Abstract:
A hydrocarbon reformer comprising a plurality of sequential reforming stages. The first stage has relatively low catalytic activity to minimize heat buildup in exothermic catalysis, which may be achieved by having a short residence time and/or relatively low catalytic capability, such that not all of the fuel and air passing through the first stage is catalyzed, thereby preventing thermal excess in the first stage and consequent bed erosion. Exothermic combustion near the front edge of the reformer produces water and carbon dioxide, but little hydrogen, while consuming some of the hydrocarbon and oxygen. Endothermic reactions in the following stages produce hydrogen and carbon monoxide while consuming the remaining hydrocarbon fuel and oxygen in a combination of steam- and dry-reforming processes. In each succeeding stage, the catalytic capability is increased as are the length of the stage and residence time of the reactants.

Description:
RELATIONSHIP TO OTHER APPLICATIONS AND PATENTS  
       [0001]     The present application is a Continuation-In-Part of a pending U.S. patent application Ser. No. 11/395,672, filed Mar. 31, 2006. 
     
    
     TECHNICAL FIELD  
       [0002]     The present invention relates to hydrocarbon reformers for producing hydrogen-rich fuel for fuel cells; more particularly, to such a reformer comprising a plurality of sequential reforming stages; and most particularly, to a staged reformer system supporting both exothermic and endothermic reforming wherein reforming is controlled and limited in sequential stages to prevent thermal degradation of the reformer and provide high-efficiency reforming of the hydrocarbon fuel.  
       BACKGROUND OF THE INVENTION  
       [0003]     Fuel reformers are well known in the art as devices for converting hydrocarbons to reformate containing hydrogen (H 2 ) and carbon monoxide (CO) as fuel for fuel cell systems, and especially for solid oxide fuel cell (SOFC) systems. A type of fuel reformer used in such an application provides a series of staged chemical reactions that include a fast exothermic combustion reaction stage coupled with or followed by a slower endothermic fuel reforming stage. The exothermic reactions are self-sustaining, even autocatalytic. The higher the reaction rate, the higher the temperature; and the higher the temperature, the higher the reaction rate. The endothermic reactions, which may include the decomposition of H 2 O and CO 2  in the presence of carbon to yield H 2  and CO, are slower and by definition require input of heat.  
         [0004]     Typically, when a fuel reformer is coupled to a fuel cell, several modes of reformer operation occur, including:  
         [0005]     Reformer ignition and heat-up: During this mode, the reformer receives high temperature combusted gases (1500 C to 1700 C) for a short period such as, for example, 5 to 15 seconds, to initially heat the reforming substrate to around  500 C. Once heated, the flow of high temperature combustion gases is turned off for a short time, for example, 0.5 to 1 second to extinguish the burning gases.  
         [0006]     Initial exothermic operation of the reformer: Following extinguishing of the burning gases, fuel to the reformer is turned back on during this mode and the incoming fuel is adjusted to a rich reforming mixture for initial CPOx exothermic reforming in the reformer. At this time, the fuel cell stack is cold, the system combustor is not operating to produce heat and the reformate from the reformer simply passes through the fuel cell stack as does the cold cathode air. During this mode (for example, about 10 seconds) the leading edge of the intake side of the reformer sees relatively high temperatures because of the rich mixture with no recycle.  
         [0007]     Transition to endothermic reforming: During this transition mode, the fuel cell stack anode heats up from the warm/hot reforming gases and the system combustor ignites to preheat the cathode air. The heat from the system combustor, now burning on raw reformate coming form the cold stack anode, serves to provide heat to the reformer. At the same time, the reformer receives a portion of pure reformate, as recycle from the cold anode. Throughout the transition period, as the heat input, the amount of recycle, and the composition of the recycle to the reformer are contrantly and controllably varied, a varying degree of temperature gradients is experienced across the reformer. Up until the fuel cell reaches its final operating temperature, (for example, about 10 minutes), the leading edge of the intake side of the reformer gets hot due to the CPOx operation with recycle addition.  
         [0008]     Fully endothermic reforming mode: In this mode the fuel cell stack is controlled to operate at a certain desired fuel utilization. To achieve highest reforming efficiency, the amount of air to the reformer is reduced. As a result, the front edge of the reformer becomes relatively cool as compared to its temperature during the transition mode. During the endothermic reforming mode, the amount of molecular oxygen available to the reformer has been reduced so that the temperature of the leading edge of the reformer can only heat the fuel mixture from its initial 150 C to about 500 C. This temperature is too low for complete endothermic reforming to occur at the leading edge of the reformer resulting in local precipitation of carbon and then coking during further temperature spikes.  
