, as indicated by arrow R to prevent the reactant 4134 from sticking to the inner wall 41 19, and/or to release reactant 4134 that may stick to the inner wall 41 19. A barrel heater 41 17 placed near the inner wall 41 19 can also reduce reactant sticking, in addition to or in lieu of the foregoing features. In a least some embodiments, it is expected that the reactant 4134 will be less likely to stick when warm. [00168] The reactant 4134 can include a variety of suitable compositions, e.g., compositions that provide a hydrogen donor to the reaction zone 41 1 1 . In representative embodiments, the reactant 4134 can include biomass constituents, e.g., municipal solid waste, commercial waste, forest product waste or slash, cellulose, lignocellulose, hydrocarbon waste (e.g., tires), and/or others. After being compacted, these waste products can be highly subdivided, meaning that they can readily absorb incident radiation due to rough surface features and/or surface features that re-reflect and ultimately absorb incident radiation. This property can further improve the efficiency with which the reactant 4134 heats up in the reaction zone 41 1 1 .

[00169] Once the reactant 4134 has been delivered to the reaction zone 41 1 1 , it receives heat from the incident solar energy 4103 or another source, and undergoes an endothermic reaction. The reaction zone 41 1 1 can have an annular shape and can include insulation 4120 to prevent heat from escaping from the vessel 41 10. In one embodiment, the endothermic reaction taking place at the reaction zone 41 1 1 includes dissociating methane, and reforming the carbon and hydrogen constituents into elemental carbon and diatomic hydrogen, or other carbon compounds (e.g., oxygenated carbon in the form of carbon monoxide or carbon dioxide) and hydrogen compounds. The resulting product 4146 can include gaseous portions (indicated by arrow G), which passed annularly inwardly from the reaction zone 41 1 1 to be collected by the product removal system 4140. Solid portions 4144 (e.g., ash and/or other byproducts) of the product 4146 are also collected by the product removal system 4140.

[00170] The product removal system 4140 can include an inner screw 4141 positioned in the first axial opening 4135 within the outer screw 4131 . The inner screw 4141 can include an inner screw shaft 4142 and inner screw threads 4143. The inner screw 4141 can also rotate about the rotation axis 41 15, as indicated by arrow I, in the same direction as the outer screw 4131 or in the opposite direction. The inner screw 4141 includes a second axial passage 4145 having openings that allow the gaseous product G to enter. The gaseous product G travels down the second axial opening 4145 to be collected and, in at least some instances, further processed (e.g., to isolate the carbon produced in the reaction from the hydrogen produced in the reaction). In particular embodiments, the gaseous product G can exchange additional heat with the incoming reactant 4134 via an additional heat exchanger (not shown in Figure 17) to cool the product G and heat the reactant 4134. In other embodiments, the gaseous product G can be cooled by driving a Stirling engine or other device to generate mechanical and/or electric power. As the inner screw 4141 rotates, it carries the solid portions 4144 of the product 4146 downwardly and to the left as shown in Figure 17. The solid products 4144 (and the gaseous product G) can convey heat via conduction to the outer screw 4131 to heat the incoming reactant 4134, after which the solid portions 4144 can be removed for use. For example, nitrogenous and/or sulfurous products from the reaction performed at the reaction zone 41 1 1 can be used in agricultural or industrial processes. The products and therefore the chemical and physical composition of the solid portions can depend on the characteristics of the incoming reactants, which can vary widely, e.g., from municipal solid waste to industrial waste to biomass.

[00171] As discussed above with reference to Figures 15 and 16, the system 4100 can include features that direct energy (e.g., heat) into the reaction zone 41 1 1 even when the available solar energy is insufficient to sustain the reaction. In an embodiment shown in Figure 16, the supplemental heat source 4180 can include combustion reactants 4182 (e.g., an oxidizer and/or a hydrogen-containing combustible material) that is directed through a delivery tube 4184 positioned in the second axial opening 4145 to a combustor or combustor zone 4183 that is in thermal communication with the reaction zone 41 1 1 . During the night or other periods of time when the incident solar energy is low, the supplemental heat source 4180 can provide additional heat to the reaction zone 41 1 1 to sustain the endothermic reaction taking place therein.

[00172] One feature of an embodiment described above with reference to Figure 17 is that the incoming reactant 4134 can be in close or intimate thermal communication with the solid product 4144 leaving the reaction zone. In particular, the outer screw shaft 4132 and outer screw threads 4133 can be formed from a highly thermally conductive material, so as to receive heat from the solid product 4144 carried by the inner screw 4141 , and deliver the heat to the incoming reactant 4134. An advantage of this arrangement is that it is thermally efficient because it removes heat from products that would otherwise be cooled in a manner that wastes the heat, and at the same time heats the incoming reactants 4134, thus reducing the amount of heat that must be produced by the solar collector 4101 (Figure 15) and/or the supplemental heat source 4180. By improving the efficiency with which hydrogen and/or carbon or other building blocks are produced in the reactor vessel 41 10, the reactor system 4100 can increase the commercial viability of the renewable reactants and energy sources used to produce the products.

[00173] Still further embodiments of suitable reactors with solar conveyors are disclosed in issued U.S. Patent No. 8,187,549, incorporated herein by reference.

Representative Reactors with Solar Concentrators

[00174] Figure 18 is a partially schematic, partial cross-sectional illustration of a system 5100 having a reactor 51 10 coupled to a solar concentrator 5120 in accordance with the particular embodiment of the technology. In one aspect of this embodiment, the solar concentrator 5120 includes a dish 5121 mounted to pedestal 5122. The dish 5121 can include a concentrator surface 5123 that receives incident solar energy 5126, and directs the solar energy as focused solar energy 5127 toward a focal area 5124. The dish 5121 can be coupled to a concentrator actuator 5125 that moves the dish 5121 about at least two orthogonal axes in order to efficiently focus the solar energy 5126 as the earth rotates. As will be described in further detail below, the concentrator actuator 5125 can also be configured to deliberately position the dish 5121 to face away from the sun during a cooling operation.

