Process for converting carbon monoxide and water in a reformate stream and apparatus therefore

Abstract

A process for converting carbon monoxide and water in a reformate stream into carbon dioxide and hydrogen comprising: generating a reformate by reacting a hydrocarbon via partial oxidation, steam reforming, or both, including autothermal reforming; and promoting a water gas shift in the reformate in the presence of a platinum group metal selected from the group consisting of platinum, palladium, iridium, osmium, rhodium and mixtures thereof, supported on zirconium oxide. The platinum group metal advantageously may be supported directly on a monolithic substrate composed of zirconium oxide.

We claim:  
     
         1 . A process for converting carbon monoxide and water in a reformate stream into carbon dioxide and hydrogen comprising: 
 generating a reformate by reacting a hydrocarbon via partial oxidation, steam reforming, or both, including autothermal reforming; and    reacting the reformate in the presence of a platinum group metal selected from the group consisting of platinum, palladium, iridium, osmium, rhodium and mixtures thereof.    
     
     
         2 . The process of  claim 1  wherein the platinum group metal is supported on a material selected from the group consisting of an oxide of zirconium, titanium and mixtures thereof.  
     
     
         3 . The process of  claim 1  wherein the reacting the reformate step includes maintaining the reaction at a temperature between about 200° C. to about 650° C.  
     
     
         4 . The process of  claim 2  wherein the reacting the reformate step includes maintaining the reaction at a temperature between about 200° C. to about 650° C.  
     
     
         5 . The process of  claim 1  wherein the reacting the reformate step includes maintaining the reaction at a temperature between about 150° C. and about 320° C., more preferably between 200° C. and 320° C., and even more preferably between 230-290° C. at an inlet of the second reactor section.  
     
     
         6 . The process of  claim 2  wherein the reacting the reformate step includes maintaining the reaction at a temperature between about 200° C. to about 320° C.  
     
     
         7 . The process of  claim 1  wherein the reacting the reformate step includes maintaining the reaction at a first temperature between about 230° C. to about 290° C. at an inlet of a reactor section containing the catalyst and at a second temperature between about 200° C. and about 240° C. at an outlet end of the reactor section.  
     
     
         8 . The process of  claim 2  wherein the reacting the reformate step includes maintaining the reaction at a first temperature between about 230° C. to about 290° C. at an inlet of a reactor section containing the catalyst and at a second temperature between about 200° C. and about 240° C. at an outlet end of the reactor section.  
     
     
         9 . The process of  claim 1  including the step of reacting the reformate in the presence of an iron containing catalyst before reacting the reformate in the presence of the platinum group metal.  
     
     
         10 . The process of  claim 2  including the step of reacting the reformate in the presence of an iron containing catalyst before reacting the reformate in the presence of the platinum group metal.  
     
     
         11 . The process of  claim 3  including the step of reacting the reformate in the presence of an iron containing catalyst before reacting the reformate in the presence of the platinum group metal.  
     
     
         12 . The process of  claim 9  wherein the step of reacting the reformate in the presence of an iron containing catalyst includes maintaining the reaction at a temperature between about 300° C. and about 650° C.  
     
     
         13 . The process of  claim 10  wherein the step of reacting the reformate in the presence of an iron containing catalyst includes maintaining the reaction at a temperature between about 300° C. and about 650° C.  
     
     
         14 . The process of  claim 11  wherein the step of reacting the reformate in the presence of an iron containing catalyst includes maintaining the reaction at a temperature between about 300° C. and about 650° C.  
     
     
         15 . The process of  claim 9  wherein the step of reacting the reformate in the presence of an iron containing catalyst includes maintaining the reaction at a temperature between about 350° C. and 540° C.  
     
     
         16 . The process of  claim 10  wherein the step of reacting the reformate in the presence of an iron containing catalyst includes maintaining the reaction at a temperature between about 350° C. and about 540° C.  
     
     
         17 . The process of  claim 11  wherein the step of reacting the reformate in the presence of an iron containing catalyst includes maintaining the reaction at a temperature between about 350° C. and about 540° C.  
     