         [0009]     Prior art hydrocarbon reformers typically comprise a catalyst bed formed of an inert substrate coated with an active catalytic wash coat. The substrate is typically porous, presenting a large surface area for catalysis. A serious problem for prior art catalyst beds is that intense exothermic catalysis and/or combustion occurs at the leading edge of the bed, during certain exothermic modes of operation, where the concentration of reactants entering the reformer is highest and the dispersal of heat is lowest, causing rapid heat release and heat buildup resulting in unacceptably elevated substrate, washcoat, and catalyst temperatures along the leading edge. Heat is thereby released directly into the catalyst material, the substrate, and the fluid stream. It is believed that temperatures at the beginning of the catalyst bed of a prior art reformer can reach more than 1750° C. because of this rapid exothermic release. During sustained use of the reformer, the catalyst bed is progressively eroded, ablated, or otherwise thermally deactivated along the leading edge, resulting in a progressively smaller bed and eventual failure of the reformer. It is difficult to remove heat from the front edges of a prior art catalyst and substrate to control the exothermic reactions, which area dominates but a small part geometrically of a reformer. This leads to a major problem in design, durability, and performance of prior art reformers.  
         [0010]     What is needed in the hydrocarbon reforming art is a staged reformer that can support all these modes of operation without either catastrophic failure, reduced durability, or deactivation of reformer operation.  
         [0011]     It is a principal object of the present invention to provide high-efficiency, high-throughput, and durable reforming.  
       SUMMARY OF THE INVENTION  
       [0012]     Briefly described, a hydrocarbon reformer in accordance with the invention comprises a plurality of sequential reforming stages that may or may not be separated by non-reforming mixing spaces therebetween. Each of the stages may reside inside a common housing. The entire reformer is a heat exchange reformer wherein it adds heat to endothermic reactions and removes heat from exothermic reactions, as needed, to prevent carbon build-up, coking and substrate/bed degradation.  
         [0013]     The first reforming stage, is arranged to have relatively low catalytic activity, to minimize heat buildup during CPOx exothermic catalysis. This may be achieved by having a relatively short residence time, governed by geometric constraints, and/or relatively low catalytic capability, governed by catalyst loading constraints, such that not all of the fuel and air passing through the first stage is catalyzed, thereby preventing thermal excess in the first stage and consequent bed erosion. Preferably, this stage reacts about one-quarter of the fuel. The fast exothermic combustion reaction near the front edge of the catalyst produces largely water and carbon dioxide, but little hydrogen, while consuming some of the hydrocarbon and oxygen. The endothermic reactions in the subsequent stages reduce hydrogen and carbon monoxide while consuming water, carbon dioxide, and the remaining hydrocarbon fuel and oxygen in a combination of steam- and dry-reforming processes.  
         [0014]     In a second stage following the first stage in series, the activity of the catalytic material is increased as are the length of the stage and residence time of the reactants.  
         [0015]     Preferably, this stage reacts about one-half of the fuel.  
         [0016]     The third stage, following the second stage in series, carries a relatively high level of catalytic loading and has a relatively long residence time, which stage reacts the remainder of the fuel.  
         [0017]     Preferably, the thermal conductivity of the substrate material increases in each successive stage to conduct excess heat from the first stage exothermic portion (leading edge) of the reformer to the subsequent endothermic portions. 
