Abstract:
Preferred embodiments of the present invention generate a synthesis gas with a molar ratio of hydrogen to carbon monoxide of approximately 2:1 required for Fischer-Tropsch synthesis. Additional hydrogen produced in the steam reforming of methane beyond the requirements for the Fischer-Tropsch reaction is separated from the product gases of the reformer by the use of a hydrogen permeable membrane. Air is passed over the outside of the tube. As the hydrogen contacts the air, it is combusted with oxygen in the air to form water and release the heat necessary to drive the steam reforming reaction.

Description:
RELATED APPLICATIONS 
     This application claims priority to U.S. Provisional Patent Application No. 60/328,035, filed Oct. 9, 2001, incorporated herein by reference. 
    
    
     STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH 
     Not applicable. 
     FIELD OF THE INVENTION 
     The present invention generally relates to auto-thermal heating of an endothermic reaction by combusting a reaction by-product. More particularly, the present invention relates to an apparatus and method for producing synthesis gas from methane by an endothermic steam reforming reaction wherein a hydrogen permeable membrane separates excess hydrogen produced by the reaction and the excess hydrogen is combusted to provide heat to the endothermic steam reforming reaction. 
     BACKGROUND OF THE INVENTION 
     Large quantities of methane, the main component of natural gas, are available in many areas of the world. However, a significant portion of that natural gas is situated in areas that are geographically remote from population and industrial centers (“stranded gas”). The costs of compression, transportation, and storage often makes the stranded gas&#39; use economically unattractive. Consequently, the stranded natural gas is often flared. Flaring not only wastes the energy content and any possible economic value the natural gas may have but also creates environmental concerns. 
     To improve the economics of natural gas transportation and utilization, much research has focused on using the methane component of natural gas as a starting material for the production of higher hydrocarbons and hydrocarbon liquids. The conversion of methane to hydrocarbons is typically carried out in two steps. In the first step, methane is reacted to produce carbon monoxide and hydrogen (i.e., synthesis gas or “syngas”). In a second step, the syngas is converted to higher hydrocarbon products by processes such as Fischer-Tropsch synthesis. For example, fuels with boiling points in the middle distillate range, such as kerosene and diesel fuel, and hydrocarbon waxes may be produced from the syngas. In addition, syngas may be used for the manufacture of ammonia, hydrogen, methanol, and other chemicals. Less traditional uses of syngas continue to be developed and have increased in importance in recent years, such as in the production of acetic acid and acetic anhydride manufacture. Among the promising new developments in syngas chemistry are routes to ethylene. 
     The syngas routes may be attractive in themselves, regardless of raw materials used; they may also provide the option to use alternative and ultimately cheaper raw materials such as coal and, in certain circumstances, natural gas. One of the attractions of syngas is that it can be manufactured from almost any raw material containing carbon; hence, the availability of feedstock is ensured. 
     The cost of syngas can be highly variable, depending on the effluent hydrogen/carbon monoxide ratio desired, the raw materials available, the production process, the scale of operation and extent of integration with other processes, and other factors. As described below, the current methods for producing syngas all have negative aspects, which result in inefficiencies, and in turn, a higher cost of producing syngas. 
     There are currently three primary reactions for converting methane to syngas. Those methods include: steam reforming (the most widespread), dry reforming (also called CO 2  reforming), and partial oxidation. Steam reforming, dry reforming, and partial oxidation proceed according to the following reactions respectively:
 
CH 4 +H 2 O+heat→CO+3H 2   (1)
 
CH 4 +CO 2 +heat→2CO+2H 2   (2)
 
CH 4 +½O 2 →CO+2H 2 +heat  (3)
 
For a general discussion of steam reforming, dry (or CO 2 ) reforming, and partial oxidation, please refer to H AROLD  G UNARDSON   , Industrial Gases in Petrochemical Processing  41-80 (1998), the contents of which are incorporated herein by reference for all purposes.
 
     As noted in reaction 1, steam reforming is endothermic (requires heat); therefore, heat must be supplied to drive the reaction. One way to provide the necessary heat is to burn a portion of the available natural gas in process heaters. However, because some of the available natural gas is burned to heat the reactor, less natural gas is available to be converted to synthesis gas and the overall yield is lower than if all of the natural gas were converted to syngas. Other methods of supplying heat to the steam reforming reaction at remote well sites are often cost prohibitive. In addition, the steam reforming reaction is relatively slow, thereby requiring relatively long reactor residence times and correspondingly large reactors. These typically large steam reforming plants are usually not practical to set up at remote natural gas well sites. 