     
         18 . The process of  claim 5  including the steps of: 
 reacting the reformate in the presence of an iron containing catalyst before reacting the reformate in the presence of the platinum group metal; and,  
 maintaining the reaction in the presence of the iron containing catalyst at a temperature between about 300° C. and about 650° C. when in the presence of the iron containing catalyst.  
 
     
     
         19 . The process of  claim 6  including the steps of: 
 reacting the reformate in the presence of an iron containing catalyst before reacting the reformate in the presence of the platinum group metal; and,  
 maintaining the reaction in the presence of the iron containing catalyst at a temperature between about 300° C. and about 650° C. when in the presence of the iron containing catalyst.  
 
     
     
         20 . The process of  claim 1  wherein the reacting the reformate in the presence of a platinum group metal selected from the group consisting of platinum, palladium, iridium, osmium, rhodium and mixtures thereof includes reacting the reformate first in the presence of a first portion of said catalyst at a first temperature between about 300° C. to about 650° C. and then reacting the resultant reformate in the presence of a second portion of said catalyst while maintaining the reaction at a second temperature between about 200° C. and about 400° C.  
     
     
         21 . The process of  claim 2  wherein the reacting the reformate in the presence of a platinum group metal selected from the group consisting of platinum, palladium, iridium, osmium, rhodium and mixtures thereof includes reacting the reformate first in the presence of a first portion of said catalyst at a first temperature between about 300° C. to about 650° C. and then reacting the resultant reformate in the presence of a second portion of said catalyst while maintaining the reaction at a second temperature between about 200° C. and about 400° C.  
     
     
         22 . The process of  claim 1  wherein the reacting the reformate in the presence of a platinum group metal selected from the group consisting of platinum, palladium, iridium, osmium, rhodium and mixtures thereof includes reacting the reformate first in the presence of a first portion a body of said catalyst at a first temperature between about 350° C. to about 540° C. and then reacting the resultant reformate in the presence of a second portion of the body of said catalyst while maintaining the reaction at a second temperature between about 200° C. and about 400° C.  
     
     
         23 . The process of  claim 2  wherein the reacting the reformate in the presence of a platinum group metal selected from the group consisting of platinum, palladium, iridium, osmium, rhodium and mixtures thereof includes reacting the reformate first in the presence of a first portion of said catalyst at a first temperature between about 300° C. to about 540° C. and then reacting the resultant reformate in the presence of a second portion of said catalyst while maintaining the reaction at a second temperature between about 200° C. and about 400° C.  
     
     
         24 . The process of  claim 1  wherein the reacting the reformate in the presence of a platinum group metal selected from the group consisting of platinum, palladium, iridium, osmium, rhodium and mixtures thereof includes: 
 providing a body of said catalyst for traverse of the reformate there along from a beginning of the catalyst body through an end of the catalyst body; and,  
 maintaining a gradient of reaction temperatures along the body, the gradient decreasing in temperature from the beginning of the body to the end of the body.  
 
     
     
         25 . The process of  claim 2  wherein the reacting the reformate in the presence of a platinum group metal selected from the group consisting of platinum, palladium, iridium, osmium, rhodium and mixtures thereof includes: 
 providing a body of said catalyst for traverse of the reformate there along from a beginning of the catalyst body through an end of the catalyst body; and,  
 maintaining a gradient of reaction temperatures along the body, the gradient decreasing in temperature from the beginning of the body to the end of the body.  
 
     
     
         26 . The process of  claim 24  wherein the gradient is defined by a first temperature near the beginning of the body between about 260° C. to about 650° C. and a second temperature near the end of the body between about 175° C. to about 345° C.  
     
     
         27 . The process of  claim 25  wherein the gradient is defined by a first temperature near the beginning of the body between about 260° C. to about 650° C. and a second temperature near the end of the body between about 175° C. to about 345° C.  
     
     
         28 . The process of  claim 26  wherein the gradient is defined by a first temperature near the beginning of the body between about 260° C. to about 650° C. and a second temperature near the end of the body between about 175° C. to about 300° C.  
     
