Mechanism insight into ethylene oligomerization on zeolite K-LTA surface: A DFT and kMC study

Abstract

The regeneration gas used in the K-LTA zeolite dryer of the MTO plant is planning to be changed from high purity nitrogen to the top gas of the demethanizer tower with high ethylene content, which is helpful to energy saving and emission reduction. However, there is a risk of ethylene oligomerization and carbon deposition when the regeneration gas passes through the K-LTA zeolite. The reaction mechanism of ethylene oligomerization on the K-LTA zeolite surface must be clarified. DFT calculations showed that ethylene could be physically adsorbed on Si–OH, Al–OH, the incomplete α- and β-cage on [100]-D4R-e surface. Butoxide forms through ethylene dimerization by stepwise and concerted mechanisms first. Then the reaction of ethylene and butoxide to n-hexyloxide leads to the continued growth of the carbon chain. The oligomerization reaction barriers of rate-determining steps are between 1.65∼1.75 eV, which is more difficult to occur than other zeolites. The ethylene oligomerization reaction can be divided into stepwise polymerization path, concerted polymerization path and concerted butene path. kMC simulation found that the dominant reaction paths are different under different temperatures. When the regeneration temperature reaches 473 K, trace n-butene is generated. At 513 K, ethylene oligommerization occurs and carbon deposition is formed. The results put forward higher requirements for strictly controlling the temperature of the dryer to ensure the excellent performance of K-LTA zeolite.