Non-pyrophoric water-gas shift reaction catalysts

Abstract

The invention provides a process, catalyst and apparatus for carrying out the water-gas shift reaction comprising employing a low-pyrophoricity water-gas shift reaction catalyst; wherein the low-pyrophoricity water-gas shift reaction catalyst comprises a solid high heat capacity particulate support impregnated with: (i) a reducible metal oxide and (ii) a catalytic agent.

What is claimed:  
     
         1 . A process for carrying out the water-gas shift reaction, comprising employing a low-pyrophoricity water-gas shift reaction catalyst; wherein the low-pyrophoricity water-gas shift reaction catalyst comprises a solid high heat capacity particulate support impregnated with: 
 (i) a reducible metal oxide and    (ii) a catalytic agent.    
     
     
         2 . The process of  claim 1 , wherein the water-gas shift reaction catalyst comprises not more than 50% by weight of the reducible metal oxide.  
     
     
         3 . The process of  claim 2 , wherein the reducible metal oxide is in the range of 0.5-35% by weight.  
     
     
         4 . The process of  claim 1 , wherein the particulate support is a high strength support in a durable and rigid form.  
     
     
         5 . The process of  claim 4 , wherein the particulate support is activated alumina.  
     
     
         6 . The process of  claim 5 , wherein the activated alumina has a BET effective surface area of at least 10 m 2 /g.  
     
     
         7 . The process of  claim 1 , wherein the reducible metal oxide comprises one or more of the oxides of Cr, V, Mo, Nd, Pr, Ti, Fe, Ni, Mn, Co, or Ce.  
     
     
         8 . The process of  claim 7 , wherein the reducible metal oxide comprises one or more of the oxides of Ce, Cr, Fe, or Mn.  
     
     
         9 . The process of  claim 1 , wherein the reducible metal oxide consists of the oxides of Ce.  
     
     
         10 . The process of  claim 1 , wherein the catalytic agent comprises one or more of Pt, Pd, Cu, Fe, Rh, or Au or an oxide thereof.  
     
     
         11 . The process of  claim 10 , wherein the catalytic agent is Cu or an oxide thereof.  
     
     
         12 . The process of  claim 11 , wherein the high heat capacity support comprises alumina particles with a mesh size of 12 or greater.  
     
     
         13 . The process of  claim 12 , wherein the reducible metal oxide consists of the the oxides of Cr and Ce.  
     
     
         14 . The process of  claim 12 , wherein the reducible metal oxide consists of the oxides of Cr.  
     
     
         15 . The process of  claim 12 , wherein the reducible metal oxide consists of the oxides of Ce.  
     
     
         16 . The process of  claim 11 , wherein copper or an oxide thereof is in the range of 4-20% by weight, calculated as CuO.  
     
     
         17 . The process of  claim 10 , wherein the catalytic agent is Pt or an oxide thereof.  
     
     
         18 . The process of  claim 17 , wherein the particulate support comprises alumina particles with a mesh size of 12 or greater.  
     
     
         19 . The process of  claim 18 , wherein the reducible metal oxide consists of the oxides of Ce.  
     
     
         20 . The process of  claim 1 , wherein the low-pyrophoricity water-gas shift reaction catalyst comprises (i) alumina support particles with a mesh size of 12 or greater and a BET surface area of at least 10 m 2 /g, (ii) up to 25% by weight of an oxide of Ce, calculated as CeO 2 , impregnated in the support particles, and (iii) between 4 and 14% by weight catalytic agent wherein the catalytic agent is Cu or an oxide thereof, calculated as CuO; and 
 wherein the process for carrying out the water-gas shift reaction comprises the steps of: 
 a) providing an input gas stream comprising carbon monoxide and water vapor;  
 b) contacting the input gas stream with the low-pyrophoricity water-gas shift reaction catalyst; and  
 c) catalyzing the water-gas shift reaction with the low-pyrophoricity water-gas shift reaction catalyst;  
   wherein the input gas stream includes: 
 (i) between about 1% by volume and about 10% by volume CO,  
 (ii) at least 10% by volume hydrogen, and  
 (iii) at least 10% by volume H 2 O; and  
   wherein the input gas stream is characterized by a space velocity and wherein the space velocity is at least 500 hr −1  VHSV.    
     