[00175] The reactor 51 10 can include one or more reaction zones 51 1 1 , shown in Figure 18 as a first reaction zone 51 1 1 a and second reaction zone 51 1 1 b. In a particular embodiment, the first reaction zone 51 1 1 a is positioned at the focal area 5124 to receive the focused solar energy 5127 and facilitate a dissociation reaction or other endothermic reaction. Accordingly, the system 5100 can further include a distribution/collection system 5140 that provides reactants to the reactor 51 10 and collects products received from the reactor 51 10. In one aspect of this embodiment, the distribution/collection system 5140 includes a reactant source 5141 that directs a reactant to the first reaction zone 51 1 1 a, and one or more product collectors 5142 (two are shown in Figure 18 as a first product collector 5142a and a second product collector 5142b) that collect products from the reactor 51 10. When the reactor 51 10 includes a single reaction zone (e.g. the first reaction zone 51 1 1 a) the product collectors 5142a, 5142b can collect products directly from the first reaction zone 51 1 1 a. In another embodiment, intermediate products produced at the first reaction zone 51 1 1 a are directed to the second reaction zone 51 1 1 b. At the second reaction zone 51 1 1 b, the intermediate products can undergo an exothermic reaction, and the resulting products are then delivered to the product collectors 5142a, 5142b along a product flow path 5154. For example, in a representative embodiment, the reactant source 5141 can include methane and carbon dioxide, which are provided (e.g., in an individually controlled manner) to the first reaction zone 51 1 1 a and heated to produce carbon monoxide and hydrogen. The carbon monoxide and hydrogen are then provided to the second reaction zone 51 1 1 b to produce methanol in an exothermic reaction. Further details of this arrangement and associated heat transfer processes between the first reaction zone 51 1 1 a and second reaction zone 51 1 1 b are described in more detail below.

[00176] In at least some instances, it is desirable to provide cooling to the reactor 51 10, in addition to the solar heating described above. For example, cooling can be used to remove heat produced by the exothermic reaction being conducted at the second reaction zone 51 1 1 b and thus allow the reaction to continue. When the product produced at the second reaction zone 51 1 1 b includes methanol, it may desirable to further cool the methanol to a liquid to provide for convenient storage and transportation. Accordingly, the system 5100 can include features that facilitate using the concentrator surface 5123 to cool components or constituents at the reactor 51 10. In a particular embodiment, the system 5100 includes a first heat exchanger 5150a operatively coupled to a heat exchanger actuator 5151 b that moves the first heat exchanger 5150a relative to the focal area 5124. The first heat exchanger 5150a can include a heat exchanger fluid that communicates thermally with the constituents in the reactor 51 10, but is in fluid isolation from these constituents to avoid contaminating the constituents and/or interfering with the reactions taking place in the reactor 51 10. The heat exchanger fluid travels around a heat exchanger fluid flow path 5153 in a circuit from the first heat exchanger 5150a to a second heat exchanger 5150b and back. At the second heat exchanger 5150b, the heat exchanger fluid receives heat from the product (e.g. methanol) produced by the reactor 51 10 as the product proceeds from the second reaction zone 51 1 1 b to the distribution/collection system 5140. The heat exchanger fluid flow path 5153 delivers the heated heat exchanger fluid back to the first heat exchanger 5150a for cooling. One or more strain relief features 5152 in the heat exchanger fluid flow path 5153 (e.g., coiled conduits) facilitate the movement of the first heat exchanger 5150a. The system 5100 can also include a controller 5190 that receives input signals 5191 from any of a variety of sensors, transducers, and/or other elements of the system 5100, and, in response to information received from these elements, delivers control signals 5192 to adjust operational parameters of the system 5100.

[00177] Figure 19 illustrates one mechanism by which the heat exchanger fluid provided to the first heat exchanger 5150a is cooled. In this embodiment, the controller 5190 directs the heat exchanger actuator 5151 to drive the first heat exchanger 5150a from the position shown in Figure 18 to the focal area 5124, as indicated by arrows A. In addition, the controller 5190 can direct the concentrator actuator 5125 to position the dish 5121 so that the concentrator surface 5123 points away from the sun and to an area of the sky having very little radiant energy. In general, this process can be completed at night, when it is easier to avoid the radiant energy of the sun and the local environment, but in at least some embodiments, this process can be conducted during the daytime as well. A radiant energy sensor 5193 coupled to the controller 5190 can detect when the incoming solar radiation passes below a threshold level, indicating a suitable time for positioning the first heat exchanger 5150a in the location shown in Figure 19.

[00178] With the first heat exchanger 5150a in the position shown in Figure 19, the hot heat transfer fluid in the heat exchanger 5150a radiates emitted energy 5128 that is collected by the dish 5121 at the concentrator surface 5123 and redirected outwardly as directed emitted energy 5129. An insulator 5130 positioned adjacent to the focal area 5124 can prevent the radiant energy from being emitted in direction other than toward the concentrator surface 5123. By positioning the concentrator surface 5123 to point to a region in space having very little radiative energy, the region in space can operate as a heat sink, and can accordingly receive the directed emitted energy 5129 rejected by the first heat exchanger 5150a. The heat exchanger fluid, after being cooled at the first heat exchanger 5150a returns to the second heat exchanger 5150b to absorb more heat from the product flowing along the product flow path 5154. Accordingly, the concentrator surface 5123 can be used to cool as well as to heat elements of the reactor 51 10. [00179] In a particular embodiment, the first heat exchanger 5150a is positioned as shown in Figure 18 during the day, and as positioned as shown in Figure 19 during the night. In other embodiments, multiple systems 5100 can be coupled together, some with the corresponding first heat exchanger 5150a positioned as shown in Figure 18, and others with the first heat exchanger 5150a positioned as shown in Figure 19, to provide simultaneous heating and cooling. In any of these embodiments, the cooling process can be used to liquefy methanol, and/or provide other functions. Such functions can include liquefying or solidifying other substances, e.g., carbon dioxide, ethanol, butanol or hydrogen.

