System for hydrogen generation through steam reforming of hydrocarbons and intergrated chemical reactor for hydrogen production from hydrocarbons

Abstract

The present invention provides a reactor, which includes: a unitary shell assembly having an inlet and an outlet; a flow path extending within the shell assembly from the inlet to the outlet, the flow path having a steam reformer section with a first catalyst and a water gas shift reactor section with a second catalyst, the steam reformer section being located upstream of the water gas shift reactor section; a heating section within the shell assembly and configured to heat the steam reformer section; and a cooling section within the shell assembly and configured to cool the water gas shift reactor section. The present invention also provides a simplified hydrogen production system, which includes the catalytic steam reforming and subsequent high temperature water gas shift of low-sulfur (<100 ppm by mass) hydrocarbon fuels followed by hydrogen purification through the pressure swing adsorption (PSA). The integrated reactor offers significant advantages such as lower heat loss, lower parts count, lower thermal mass, and greater safety than the many separate components employed in conventional and is especially well-suited to applications where less than 15,000 standard cubic feet per hour of hydrogen are required. The improved system also may be started, operated and shut down more simply and quickly than what is currently possible in conventional systems. The improved system preferably employs active temperature control for added safety of operation. The hydrogen product is of high purity, and the system may be optionally operated with a feedback control loop for added purity.

1 . A reactor, comprising: 
 a unitary shell assembly having at least a first inlet, a first outlet, a second inlet and a second outlet;    a first flow path extending within said shell assembly from said first inlet to said first outlet, said first flow path having a steam reformer section comprising a steam reforming catalyst, and a water gas shift reactor section comprising a water-gas shift catalyst, said steam reformer section being located upstream of said water gas shift reactor section; and    a second flow path extending within said shell assembly from said second inlet to said second outlet, said second flow path having a cooling section configured to cool said water gas shift reactor section and a heating section configured to heat said steam reformer section, wherein said cooling section and said heating section are fluidly connected,    wherein said heating section is downstream of said cooling section along said second flow path, and    wherein said first and second flowpaths are not fluidly connected.    
     
     
         2 - 43 . (canceled)  
     
     
         44 . The reactor of  claim 1 , wherein said flow path includes a preheat section located upstream of said steam reformer section.  
     
     
         45 . The reactor of  claim 44 , wherein said preheat section includes a packing material.  
     
     
         46 . The reactor of  claim 45 , wherein said packing material is a sulfur absorbent bed.  
     
     
         47 . The reactor of  claim 1 , wherein said flow path includes an adiabatic water gas shift reactor section located downstream of said water gas shift reactor section.  
     
     
         48 . The reactor of  claim 1 , wherein: 
 said steam reformer section and said water gas shift reactor section are formed of an array of tubes;    said flow path includes an inlet tube header located upstream of said steam reformer section; and    said flow path includes an outlet tube header located downstream of said water gas shift reactor section.    
     
     
         49 . The reactor of  claim 48 , wherein the interior of the tubes is provided with a catalyst in the form of at least one selected from the group consisting of a coating, a monolith, a loose packing of pellets, extrudates, and mixtures thereof.  
     
     
         50 . The reactor of  claim 1 , wherein said shell assembly includes: 
 a means of thermal expansion relief;    at least one inlet to said cooling section configured to receive a cooling medium; and    at least one outlet for said cooling section.    
     
     
         51 . The reactor of  claim 50 , wherein said shell assembly includes: 
 at least one inlet to said heating section configured to receive a heating medium; and    at least one outlet for said heating section.    
     
     
         52 . The integral reactor of  claim 48 , wherein said tubes in said array of tubes have an exterior surface configured to aid heat transfer between said heating section and said steam reformer section, and between said cooling section and said water gas shift reactor section.  
     
     
         53 . The reactor of  claim 52 , wherein said exterior surface of said tubes are configured with at least one configuration selected from the group consisting of twisted tubes, finned tubes, rifled tubes, plate fins, loose packing material, and combinations thereof.  
     
     
         54 . The reactor of  claim 48 , further comprising baffles within said shell assembly and provided exterior of said tubes, said baffles being configured to force a heat transfer medium flowing outside said tubes across the array of tubes in a direction substantially normal to a longitudinal axis of said tubes.  
     
     
         55 . The reactor of  claim 54 , wherein said baffles have a modified surface area.  
     
     
         56 . The reactor of  claim 1 , further comprising a catalytic burner configured to heat at least one of a heating medium provided within said heating section and a cooling medium provided within said cooling section.  
     