     
         29 . The process of  claim 25  wherein the gradient is defined by a first temperature near the beginning of the body between about 350° C. to about 650° C. and a second temperature near the end of the body between about 175° C. to about 275° C.  
     
     
         30 . The process of  claim 2  wherein the reacting the reformate step includes maintaining the reaction at a temperature between about 150° C. to about 250° C.  
     
     
         31 . The process of  claim 1  wherein the step of reacting the reformate in the presence of a platinum group metal selected from the group consisting of platinum, palladium, iridium, osmium, rhodium and mixtures thereof, includes: 
 introducing a predetermined amount of oxygen into the reformate for a desired period of time; and,  
 promoting oxidation of constituents in the reformate by the presence of the catalyst to generate heat to a desired temperature in the catalyst.  
 
     
     
         32 . The process of  claim 2  wherein the step of reacting the reformate in the presence of a platinum group metal selected from the group consisting of platinum, palladium, iridium, osmium, rhodium and mixtures thereof, includes: 
 introducing a predetermined amount of oxygen into the reformate for a desired period of time; and,  
 promoting oxidation of constituents in the reformate by the presence of the catalyst to generate heat to a desired temperature in the catalyst.  
 
     
     
         33 . The process of  claim 2  wherein the generating a reformate step provides a resulting reformate having carbon monoxide, carbon dioxide, nitrogen, hydrogen, and water, wherein the water constitutes above 10% of the reformate by volume.  
     
     
         34 . The process of  claim 1  wherein the generating step includes generating a reformate having a carbon monoxide concentration of greater than about 10% by volume.  
     
     
         35 . The process of  claim 2  wherein the generating step includes generating a reformate having a carbon monoxide concentration of greater than about 10% by volume.  
     
     
         36 . The process of  claim 1  wherein the generating step includes generating a reformate having a water concentration of greater than about 15% by volume.  
     
     
         37 . The process of  claim 2  wherein the generating step includes generating a reformate having a water concentration of greater than about 15% by volume.  
     
     
         38 . The process of  claim 34  wherein the generating step includes generating a reformate having a water concentration of greater than about 15% by volume.  
     
     
         39 . The process of  claim 35  wherein the generating step includes generating a reformate having a water concentration of greater than about 15% by volume.  
     
     
         40 . The process of  claim 1  wherein the generating step includes generating a reformate having an aliphatic hydrocarbon concentration between about 0.01% to about 0.50% by volume.  
     
     
         41 . The process of  claim 2  wherein the generating step includes generating a reformate having an aliphatic hydrocarbon concentration between about 0.01% to about 0.50% by volume.  
     
     
         42 . The process of  claim 38  wherein the generating step includes generating a reformate having an aliphatic hydrocarbon concentration between about 0.01% to about 0.50% by volume.  
     
     
         43 . The process of  claim 39  wherein the generating step includes generating a reformate having an aliphatic hydrocarbon concentration between about 0.01% to about 0.50% by volume.  
     
     
         44 . The process of  claim 1  wherein the generating step includes generating a reformate having one or more non-aliphatic hydrocarbon constituents selected from the group of: an alcohol, an ester, an ether, an acid, an aldehyde, an unsaturated non-aromatic, an aromatic, and a cyclic.  
     
     
         45 . The process of  claim 2  wherein the generating step includes generating a reformate having one or more non-aliphatic, carbon-based constituents selected from the group of: an alcohol, an ester, an ether, an acid, an aldehyde, an unsaturated non-aromatic, an aromatic, and a cyclic.  
     
     
         46 . The process of  claim 42  wherein the generating step includes generating a reformate having one or more non-aliphatic hydrocarbon constituents selected from the group of: an alcohol, an ester, an ether, an acid, an aldehyde, an unsaturated non-aromatic, an aromatic, and a cyclic.  
     
     
         47 . The process of  claim 43  wherein the generating step includes generating a reformate having one or more non-aliphatic hydrocarbon constituents selected from the group of: an alcohol, an ester, an ether, an acid, an aldehyde, an unsaturated non-aromatic, an aromatic, and a cyclic.  
     