[00180] In particular embodiments, the reactants delivered to the reactor 51 10 are selected to include hydrogen, which is dissociated from the other elements of the reactant (e.g. carbon, nitrogen, boron, silicon, a transition metal, and/or sulfur) to produce a hydrogen-based fuel (e.g. diatomic hydrogen) and a structural building block that can be further processed to produce durable goods. Such durable goods include graphite, graphene, and/or polymers, which may be produced from carbon structural building blocks, and other suitable compounds formed from hydrogenous or other structural building blocks. Further details of suitable processes and products are disclosed in the following co-pending U.S. Patent Applications: 13/027,208 titled "CHEMICAL PROCESSES AND REACTORS FOR EFFICIENTLY PRODUCING HYDROGEN FUELS AND STRUCTURAL MATERIALS, AND ASSOCIATED SYSTEMS AND METHODS"; 13/027,214 titled "ARCHITECTURAL CONSTRUCT HAVING FOR EXAMPLE A PLURALITY OF ARCHITECTURAL CRYSTALS" (Attorney Docket No. 69545.8701 US); and 12/027,068 titled "CARBON- BASED DURABLE GOODS AND RENEWABLE FUEL FROM BIOMASS WASTE DISSOCIATION" (Attorney Docket No. 69545.9002US), all of which were filed February 14, 201 1 and are incorporated herein by reference.

[00181] Figure 20 illustrates a system 5300 having a reactor 5310 with a movable dish 5321 configured in accordance another embodiment of the disclosed technology. In a particular aspect of this embodiment, the reactor 5310 includes a first reaction zone 531 1 a and a second reaction zone 531 1 b, with the first reaction zone 531 1 a receiving focused solar energy 5127 when the dish 5321 has a first position, shown in solid lines in Figure 19. The dish 5321 is coupled to a dish actuator 5331 that moves the dish 5321 relative to the reaction zones 531 1 a, 531 1 b. Accordingly, during a second phase of operation, the controller 5190 directs the dish actuator 5331 to move the dish 5321 to the second position shown in dashed lines in Figure 20. In one embodiment, this arrangement can be used to provide heat to the second reaction zone 531 1 b when the dish 5321 is in the second position. In another embodiment, this arrangement can be used to cool the second reaction zone 531 1 b. Accordingly, the controller 5190 can direct the concentrator actuator 5125 to point the dish 5321 to a position in the sky having little or no radiant energy, thus allowing the second reaction zone 531 1 b to reject heat to the dish 5321 and ultimately to space, in a manner generally similar to that described above with reference to Figures 18 and 19.

[00182] Still further embodiments of suitable reactors with solar concentrators are disclosed in issued U.S. Patent No. 8,187,550, incorporated herein by reference.

Representative Reactors with Induction Heating

[00183] Figure 21 is a partially schematic, partial cross-sectional illustration of a system 6100 having a reactor 61 10 configured in accordance with an embodiment of the presently disclosed technology. In one aspect of this embodiment, the reactor 61 10 includes a reactor vessel 61 1 1 having a reaction or induction zone 6123 which is heated by an induction coil 6120. The induction coil 6120 can be a liquid-cooled, high frequency alternating current coil coupled to a suitable electrical power source 6121 . The reactor vessel 61 1 1 can further include an entrance port 61 12 coupled to a precursor gas source 6101 to receive a suitable precursor gas, and an exit port 61 13 positioned to remove spent gas and/or other constituents from the vessel 61 1 1 . In a particular embodiment, the precursor gas source 6101 carries a hydrocarbon gas (e.g., methane), which is dissociated into carbon and hydrogen at the induction zone 6123. The carbon is then deposited on a substrate to form a product, as is described further below, and the hydrogen and/or other constituents are removed for further processing, as is also described further below.

[00184] The reaction vessel 61 1 1 houses a first support 61 14a having a first support surface 61 15a, and a second support 61 14b having a second support surface 61 15b facing toward the first support surface 61 15a. Each support 61 14a, 61 14b can carry a substrate upon which one or more constituents of the precursor gas are deposited. For example, the first support 61 14a can carry a first substrate 6130a and the second support 61 14b can carry a second substrate 6130b. In a representative embodiment in which the precursor gas is selected to deposit carbon, the first and second substrates 6130a, 6130b can also include carbon, e.g., in the form of graphite or a constituent of steel. When the precursor gas includes a different deposition element (e.g., nitrogen and/or boron), the composition of the first and second substrates 6130a, 6130b can be different. Each of the substrates 6130a, 6130b can have an initially exposed surface facing the other. Accordingly, the first substrate 6130a can have an exposed first surface 6131 a facing toward a second exposed surface 6131 b of the second substrate 6130b. The remaining surfaces of each substrate 6130a, 6130b can be insulated to prevent or significantly restrict radiation losses from these surfaces. The supports 61 14a, 61 14b can insulate at least one surface of each of the substrates 6130a, 6130b. The other surfaces (other than the exposed first and second substrates 6131 a, 6131 b) can be protected by a corresponding insulator 6132. The insulator 6132 can be formed from a suitable high temperature ceramic or other material.

[00185] The system 6100 can further include a controller 6190 that receives input signals 6191 from any of a variety of sensors, transducers, and/or other elements of the system 6100, and in response to information received from these elements, delivers control signals 6192 to adjust operational parameters of the system 6100. These parameters can include the pressures and flow rates with which the gaseous constituents are provided to and/or removed from the reactor vessel 61 1 1 , the operation of the induction coil 6120 and associated power source 6121 , and the operation of a separator 6103 (described below), among others.

[00186] In operation, the precursor gas source 6101 supplies gas to the induction zone 6123, the induction coil 6120 is activated, and the precursor gas dissociates into at least one constituent (e.g., carbon) that is deposited onto the first and second substrates 6130a, 6130b. The constituent can be deposited in an epitaxial process that preserves the crystal grain orientation of the corresponding substrate 6130a, 6130b. Accordingly, the deposited constituent can also have a crystal and/or other self-organized structure. As the constituent is deposited, it forms a first formed structure or product 6140a at the first substrate 6130a, and a second formed structure or product 6140b at the second substrate 6130b. The first and second formed structures 6140a, 6140b each have a corresponding exposed surface 6141 a, 6141 b facing toward the other. The structures 6140a, 6140b can have the same or different cross-sectional shapes and/or areas, and/or can have non-crystalline, single crystal or multicrystal organizations, depending upon the selected embodiment. Radiation emitted by the first exposed surface 6131 a of the first substrate 6130a, and/or by the first exposed surface 6141 a of the first formed structure 6140a (collectively identified by arrow R1 ) is received at the second exposed surface 6141 b of the second formed structure 6140b, and/or the second exposed surface 6131 b of the second substrate 6130b. Similarly, radiation emitted by the second exposed surface 6141 b of the second formed structure 6140b and/or the second exposed surface 6131 b of the second substrate 6130b (collectively identified by arrow R2) is received at the first formed structure 6140a and/or the first substrate 6130a.