     Partial oxidation of hydrocarbons can also be used to produce syngas. Partial oxidation of hydrocarbons to produce syngas typically takes place in the presence of a catalyst. In catalytic partial oxidation (“CPOX”), natural gas is mixed with air, oxygen-enriched air, or oxygen, and introduced to a catalyst at elevated temperature and pressure. The methane reacts exothermically with oxygen to form syngas. A specific example of a CPOX process is set forth in U.S. Pat. No. 5,510,056 to Jacobs, et al., incorporated herein by reference for all purposes. 
     Recently, CPOX of methane has attracted much attention due to its inherent advantages, such as the fact that due to the significant heat that is released during the process, there is no requirement for the continuous input of heat in order to maintain the reaction. This is in contrast to steam reforming processes, which generally use external gas firing that decreases total liquid product yields (discussed above). CPOX also has space saving advantages. CPOX is a very fast reaction; therefore, reactor residence times are much less than those needed for steam reforming and thus, smaller reactors are acceptable. In addition, CPOX produces syngas with the optimal 2:1 H 2 :CO molar ratio for Fischer-Tropsch reactions, and has a simplified catalytic reaction plant section. 
     CPOX is not without its drawbacks. In CPOX, oxygen and methane must be mixed in the presence of a catalyst. Mixing of these components in certain temperature and pressure regimes can potentially lead to explosions, fires, and equipment failures. Because of this, CPOX has so far been substantially limited to low pressures due to the safety concerns. In addition, although it is possible to conduct a partial oxidation reaction in the presence of air or oxygen-enriched air it is often preferable to conduct the reaction in the presence of substantially pure oxygen because if other than substantially pure oxygen is used, diluants in the air (e.g., N 2 ) will require the use of a much larger reactor, thus increasing the cost to build and operate and reducing or eliminating the size advantage of CPOX over steam reforming. Unfortunately, separation, compression, and handling of the substantially pure oxygen can be very expensive. 
     Another process for producing syngas is autothermal reforming (“ATR”). ATR is basically a combination of partial oxidation and steam reforming carried out in a single reactor. The heat released by the exothermic partial oxidation reaction is used to drive an endothermic steam reforming reaction in another part of the reactor. 
     One of the features of ATR is that it requires no external fuel. ATR also reduces, but does not eliminate, some of the safety issues involved with CPOX because a burner is used. The burner allows for the safe mixing and combustion of methane with oxygen. However, ATR also has negative aspects. For example, large amounts of CO 2  are generated in the partial oxidation portion of an ATR reactor. This reduces the overall conversion of methane to CO. Additionally, removal of that CO 2  increases the expense of the overall processing scheme. A detailed discussion of ATR is included on pages 61-66 of the G UNARDSON  referenced cited above. 
     With regard to the membrane art, research done by Prabhu, Radhakrishnan, and Oyama (P RABHU, ET AL.,    Supported Nickel Catalysts for Carbon Dioxide Reforming of Methane in Plug Flow and Membrane Reactors , A PPLIED  C ATALYSIS  A: G ENERAL  241-52 (1999) (“P RABHU, ET AL .”)), incorporated herein by reference in its entirety for all purposes, discloses the use of a hydrogen permeable membrane to separate hydrogen from the reaction product of a dry reforming reaction to shift equilibrium conditions and increase the methane conversion in the reactor. As is shown in FIG. 9 of P RABHU, ET AL ., the Vycor® membrane used was effective up to a temperature of at least 1023 K. It should be noted that the P RABHU, ET AL . reference does not teach the combustion of the permeated hydrogen and instead uses a Hoskins tubular furnace to drive the endothermic dry reforming reaction. Likewise, U.S. Pat. No. 5,637,259 to Galuszka et al., incorporated herein by reference for all purposes, discloses the use of a hydrogen permeable membrane to separate hydrogen from the reaction product of a dry reforming reaction and a catalytic partial oxidation reaction to shift equilibrium conditions and increase the methane conversion and the H 2  and CO selectivities in the reactor. Like P RABHU ET AL ., Galuszka et al. does not teach the combustion of the separated hydrogen to drive the reaction or the use of a membrane in conjunction with a stream reforming reaction. 
     Because syngas is used in both methanol, Fischer-Tropsch, and other syntheses, the demand for syngas remains high. This has fueled syngas research, which has resulted in processes such as steam reforming, CPOX, and ATR. However, while these competing processes have benefits, they also have flaws or limitations, which ultimately limit their utility. Therefore, there exists a need for new processes that exhibit at least some of the positive features of these competing processes, while reducing or eliminating the negative features or limitations. 
