High temperature water-gas shift step in the production of clean hydrogen rich synthesis gas from gasified biomass

The possibility of using the water-gas shift (WGS) step for tuning the H2/CO-ratio in synthesis gas produced from gasified biomass has been investigated in the CHRISGAS (Clean Hydrogen Rich Synthesis Gas) project. The synthesis gas produced will contain contaminants such as H2S, NH3 and chloride components. As the most promising candidate FeCr catalyst, prepared in the laboratory, was tested. One part of the work was conducted in a laboratory set up with simulated gases and another part in real gases in the 100 kW Circulating Fluidized Bed (CFB) gasifier at Delft University of Technology. Used catalysts from both tests have been characterized by XRD and N2 adsoption/desorption at −196 °C.In the first part of the laboratory investigation a laboratory set up was built. The main gas mixture consisted of CO, CO2, H2, H2O and N2 with the possibility to add gas or water-soluble contaminants, like H2S, NH3 and HCl, in low concentration (0–3 dm3 m−3). The set up can be operated up to 2 MPa pressure at 200–600 °C and run un-attendant for 100 h or more. For the second part of the work a catalytic probe was developed that allowed exposure of the catalyst by inserting the probe into the flowing gas from gasified biomass.The catalyst deactivates by two different causes. The initial deactivation is caused by the growth of the crystals in the active phase (magnetite) and the higher crystallinity the lower specific surface area. The second deactivation is caused by the presence of catalytic poisons in the gas, such as H2S, NH3 and chloride that block the active surface.The catalyst subjected to sulphur poisoning shows decreased but stable activity. The activity shows strong decrease for the ammonia and HCl poisoned catalysts. It seems important to investigate the levels of these compounds before putting a FeCr based shift step in industrial operation. The activity also decreased after the catalysts had been exposed to gas from gasified biomass. The exposed catalysts are not re-activated by time on stream in the laboratory set up, which indicates that the decrease in CO2-ratio must be attributed to irreversible poisoning from compounds present in the gas from the gasifier.It is most likely that the FeCr catalyst is suitable to be used in a high temperature shift step, for industrial production of synthesis gas from gasified biomass if sulphur is the only poison needed to be taken into account. The ammonia should be decomposed in the previous catalytic reformer step but the levels of volatile chloride in the gas at the shift step position are not known.

► An investigation of the use of the water-gas-shift step for tuning the H2/CO-ratio in synthesis gas from gasified biomass.
►  Laboratory experiments to expose the catalyst to contaminants, like H2S, NH3 and HCl.
► A catalytic probe was used in the flowing gas from gasified biomass.
► Deactivation caused by crystal growth in the active phase and by poisons blocking the active surface.
► The catalyst activity decreases when exposed to HCl, NH3 and gas from a biomass gasifier.