Methanol steam reforming catalysts

Abstract

Novel catalysts, substantially free of Cu and Zn, useful for the reformation of methanol and steam into H 2 for use in hydrogen fuel cells and their use are described herein.

1 - 20 . (canceled) 
     
     
         21 . A method of making a catalyst for reforming methanol and steam into hydrogen gas for use in hydrogen fuel cells, the method comprising:
 (a) forming a first aqueous solution comprising:
 a complex or salt of a first metal, 
 a complex or salt of a second element capable of forming an alloy with the first metal, and 
 a complex or salt of at least one promoter element; 
   (b) forming a second aqueous solution comprising sodium carbonate;   (c) adding a solid support to the second aqueous solution to form a slurry;   (d) mixing the first aqueous solution with the slurry to form a second slurry;   (e) milling the second slurry;   (f) drying the second slurry to form a pre-catalyst; and   (g) calcining the pre-catalyst to form a catalyst.   
     
     
         22 . The method of  claim 21 , wherein the first metal is selected from the group consisting of Pt and Pd. 
     
     
         23 . The method of  claim 21 , wherein the second element capable of forming an alloy with the first metal is Ga. 
     
     
         24 . The method of  claim 23 , wherein the at least one promoter element is Zr. 
     
     
         25 . The method of  claim 24 , wherein the first aqueous solution further comprises a complex or salt of a second promoter element, and wherein the second promoter element is Y. 
     
     
         26 . The method of  claim 25 , wherein the first aqueous solution further comprises a complex or salt of a third promoter element, and wherein the third promoter element is Ba. 
     
     
         27 . The method of  claim 24 , wherein the first aqueous solution further comprises a complex or salt of a second promoter element, and wherein second promoter element is Ba. 
     
     
         28 . The method of  claim 27 , wherein the first aqueous solution further comprises a complex or salt of a third promoter element, and wherein the third promoter element is Fe. 
     
     
         29 . The method of  claim 21 , wherein the solid support is CeO 2 . 
     
     
         30 . The method of  claim 21 , wherein the catalyst for reforming methanol and steam into hydrogen gas for use in hydrogen fuel cells comprises:
 a catalytic component comprising:
 Pd present as an oxide and in a range of 0.5% to 10% of a total weight of the catalyst; 
 a second element capable of forming an alloy with Pd when the catalyst is in the presence of methanol and water vapor, wherein the second element selected from the group consisting of Sc, Nb, Ta, B, Al, Ga, In, Ti, Ge, Sn, and Pb, wherein a molar ratio of the second element to the Pd ranges from 1:5 to 1:1; and 
 at least one promoter element present as an oxide, the at least one promoter element selected from group consisting of Li, N a, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Fe, Y, Zr, and combinations thereof, wherein the at least one promoter element is present in a range of greater than 0% to 10% of the total weight of the catalyst; and 
   a solid support having the catalytic component disposed thereon, the support selected from the group consisting of alumina, silica, CeO 2 , ceramics, carbon, and mixtures thereof, wherein the support has a surface area greater than 5 m 2 /g, wherein the catalyst is free of Cu and Zn.   
     
     
         31 . A method of reforming methanol and steam to hydrogen gas, the method comprising:
 a. heating a methanol water solution to form a methanol water vapor;   b. feeding the vapor to a methanol reformation apparatus containing a methanol water reformation catalyst, wherein the catalyst is heated to at least about 200° C.; and   c. contacting the vapor with the heated catalyst.   
     
     
         32 . The method of  claim 31 , wherein the catalyst is heated to a temperature ranging from about 350° C. to about 425° C. 
     
     
         33 . The method of  claim 31 , wherein the catalyst comprises:
 a catalytic component comprising:
 Pd present as an oxide and in a range of 0.5% to 10% of a total weight of the catalyst; 
 a second element capable of forming an alloy with Pd when the catalyst is in the presence of methanol and water vapor, wherein the second element selected from the group consisting of Sc, Nb, Ta, B, Al, Ga, In, Ti, Ge, Sn, and Pb, wherein a molar ratio of the second element to the Pd ranges from 1:5 to 1:1; and 
 at least one promoter element present as an oxide, the at least one promoter element selected from group consisting of Li, N a, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Fe, Y, Zr, and combinations thereof, wherein the at least one promoter element is present in a range of greater than 0% to 10% of the total weight of the catalyst; and 
   a solid support having the catalytic component disposed thereon, the support selected from the group consisting of alumina, silica, CeO 2 , ceramics, carbon, and mixtures thereof, wherein the support has a surface area greater than 5 m 2 /g, wherein the catalyst is free of Cu and Zn.   
     
     
         34 . The method of  claim 33 , wherein the second element capable of forming an alloy with Pd when the catalyst is in the presence of methanol and water is Ga. 
     
     
         35 . The method of  claim 34 , wherein the at least one promoter element is Zr. 
     
     
         36 . The method of  claim 35 , wherein the catalytic component further comprises a second promoter element present as an oxide, and wherein the second promoter element is Y. 
     
     
         37 . The method of  claim 36 , wherein the catalytic component further comprises a third promoter element present as an oxide, and wherein the third promoter element is Ba. 
     
     
         38 . The method of  claim 35 , wherein the catalytic component further comprises a second promoter element present as an oxide, and wherein the second promoter element is Ba. 
     
     
         39 . The method of  claim 38 , wherein the catalytic component further comprises a third promoter element present as an oxide, and wherein the third promoter element is Fe. 
     
     
         40 . The method of  claim 33 , wherein the solid support is CeO 2 .