     SUMMARY OF THE INVENTION 
     The present invention embodies some of the positive features of steam reforming, CPOX, and ATR, while reducing some of the negative aspects. The result is a hybrid process that approaches the relatively high yield of partial oxidation while reducing the safety and pressure concerns. Like ATR, the new process uses internal combustion to heat the process, but greatly reduces the CO 2  generation and safety concerns of ATR. 
     In a preferred embodiment of the present invention, an apparatus for producing syngas includes a steam reforming catalyst bed, a hydrogen permeable membrane, and a substantially enclosed combustion zone, where the hydrogen permeable membrane separates the catalyst bed from the combustion zone. 
     In another preferred embodiment of the present invention, a process for producing syngas includes contacting a feed stream of methane and water with a catalyst in a reaction zone maintained at steam reforming conditions effective to produce an effluent stream of hydrogen and carbon monoxide at a ratio of about 3:1 and removing excess hydrogen via a hydrogen permeable membrane to produce an effluent stream of hydrogen and carbon monoxide at a ratio of about 2:1. The removed excess hydrogen is combusted in a combustion zone to provide heat to drive the endothermic steam reforming reaction in the reaction zone. 
     Another preferred embodiment comprises a reactor system for carrying out an endothermic reaction to form reaction products comprising a first substantially enclosed reactor zone and a second substantially enclosed reactor zone in physical and thermal contact with the first reactor zone. The physical interface between the first and second reactor zones defines a contact surface, where at least a portion of the contact surface (and possibly the entire contact surface) comprises a selectively permeable membrane for allowing a first gas, such as hydrogen, to pass from the second reactor zone to the first reactor zone. The first reactor zone is adapted for combusting the first gas and the second reactor zone is preferably adapted for carrying out an endothermic reaction, such as steam or dry reforming of a hydrocarbon, which produces a gaseous reaction product, such as syngas. The combustion of the first gas supplies heat to at least partially (and possibly completely) drive the endothermic reaction. 
     The preferred reactor system can be designed such that the second reactor zone is substantially contained within the first reactor zone, the second reactor zone is adjacent to, but not substantially contained within, the first reactor zone, or the first reactor zone is substantially contained within the second reactor zone. 
     The second reactor zone preferably contains a catalyst to catalyze the endothermic reaction, and the first reactor zone preferably contains a means for initiating the combustion of the first gas, such as described herein. 
     Another preferred embodiment further comprises a third substantially enclosed zone in physical contact with the second reactor zone, the physical interface between the second reactor zone and the third zone defines another contact surface, where at least a portion of (and possibly all of) the contact surface comprises a selectively permeable membrane for allowing the first gas to pass from the second reactor zone to the third zone. Also preferably included is a recycle stream for recycling the first gas from the third zone into the first zone. 
     Another preferred embodiment includes a method for conducting an endothermic reaction, including providing a first reactor defining a reaction zone and having a feed stream intake opening and a product stream outlet opening; providing a second reactor defining a combustion zone and having an oxygen intake opening and an exhaust opening; providing a selectively permeable membrane between and separating the reaction zone and the combustion zone; conducting an endothermic reaction, preferably the steam reforming of the methane to produce syngas, which produces excess combustible gas, preferably hydrogen, in the reaction zone, where at least some of the excess combustible gas permeates through the selectively permeable membrane into the combustion zone; and combusting at least some of the permeated excess combustible gas in the combustion zone, where heat generated by the combustion of the combustible gas drives the endothermic reaction in the reaction zone. 
     Another preferred embodiment includes a method for producing syngas with a hydrogen to carbon monoxide ratio of about 2:1 comprising the steps of providing a combustion reactor having an oxygen intake opening and an exhaust opening; providing a steam reforming reactor having walls and a feed stream intake opening and a product stream outlet opening, wherein the steam reforming reactor is substantially inside of the combustion reactor and the walls of the steam reforming reactor comprise a substantially hydrogen only permeable membrane; providing a catalyst system inside of the steam reforming reactor to catalyze the steam reforming of methane to produce syngas with a hydrogen to carbon monoxide ratio of about 3:1, wherein about ⅓ of the hydrogen generated permeates through the substantially hydrogen only permeable membrane into the combustion reactor; and combusting the permeated hydrogen in the combustion reactor to provide heat to drive the endothermic steam reforming reaction in the steam reforming reactor. 