[00187] As the formed structures 6140a, 6140b grow, the exit port 61 13 provides an opening through which residual constituents from the dissociated precursor gas and/or non-dissociated quantities of the precursor gas can pass. These constituents are directed to a collection system 6102, which can include a separator 6103 configured to separate the constituents into two or more flow streams. For example, the separator 6103 can direct one stream of constituents to a first product collector 6104a, and a second stream of constituents to a second product collector 6104b. In a particular embodiment, the first product collector 6104a can collect pure or substantially pure hydrogen, which can be delivered to a hydrogen-based fuel cell 6105 or other device that requires hydrogen at a relatively high level of purity. The second stream of constituents directed to the second product collector 6104b can include hydrogen mixed with other elements or compounds. Such elements or compounds can include methane or another undissociated precursor gas, and/or carbon (or another element or compound targeted for deposition) that was not deposited on the first substrate 6130a or the second substrate 6130b. These constituents can be directed to an engine 6106, for example, a turbine engine or another type of internal combustion engine that can burn a mixture of hydrogen and the other constituents. The engine 6106 and/or the fuel cell 6105 can provide power for any number of devices, including the electrical power source 6121 for the induction coil 6120. In another aspect of this embodiment, at least some of the constituents (e.g., undissociated precursor gas) received at the second collector 6104b can be directed back into the reactor 61 10 via the entrance port 61 12. [00188] An advantage of the foregoing arrangement is that the radiation losses typically encountered in a chemical vapor deposition apparatus can be avoided by positioning multiple substrates in a manner that allows radiation emitted from one surface to be received by another surface that is also targeted for deposition. In a particular embodiment shown in Figure 21 , two substrates are shown, each having a single exposed surface facing the other. In other embodiments, additional substrates can be positioned (e.g., in a plane extending inwardly and/or outwardly transverse to the plane of Figure 20) to allow additional exposed surfaces of a formed product to radiate heat to corresponding surfaces of other formed products.

[00189] Another advantage of the foregoing arrangement is that it can be used to produce a structural building block and/or an architectural construct, as well as clean burning hydrogen fuel from a hydrogen donor. When the precursor gas includes a hydrocarbon, the architectural construct can include graphene and/or another carbon-bearing material, for example, a material that can be further processed to form a carbon-based composite or a carbon-based polymer. In other embodiments, the precursor gas can include other elements (e.g., boron, nitrogen, sulfur, silicon, and/or a transition metal) than can also be used to form structural building blocks that contain the element, and/or architectural constructs formed from the building blocks. Suitable processes and representative architectural constructs are further described in the following co-pending U.S. Patent Applications, all of which were filed on February 14, 201 1 and are incorporated herein by reference: Application No. 13/027,208; Application No. 13/027,214; and Application No. 13/027,068.

[00190] One feature of an embodiment described above with reference to Figure 21 is that it may be conducted in a batch process. For example, each of the first and second formed structures 6140a, 6140b can be grown by a particular amount and then removed from the reaction vessel 61 1 1 . In other embodiments, the products can be formed in a continuous manner, without the need for halting the reaction to remove the product.

[00191] Still further embodiments of suitable reactors with induction heating are disclosed in pending U.S. Application No. 13/027,215, filed February 14, 201 1 , and incorporated herein by reference. Representative Reactors Using Engine Heat

[00192] Figure 22 is a partially schematic illustration of system 7100 that includes a reactor 71 10 in combination with a radiant energy/reactant source 7150 in accordance with another embodiment of the technology. In this embodiment, the radiant energy/reactant source 7150 includes an engine 7180, e.g., an internal combustion engine having a piston 7182 that reciprocates within a cylinder 7181 . In other embodiments, the engine 7180 can have other configurations, for example, an external combustion configuration. In an embodiment shown in Figure 21 , the engine 7180 includes an intake port 7184a that is opened and closed by an intake valve 7183a to control air entering the cylinder 7181 through an air filter 7178. The air flow can be unthrottled in an embodiment shown in Figure 22, and can be throttled in other embodiments. A fuel injector 7185 directs fuel into the combustion zone 7179 where it mixes with the air and ignites to produce the combustion products 7152. Additional fuel can be introduced by an injection valve 7189a. The combustion products 7152 exit the cylinder 7181 via an exhaust port 7184b controlled by an exhaust valve 7183b. Further details of representative engines and ignition systems are disclosed in co-pending U.S. Application No. 12/653,085 filed on December 7, 2010, and incorporated herein by reference.

[00193] The engine 7180 can include features specifically designed to integrate the operation of the engine with the operation of the reactor 71 10. For example, the engine 7180 and the reactor 71 10 can share fuel from a common fuel source 7130 which is described in further detail below. The fuel is provided to the fuel injector 7185 via a regulator 7186. The engine 7180 can also receive end products from the reactor 71 10 via a first conduit or passage 7177a, and water (e.g., liquid or steam) from the reactor 71 10 via a second conduit or passage 7177b. Further aspects of these features are described in greater detail below, following a description of the other features of the overall system 7100.