     
         21 . The process of  claim 1 , wherein the low-pyrophoricity water-gas shift reaction catalyst comprises (i) alumina support particles with a mesh size of 12 or greater and a BET surface area of at least 10 m 2 /g, (ii) up to 15% by weight of an oxide of chromium, calculated as Cr 2 O 3 , impregnated in the support particles; and (iii) between 4 and 14% by weight catalytic agent, wherein the catalytic agent is copper or an oxide thereof, calculated as CuO; and 
 wherein the process for carrying out the water-gas shift reaction comprises the steps of: 
 a) providing an input gas stream comprising carbon monoxide and water vapor;  
 b) contacting the input gas stream with the low-pyrophoricity water-gas shift reaction catalyst; and  
 c) catalyzing the water-gas shift reaction with the low-pyrophoricity water-gas shift reaction catalyst;  
   wherein the input gas stream includes: 
 (i) between about 1% by volume and about 10% by volume CO,  
 (ii) at least 10% by volume hydrogen, and  
 (iii) at least 10% by volume H 2 O; and  
   wherein the input gas stream is characterized by a space velocity and wherein the space velocity is at least 500 hr −1  VHSV.    
     
     
         22 . The process of  claim 1 , wherein the low-pyrophoricity water-gas shift reaction catalyst comprises (i) alumina support particles with a mesh size of 12 or greater and a BET surface area of at least 10 m 2 /g, (ii) up to 25% by weight of an oxide of cerium, calculated as CeO 2  impregnated in the support particles; (iii) up to 10% by weight of an oxide of chromium, calculated as Cr 2 O 3 , impregnated in the support particles; and (iv) between 4 and 14% by weight catalytic agent, wherein the catalytic agent is copper or an oxide thereof, calculated as CuO; and 
 wherein the process for carrying out the water-gas shift reaction comprises the steps of: 
 a) providing an input gas stream comprising carbon monoxide and water vapor;  
 b) contacting the input gas stream with the low-pyrophoricity water-gas shift reaction catalyst; and  
 c) catalyzing the water-gas shift reaction with the low-pyrophoricity water-gas shift reaction catalyst;  
   wherein the input gas stream includes: 
 (i) between about 1% by volume and about 10% by volume CO,  
 (ii) at least 10% by volume hydrogen, and  
 (iii) at least 10% by volume H 2 O; and  
   wherein the input gas stream is characterized by a space velocity and wherein the space velocity is at least 500 hr −1  VHSV.    
     
     
         23 . The process of  claim 1 , wherein the catalyst comprises (i) alumina support particles with a mesh size of 12 or greater and a BET surface area of at least 10 m 2 /g, (ii) up to 25% by weight of an oxide of cerium, calculated as CeO 2 , impregnated in the alumina support particles; and (iii) between 0.1 and 1.0% by weight of a catalytic agent wherein the catalytic agent is Pt or an oxide thereof, calculated as Pt; 
 wherein the process for carrying out the water-gas shift reaction comprises the steps of: 
 a) providing an input gas stream comprising carbon monoxide and water vapor;  
 b) contacting the input gas stream with the low-pyrophoricity water-gas shift reaction catalyst; and  
 c) catalyzing the water-gas shift reaction with the low-pyrophoricity water-gas shift reaction catalyst;  
   wherein the input gas stream includes: 
 (i) between about 0.1% by volume and about 5% by volume CO,  
 (ii) at least 10% by volume hydrogen, and  
 (iii) at least 10% by volume H 2 O; wherein the input gas stream is characterized by a space velocity; and  
   wherein the space velocity is at least 500 hr −1  VHSV.    
     
     
         24 . An apparatus for carrying out the water-gas shift reaction, the apparatus comprising a low-pyrophoricity water-gas shift reaction catalyst; wherein the low-pyrophoricity water-gas shift reaction catalyst comprises a durable, high heat capacity particulate support impregnated with: 
 (i) less than 50% by weight of an oxide of Ce, calculated as CeO 2 ; and    (ii) a catalytically effective amount of a catalytic agent; and    wherein the particulate support comprises alumina particles with a mesh size of 12 or greater.    
     
     
         25 . The apparatus of  claim 24 , wherein the particulate support is activated alumina with a BET effective surface area of at least 10 m 2 /g.  
     
     
         26 . The apparatus of  claim 24 , wherein the catalytic agent comprises one or more of Pt, Pd, Cu, Fe, Rh, Au or an oxide thereof.  
     
     
         27 . The apparatus of  claim 24 , wherein the low-pyrophoricity water-gas shift reaction catalyst comprises (i) alumina support particles with a mesh size of 12 or greater and a BET surface area of at least 10 m 2 /g, (ii) up to 25% by weight of an oxide of cerium, calculated as CeO 2 , impregnated in the support particles; and (iii) between 4 and 14% by weight catalytic agent wherein the catalytic agent is copper or an oxide thereof, calculated as CuO; and 
 wherein an input gas stream contacts the low-pyrophoricity water-gas shift reaction catalyst;    wherein the input gas stream includes: (i) between about 1% by volume and about 10% by volume CO, (ii) at least 10% by volume hydrogen, and (iii) at least 10% by volume H 2 O; wherein the input gas stream is characterized by a space velocity and wherein the space velocity is at least 500 hr −1  VHSV.    
     
