Precious metal catalysts in the clean-up of biomass gasification gas part 2: Performance and sulfur tolerance of rhodium based catalysts

• Published in: Fuel processing technology 2011-10, Vol.92 (10), p.1881-1889
• Main Authors: Rönkkönen, H., Simell, P., Niemelä, M., Krause, O.
• Format: Article
• Language: English
• Subjects: active sites; ammonia; Applied sciences; Aromatic hydrocarbon decomposition; biofuels; Biomass; catalysts; cleaning; Energy; Energy. Thermal use of fuels; Exact sciences and technology; Fuels; Gas clean-up; Gasification; hydrogen sulfide; methane; Natural energy; oxidation; Rh catalyst; rhodium; screening; sulfur; temperature
• ISSN: 0378-3820; 1873-7188
• DOI: 10.1016/j.fuproc.2011.05.004

Rh, Pt, and Pt-Rh catalysts on modified commercial zirconia support (m-ZrO 2) were screened for the clean-up of gasification gas from tar, methane, and ammonia both in the absence and presence of H 2S while varying the Rh metal content from 0.5 to 5 w-%. Our goal was to optimize the composition of the Rh/m-ZrO 2 catalyst in view of the production of ultra clean gas applicable for liquid biofuels synthesis. In the presence of 100 ppm sulfur, increasing Rh concentration from 0.5 to 5 w-% did not greatly improve the activity of the catalyst. The bimetallic Pt/Rh/m-ZrO 2 catalyst was also less active than the 0.5 w-% Rh/m-ZrO 2 catalyst. Furthermore, the Rh/m-ZrO 2 catalyst regained its performance at the set point of 800 °C when the sulfur feed was turned off even after exposures to 500–1000 ppm sulfur. Our data allow us to suggest that in the presence of sulfur, the active sites responsible for the reforming reactions are poisoned, but less impact occurs on sites responsible for oxidation reactions. Furthermore, the screening experiments allow to suggest that the Rh/m-ZrO 2 catalyst could be applicable to hot gas cleaning in the presence of sulfur (> 50 ppm) at above 800 °C using a moderate gas hourly space velocity of approximately 3400 1/h. Since biomass gasification gas generally contains sulfur, the 0.5 w-% Rh/m-ZrO 2 catalyst could be a promising option for gasification gas clean-up applications at temperatures above 800 °C where it reduces tar to very low levels. ► We studied Rh/m-ZrO 2 and Rh/Pt/m-ZrO 2 catalysts in clean-up of gasification gas. ► Increase in Rh concentration did not greatly improve activity with H 2S in the feed. ► Bimetallic Pt/Rh/m-ZrO 2 catalyst was less active than the 0.5 w-% Rh/m-ZrO 2. ► Rh/m-ZrO2 regained its performance at 800°C even after 500 ppm H 2S exposures. ► For high tar conversion with Rh/m-ZrO 2, >800 °C and moderate GHSV are required.