[00194] The system 7100 shown in Figure 22 also includes heat exchangers and separators configured to transfer heat and segregate reaction products in accordance with the disclosed technology. In a particular aspect of this embodiment, the system 7100 includes a steam/water source 7140 that provides steam to the reactor vessel 71 1 1 to facilitate product formation. Steam from the steam/water source 7140 can be provided to the reactor 71 10 via at least two channels. The first channel includes a first water path 7141 a that passes through a first heat exchanger 7170a and into the reactor vessel 71 1 1 via a first steam distributor 71 16a. Products removed from the reactor vessel 71 1 1 pass through a reactor product exit port 71 17 and along a products path 7161 . The products path 7161 passes through the first heat exchanger 7170a in a counter-flow or counter-current manner to cool the products and heat the steam entering the reactor vessel 71 1 1 . The products continue to a reaction product separator 7171 a that segregates useful end products (e.g., hydrogen and carbon or carbon compounds). At least some of the products are then directed back to the engine 7180, and other products are then collected at a products collector 7160a. A first valve 7176a regulates the product flow. Water remaining in the products path 7161 can be separated at the reaction product separator 7171 a and returned to the steam/water source 7140.

[00195] The second channel via which the steam/water source 7140 provides steam to the reactor 71 10 includes a second water path 7141 b that passes through a second heat exchanger 7170b. Water proceeding along the second water path 7141 b enters the reactor 71 10 in the form of steam via a second stream distributor 71 16b. This water is heated by combustion products that have exited the combustion zone 7179 and passed through the transfer passage 71 18 (which can include a transmissive surface 71 19) along a combustion products path 7154. The spent combustion products 7152 are collected at a combustion products collector 7160b and can include nitrogen compounds, phosphates, re-used illuminant additives (e.g., sources of sodium, magnesium and/or potassium), and/or other compositions that may be recycled or used for other purposes (e.g., agricultural purposes). The illuminant additives can be added to the combustion products 7152 (and/or the fuel used by the engine 7180) upstream of the reactor 71 10 to increase the amount of radiant energy available for transmission into the reaction zone 71 12.

[00196] In addition to heating water along the second water path 7141 b and cooling the combustion products along the combustion products path 7154, the second heat exchanger 7170b can heat the hydrogen donor passing along a donor path 7131 to a donor distributor 71 15 located within the reactor vessel 71 1 1 . The donor vessel 7130 houses a hydrogen donor, e.g., a hydrocarbon such as methane, or a nitrogenous donor such as ammonia. The donor vessel 7130 can include one or more heaters 7132 (shown as first heater 7132a and a second heater 7132b) to vaporize and/or pressurize the hydrogen donor within. A three-way valve 7133 and a regulator 7134 control the amount of fluid and/or vapor that exits the donor vessel 7130 and passes along the donor path 7131 through the second heat exchanger 7170b and into the reactor vessel 71 1 1 . As discussed above, the hydrogen donor can also serve as a fuel for the engine 7180, in at least some embodiments, and can be delivered to the engine 7180 via a third conduit or passage 7177c.

[00197] In the reactor vessel 71 1 1 , the combustion products 7152 pass through the combustion products passage 71 18 while delivering radiant energy and/or reactants through the transmissive surface 71 19 into the reaction zone 71 12. After passing through the second heat exchanger 7170b, the combustion products 7152 can enter a combustion products separator 7171 b that separates water from the combustion products. The water returns to the steam/water source 7140 and the remaining combustion products are collected at the combustion products collector 7160b. In a particular embodiment, the separator 7171 b can include a centrifugal separator that is driven by the kinetic energy of the combustion product stream. If the kinetic energy of the combustion product stream is insufficient to separate the water by centrifugal force, a motor/generator 7172 can add energy to the separator 7171 b to provide the necessary centrifugal force. If the kinetic energy of the combustion product stream is greater than is necessary to separate water, the motor/generator 7172 can produce energy, e.g., to be used by other components of the system 7100. The controller 7190 receives inputs from the various elements of the system 7100 and controls flow rates, pressures, temperatures, and/or other parameters.

[00198] The controller 7190 can also control the return of reactor products to the engine 7180. For example, the controller can direct reaction products and/or recaptured water back to the engine 7180 via a series of valves. In a particular embodiment, the controller 7190 can direct the operation of the first valve 7176a which directs hydrogen and carbon monoxide obtained from the first separator 7171 a to the engine 7180 via the first conduit 7177a. These constituents can be burned in the combustion zone 7179 to provide additional power from the engine 7180. In some instances, it may be desirable to cool the combustion zone 7179 and/or other elements of the engine 7180 as shown. In such instances, the controller 7190 can control a flow of water or steam to the engine 7180 via second and third valves 7176b, 7176c and the corresponding second conduit 7177b.

[00199] In some instances, it may be desirable to balance the energy provided to the reactor 71 10 with energy extracted from the engine 7180 used for other proposes. According, the system 7100 can included a proportioning valve 7187 in the combustion products stream that can direct some combustion products 7152 to a power extraction device 7188, for example, a turbo-alternator, turbocharger or a supercharger. When the power extraction device 7188 includes a supercharger, it operates to compress air entering the engine cylinder 7181 via the intake port 7184a. When the extraction device 7188 includes a turbocharger, it can include an additional fuel injection valve 7189b that directs fuel into the mixture of combustion products for further combustion to produce additional power. This power can supplement the power provided by the engine 7180, or it can be provided separately, e.g., via a separate electrical generator.

[00200] As is evident from the forgoing discussion, one feature of the system 7100 is that it is specifically configured to conserve and reuse energy from the combustion products 7152. Accordingly, the system 7100 can include additional features that are designed to reduce energy losses from the combustion products 7152. Such features can include insulation positioned around the cylinder 7181 , at the head of the piston 7182, and/or at the ends of the valves 7183a, 7183b. Accordingly, the insulation prevents or at least restricts heat from being conveyed away from the engine 7180 via any thermal channel other than the passage 71 18.

[00201] One feature of at least some of the foregoing embodiments is that the reactor system can include a reactor and an engine linked in an interdependent manner. In particular, the engine can provide waste heat that facilitates a dissociation process conducted at the reactor to produce a hydrogen-based fuel and a non-hydrogen based structural building block. The building block can include a molecule containing carbon, boron, nitrogen, silicon and/or sulfur, and can be used to form an architectural construct. Representative examples of architectural constructs, in addition to the polymers and composites described above are described in further detail in co-pending U.S. Application No. 12/027,214, previously incorporated herein by reference. An advantage of this arrangement is that it can provide a synergy between the engine and the reactor. For example, the energy inputs normally required by the reactor to conduct the dissociation processes described above can be reduced by virtue of the additional energy provided by the combustion product. The efficiency of the engine can be improved by adding clean- burning hydrogen to the combustion chamber, and/or by providing water (e.g., in steam or liquid form) for cooling the engine. Although both the steam and the hydrogen-based fuel are produced by the reactor, they can be delivered to the engine at different rates and/or can vary in accordance with different schedules and/or otherwise in different manners.