     
         57 . The reactor of  claim 56 , wherein said catalytic burner is provided within said shell assembly.  
     
     
         58 . The reactor of  claim 56 , wherein said catalytic burner includes at least one inlet for fuel delivery.  
     
     
         59 . The reactor of  claim 56 , wherein said catalytic burner includes at least one selected from the group consisting of a means for mixing fuel and heated air, a means for preheating and/or igniting, at least one temperature sensor, and combinations thereof.  
     
     
         60 . The reactor of  claim 1 , wherein said steam reforming catalyst is substantially resistant to poisoning by sulfur and molecular oxygen.  
     
     
         61 . The reactor of  claim 1 , wherein said water-gas shift catalyst is substantially resistant to poisoning by sulfur.  
     
     
         62 . The reactor of  claim 1 , further comprising: 
 an insulation assembly provided on at least a portion of an exterior of said shell assembly; and    an outer housing provided on an exterior of said insulation assembly.    
     
     
         63 . (canceled)  
     
     
         64 . The reactor of  claim 1 , wherein said unitary shell assembly is a pressurized shell assembly.  
     
     
         65 . The reactor of  claim 1 , wherein said unitary shell assembly is a gas-tight shell assembly.  
     
     
         66 . The reactor of  claim 1 , wherein said shell assembly further comprises an insulating layer.  
     
     
         67 . The reactor of  claim 66 , wherein said insulating layer is contiguous or non-contiguous.  
     
     
         68 . The reactor of  claim 1 , wherein said first and second steam reforming catalyst and said water-gas shift catalyst are the same or different.  
     
     
         69 . The reactor of  claim 1 , wherein said steam reforming catalyst is in admixture with said water-gas shift catalyst.  
     
     
         70 . The reactor of  claim 1 , wherein said water-gas shift catalyst is in admixture with said steam reforming catalyst.  
     
     
         71 . The reactor of  claim 1 , wherein said shell assembly comprises a plurality of inlets.  
     
     
         72 . The reactor of  claim 1 , wherein said shell assembly comprises a plurality of outlets.  
     
     
         73 . The reactor of  claim 1 , wherein said shell assembly comprises a tube side and a shell side.  
     
     
         74 . The reactor of  claim 73 , wherein said tube side forms a continuous pressure vessel.  
     
     
         75 . A reactor for the production of hydrogen from at least one selected from the group consisting of natural gas, propane, liquefied petroleum gas, alcohols, naphtha, hydrocarbon fuels and mixtures thereof, said reactor comprising: 
 a unitary shell assembly having at least a first inlet, a first outlet, a second inlet, and a second outlet;    a first flow path extending within said shell assembly from said first inlet to said first outlet, said first flow path comprising a convectively-heated catalytic steam reformer comprising a steam reforming catalyst, and a convectively-cooled water gas shift reactor comprising a water-gas shift catalyst;    a second flow path extending within said shell assembly from said second inlet to said second outlet,    wherein said first and second flow paths are not fluidly connected;    wherein the steam reformer is upstream of the water-gas shift reactor in said first flow path; and    wherein the steam reformer is positioned downstream of the water-gas shift reactor along said second flow path.    
     
     
         76 - 85 . (canceled)  
     
     
         86 . The reactor of  claim 52 , wherein said tubes are selected from the group consisting of twisted tubes, finned tubes, rifled tubes, and combinations thereof.  
     
     
         87 . The reactor of  claim 1 , wherein said steam reforming catalyst comprises a catalytically active metal selected from the group consisting of group VIIIB metals, ruthenium, iridium, rhodium, platinum, palladium and mixtures thereof supported upon a ceramic support.  
     
     
         88 . The reactor of  claim 75 , wherein said first flow path includes a preheat section located upstream of said steam reformer.  
     
     
         89 . The reactor of  claim 88 , wherein said preheat section includes a packing material.  
     
     
         90 . The reactor of  claim 89 , wherein said packing material is a sulfur absorbent bed.  
     
     
         91 . The reactor of  claim 75 , wherein: 
 said steam reformer and said water gas shift reactor are formed of an array of tubes;    said first flow path includes an inlet tube header located upstream of said steam reformer; and    said first flow path includes an outlet tube header located downstream of said water gas shift reactor.    
     
     
         92 . The reactor of  claim 91 , wherein the interior of the tubes is provided with at least one of the catalysts in the form of at least one selected from the group consisting of a coating, a monolith, a loose packing of pellets, extrudates, and mixtures thereof.  
     