     
    
     BRIEF DESCRIPTION OF THE DRAWINGS  
       [0018]     The present invention will now be described, by way of example, with reference to the accompanying drawings, in which:  
         [0019]      FIG. 1  is a schematic elevational longitudinal cross-sectional view of a prior art single-stage CPOx reformer;  
         [0020]      FIG. 2  is a graph showing temperature longitudinally through the prior art single-stage CPOx reformer shown in  FIG. 1 , when reforming isooctane;  
         [0021]      FIG. 3  is a graph like that shown in  FIG. 2  when the hydrocarbon fuel is methane;  
         [0022]      FIG. 4  is a view like that shown in  FIG. 1 , showing progressive destruction during use of the leading edge of a prior art catalyst having a metal substrate;  
         [0023]      FIG. 5  is a view like that shown in  FIG. 4  for a prior art catalyst having a ceramic substrate;  
         [0024]      FIG. 6  is a schematic elevational longitudinal cross-sectional view of a two-stage reformer in accordance with the invention;  
         [0025]      FIG. 7  is a schematic elevational longitudinal cross-sectional view of a three-stage reformer in accordance with the invention;  
         [0026]      FIG. 8  is a schematic drawing showing formation of a first catalytic bed by using a plurality of layered corrugated sheets;  
         [0027]      FIG. 9  is a schematic drawing showing formation of a second catalytic bed by alternating corrugated and non-corrugated sheets;  
         [0028]      FIG. 10  is a schematic drawing showing the arrangement shown in  FIG. 8  rolled into a spiral catalytic bed;  
         [0029]      FIG. 11  is a schematic drawing showing the arrangement shown in  FIG. 8  folded into a stacked catalytic bed having a cylindrical cross-sectional shape;  
         [0030]      FIG. 12  is a schematic elevational longitudinal cross-sectional drawing of a first three-stage reformer in accordance with the invention, showing staged porosity of the catalyst;  
         [0031]      FIG. 13  is a schematic elevational longitudinal cross-sectional drawing of a second three-stage reformer in accordance with the invention, showing an increasing number of open catalytic channels;  
         [0032]      FIG. 14  is a schematic elevational longitudinal cross-sectional drawing of a third three-stage reformer in accordance with the invention, showing a progressively larger cross-sectional area in discrete stages; and  
         [0033]      FIG. 15  is a schematic elevational longitudinal cross-sectional drawing of a fourth three-stage reformer in accordance with the invention, showing a progressively larger cross-sectional area formed by a conic shape. 
     
    
     DESCRIPTION OF THE PREFERRED EMBODIMENTS  
       [0034]     The distinctions and benefits of the present invention may be better appreciated by first considering the elements and limitations of a prior art catalytic reformer.  
         [0035]     Referring to  FIGS. 1 through 5 , a prior art hydrocarbon catalytic reformer  10  includes a housing  12  having an inlet  14  and outlet  16 . Disposed within housing  12  is a catalyst bed  18  having porosity in at least a longitudinal direction  20 . Bed  18  typically includes a durable non-catalytic substrate coated with a washcoat including or supporting catalytic means. The substrate is formed typically of either a metal or a ceramic, as discussed further below. Conventional means for controlling overall temperature, fuel flow rate, air flow rate, and the like are assumed but not shown in  FIG. 1 .  
         [0036]     In operation, a mixture  22  of hydrocarbon and oxygen, typically in the form of air, is introduced into reformer  10  through inlet  14  and thence through a mixture preparation unit  15  and fluid mixing zone  17 . The mixture then is passed through catalyst bed  18  wherein the hydrocarbon fuel and air are converted to a reformate  24  comprising a mixture of molecular hydrogen and carbon monoxide.  
         [0037]     As noted above, a shortcoming of a prior art reformer such as reformer  10  is that the leading edge  26  of catalyst bed  18  becomes severely overheated by intensely exothermic catalytic reaction of the hydrocarbon and oxygen.  FIGS. 2 and 3  show the intense onset heating of the catalyst bed for isooctane ( FIG. 2 , curve  30 ) and methane ( FIG. 3 , curve  40 ) in exothermic mode. A result of this overheating is that the catalyst bed is progressively eroded; further, some of the hydrocarbon is fully oxidized to water and carbon dioxide, which can be recovered as hydrogen and carbon monoxide only through subsequent endothermic reforming farther along in the reformer as described below.  
         [0038]     Referring to  FIGS. 4 and 5 , the impact of catalyst substrate material is shown on a prior art CPOx reformer. The catalyst bed  18   a  shown in  FIG. 4  includes a metal substrate, whereas the catalyst bed  18   b  shown in  FIG. 5  includes a ceramic substrate. Higher temperatures prevail within substrates formed of relatively low-conductivity materials such as ceramics, whereas generally lower temperatures prevail within substrates formed of relatively high-conductivity materials, for example, NiAl alloy or copper. The metal substrate having high conductivity acts to spread out the heat generated by the exothermic CPOx reaction, creating a uniform heat front (shaded area), whereas the ceramic substrate having low conductivity allows the heat front to propagate nonuniformly (shaded area) into the catalyst bed. In either case, the catalyst bed suffers thermal erosion over time of use, resulting in a recession of bed edge  26  to a new bed edge  26   a  or  26   b  which continues to recede with continued use of the reformer, leaving a burned-out catalyst zone  28 . The over-temperature situation affects a) the catalytic activity of the reforming catalyst due to sintering of the washcoat and subsequent loss of surface area; b) adhesion of the washcoat to the metallic substrate due to thermal stresses; and, c) structural integrity of the substrate as most useful alloys melt in the 1300° C.-1500° C. temperature range. As the catalyst and substrate are progressively destroyed, the exothermic front at edges  26   a , 26   b  moves downstream through the entire catalyst bed, leading to total failure of the reformer.  