[00202] Still further embodiments of suitable reactors with using engine heat are disclosed in pending U.S. Application No. 13/027,198, filed February 14, 201 1 , and incorporated herein by reference.

Representative Exothermic/Endothermic Reactors

[00203] Figure 23 is a partially schematic, cross-sectional illustration of particular components of the system 8100, including the reactor vessel 8101 . The reactor vessel 8101 includes the first reaction zone 81 10 positioned toward the upper left of Figure 23 (e.g., at a first reactor portion) to receive incident solar radiation 8106, e.g., through a solar transmissive surface 8107. The second reaction zone 8120 is also positioned within the reactor vessel 8101 , e.g., at a second reactor portion, to receive products from the first reaction zone 81 10 and to produce an end product, for example, methanol. Reactant sources 8153 provide reactants to the reactor vessel 8101 , and a product collector 8123 collects the resulting end product. A regulation system 8150, which can include valves 8151 or other regulators and corresponding actuators 8152, is coupled to the reactant sources 8153 to control the delivery of reactants to the first reaction zone 81 10 and to control other flows within the system 8100. In other embodiments, the valves can be replaced by or supplemented with other mechanisms, e.g., pumps.

[00204] In a particular embodiment, the reactant sources 8153 include a methane source 8153a and a carbon dioxide source 8153b. The methane source 8153a is coupled to a first reactant valve 8151 a having a corresponding actuator 8152a, and the carbon dioxide source 8153b is coupled to a second reactant valve 8151 b having a corresponding actuator 8152b. The reactants pass into the reaction vessel 8101 and are conducted upwardly around the second reaction zone 8120 and the first reaction zone 81 10 as indicated by arrows A. As the reactants travel through the reactor vessel 8101 , they can receive heat from the first and second reaction zones 81 10, 8120 and from products passing from the first reaction zone 81 10 to the second reaction zone 8120, as will be described in further detail later. The reactants enter the first reaction zone 81 10 at a first reactant port 81 1 1 . At the first reaction zone 81 10, the reactants can undergo the following reaction:

CH₄ + C0₂ + HEAT→ 2CO + 2H₂ [Equation 13]

[00205] In a particular embodiment, the foregoing endothermic reaction is conducted at about 900°C and at pressures of up to about 1 ,500 psi. In other embodiments, reactions with other reactants can be conducted at other temperatures at the first reaction zone 81 10. The first reaction zone 81 10 can include any of a variety of suitable catalysts, for example, a nickel/aluminum oxide catalyst. In particular embodiments, the reactants and/or the first reaction zone 81 10 can be subjected to acoustic pressure fluctuation (in addition to the overall pressure changes caused by introducing reactants, undergoing the reaction, and removing products from the first reaction zone 81 10) to aid in delivering the reactants to the reaction sites of the catalyst. In any of these embodiments, the products produced at the first reaction zone 81 10 (e.g. carbon monoxide and hydrogen) exit the first reaction zone 81 10 at a first product port 81 12 and enter a first heat exchanger 8140a. The first products travel through the first heat exchanger 8140a along a first flow path 8141 and transfer heat to the incoming reactants traveling along a second flow path 8142. Accordingly, the incoming reactants can be preheated at the first heat exchanger 8140a, and by virtue of passing along or around the outside of the first reaction zone 81 10. In particular embodiments, one or more surfaces of the first heat exchanger 8140a can include elements or materials that absorb radiation at one frequency and re-radiate it at another. Further details of suitable materials and arrangements are disclosed above.

[00206] The first products enter the second reaction zone 8120 via a second reactant port 8121 and a check valve 8156 or other flow inhibitor. The check valve 8156 is configured to allow a one-way flow of the first products into the second reaction zone 8120 when the pressure of the first products exceeds the pressure in the second reaction zone 8120. In other embodiments, the check valve 8156 can be replaced with another mechanism, e.g., a piston or pump that conveys the first products to the second reaction zone 8120.

[00207] At the second reaction zone 8120, the first products from the first reaction zone 81 10 undergo an exothermic reaction, for example:

2CO + 2H₂ + 2Ή₂→ CH₃OH + HEAT [Equation 14]

[00208] The foregoing exothermic reaction can be conducted at a temperature of approximately 250°C and in many cases at a pressure higher than that of the endothermic reaction in the first reaction zone 81 10. To increase the pressure at the second reaction zone 8120, the system 8100 can include an additional constituent source 8154 (e.g. a source of hydrogen) that is provided to the second reaction zone 8120 via a valve 8151 c and corresponding actuator 8152c. The additional constituent (e.g. hydrogen, represented by 2'H₂ in Equation 21 ) can pressurize the second reaction zone with or without necessarily participating as a consumable in the reaction identified in Equation 14. In particular, the additional hydrogen may be produced at pressure levels beyond 1 ,500 psi, e.g., up to about 5,000 psi or more, to provide the increased pressure at the second reaction zone 8120. In a representative embodiment, the additional hydrogen may be provided in a separate dissociation reaction using methane or another reactant. For example, the hydrogen can be produced in a separate endothermic reaction, independent of the reactions at the first and second reaction zones 81 10, 8120, as follows:

CH₄ + HEAT→ C + 2H₂ [Equation 15]

[00209] In addition to producing hydrogen for pressurizing the second reaction zone 8120, the foregoing reaction can produce carbon suitable to serve as a building block in the production of any of a variety of suitable end products, including polymers, self-organizing carbon-based structures such as graphene, carbon composites, and/or other materials. Further examples of suitable products are included in co-pending U.S. Application No. 12/027,214 previously concurrently herewith and incorporated herein by reference.