     
         93 . The reactor of  claim 91 , wherein each of said tubes in said array of tubes has an exterior surface configured to aid heat transfer.  
     
     
         94 . The reactor of  claim 93 , wherein said exterior surface of each of said tubes is configured with at least one configuration selected from the group consisting of plate fins, loose packing material, and combinations thereof.  
     
     
         95 . The reactor of  claim 91 , wherein said tubes are selected from the group consisting of twisted tubes, finned tubes, rifled tubes, and combinations thereof.  
     
     
         96 . The reactor of  claim 91 , further comprising baffles within said shell assembly and provided exterior of said tubes, said baffles being configured to force a heat transfer medium flowing outside said tubes across the array of tubes in a direction substantially normal to a longitudinal axis of said tubes.  
     
     
         97 . The reactor of  claim 96 , wherein said baffles have a modified surface area.  
     
     
         98 . The reactor of  claim 75 , wherein said convectively-cooled water-gas shift reactor comprises a cooling section; 
 wherein said shell assembly comprises a means of thermal expansion relief;    and wherein said second inlet is configured to receive a cooling medium.    
     
     
         99 . The reactor of  claim 98 , wherein said convectively-heated catalytic steam reformer comprises a heating section; 
 wherein said second inlet is configured to receive a heating medium.    
     
     
         100 . The reactor of  claim 75 , wherein said convectively-cooled water-gas shift reactor comprises a cooling section, and wherein said convectively-heated catalytic steam reformer comprises a heating section; and 
 wherein said reactor for the production of hydrogen further comprises a burner configured to heat at least one of a heating medium provided within said heating section and a cooling medium provided within said cooling section.    
     
     
         101 . The reactor of  claim 100 , wherein said burner is a catalytic burner.  
     
     
         102 . The reactor of  claim 100 , wherein said burner is provided within said shell assembly.  
     
     
         103 . The reactor of  claim 100 , wherein said burner includes at least one inlet for fuel delivery.  
     
     
         104 . The reactor of  claim 100 , wherein said burner includes at least one selected from the group consisting of a means for mixing fuel and heated air, a means for preheating and/or igniting, at least one temperature sensor, and combinations thereof.  
     
     
         105 . The reactor of  claim 75 , wherein said steam reforming catalyst is substantially resistant to poisoning by sulfur and molecular oxygen.  
     
     
         106 . The reactor of  claim 75 , wherein said water-gas shift catalyst is substantially resistant to poisoning by sulfur.  
     
     
         107 . The reactor of  claim 75 , further comprising: 
 an insulation assembly provided on at least a portion of an exterior of said shell assembly; and    an outer housing provided on an exterior of said insulation assembly.    
     
     
         108 . The reactor of  claim 75 , wherein said convectively-cooled water-gas shift reactor comprises a cooling section, and wherein said convectively-heated catalytic steam reformer comprises a heating section; and 
 wherein said second flow path is defined by said cooling section and said heating section, wherein said cooling section and said heating section are fluidly connected.    
     
     
         109 . The reactor of  claim 75 , wherein said unitary shell assembly is a pressurized shell assembly.  
     
     
         110 . The reactor of  claim 75 , wherein said unitary shell assembly is a gas-tight shell assembly.  
     
     
         111 . The reactor of  claim 75 , wherein said shell assembly further comprises an insulating layer.  
     
     
         112 . The reactor of  claim 111 , wherein said insulating layer is contiguous or non-contiguous.  
     
     
         113 . The reactor of  claim 111 , wherein said catalysts are the same or different.  
     
     
         114 . The reactor of  claim 75 , wherein said steam reforming catalyst is in admixture with said water-gas shift catalyst.  
     
     
         115 . The reactor of  claim 75 , wherein said water-gas shift catalyst is in admixture with said steam reforming catalyst.  
     
     
         116 . The reactor of  claim 75 , wherein said shell assembly comprises a plurality of inlets.  
     
     
         117 . The reactor of  claim 75 , wherein said shell assembly comprises a plurality of outlets.  
     
     
         118 . The reactor of  claim 75 , wherein said shell assembly comprises a tube side and a shell side.  
     
     
         119 . The reactor of  claim 118 , wherein said tube side forms a continuous pressure vessel.  
     
     
         120 . The reactor of  claim 75 , wherein said steam reforming catalyst comprises a catalytically active metal selected from the group consisting of group VIIIB metals, ruthenium, iridium, rhodium, platinum, palladium and mixtures thereof supported upon a ceramic support.  
     
     
         121 - 153 . (canceled)