     
         48 . The process of  claim 2  wherein the generating step includes generating a reformate having an amount of unconverted hydrocarbon fuel.  
     
     
         49 . The process of  claim 1  wherein the generating step includes generating a reformate that includes hydrogen sulfide.  
     
     
         50 . The process of  claim 2  wherein the generating step includes generating a reformate that includes hydrogen sulfide.  
     
     
         51 . The process of  claim 1  wherein the generating step includes partial oxidation and the reformate includes ammonia.  
     
     
         52 . The process of  claim 2  wherein the generating step includes partial oxidation and the reformate includes ammonia.  
     
     
         53 . A process for converting carbon monoxide and water in a reformate stream into carbon dioxide and hydrogen via a water-gas-shift reaction, comprising: 
 generating a reformate by reacting a hydrocarbon via partial oxidation, steam reforming, or both;    reacting the reformate in the presence of a catalyst that (i) promotes a water gas shift reaction of carbon monoxide to carbon dioxide and (ii) is active and stable, at temperatures between about 200° C. to about 650° C.    
     
     
         54 . The process of  claim 53  including the step of reacting the reformate in the presence of a platinum group metal selected from the group consisting of platinum, palladium, iridium, osmium, rhodium and mixtures thereof.  
     
     
         55 . The process of  claim 54  including the step of supporting the platinum group metal is supported on a material selected from the group consisting of: an oxide of zirconium, an oxide of titanium and mixtures thereof.  
     
     
         56 . A process for converting carbon monoxide and water in a reformate stream into carbon dioxide and hydrogen comprising via a water-gas-shift reaction, comprising: 
 generating a reformate by reacting a hydrocarbon via partial oxidation, steam reforming, or both; and,    reacting the reformate in the presence of a catalyst that promotes water gas shift of carbon monoxide to carbon dioxide and is resistant to loss of activity by exposure to any one of the constituents selected from the group of: sulfur, hydrogen sulfide, ethylene, benzene, air and condensed water.    
     
     
         57 . A reactor comprising: 
 a first reactor section configured to produce reformate by a process selected from the group of partial oxidation, steam reforming, or a combination thereof;    a second reactor section in communication with the first reactor section so as to receive the reformate;    a catalyst in the second reactor section comprising, a platinum group metal selected from the group consisting of platinum, palladium, iridium, osmium, rhodium and mixtures thereof; and,    a support material, for the platinum group metal, selected from the group consisting of an oxide of zirconium, titanium and mixtures thereof.    
     
     
         58 . The reactor of  claim 57 , further comprising a monolithic base in the second reaction section upon which the catalyst and support are dispersed.  
     
     
         59 . The reactor, as defined in  claim 57 , wherein the platinum group metal is platinum and the support material is an oxide of zirconium.  
     
     
         60 . The reactor, as defined in  claim 59 , wherein platinum is in the range of from about 0.1% to about 3% by weight with respect to the oxide of zirconium.  
     
     
         61 . The reformer of  claim 59 , wherein the catalyst is deployed as a wash-coat of an oxide of zirconium on a monolithic base, and the platinum being impregnated on of the oxide of zirconium by an incipient wetness process employing a non-halogenated salt of platinum.  
     
     
         62 . The reactor, as defined in  claim 59 , wherein the oxide of zirconium has a surface area approximately about 50 m. 2 /g., a pore volume of approximately about 0.3 cm. 3 /g., and a median pore diameter greater than about 15 nm.  
     
     
         63 . The reactor, as defined in  claim 59 , wherein the catalyst is formed by dispersing a non-halogenated platinum salt on a material selected from the group consisting of an oxide of zirconium and titanium, and mixtures thereof.  
     
     
         64 . The reactor, as defined in  claim 57 , wherein the catalyst is resistant to poisoning by sulfur, hydrogen sulfide, ethylene, benzene, air and condensed water.  
     
     
         65 . The reactor, as defined in  claim 57 , wherein the catalyst is stable at temperatures between about 200° C. and 650° C.  
     