     Another preferred embodiment includes a process for producing a syngas stream with a hydrogen to carbon monoxide molar ratio of a predetermined amount, such as 2:1, the process comprising a means for steam reforming a hydrocarbon containing feed stream, such as methane or natural gas, to produce a syngas stream with a hydrogen to carbon monoxide ratio of greater than the predetermined amount, such as a catalyst system for steam reforming; a means for in-situ separating excess hydrogen from the syngas stream; and a means for combusting at least a portion of the excess hydrogen to produce heat to drive the means for steam reforming. In addition, preferably, there is included a means for supplying oxygen to the means for combusting and a means for exhausting the combusted hydrogen from the means for combusting. 
     The catalyst system preferably comprises a catalyst support and a catalyst, such as described herein. 
     Another preferred embodiment includes a reactor system for carrying out steam reforming of methane to produce synthesis gas, the reactor system comprising a first reactor comprising a steam reforming zone containing a catalyst bed, a reactant gas inlet and a product gas outlet; a second reactor at least partially surrounding the first reactor and comprising an H 2  combustion zone, an oxygen inlet and an exhaust gas outlet; and a thermally conductive substantially H 2  only permeable membrane disposed between the reforming zone and the combustion zone. The catalyst bed contains a catalyst capable of catalyzing the steam reforming of methane to produce synthesis gas under reaction promoting conditions. 
     Another preferred embodiment includes a method of reducing the H 2 :CO molar ratio of a synthesis gas stream comprising providing a reactor system including: a first reactor having a steam reforming zone containing a catalyst bed, a reactant gas inlet and a synthesis gas outlet, a second reactor at least partially surrounding the first reactor and comprising a combustion zone, an air inlet and an exhaust gas outlet, and a thermally conductive substantially hydrogen only permeable membrane disposed between the reforming zone and said combustion zone; contacting a mixture of methane and steam in the steam reforming zone with a catalyst capable of catalyzing the reaction CH 4 +H 2 OH 2 +CO under reaction promoting conditions to provide a stream of product gas comprising hydrogen and carbon monoxide in a molar ratio of about 3:1; maintaining a higher gas pressure in the first reactor than in the second reactor, such that a portion of the hydrogen product gas passes through the membrane into the combustion zone; mixing a source of oxygen with the portion of hydrogen product gas in the combustion zone; igniting the hydrogen and oxygen in the combustion zone to produce heat; conducting at least a portion of the heat into the steam reforming zone such that the steam reforming reaction is at least partially sustained by the heat; and harvesting a modified synthesis gas stream comprising a molar ratio less than about 3:1 of H 2 :CO. Preferably, the method also includes harvesting a modified synthesis gas stream having a molar ratio of H 2 :CO of about 2:1. 
     Another preferred embodiment includes a reactor system for carrying out an endothermic reaction to form reaction products, the reactor system comprising a first substantially enclosed reactor zone; a second substantially enclosed reactor zone in thermal contact with the first reactor zone; and a selectively permeable membrane system separating the first reactor zone from the second reactor zone. The second reactor zone is adapted for carrying out the endothermic reaction which produces a first combustible gas. The selectively permeable membrane system is adapted to help extract the first combustible gas from the first reactor zone into the second reactor zone. The first reactor zone is adapted for combusting the first combustible gas, and the combustion of the first combustible gas supplies heat to at least partially drive the endothermic reaction. 
     Another preferred embodiment includes a reactor system for carrying out an endothermic reaction, the reactor system comprising a reaction zone substantially enclosed by a selectively permeable membrane; a combustion zone surrounding the selectively permeable membrane, wherein the combustion zone is substantially enclosed by a reactor shell. The reactor shell has an oxygen inlet and an exhaust outlet. The reaction zone has a reactant inlet and a product outlet. The reactor system comprises a plurality of sections including at least an anterior section and a posterior section (and preferably, but not necessarily, an intermediate section), and the plurality of section are detachable from each other when the reactor system is not in use. 
     The present invention generally avoids some of the negative features of steam or dry reforming, CPOX, and ATR, while capturing some of the benefits of these processes. The result is a more efficient, lower cost syngas process. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       For a more detailed understanding of the present invention, reference is now made to the accompanying figures. In the accompanying of figures substantially similar components have been identically numbered for ease of reference. 
         FIG. 1  is a cross-sectional schematic drawing of a first embodiment of the present invention. 
         FIG. 2  is a cross-sectional schematic drawing of a second embodiment of the present invention. 