[00210] The reaction at the second reaction zone 8120 can be facilitated with a suitable catalyst, for example, copper, zinc, aluminum and/or compounds including one or more of the foregoing elements. The product resulting from the reaction at the second reaction zone 8120 (e.g. methanol) is collected at the product collector 8123. Accordingly, the methanol exits the second reaction zone 8120 at a second product port 8122 and passes through a second heat exchanger 8140b. At the second heat exchanger 8140b, the methanol travels along a third flow path 8143 and transfers heat to the incoming constituents provided to the first reaction zone 81 10 along a fourth flow path 8144. Accordingly, the two heat exchangers 8140a, 8140b can increase the overall efficiency of the reactions taking place in the reactor vessel 8101 by conserving and recycling the heat generated at the first and second reaction zones.

[00211] In a particular embodiment, energy is provided to the first reaction zone 81 10 via the solar concentrator 8103 described above with reference to Figure 23. Accordingly, the energy provided to the first reaction zone 81 10 by the solar collector 8103 will be intermittent. The system 8100 can include a supplemental energy source that allows the reactions to continue in the absence of sufficient solar energy. In particular, the system 8100 can include a supplemental heat source 8155. For example, the supplemental heat source 8155 can include a combustion reactant source 8155a (e.g. providing carbon monoxide) and an oxidizer source 8155b (e.g. providing oxygen). The flows from the reactant source 8155a and oxidizer source 8155b are controlled by corresponding valves 8151 d, 8151 e, and actuators 8152d, 8152e. In operation, the reactant and oxidizer are delivered to the reactor vessel 8101 via corresponding conduits 8157a, 8157b. The reactant and oxidizer can be preheated within the reactor vessel 8101 , before reaching a combustion zone 8130, as indicated by arrow B. At the combustion zone 8130, the combustion reactant and oxidizer are combusted to provide heat to the first reaction zone 81 10, thus supporting the endothermic reaction taking place within the first reaction zone 81 10 in the absence of sufficient solar energy. The result of the combustion can also yield carbon dioxide, thus reducing the need for carbon dioxide from the carbon dioxide source 8153b. The controller 8190 can control when the secondary heat source 8155 is activated and deactivated, e.g., in response to a heat or light sensor.

[00212] In another embodiment, the oxygen provided by the oxidizer source 8155b can react directly with the methane at the combustion zone 8130 to produce carbon dioxide and hydrogen. This in turn can also reduce the amount of carbon dioxide required at the first reaction zone 81 10. Still further embodiments of suitable exothermic/endothermic reactors are disclosed in pending U.S. Application No. 13/027,060, filed February 14, 201 1 , and incorporated herein by reference.

[00213] From the foregoing, it will appreciated that specific embodiments of the technology have been described herein for purposes of illustration, but that various modifications may be made without deviating from the technology. For example, certain embodiments of the processes described above were described in the context of methane. In other embodiments, other hydrocarbon fuels or non-carbon- containing hydrogen donors can undergo similar processes to form hydrogen-based fuels and architectural constructs. The waste heat provided by the engine can be supplemented by other waste heat sources, e.g., waste heat from regenerative braking.

[00214] Certain aspects of the technology described in the context of particular embodiments may be combined or eliminated in other embodiments. For example, in some embodiments, selected heat exchangers can be eliminated or combined. Further while advantages associated with certain embodiments of the technology have been described in the context of those embodiments, other embodiments may also exhibit such advantages, and not all embodiments need necessarily exhibit such advantages to fall within the scope of the present disclosure. Accordingly, the present disclosure and associated technology can encompass other embodiments not expressly shown or described herein.

Claims

CLAIMS I claim:

1 . A chemical reactor system, comprising:

an engine having a combustion region;

an exhaust passage coupled to the engine to receive exhaust products from the combustion region, the exhaust passage at least partially enclosing a passage interior region;

a reactor having an external heat transfer surface positioned in the passage interior region, the reactor further having a reaction zone positioned in a region enclosed by the external heat transfer surface;

a hydrogen donor source;

a donor passage coupled in fluid communication with the hydrogen donor source and the reaction zone of the reactor; and

a product passage coupled to the reaction zone to receive a reaction product from the reaction zone.

2. The system of claim 1 wherein the product passage is a first product passage positioned to receive hydrogen from the reaction zone, and wherein the system further comprises a second product passage positioned to receive a carbon- bearing product from the reaction zone.

3. The system of claim 2, further comprising a porous medium positioned between the first product passage and the second product passage, the porous medium being selective for hydrogen.

4. The system of claim 2, further comprising a galvanic circuit coupled between the first and second product passages to pressurize hydrogen in the first product passage.

5. The system of claim 1 , further comprising at least one heat transfer element carried by the external heat transfer surface and projecting into the passage interior region.

6. The system of claim 5 wherein the exhaust passage is elongated along a flow axis, and wherein the at least one heat transfer element is arranged in an at least partially spiral manner relative to the flow axis.

7. The system of claim 6, further comprising a turbine coupled to the exhaust passage downstream of the reactor.

8. The system of claim 1 wherein the reaction zone is bounded in part by a porous surface, the porous surface being transmissive to hydrogen and not transmissive to carbon compounds.

9. The system of claim 1 , further comprising an electrically powered heater positioned in thermal communication with the reaction zone.

10. The system of claim 9 wherein the electrically powered heater includes at least one of an inductive heater and a resistive heater.

1 1 . The system of claim 1 wherein the electrically powered heater is positioned within the reaction zone.

12. The system of claim 1 wherein the engine and reactor are carried by a vehicle, and wherein the vehicle includes a regenerative brake coupled to an electricity storage medium.

13. The system of claim 1 , further comprising a heat exchanger coupled in thermal communication with the donor passage to transfer heat to a flow volume in the donor passage.

14. The system of claim 13, further comprising a liquid cooling system coupled to the engine to cool the engine, the liquid cooling system including working fluid passage, and wherein the heat exchanger includes:

a first heat exchanger passage coupled to the donor passage; and

a second heat exchanger passage coupled to the working fluid passage and in thermal communication with the first heat exchanger passage at the heat exchanger.

15. The system of claim 13 wherein the heat exchanger includes:

a first heat exchanger passage coupled to the donor passage; and

a second heat exchanger passage coupled to the product passage and in thermal communication with the first heat exchanger passage at the heat exchanger.