     
         28 . The apparatus of  claim 24 , wherein the low-pyrophoricity water-gas shift reaction catalyst comprises (i) alumina support particles with a mesh size of 12 or greater and a BET surface area of at least 10 m 2 /g, (ii) up to 15% by weight of an oxide of chromium, calculated as Cr 2 O 3 , impregnated in the support particles; and (iii) between 4 and 14% by weight catalytic agent wherein the catalytic agent is copper or an oxide thereof, calculated as CuO; and 
 wherein an input gas stream contacts the low-pyrophoricity water-gas shift reaction catalyst;    wherein the input gas stream includes: (i) between about 1% by volume and about 10% by volume CO, (ii) at least 10% by volume hydrogen, and (iii) at least 10% by volume H 2 O; wherein the input gas stream is characterized by a space velocity and wherein the space velocity is at least 500 hr −1  VHSV.    
     
     
         29 . The apparatus of  claim 24 , wherein the low-pyrophoricity water-gas shift reaction catalyst comprises (i) alumina support particles with a mesh size of 12 or greater and a BET surface area of at least 10 m 2 /g, (ii) up to 25% by weight of an oxide of cerium, calculated as CeO 2  impregnated in the support particles; (iii) up to 10% by weight of an oxide of chromium, calculated as Cr 2 O 3 , impregnated in the support particles; and (iv) between 4 and 14% by weight catalytic agent, wherein the catalytic agent is copper or an oxide thereof, calculated as CuO; and 
 wherein an input gas stream contacts the low-pyrophoricity water-gas shift reaction catalyst;    wherein the input gas stream includes: (i) between about 1% by volume and about 10% by volume CO, (ii) at least 10% by volume hydrogen, and (iii) at least 10% by volume H 2 O; wherein the input gas stream is characterized by a space velocity and wherein the space velocity is at least 500 hr −1  VHSV.    
     
     
         30 . The apparatus of  claim 24 , wherein the low-pyrophoricity water-gas shift reaction catalyst comprises (i) alumina support particles with a mesh size of 12 or greater and a BET surface area of at least 10 m 2 /g, (ii) up to 25% by weight of an oxide of cerium, calculated as CeO 2 , impregnated in the alumina support particles; and (iii) between 0.1 and 1.0% catalytic agent wherein the catalytic agent is Pt or an oxide thereof, calculated as Pt; and 
 wherein an input gas stream contacts the low-pyrophoricity water-gas shift reaction catalyst;    wherein the input gas stream includes: (i) between about 0. 1% by volume and about 5% by volume CO, (ii) at least 10% by volume hydrogen, and (iii) at least 10% by volume H 2 O; wherein the input gas stream is characterized by a space velocity and wherein the space velocity is at least 500 hr −1  VHSV.    
     
     
         31 . A low-pyrophoricity water-gas shift reaction catalyst, comprising high heat capacity support particles of a mesh size of 12 or greater impregnated with: 
 (i) a reducible metal oxide; and    (ii) a catalytic agent.    
     
     
         32 . The low-pyrophoricity water-gas shift reaction catalyst of  claim 31 , wherein the reducible metal oxide comprises one or more of the oxides of Cr, V, Mo, Nd, Pr, Ti, Fe, Ni, Mn, Co, or Ce.  
     
     
         33 . The low-pyrophoricity water-gas shift reaction catalyst of  claim 32 , wherein the high heat capacity support particles are activated alumina.  
     
     
         34 . The low-pyrophoricity water-gas shift reaction catalyst of  claim 33 , wherein the catalytic agent is Cu or an oxide thereof.  
     
     
         35 . The low-pyrophoricity water-gas shift reaction catalyst of  claim 34 , wherein the reducible metal oxide consists of the oxides of Ce.  
     
     
         36 . The low-pyrophoricity water-gas shift reaction catalyst of  claim 34 , wherein the reducible metal oxide consists of the oxides of Cr.  
     
     
         37 . The low-pyrophoricity water-gas shift reaction catalyst of  claim 34 , wherein the reducible metal oxide consists of the oxides of Cr and Ce.  
     
     
         38 . The low-pyrophoricity water-gas shift reaction catalyst of  claim 34 , wherein the catalytic agent is in the range of 4-20% by weight, calculated as CuO.  
     
     
         39 . The low-pyrophoricity water-gas shift catalyst of  claim 31 , wherein the reducible metal oxide is in the range of 0.5-35% by weight.  
     
     
         40 . The low-pyrophoricity water-gas shift reaction catalyst of  claim 33 , wherein the catalytic agent is Pt or an oxide thereof.  
     
     
         41 . The low-pyrophoricity water-gas shift reaction catalyst of claim  40 , wherein the reducible metal oxide consists of the oxides of Ce.