         [0039]     The only way to prevent such burn-out failure is to provide cooling of the leading edge of the catalyst bed. Active cooling, for example, by circulation of a coolant through the bed, is impractical and also is undesirable because it removes heat from the system which is beneficial in the later endothermic reforming stages and thus reduces the thermal efficiency of the reformer.  
         [0040]     Referring to  FIG. 6 , an embodiment  110  of an improved hydrocarbon reformer comprises a housing  112  having an inlet  114  and an outlet  116 . A catalyst bed  118  is divided into first and last stages  118   a ,  118   b , preferably but not necessarily separated by an intermediate chamber  119 .  
         [0041]     Preferably, first stage  118   a  comprises a metal catalyst substrate and last stage  118   b  comprises a ceramic catalyst substrate. The stage  118   b  substrate is preferably a cast honeycomb ceramic monolith as is well known in the art. Mixture  22  enter first stage  118   a  having been preheated conventionally to a preferable temperature of up to 500° C. to enable lower O/C ratios while retaining resistance to carbon formation. First stage  118   a  is formed as described below such that coated catalytic and non-catalytic flow channels are interlaced generally in the flow direction. Catalytic reactions occur in only the coated (“hot”) catalytic channels, leading to a strong temperature increase in those channels. However, the non-coated (“cold”) channels do not promote chemical reaction and thus act as cooling channels in the manner of a heat exchanger such that the fluid temperatures in the hot channels are suppressed below temperatures seen in prior art reformer catalyst beds  18  and the metal substrate temperatures remain well below distress temperatures. Thus it is seen that hot gas, cold channels, and metal temperatures can be controlled by the size and arrangement of the coated and non-coated channels as well as by selective catalytic coating.  
         [0042]     The catalytic material coating in the first stage active channels is not as fully loaded with catalyst metal per unit area as a prior art CPOx reformer  10 , nor as a last stage  118   b  as described below, to further suppress catalytic activity in first stage  118   a . Preferably, first stage  118   a  reacts less than one-half of the fuel in mixture  22 . A preferred catalytic material for first stage  118   a  includes Rainey nickel and/or a noble metal, depending upon the fuel. A preferred catalyst carrier is hexa-aluminate or a highly-stabilized alumina, which is desirable for high washcoat surface area and catalyst dispersion stability.  
         [0043]     The function of first stage  118   a  is to carry out sufficient combustion early in the stage (without damaging the catalyst bed) and exothermic reforming to provide a hot mixture of hydrocarbon, H 2 O, CO, CO 2 , N 2 , and H 2  to the latter portions of first stage  118   a  and last stage  118   b  wherein a mixture of dry (exothermic) and wet (endothermic) reforming is carried out to produce a reformate  124  comprising ideally only N 2 , CO, and H 2 .  
         [0044]     Gases from the first stage hot and cold channels preferably mix at the end of first stage  118   a  in intermediate chamber  119 . Initial temperatures in last stage  118   b  are substantially lower than in first stage  118   a  because much heat has already been removed from the system by endothermic reforming in the latter portions of first stage  118   a . Last stage  118   b  is formed having a plurality of parallel flow channels similar to the structure of first stage  118   a , and all the flow channels are coated with noble metal catalyst to endothermically react the remaining hydrocarbon fuel and complete the conversion of water and CO 2  into H 2  and CO. A currently preferred catalyst may include dopants comprising rhodium, platinum, and iridium, and a currently preferred washcoat is a high performing alumina matrix.  
         [0045]     Referring to  FIG. 7 , an embodiment  210  of an improved reformer comprises three stages, including an intermediate stage  218   c  and another intermediate chamber  219   a  disposed between first and last stages  218   a , 218   b  as shown for embodiment  110  in  FIG. 6 . Remixing of the reactants and reaction products occurs in second intermediate chamber  219   a  prior to entry into last stage  218   b  The catalyst bed is formed of parallel channels as in the first and last stages, and as in the first stage only a portion (preferably one-half) of the flow channels are catalytically active. However, preferably the noble metal loading of the catalytic material is increased over that in first stage  118   a  to help maintain (by exothermic combustion) the temperatures required for endothermic reforming through the second and third stages, but preferably is less than the noble metal loading in the last stage. Preferably, intermediate stage  218   c  reacts approximately one-half of the hydrocarbon fuel entered to first stage  218   a  in mixture  22  to produce reformate  224 . A currently preferred catalytic material may be doped with rhodium, iridium, or combination thereof, and a currently preferred washcoat is a stabilized alumina matrix.  
