Auto-oxidation and internal heating type reforming reactor apparatus for hydrogen production

Abstract

An auto-oxidation and internal heating type reforming method and apparatus for hydrogen production are disclosed for use in a process in which a gaseous mixture of a hydrocarbon or an aliphatic alcohol with water vapor is fed into contact with a mass of a reforming catalyst to bring about a reforming reaction of the gaseous mixture to produce hydrogen, wherein a small amount of an oxidizing catalyst is admixed with the reforming catalyst in that mass; and a small amount of oxygen is admixed with the gaseous mixture, whereby a portion of the hydrocarbon or aliphatic alcohol is exothermally oxidized to generate a quantity of heat required to reform the gaseous mixture of the hydrocarbon or aliphatic alcohol with water vapor.

What is claimed is:  
     
         1 . An auto-oxidation and internal heating type reforming method for hydrogen production for use in a process in which a gaseous mixture of a hydrocarbon or an aliphatic alcohol with water vapor is fed into contact with a mass of a reforming catalyst to bring about a reforming reaction of the gaseous mixture therewith to produce hydrogen, characterized in that the method comprises the steps of: 
 admixing a small amount of an oxidizing catalyst with said reforming catalyst in said mass; and    admixing a small amount of oxygen with the gaseous mixture of said hydrocarbon or aliphatic alcohol with water vapor,    whereby a portion of said hydrocarbon or aliphatic alcohol is exothermally oxidized to generate an amount of heat required to reform said gaseous mixture of said hydrocarbon or aliphatic alcohol with water vapor.    
     
     
         2 . A reforming method set forth in  claim 1 , characterized in that said small amount of oxygen is admixed with the gaseous mixture of said hydrocarbon or aliphatic alcohol with water vapor prior to said gaseous mixture coming into contact with said reforming catalyst.  
     
     
         3 . A reforming method as set forth in  claim 1 , characterized in that said small amount of oxygen is admixed with the gaseous mixture of said hydrocarbon or aliphatic alcohol with water vapor, after the gaseous mixture comes into contact with said reforming catalytic mass and is thereby in part reformed.  
     
     
         4 . A reforming method set forth in  claim 1 , characterized in that said small amount of oxygen is in part admixed with the gaseous mixture of said hydrocarbon or aliphatic alcohol with water vapor prior to said gaseous mixture coming into contact with reforming catalyst, and a remainder of said small amount of oxygen is admixed with the resultant gaseous mixture after said resultant gaseous mixture comes in contact with said reforming catalyst and is thereby in part reformed.  
     
     
         5 . A reforming method as set forth in any one of  claims 1  to  4 , characterized in that said oxidizing catalyst is distributively admixed with said reforming reaction catalyst in said mass.  
     
     
         6 . A reforming method as set forth in any one of  claims 1  to  5 , characterized in that the method further comprises the step of passing air through a separation membrane to produce an oxygen gas having an increased concentration of oxygen which when exothermally reacted with said hydrocarbon or aliphatic alcohol is sufficient to generate a quantity of heat required for said reforming reaction.  
     
     
         7 . A reforming method as set forth in any one of  claims 1  to  6 , characterized in that the method further comprises the steps of: producing a said small amount of oxygen from a water electrolytic cell; and feeding hydrogen generated from said water electrolytic cell into a region downstreams of a shift reaction.  
     
     
         8 . A reforming method as set forth in any one of  claims 1  to  7 , characterized in that the method further comprises the steps of: using a reforming reaction catalyst loaded bed and a shift catalyst loaded bed partitioned by wall surfaces; and transferring heat generated by a shift reaction in said shift catalysis loaded bed into said reforming reaction catalyst loaded bed.  
     
     
         9 . A reforming method as set forth in any one of  claims 1  to  7 , characterized in that the method further comprises the steps of: maintaining an operating pressure for said reforming reaction in a range between 6 kg/cm 2  and 8 kg/cm 2  and passing such gaseous mixtures including hydrogen though a membrane separator, thereby to raise a concentration of hydrogen while removing carbon monoxide (CO) generated as a by-product.  
     
     
         10 . An auto-oxidation and internal heating type reforming reactor apparatus for hydrogen production for use in a process in which a gaseous mixture of a hydrocarbon or an aliphatic alcohol with water vapor is fed into contact with a mass of a reforming catalyst to bring about a reforming reaction of the gaseous mixture therewith to produce hydrogen, characterized in that the apparatus includes means for admixing a small amount of an oxidizing catalyst distributively with said reforming catalyst in said mass.  
     
     
         11 . A reforming reactor apparatus as set forth in  claim 10 , characterized in that the apparatus further includes: a reforming reaction catalyst loaded bed having a reforming reaction catalyst and a small amount of an oxidizing catalyst distributively admixed therewith; and a thin layer of an oxidizing catalyst disposed behind and/or ahead of said reforming reaction catalyst loaded bed.  
     
     
         12 . A reforming reactor apparatus as set forth in  claim 10  or  claim 11 , characterized in that the apparatus includes a or said reforming reaction catalyst loaded bed and a shift catalyst loaded bed which are partitioned by wall surfaces and is configured so as to transfer heat generated by a shift reaction in said shift catalyst loaded bed to said reforming reaction catalyst loaded bed.  
     
     
         13 . An auto-oxidation and internal heating type reforming reactor apparatus, characterized in that the apparatus includes an outer cylinder reaction catalyst bed loaded with a reforming reaction catalyst, and an inner cylinder catalyst bed comprising a reaction catalyst bed loaded with a or the reforming reaction catalyst containing a small amount of an oxidizing catalyst in an upstream side thereof and a shift catalyst bed loaded with a shift catalyst in a downstream side thereof, the apparatus being configured so as to transfer heat generated in said inner cylinder though wall surfaces thereof to said outer cylinder reaction catalyst bed, the apparatus further including a means for feeding a small amount of oxygen or air into a reaction mixture prior to said reaction mixture moving from an outer cylinder to an inner cylinder.