         FIG. 3  is a cross-sectional schematic drawing of a third embodiment of the present invention. 
         FIG. 4  is a cross-sectional schematic drawing of a fourth embodiment of the present invention. 
         FIG. 5  is a cross-sectional schematic drawing of a fifth embodiment of the present invention. 
         FIG. 6  is a cross-sectional schematic drawing of a sixth embodiment of the present invention. 
     
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     Referring now to  FIG. 1 , one embodiment of the present system, reformer reactor  160  includes a steam reforming reaction chamber  120 , a reactor inlet  60  and a syngas outlet  70 . Reaction chamber  120  is substantially encased by a hydrogen permeable membrane  130  and a combustion zone  140 . Combustion zone  140  is substantially encased by a refractory lining  100  and metal shell  110  having an air inlet  80  and an exhaust opening  90 . The reaction chamber  120  includes a catalyst system as herein defined. 
     In operation, methane stream  10  and water stream  20  are blended to comprise a methane-water feed stream  150 . Methane-water feed stream  150  enters steam reforming reaction chamber  120 , where a steam reforming reaction takes place accordingly. Excess hydrogen is separated internally by use of substantially hydrogen only permeable membrane  130  in the reformer reactor. This excess hydrogen feeds into combustion zone  140 . Air  40  is drawn into the combustion chamber  140  through air inlet  80  where it is combusted with the excess hydrogen to supply heat to and drive the endothermic steam reforming reaction taking place in reaction chamber  120 . The exhaust  50 , composed of the product of the hydrogen combustion along with any other gases in the combustion chamber, are then exhausted through the exhaust opening  90 . The combustion can be initiated by catalyst in the combustion zone, by establishing a flame or spark, by auto-ignition, or by any other acceptable method. The heat generated from the hydrogen combustion maintains the high temperatures necessary for steam reforming inside reaction chamber  120 , resulting in a product stream  30  containing primarily syngas which exits chamber  120  via syngas outlet  70 . 
     Referring now to  FIG. 2 , a second embodiment of the present system, reformer reactor  160  includes a steam reforming reaction chamber  120 , a reactor inlet  60  and a syngas outlet  70 . Reaction chamber  120  is encased by a hydrogen permeable membrane  130 , refractory lining  170 , and metal shell  180 . Combustion zone  140  is encased by a refractory lining  100  and metal shell  110  having an air inlet  80  and an exhaust opening  90 . The reaction chamber  120  includes a catalyst system as herein defined. 
     In operation, methane stream  10  and water stream  20  are blended to comprise a methane-water feed stream  150 . Methane-water feed stream  150  enters steam reforming reaction chamber  120 , where a steam reforming reaction takes place accordingly. Excess hydrogen is separated internally by use of substantially hydrogen only permeable membrane  130  in the reformer reactor. This excess hydrogen feeds into combustion zone  140 . Air  40  is drawn into the combustion chamber  140  through air inlet  80  where it is combusted with the excess hydrogen to supply heat and drive the endothermic steam reforming reaction taking place in reaction chamber  120 . The product of the hydrogen combustion, along with any other gases in the combustion chamber are then exhausted through the exhaust opening  90 . The combustion can be initiated by catalyst in the combustion zone, by establishing a flame or spark, by auto-ignition, or by any other acceptable method. The heat generated from the hydrogen combustion maintains the high temperatures necessary for steam reforming inside reaction chamber  120 , resulting in a product stream  30  containing primarily syngas which exits chamber  120  via outlet  70 . 
     Referring now to  FIG. 3 , there is shown an adjustable stackable embodiment of the present invention. In this embodiment, four individual components  200 ,  210 ,  220 , and  230  of the reactor system  160  can be assembled to form an assembled reactor system, (such as, for example, the reactor system of FIG.  1 ). The component interfaces  190  are designed, as is well known in the art, to connect and interface such that overall reactor performance is not substantially hindered. It is also envisioned that the embodiment of  FIG. 3  could be expanded or contracted in size by varying the number of intermediate sections (e.g.,  210  and  220 ) from one to several. The optimal length, as also with FIG.  1  and  FIG. 2 , is to be determined by one of ordinary skill in the art and may vary depending on the ultimate product stream application and the physical limitations of the manufacturing materials. 