         [0046]     Referring to  FIGS. 8 through 11 , structures for any or all of first, intermediate, and last stages  218   a , 218   c , 218   b  may be readily formed by configuring metal substrates in any of several configurations, as is well known in the prior art and preferably as disclosed in great structural detail in the incorporated US patent references on total catalytic combustion. One or both surfaces of flat metal sheet stock may be coated to a catalytic washcoat and loaded with the appropriate noble metals. After corrugation, the catalytic stock may be folded or chopped and layered, either with or without non-corrugated stock interleaved, to create the plurality of flow channels described above. Catalytic stages of a reformer in accordance with the invention may be formed by selection of which surfaces to coat, how heavily to load the catalyst with noble metals, and how to corrugate and fold the metal substrates.  
         [0047]      FIG. 8  shows end views of two corrugated sheets  150   a , 150   b  joined together with their corrugations 180° out of phase to form flow channels  152  therebetween. It will be seen that when both of the opposing surfaces  154   a , 154   b  of the sheets are coated with catalyst, the flow channels will be fully active; when only one of the opposing surfaces is coated, the flow channels will be only half-active; and when neither of the opposing surfaces is coated, the flow channels will be catalytically inactive. In addition, as described above, the noble metal loading of the coated catalyst may be varied to further fine-tune the catalytic capabilities of the assembled reformer stage.  
         [0048]     Referring to  FIG. 10 , corrugated sheets  150   a , 150   b  are shown rolled into a double-spiral reformer stage  160  wherein the corrugations are generally out of phase. Note that full contact and strict phase relationship between the corrugations is not necessary because each spiral convolution (e.g.  162   a ) is entirely independent of the other (e.g.  162   b ). Sheets  150   a ,  150   b  may also be arranged in a stacked relationship, or a single corrugated sheet  150  may be folded within a housing  112  as shown in  FIG. 11  to form any desired cross-sectional shape for reformers  110 , 210 .  
         [0049]     Referring to  FIG. 9 , a reformer may also be configured of alternating corrugated sheets  150  and flat sheets  156 , with the same surface coating considerations just described.  
         [0050]     In the present invention, several design features enable a fuel reformer to operate with high efficiency over a broad range of operating parameters while maintaining durability and life. In exothermic CPOx mode, the reactor is challenged with a very hot inlet section followed by an adiabatic or endothermic reforming section of medium temperature (ca. 800° C.). In full endothermic mode, the reactor is challenged to provide large amounts of heat transfer to sustain the endothermic reactions without the onset of large amounts of carbon, especially in the front section which is designed for high-temperature operation and can become coked if the temperature becomes too low. Thus any or all of three key parameters may be employed to regulate the longitudinal heat profile through an exothermic/endothermic reformer: residence time, chemical kinetics and diffusion effects, and substrate materials.  
         [0051]     Referring now to  FIG. 12 , a first embodiment  310  of an improved reformer in accordance with the invention comprises three stages, including a short first stage  318   a , a longer intermediate stage  318   b , and a long last stage  318   c . The catalyst bed is formed of metallic or ceramic open cell foam having progressively decreasing foam density. By decreasing the density of several foam structures within a constant cross-section reforming channel, the residence time may be varied to provide a short residence time early in the reformer during exothermic operation and then longer residence times later in the reformer during endothermic reforming. For example, in first stage  318   a , the foam density is about 80 ppi and the operating temperature is about 1000-1100° C.; in second stage  318   b , the foam density is about 20 ppi and the operating temperature is about 900° C.; and in third stage  318   c , the foam density is about 5 ppi and the operating temperature is about 800° C. Preferably, intermediate stage  318   b  reacts approximately one-half of the hydrocarbon fuel entered to first stage  318   a.    
         [0052]     Referring to  FIG. 13 , a second embodiment  410  of an improved reformer in accordance with the invention comprises three stages, including a short first stage  418   a , a longer intermediate stage  418   b , and a long last stage  418   c . The catalyst bed is formed of metallic or ceramic open cell foam or monolithic channels. A portion of the potential channels are blocked in first stage  418   a , for example one half the channels, such that reactants are accelerated through the remaining open channels and thus the residence time in first stage  418   a  is short. In second stage  418   b , more channels are open, for example three-quarters of all the potential flow channels, such that reactants are significantly slowed and residence time in second stage  418   b  is increased. In third stage  418   c , all flow channels are open, such that reactants are further slowed and residence time is further increased to permit endothermic reforming. Mixing chambers  419   a , 419   b  may be included between the stages as desired, as described above for embodiment  210 .  
