Catalyst for a Catalytic Process Which is Used to Obtain Hydrogen from Bioethanol and/or Ethanol, Catalyst-Preparation Method and Use Thereof in Said Catalytic Process

Abstract

The invention relates to a catalyst which is used to obtain hydrogen or a hydrogen-rich gas that is suitable for use in fuel cells or other applications from bioethanol and/or ethanol, comprising a support, a promoter agent and an active phase which is incorporated into the support, said catalyst taking the form of a calcinated solid in which the support comprises at least one oxide with high surface mobility and is modified with the promoter agent. According to the invention, the promoter agent comprises at least one oxide of a rare earth that is selected from the lanthanide group and the active phase comprises at least one oxide of a transition metal from group VIII or IB.

1 . A catalyst for obtaining hydrogen or a hydrogen-rich gas from bioethanol and/or ethanol which comprises a support, a promoter agent and an active phase which is incorporated into the support, wherein the catalyst is a calcinated solid in which
 the support comprises at least one oxide with high surface mobility and is modified with the promoter agent,   the promoter agent is at least one oxide of a rare earth that is selected from the lanthanide group, and   the active phase comprises at least one oxide of a transition metal from group VIII or IB.   
   
   
       2 . A catalyst according to  claim 1 , wherein
 the high surface mobility oxide is zirconium oxide;   the promoter agent is selected from among oxides of lanthanum, oxides of cerium and combinations thereof;   the active phase is selected from the group consisting of nickel, cobalt and combinations thereof.   
   
   
       3 . A catalyst according to  claim 1 , wherein the catalyst consists of cobalt oxide as transition metal of the active phase, zirconium oxide as high surface mobility oxide and lanthanum oxide as promoter agent, and in that it displays an X-ray diffractogram with diffraction lines and peaks corresponding to, 
     
       
         
               
               
               
             
                   
                   
               
                   
                   
                 Relative 
               
                   
                 2θ 
                 Intensity 
               
                   
                   
               
                   
                 24.31 
                 W 
               
                   
                 28.28 
                 VS 
               
                   
                 31.52 
                 S 
               
                   
                 40.84 
                 W 
               
                   
                 44.94 
                 W 
               
                   
                 50.24 
                 M 
               
                   
                 55.56 
                 S 
               
                   
                 62.96 
                 S 
               
                   
                 71.32 
                 S 
               
                   
                 77.44 
                 S 
               
                   
                 89.96 
                 VW 
               
                   
                   
               
           
              
              
              
              
             
             
              
              
              
              
              
              
              
              
              
              
              
              
             
          
         
       
       where 
       VS is a very strong relative intensity corresponding to a percentage of 80-100 with respect to the most intense peak, 
       S is a strong relative intensity corresponding to a percentage of 60-80 with respect to the most intense peak, 
       M is a medium relative intensity corresponding to a percentage of 40-60 with respect to the most intense peak, 
       W is a weak relative intensity corresponding to a percentage of 20-40 with respect to the most intense peak, 
       VW is a very weak relative intensity corresponding to a percentage of 0-20 with respect to the most intense peak. 
     
   
   
       4 . A catalyst according to  claim 1 , wherein the high surface mobility oxide has been calcined prior to being modified with the promoter agent. 
   
   
       5 . A catalyst according to  claim 1 , wherein the modified support has been calcined prior to incorporating the active phase. 
   
   
       6 . A catalyst according to  claim 1  wherein the catalyst has been calcined at a temperature of at least 600° C. 
   
   
       7 . A catalyst according to  claim 1  which comprises
 1 to 30% by weight of the promoter agent;   1 to 15% by weight of the active phase.   
   
   
       8 . A catalyst according to  claim 1  which comprises
 5 to 11% by weight of the promoter agent;   3 to 10% by weight of the active phase.   
   
   
       9 . A catalyst according to  claim 1  which comprises
 8 to 10% by weight of the promoter agent;   5 to 7% by weight of the active phase.   
   
   
       10 . A catalyst according to  claim 1  wherein the promoter agent is lanthanum oxide and the active phase is cobalt or cobalt oxide. 
   
   
       11 . A process for preparing the catalyst of  claim 1  which comprises
 a first stage in which the high surface mobility oxide is modified with the promoter agent in order to obtain the modified support,   a second stage in which the active phase is incorporated into the modified support in order to obtain a precursor of the catalyst,   a third stage in which the precursor is subjected to calcination at a temperature of at least 600° C.   
   