     When in assembled operation, methane stream  10  and water stream  20  are blended to comprise a methane-water feed stream  150 . Methane-water feed stream  150  enters catalyst filled steam reforming reaction chamber  120  via reactor inlet  60 , where a steam reforming reaction takes place accordingly. Excess hydrogen is separated internally by use of substantially hydrogen only permeable membrane  130  in the reformer reactor. This excess hydrogen feeds into combustion zone  140 . Air  40  is drawn into the combustion chamber  140  through air inlet  80  where it is combusted with the excess hydrogen to supply heat to and drive the endothermic steam reforming reaction taking place in reaction chamber  120 . The product of the hydrogen combustion, along with any other gases in the combustion chamber are then exhausted through the exhaust opening  90 . The combustion can be initiated by catalyst in the combustion zone, by establishing a flame or spark, by auto-ignition or by any other acceptable method. The heat generated from the hydrogen combustion maintains the high temperatures necessary for steam reforming inside reaction chamber  120 , resulting in a product stream  30  containing primarily syngas which exits chamber  120  via outlet  70 . 
     It is envisioned that the stackable system embodied in  FIG. 3  should not be limited to a reactor in which the reaction zone  120  is completely enclosed in the combustion zone  140 . It is envisioned that other embodiments of the present invention, such as those of  FIGS. 2 ,  3 ,  4 ,  5 , and  6 , can also be configured as an assembly of multiple components. This stackable assembly will ease the transportability and assembly of the reactor system, thereby increasing its flexibility and mobility. Hence, this stackable embodiment can be a valuable tool for processing natural gas at remote locations. 
     Referring now to  FIG. 4 , there is shown an embodiment of the present invention in which the reaction chamber  120  is not completely enclosed within the combustion chamber  140 . In  FIG. 4 , reformer reactor  160  includes a steam reforming reaction chamber  120 , a reactor inlet  60  and a syngas outlet  70 . Reaction chamber  120  is partially encased by a hydrogen permeable membrane  130  and a combustion zone  140 . The remainder of reaction chamber  120  is encased by a reactor liner  175  comprised of refractory lining  170  and metal shell  180 . Combustion zone  140  is encased by a refractory lining  100  and a metal shell  110  having an air inlet  80  and an exhaust opening  90 . The reaction chamber  120  includes a catalyst system as herein defined. 
     In operation, methane stream  10  and water stream  20  are blended to comprise a methane-water feed stream  150 . Methane-water feed stream  150  enters steam reforming reaction chamber  120 , where a steam reforming reaction takes place accordingly. Excess hydrogen is separated internally by use of substantially hydrogen only permeable membrane  130  in the reformer reactor. This excess hydrogen feeds into combustion zone  140 . Air  40  is drawn into the combustion chamber  140  through air inlet  80  where it is combusted with the excess hydrogen to supply heat to and drive the endothermic steam reforming reaction taking place in reaction chamber  120 . The exhaust  50 , composed of the product of the hydrogen combustion along with any other gases in the combustion chamber, is then exhausted through the exhaust opening  90 . The combustion can be initiated by catalyst in the combustion zone  140 , by establishing a flame or spark, by auto-ignition, or by any other acceptable method. The heat generated from the hydrogen combustion maintains the high temperatures necessary for steam reforming inside reaction chamber  120 , resulting in a product stream  30  containing primarily syngas which exits chamber  120  via syngas outlet  70 . 
     Referring now to  FIG. 5 , there is shown an embodiment of the present invention which includes a combustion zone  140  encasing a portion of the reaction zone  120  and a recycle zone  300  encasing another portion of the reaction zone  120 . Excess hydrogen permeates through substantially hydrogen only permeable membrane  130  into combustion zone  140  and recycle zone  300 . At least a portion of the hydrogen permeating into the recycle zone  300  is recycled into combustion zone  140  where it is combusted with the hydrogen permeating directly into the combustion zone  140  from the reaction zone  120 . 
     In operation, methane stream  10  and water stream  20  are blended to comprise a methane-water feed stream  150 . Methane-water feed stream  150  enters steam reforming reaction chamber  120 , where a steam reforming reaction takes place accordingly. Excess hydrogen is separated internally by use of substantially hydrogen only permeable membrane  130  in the reformer reactor. This excess hydrogen feeds into combustion zone  140  and recycle zone  300 . At least a portion of the hydrogen permeating into the recycle zone  300  is recycled back into the combustion zone  140  via recycle stream  250 . Air  40  is drawn into the combustion chamber  140  through air inlet  80  where it is combusted with the hydrogen that permeates directly into the combustion zone  140  and the recycle zone  250  to supply heat to and drive the endothermic steam reforming reaction taking place in reaction chamber  120 . The exhaust  50 , composed of the product of the hydrogen combustion along with any other gases in the combustion chamber, is then exhausted through the exhaust opening  90 . The combustion can be initiated by catalyst in the combustion zone, by establishing a flame or spark, by auto-ignition, or by any other acceptable method. The heat generated from the hydrogen combustion maintains the high temperatures necessary for steam reforming inside reaction chamber  120 , resulting in a product stream  30  containing primarily syngas which exits chamber  120  via syngas outlet  70 . The hydrogen recycle stream  250  allows for localization of the hydrogen combustion in instances in which it is not desirable for the combustion to take place along the entire length of the reaction zone  120 . 
