Steam reforming of hydrocarbonaceous fuels over a ni-alumina spinel catalyst

Abstract

A process for steam reforming of a hydrocarbonaceous fuel includes the steps of: providing a reactant mixture comprising H 2 O and the hydrocarbonaceous fuel; and contacting the reactant mixture with a Al 2 O 3 -yttria-stabilized ZrO 2 (YSZ)-supported NiAl 2 O 4 spinel catalyst under conditions wherein the reactant gas mixture is at least partially steam reformed into a product gas mixture including H 2 and CO. The synthesis gas (H 2 and CO) produced can be used as feed material for fuel cells. The catalyst includes a NiAl 2 O 4 spinel-based catalytically active material; and a support material comprising: Al 2 O 3 and ZrO 2 . The Al 2 O 3 -YSZ-supported NiAl 2 O 4 catalyst can be used in steam reforming of a liquid hydrocarbonaceous fuel.

We claim: 
     
         1 . A process for steam reforming of a hydrocarbonaceous fuel, comprising the steps of:
 providing a reactant mixture comprising H 2 O and the hydrocarbonaceous fuel; and   contacting the reactant mixture with a Al 2 O 3 -yttria-stabilized ZrO 2  (YSZ)-supported NiAl 2 O 4  spinel catalyst under conditions wherein the reactant gas mixture is at least partially steam reformed into a product gas mixture including H 2  and CO, and the Al 2 O 3 —YSZ-supported NiAl 2 O 4  spinel catalyst is substantially free of metallic nickel and nickel oxide.   
     
     
         2 . A process according to  claim 1 , wherein:
 the reactant mixture is in gaseous state when contacted with the Al 2 O 3 —YSZ-supported NiAl 2 O 4  spinel catalyst;   the hydrocarbonaceous fuel in liquid state at ambient temperature and atmospheric pressure;   the hydrocarbonaceous fuel is selected from the group consisting of: at least one hydrocarbon, at least one oxygen-containing fuel, at least one biofuel, at least one fossil fuel, at least one synthetic fuel and a mixture thereof;   the hydrocarbonaceous fuel is selected from the group consisting of: gasoline, diesel, biodiesel, commercial fossil-derived diesel, synthetic diesel, jet fuel, methanol, ethanol, bloethanol, methane, alcohol, and mixture thereof;   the reactant mixture comprises H 2 O in a liquid state and the hydrocarbonaceous fuel in a liquid state; said providing further comprises heating the reactant mixture to provide a gaseous reactant mixture; and said contacting comprises contacting the gaseous reactant mixture with the Al 2 O 3 —YSZ-supported NiAl 2 O 4  spinel catalyst; or said contacting is carried out at a temperature between 500° C. and 900° C.   
     
     
         3 . The process according to  claim 1 , further comprising at least one of atomizing and vaporizing the H 2 O and the hydrocarbonaceous fuel to form an emulsion before contacting the Al 2 O 3 —YSZ-supported NiAl 2 O 4  spinel catalyst; and optionally further comprising adding a surfactant to the H 2 O and the hydrocarbonaceous fuel before atomizing or vaporizing the H 2 O and the hydrocarbonaceous fuel to form the emulsion. 
     
     
         4 . The process according to  claim 1 , wherein:
 the hydrocarbonaceous fuel comprises carbon and the reactant mixture has a H 2 O:carbon molar ratio between 2.3 and 3;   the contacting is carried out with a gas hourly space velocity ranging between 300 cm 3 g −1 h −1  and 200 000 cm 3 g −1 h −1 ;   the Al 2 O 3 —YSZ-supported NiAl 2 O 4  spinel catalyst has a ratio Al 2 O 3 /YSZ ranging between 1/5 and 5/1;   the Al 2 O 3 —YSZ support consists essentially of Al 2 O 3  and YSZ and comprises between 1 w/w % to 2 w/w % of yttria and the catalyst comprises an active phase consisting essentially of the NiAl 2 O 4  spinel;   the Al 2 O 3 —YSZ-supported NiAl 2 O 4  spinel catalyst comprises a molar ratio of Ni/Al 2 O 3  smaller or equal to 1; or   the Al 2 O 3 —YSZ-supported NiAl 2 O 4  spinel catalyst comprises between 1 and 10 w/w % of nickel.   
     
     
         5 . A process according to  claim 1 , wherein:
 the hydrocarbonaceous fuel is in liquid state at ambient temperature and atmospheric pressure and the reactant mixture is in gaseous state when contacted with the Al 2 O 3 —YSZ-supported NiAl 2 O 4  spinel catalyst;   the hydrocarbonaceous fuel is selected from the group comprising: at least one hydrocarbon, at least one biofuel, at least one oxygen-containing fuel, at least one fossil fuel, at least one synthetic fuel and a mixture thereof; or   the reactant mixture comprises H 2 O in a liquid state and the hydrocarbonaceous fuel in the liquid state; said process further comprises heating the reactant mixture to provide a gaseous reactant mixture; and said contacting comprises contacting the gaseous reactant mixture with the Al 2 O 3 —YSZ-supported NiAl 2 O 4  spinel catalyst.   
     
     
         6 . The process according to  claim 1 , wherein said submitting comprises at least one of atomizing and vaporizing the H 2 O and the hydrocarbonaceous fuel to form an emulsion before contacting the Al 2 O 3 —YSZ-supported NiAl 2 O 4  spinel catalyst; and optionally further comprising adding a surfactant to the H 2 O and the hydrocarbonaceous fuel before atomizing or vaporizing the H 2 O and the hydrocarbonaceous fuel to form the emulsion. 
     
     
         7 . The process according to  claim 1 , wherein:
 said contacting is carried out at a temperature between 500° C. and 900° C., with a H  2 O:carbon molar ratio between 2.3 and 3, and a gas hourly space velocity ranging between 300 cm 3 g −1 h −1  and 200 000 cm 3 g −1 h −1 ;   the Al 2 O 3 —YSZ-supported NiAl 2 O 4  spinel catalyst is substantially free of metallic nickel and nickel oxide, comprises between 1 w/w % to 2 w/w % of yttria, and has a ratio Al 2 O 3 /YSZ ranging between 1/5 and 5/1; or   the Al 2 O 3 —YSZ support consists essentially of Al 2 O 3  and YSZ and comprises between 1 and 10 w/w % of nickel, the catalyst comprises an active phase consisting essentially of the NiAl 2 O 4  spinel, and the Al 2 O 3 —YSZ-supported NiAl 2 O 4  spinel catalyst comprises a molar ratio of Ni/Al 2 O 3  smaller or equal to 1.