   
       12 . A catalyst according to  claim 11 , wherein
 the high surface mobility oxide is zirconium oxide;   the promoter agent is selected from among the group comprising lanthanum oxide, cerium oxide and combinations thereof;   the active phase is selected from among the group comprising nickel, cobalt and combinations thereof.   
   
   
       13 . A process according to  claim 11 , wherein the high surface mobility oxide is calcined. 
   
   
       14 . A process according to  claim 11 , wherein the modified support is calcined prior to incorporating the active phase. 
   
   
       15 . A process according to  claim 14 , wherein the modified support is calcined at a temperature of at least 700° C. 
   
   
       16 . A process according to  claim 14 , wherein the modified support is calcined at a temperature of between 750° C. and 900° C. 
   
   
       17 . A process according to  claim 11 , wherein the calcination in the third stage is carried out at a temperature of between of 600° C. and 900° C. 
   
   
       18 . A process according to  claim 11 , wherein the active phase is incorporated into the modified support by means of impregnation. 
   
   
       19 . A process according to  claim 11 , wherein the active phase is incorporated into the modified support by means of adsorption in solution. 
   
   
       20 . A process according to  claim 11 , wherein the active phase is incorporated into the modified support by means of sol-gel. 
   
   
       21 . A process according to  claim 11 , wherein the active phase is incorporated into the modified support by means of microemulsion. 
   
   
       22 . A process according to  claim 11 , wherein the active phase is incorporated into the modified support by means of co-precipitation. 
   
   
       23 . A process according to any of  claims 18  to  22 , wherein following the incorporation of the active phase a drying stage is carried out. 
   
   
       24 . Method for obtaining hydrogen or a hydrogen-rich gas starting from bioethanol and/or ethanol which comprises employing the catalyst of  claim 1 . 
   
   
       25 . Method according to  claim 24 , characterised in wherein the hydrogen or a hydrogen-rich gas is suitable for use in fuel cells. 
   
   
       26 . Method according to  claim 24 , which is a catalytic process of reforming a hydrogen carrier selected from the group comprising ethanol, bioethanol and mixtures thereof, in which the hydrogen carrier is made to react with water in the presence of the catalyst, at a temperature between 600° C. and 800° C. in order to obtain a mixture of gases containing hydrogen. 
   
   
       27 . Method according to  claim 26 , wherein the water and the hydrogen carrier are made to react at a pressure of between 0 and 5 bar. 
   
   
       28 . Method according to  claim 26 , wherein the water and the hydrogen carrier are made to react at a pressure of between 0 and 3 bar. 
   
   
       29 . Method according to  claim 26 , wherein the water and the hydrogen carrier are made to react at atmospheric pressure. 
   
   
       30 . Method according to  claim 26  wherein the water and the hydrogen carrier are made to react in a hydrogen carrier/water ratio of between 1:1.25 and 1:5 v/v. 
   
   
       31 . Method according to  claim 26  wherein the water and the hydrogen carrier are made to react in a hydrogen carrier/water ratio of between 1:1.5 and 1:4 v/v. 
   
   
       32 . Method according to  claim 26  wherein the water and the hydrogen carrier are made to react in a hydrogen carrier/water ratio of 1/3 v/v±10% or 1/2 v/v+10%. 
   
   
       33 . Method according to  claim 26  wherein the water and the hydrogen carrier are made to react at a temperature of between 650° C. and 750° C. 
   
   
       34 . Method according to  claim 26  wherein the water and the hydrogen carrier are made to react at a temperature of 700° C.+5%. 
   
   
       35 . Method according to  claim 26  wherein the water that is made to react with the hydrogen carrier is in the form of steam. 
   
   
       36 . Method according to  claim 26  wherein the gas mixture including the hydrogen resulting from the reaction of the hydrogen carrier with the water is fed to a medium or high temperature fuel cell. 
   
   
       37 . Method according to  claim 26  wherein the gas mixture including the hydrogen resulting from the reaction of the hydrogen carrier with the water is subjected to a purification stage in order to convert at least part of the carbon monoxide possibly present in the gas mixture into carbon dioxide in order to obtain a purified mixture of gases, and because said mixture is fed to a fuel cell. 
   
   
       38 . Method according to  claim 37 , wherein the fuel cell is an intermediate temperature fuel cell. 
   
   
       39 . Method according to  claim 37 , wherein the fuel cell is a low temperature fuel cell.