     Referring now to  FIG. 6 , there is shown an embodiment in which the combustion chamber  14  is encased by hydrogen permeable membrane  130  and reaction chamber  120 . 
     In operation, methane stream  10  and water stream  20  are blended to comprise a methane-water feed stream  150 . Methane-water feed stream  150  enters steam reforming reaction chamber  120 , where a steam reforming reaction takes place accordingly. Excess hydrogen is separated internally by use of substantially hydrogen only permeable membrane  130  in the reformer reactor. This excess hydrogen feeds into combustion zone  140 . Air  40  is drawn into the combustion chamber  140  through air inlet  80  where it is combusted with the excess hydrogen to supply heat to and drive the endothermic steam reforming reaction taking place in reaction chamber  120 . The exhaust  50 , composed of the product of the hydrogen combustion along with any other gases in the combustion chamber, are then exhausted through the exhaust opening  90 . The combustion can be initiated by catalyst in the combustion zone, by establishing a flame or spark, by auto-ignition, or by any other acceptable method. The heat generated from the hydrogen combustion maintains the high temperatures necessary for steam reforming inside reaction chamber  120 , resulting in a product stream  30  containing primarily syngas which exits chamber  120  via syngas outlet  70 . 
     As can be seen, adding together the combustion and steam reforming reactions in the syngas generation embodiment of the present invention gives the overall reaction for syngas generation: 
               H   2     +       1   2     ⁢     O   2             -&gt;             H   2     ⁢   O     +   heat                   ⁢     (   4   )                   CH   4     +       H   2     ⁢   O     +   heat         -&gt;         CO   +     3   ⁢     H   2                       ⁢     (   1   )                   CH   4     +       1   2     ⁢     O   2             -&gt;         CO   +     2   ⁢     H   2       +   heat                   ⁢     (   3   )               
 
This overall reaction is the same as the primary reaction in a CPOX process (reaction  3 ). However, unlike CPOX, in the process of the present invention combustion is separated from the main reaction mixture and the combustion controlled by the amount of air made available to the combustion zone. This reduces many of the safety concerns present in a partial oxidation process.
 
     The hydrogen permeable material used in the present invention should be resistant to high temperatures, preferably functioning at temperatures of at least about 800° C.-1000° C. A suitable material should also conduct heat well, resist oxidation, and allow for selective hydrogen mobility through the wall. A suitable material has sufficient heat transfer capabilities if for any desired configuration of the present invention, a sufficient amount of heat is transferred to the reaction zone to achieve the heat transfer objectives of that particular embodiment. For example, in the embodiment of  FIG. 1 , the heat transfer rate is sufficient if enough heat is transferred to drive the steam reforming reaction in the reaction zone without the need for an outside heat source. An example of such a material is a ceramic ion transport membrane, or more specifically, a mixed conduction membrane. A suitable material for the hydrogen permeable membrane is the modified Vycor® (Corning, Inc.) glass material disclosed in P RABHU AND  O YAMA   , Development of a Hydrogen Selective Ceramic Membrane and Its Application for the Conversion of Greenhouse Gases , 1999 Chemical Letters 213-14 (“P RABHU AND  O YAMA ”), the contents of which are incorporated herein by reference in their entirety for all purposes. 
     It is contemplated that any configuration in which the reaction zone is separated from the combustion zone by a selectively permeable membrane which allows substantially only a predetermined gas (or gases) to permeate will fall within the scope of the present invention. By way of example only, a coiled substantially hydrogen only permeable membrane tube residing within the combustion zone and a reaction zone sandwiched between two combustion zones wherein two substantially hydrogen only permeable membranes are employed to separate the reaction zone from the two combustion zones are contemplated to be within the scope of the present invention. 
     It is also contemplated that there may be configurations of the present invention in which membrane systems or multiple membranes may be used to achieve the desired gas separation. For example, a two-stage separation may be needed to achieve the desired final separation, in which case the membrane system would consist of a first membrane to achieve the first separation and a second membrane to further separate the product of the first separation. 