     
         66 . The reactor, as defined in  claim 57 , wherein the reactor includes a source for providing an oxygen-containing gas to the second reactor section and the catalyst promotes combustion of hydrogen and carbon monoxide in the presence of oxygen.  
     
     
         67 . The reactor, as defined in  claim 9 , further comprising a temperature control for maintaining the reactor at a temperature between about 200° C. to about 650° C.  
     
     
         68 . A reactor comprising: 
 a first reactor section configured to produce reformate by a process selected from the group of partial oxidation, steam reforming, or a combination thereof;    a second reactor section in communication with the first reactor section so as to receive the reformate;    a third reactor section in communication with the second so as to receive reformate from the second reactor section;    a catalyst in the second reactor section comprising an iron-containing catalyst suitable for promoting a water-gas shift reaction at a temperature in the range of about 350° C. to about 650° C.;    a catalyst in the third reactor section comprising, a platinum group metal selected from the group consisting of platinum, palladium, iridium, osmium, rhodium and mixtures thereof; and,    a support material, for the platinum group metal, selected from the group consisting of an oxide of zirconium, titanium and mixtures thereof.    
     
     
         69 . An improved process for converting carbon monoxide and water in a reformate stream into hydrogen and carbon dioxide, characterized in that a reformate, which is generated by one or more of partial oxidation, steam reforming, autothermal reforming, is reacted in a reactor with a first catalyst, wherein the first catalyst comprises a metal selected from platinum, palladium, iridium, osmium, rhodium, and mixtures thereof, and wherein said metal is deposited on a support of a zirconium oxide.  
     
     
         70 . The process of  claim 69  wherein the step of reacting the reformate includes maintaining the reaction at a temperature in the range of about 200° C. to 650° C.  
     
     
         71 . The process of  claim 69  wherein the range of temperature is between about 200° C. and 320° C.  
     
     
         72 . The process of  claim 69  wherein the range of temperature is between about 150° and 250° C.  
     
     
         73 . The process of  claim 69  wherein the reactor has an inlet section and an outlet, and wherein the inlet section is maintained in a range of about 230° to 290° C.  
     
     
         74 . The process of  claim 73  wherein the temperature of the outlet is in the range of about 200° and 240° C. and is not greater than the temperature of the inlet.  
     
     
         75 . The process of  claim 69  further including the step of reacting the reformate stream with an iron-containing catalyst before reacting it with the first catalyst.  
     
     
         76 . The process of  claim 75  wherein the step of reacting the reformate in the presence of the iron containing catalyst includes maintaining the reaction at a temperature in the range of about 300° C. and 650° C. during contact with said iron catalyst.  
     
     
         77 . The process of  claim 69  wherein the temperature is in the range of about 350° to 540° C.  
     
     
         78 . The process of  claim 69  wherein the catalyst is disposed in a first body and a second body, wherein the first body is maintained between about 350° to 540° C. and the second body is maintained between about 200° and 400° C.  
     
     
         79 . The process of  claim 69  wherein the catalyst is provided as at least one body, wherein a gradient of temperature is provided along said body in a direction substantially the same as the direction of reformate flow through said body.  
     
     
         80 . The process of  claim 79  wherein the gradient is defined by a first temperature near the beginning of said body between about 260° and 650° C., and a second temperature near the end of the body between about 175° and 345° C., wherein the second temperature is lower that the first temperature.  
     
     
         81 . The process of  claim 69  wherein the reaction step further includes introduction of a predetermined amount of oxygen into said reaction, and promoting the oxidation of the reformate by the oxygen thereby generating heat to increase the temperature of the catalyst.  
     
     
         82 . The process of  claim 69  wherein the catalyst promotes the water/gas shift reaction and is resistant to deactivation by at least one of a sulfur-containing material, an ethylenically unsaturated or aromatic material, a nitrogen-containing material, and liquid water.  
     
     
         83 . A reactor constructed and arranged for the execution of the process of  claim 69 .  
     
     
         84 . The process of  claim 1  including the initial step of forming a monolithic base from the zirconium oxide and supporting the platinum group metal directly on the monolith.