Sulfur poisoning and regeneration of copper zeolites for NH3-SCR : Effect of SO2/SO3 ratio

Sammanfattning: The road transportation is a big source for the release of NOx emissions. NOx has been confirmed to cause negative affect on the air-quality especially in the urban areas, there are therefore regulations for allowed released amount from vehicles. The most adopted technology used for the reduction of these NOx emissions from the diesel exhaust gas is the ammonium selective catalytic reduction (NH3-SCR) using a Cu-zeolite as the catalyst in the system. The SCR catalyst can be deactivated through different mechanism, whereas poisoning by sulfur has been documented to be an important factor for the deactivation. The degree of deactivation of the catalyst has been suggested to vary depending on the catalytic material and which sulfur conditions the catalyst is exposed to, where SO3 has been indicated to cause more sever deactivation compared to SO2.  The aim of this project has been to investigate the deactivation mechanism of Cu-zeolites at different SOx conditions and evaluate potential regeneration mechanism. The project was carried out by evaluating the catalysts, Cu-BEA and Cu-SSZ-13, over different reactions that occurs in the SCR system, investigating the deactivation effect caused by SO2 poisoning and the regeneration potential. The project was then continued with the focus on the Cu-SSZ-13 catalyst investigating different SOx poisoning and regeneration conditions were investigated. In order to investigate the SO3 poisoning a generator using oxidation of SO2 to SO3 was successfully build during this project.  A kinetic model over the Cu-SSZ-13 NH3-SCR reactions was also built based on literature studies and the experimental data obtained. The results from the sulfur poisoning of Cu-BEA are based on the master thesis by Maria Arvanitidou. The fresh samples Cu-Beta and Cu-SSZ-13 exhibited similar activity, with the exception of the high formation of N2O observed over Cu-Beta under SCR conditions. The SO2 causes deactivation, especially at low temperatures. Cu-SSZ-13 exhibited more loss in activity but was able to recover more through the elevated SCR regeneration steps than the Cu-Beta. When SO2 exposure was performed together with NH3, larger deactivation was observed, likely due to ammonium sulfate species formed on the surface. The ammonium sulfate species were less thermally stable than copper sulfates, making it easier to recover the loss of activity in the Cu-SSZ-13. SO3 caused a much more sever deactivation of the SCR reactions than that of the SO2 poisoning and continued to show the lowest NOx removal activity after the regeneration process.  A difference in initial deactivation and recovery of activity between standard and fast SCR reactions was observed, indicating that the different mechanisms used are affected differently by the poisoning. The kinetic model for NH3-SCR over the Cu-SSZ-13 was successfully created when compared to the experimentally obtained data.