     It is further contemplated that the present invention is not limited to any particular directional relationship between the combustion zone flow and the reaction zone flow. For example, the arrows of  FIG. 2  indicate that the flow in the combustion chamber is countercurrent to the flow in the reaction chamber. On the other hand, in  FIG. 6 , the flow within the combustion chamber and within the reaction zone are co-current and parallel. The present invention is not limited to any particular flow relationship. It can include countercurrent, unidirectional, perpendicular, parallel, skewed, or curved flows as well as any other acceptable flow relationship so long as the desired heat transfer is maintained. 
     The present invention allows for combustion internally in the reactor system without allowing nitrogen to dilute the product gas. The pressure differential between the inside of the catalyst tube where the reforming reaction takes place and the outside of the tube where combustion takes place provides the driving force for the hydrogen permeation through the membrane. Low combustion air pressure in the combustion chamber favors the transport of hydrogen through the membrane and the rate of hydrogen permeation can be controlled by controlling the pressure differential across the membrane. It should be noted, however, that the strength of the membrane material may create an upper limit to the pressure differential which may be achieved. Additionally, the rate of hydrogen permeation may be controlled by controlling the thickness of the membrane and the size of the membrane. 
     The reaction chamber does not need to be completely enclosed by the substantially hydrogen only permeable membrane. The membrane may be only a portion of the member that encloses the reaction zone so long as the substantially hydrogen only permeable membrane is between the reaction zone and the combustion zone and the reaction zone is separate from the combustion zone. Thus, in the syngas embodiments it is contemplated to control the rate of hydrogen permeation to tailor the syngas composition to the specific downstream process requirements or to tailor the rate of combustion. By analogy, in non-syngas embodiments, it is contemplated to control the rate of flammable gas permeation to tailor the product composition or to tailor the rate of combustion. 
     It is also possible to control the rate of flammable combustion in the combustion zone to control the amount of heat transferred to the reaction zone. The rate of combustion can be controlled by controlling the amount of air (more particularly, oxygen in air) available for combustion of the permeated combustible gas. A temperature sensor can be placed in the reaction zone, and the air flow through the combustion zone adjusted until the desired reaction zone temperature is achieved. The desired temperature may vary depending upon the circumstances. 
     The following definitions shall apply for the purposes of this specification. 
     “Excess hydrogen” is defined as any hydrogen generated by the reaction in the reaction zone which is not desired to be in the product stream. Likewise, in an embodiment other than the steam reforming embodiment described, “excess combustible gas” is any gas produced in the reaction chamber which is not desired to be in the product stream and which can be ignited in the presence of oxygen to produce heat. By way of example only, in the steam reforming embodiment in which the reaction produces three hydrogens for each carbon monoxide and the desired hydrogen to carbon monoxide ration in the product stream is two hydrogens for each carbon monoxide, the one extra hydrogen produced is an excess hydrogen. 
     The term “catalyst system” as used herein means any acceptable system for catalyzing the desired reaction in the reaction zone. By way of example only, the catalyst system of a syngas steam reforming reaction usually includes a support and a catalyst. The support may be, for example, particulates, pills, beads, granules, pellets, rings, monoliths, ceramic honeycomb structures, wire gauze, or any other suitable supports as are known in the art. Likewise, the catalyst may include, for example, a conventional steam reforming catalyst such as nickel. The above examples of supports and catalysts are only examples. There are a plethora of catalysts systems known in the art which would be acceptable and are contemplated to fall within the scope of the steam reforming embodiment of the present invention. Indeed in other embodiments of the present invention not involving syngas reforming, if a catalyst system is required at all, it will be within the skill of one of ordinary skill in the art to determine the proper catalyst system by modifying an existing process in accordance with the present disclosure. 
     The term “substantially hydrogen only permeable membrane” means a membrane which does not allow a significant amount of any substance other than hydrogen to permeate through the membrane. 
     The term “drive the reaction” means to provide heat to an endothermic reaction to aid in sustentation of the reaction. A first reaction is “completely driven” by a second reaction when enough heat is provided by the second reaction to sustain the first reaction without addition of heat from another source. 
     The term “membrane system” means a plurality of complimentary membranes that work together to achieve a desired separation. For example, a two-stage separation may be needed to achieve the desired final separation, in which case the membrane system would consist of a first membrane to achieve the first separation and a second membrane to further separate the product of the first separation.