         [0053]     Referring to  FIG. 14 , a third embodiment  510  of an improved reformer in accordance with the invention comprises three stages, including a first stage  518   a , an intermediate stage  518   b , and a last stage  518   c . In this embodiment, the residence time in each sequential reformer stage is increased by increasing the cross-sectional area of the reactant flow path (in this example, the length is also shown as increasing). If the stages are cylindrical, the cross-sectional area increases by the square of the radius; thus, second stage  518   b  has about twice the cross-sectional area of first stage  518   a , and third stage  518   c  has about twice the cross-sectional area of second stage  518   b.    
         [0054]     Referring to  FIG. 15 , a fourth embodiment  610  of an improved reformer in accordance with the invention comprises three stages, including a first stage  618   a , an intermediate stage  618   b , and a last stage  618   c . Embodiment  610  is similar to embodiment  510  except that the reformer shell is conical rather than stepped, so that the increase in cross-sectional area is continuous rather than stepped between stages.  
         [0055]     In any of the staged embodiments described above, the thermal profile and rate of reaction through the reformer may be further adjusted by varying the thickness and/or doping level of the catalytic washcoat, as follows.  
         [0056]     The lower the temperature, the slower the heterogeneous reaction kinetics of molecules at the surface of the washcoated substrate. The further along the reforming path, the smaller the amount of unreacted fuel and the smaller the amount of reforming agents in the fluid, and therefore, the slower the diffusion of reactants (fuel and reforming agents such as H 2 O and CO 2 ) to the catalytic surface. This means a reduced probability that a fuel and a water molecule will meet at the same time at the right catalytic site to react and form H 2  and CO. In other words, the further downstream within the reactor, the slower the reaction and hence the lower the temperature, and hence the lower the reaction probability because of slower diffusion. These phenomena can be offset, however, by increasing the thickness of washcoat and/or by increased noble metal doping. The level of doping in the first stage can be relatively low because there is high temperature and high diffusion. In fact, it is undesirable to have large amounts of catalyst present in the front end of the reactor because this provides for high exothermic heat release which challenges reactor durability and life. A superior strategy is to dope the washcoat in proportion to the catalytic need, which generally is over the last approximately 80% of the flow path.  
         [0057]     The thickness of catalytic washcoat may be varied in a least two methods: first, by assembling a reactor in stages formed of substrate having different washcoat thicknesses; and second, by dipping a first stage only once in a catalytic slurry, a second stage twice, and a third stage three times.  
         [0058]     The thermal profile through a catalytic reformer may be further influenced by choice of materials for the catalytic substrate, which can have a large influence on heat transfer within a fuel reforming reactor. Close to the inlet, in the first stage, it is desirable to remove heat rapidly but not simply by external cooling, since retaining the heat within the reformer is useful in promoting endothermic reforming in sequential stages. Thus, the first stage substrate is preferably formed of a material having very high thermal conductivity.  
         [0059]     The construction of even the first stage may be tuned to promote longevity and thermal dissipation. For example, a high temperature ceramic substrate may form the entry portion to prevent thermal ablation as is described above. However, such a ceramic entry portion must be relatively short, preferably less than one inch, or otherwise in full endothermic reforming mode the endothermic reactions can lower the temperature in the entry portion to a point at which solid carbon is formed (coking). Further, a third substrate may be disposed between the ceramic entry portion and the high-conductivity portion. Thus, an exemplary structure for a first stage may include an entry portion formed of ceramic or ceramic oxide; a second portion formed of a high-temperature metal, such as Haynes  214 , Haynes  230 , or Fecralloy; and a third portion formed of a very high conductivity metal such as nickel aluminide or copper. Copper is preferred since its thermal conductivity is 20-30 times greater than that of other appropriate materials (˜400 W/mK) and has a melting point of 1080° C., whereas the temperature in this portion of the reactor should never exceed 900° C.  
         [0060]     While the present invention has been described by reference to various specific embodiments, it should be understood that numerous changes may be made within the spirit and scope of the inventive concepts described. Accordingly, it is intended that the invention not be limited to the described embodiments, but will have full scope defined by the language of the following claims.