16. The system of claim 13 wherein the heat exchanger includes:

a heat exchanger passage coupled to the product passage and in thermal communication with the exhaust passage, downstream of the reactor.

17. The system of claim 1 , further comprising insulation positioned around the exhaust passage.

18. The system of claim 1 wherein the reactor includes:

a first annular passage positioned inwardly from the heat transfer surface; a second annular passage positioned inwardly from the first annular passage; and

a third passage positioned inwardly from the second annular passage.

19. The system of claim 18 wherein:

the product passage is a first product passage positioned to receive hydrogen from the reaction zone, and wherein the system further comprises a second product passage positioned to receive a carbon-bearing product from the reaction zone;

the first annular passage is coupled to the donor passage; the second annular passage is coupled to the second product passage; and the third passage is coupled to the first product passage.

20. The system of claim 1 , further comprising a fuel passage coupled between the product passage and the combustion region of the engine to direct the reaction product to the combustion region.

21 . A chemical reactor system, comprising:

an engine having a combustion region;

an exhaust manifold coupled to the engine to receive exhaust products from the combustion region, the exhaust manifold having a manifold external surface the exhaust manifold further having a manifold internal surface at least partially enclosing an interior region;

insulation positioned around the external surface of the exhaust manifold; a reactor, comprising

a shell positioned in the interior region of the exhaust manifold, the shell having a shell external heat transfer surface, the shell further having a shell internal surface positioned around a reaction zone, and;

a spiral heat transfer element carried by the shell and projecting into the passage interior region;

a first wall positioned annularly inwardly from the shell internal surface and spaced radially apart from the shell internal surface to define a first annular passage;

a second wall positioned annularly inwardly from the first wall and spaced radially apart from the first wall to define a second annular passage positioned between the first and second walls, and a third passage positioned inwardly from the second wall, the second wall including a porous medium transmissive to hydrogen but not transmissive to carbon compounds;

an electrically-powered heater positioned in the second annular passage; and a galvanic circuit coupled across the second wall to pressurize the third passage;

a hydrogen donor source;

a donor passage coupled between the hydrogen donor source and the first annular passage to direct a hydrogen donor to the reaction zone a first product passage coupled to the third passage to receive hydrogen a second product passage coupled to the second annular passage to receive a carbon-bearing product;

a liquid cooling system coupled to the engine to cool the engine, the liquid cooling system including working fluid passage;

a first heat exchanger coupled between the donor passage and the working fluid passage to transfer heat from the working fluid passage to the donor passage;

a second heat exchanger coupled between the donor passage and the exhaust manifold downstream of the reactor to transfer heat from the exhaust manifold to the donor passage;

a third heat exchanger coupled between the donor passage and at least one of the first and second product passages to transfer heat from the at least one of the first and second product passages to the donor passage; and

a turbine positioned downstream of the reactor and the spiral heat transfer element.

22. A method for operating an engine and a chemical reactor, comprising: combusting a fuel in an engine to produce power and combustion products; directing the combustion products through an exhaust passage and around a reactor positioned within the exhaust passage;

transferring heat from the combustion products to a reaction zone within the reactor, via an external surface of the reactor;

directing a hydrogen donor into the reaction zone of the reactor;

dissociating the hydrogen donor into dissociation products in the reaction zone;

from the dissociation products, providing:

(a) a hydrogen-bearing constituent; and (b) a non-hydrogen bearing constituent.

23. The method of claim 22 wherein transferring heat from the combustion products to the reaction zone includes:

transferring heat from the combustion products to at least one heat transfer element carried by the reactor and projecting into an interior region of the exhaust passage; and

transferring heat from the at least one heat transfer element to the reaction zone.

24. The method of claim 23 wherein the at least one heat transfer element has a spiral shape, and wherein transferring heat from the combustion products to at least one heat transfer element includes directing the combustion products along the heat transfer element to impart a rotational flow component to the combustion products.

25. The method of claim 24, further comprising extracting kinetic energy from the combustion products by directing the combustion products through a turbine downstream of the at least one heat transfer element.

26. The method of claim 22, further comprising providing heat to the reaction zone via an electrically-powered heater.

27. The method of claim 22, wherein the engine and reactor are carried by a vehicle, and wherein the method further comprises:

braking the vehicle with a regenerative brake; and

directing electrical power obtained from the regenerative brake to the reactor.

28. The method of claim 22, further comprising:

cooling the engine with a coolant fluid; and

directing heat from the coolant fluid to the hydrogen donor before the hydrogen donor enters the reaction zone.

29. The method of claim 22, further comprising directing heat from the dissociation products to the hydrogen donor before the hydrogen donor enters the reaction zone.

30. The method of claim 22, further comprising directing heat from the combustion products to the hydrogen donor before the hydrogen donor enters the reaction zone.

31 . The method of claim 22, further comprising at least restricting heat loss from the exhaust passage with insulation positioned around the exhaust passage.

32. The method of claim 22 wherein the reactor includes:

an outwardly facing heat transfer surface positioned in the flow of combustion products;

a third passage positioned inwardly from the second annular passage; and wherein the method further comprises:

directing the hydrogen donor axially through the first annular passage in a first direction to heat the hydrogen donor;

directing the hydrogen donor axially through the second annular passage in a second direction opposite the first direction; and

directing dissociated hydrogen into the third passage.

33. The method of claim 22 wherein directing the dissociated hydrogen includes directing the dissociated hydrogen through a porous medium separating the second and third passages.

34. The method of claim 22, further comprising combusting at least a portion of the hydrogen-bearing constituent in the engine.

35. The method of claim 22, further comprising separating hydrogen from carbon-bearing constituents of the dissociation products by exposing the dissociation products to a porous medium that is transmissive to hydrogen but not transmissive to carbon compounds.

36. The method of claim 35 wherein the porous medium is a first porous medium, and wherein the method further comprises forming a second porous medium from the carbon-bearing constituents.

37. The method of claim 35, further comprising:

removing the porous medium from the reactor; and

using the porous medium to purify at least one of air or water.

38. The method of claim 35 , further comprising pressurizing the hydrogen by applying a galvanic current across the porous medium.