Effect of Methyl Chloride on Landfill Gas Dry Reforming

Landfills are the second-largest source of anthropogenic methane emissions in the U.S., accounting for 22% of CH₄ emissions. Landfill gas (LFG) is primarily composed of CH₄ and CO₂, and currently only 18% of this is used for energy. Because landfills will continue to be used for the foreseeable future, complete utilization of LFG is becoming more important as the demand for energy increases. Catalytically reforming LFG produces syngas (H₂ and CO) that can be converted to liquid fuels or mixed into the LFG stream to produce a more reactive, cleaner burning fuel. It has been demonstrated that injecting 5% syngas into a simulated LFG mixture prior to engine combustion decreases CO, UHC, and NO_x emissions by 73%, 89%, and 38%, respectively. One barrier to using LFG in a catalytic system is the contaminant content of the LFG, including chlorine and sulfur compounds, higher order hydrocarbons, and siloxanes that have the potential to poison a catalyst. Chlorinated compounds are present in LFG at 10–100ppm levels and are often found as chlorocarbons. This research explores the effect of methyl chloride on the activity of a Rh/γ-Al₂O₃ catalyst while dry reforming LFG to syngas. It has been found that methyl chloride acts as a reversible poison on the dry reforming reaction, causing a loss in dry reforming activity, decrease in syngas production, and increase in H₂/CO ratio while CH₃Cl is present in the feed. CH₃Cl exposure also decreases the acidity of the catalyst which decreases carbon formation and deactivation due to coking.