Study of Mn incorporation into SAPO framework: Synthesis, characterization and catalysis in chloromethane conversion to light olefins

MnAPSO-34 molecular sieve has been synthesized with triethylamine as the template, characterized with XRD, XRF, ³¹P, ²⁷Al and ²⁹Si NMR and FT-IR techniques and compared with SAPO-34. The template decomposition and removal have been investigated with TG–DTG–DSC coupled with mass spectrometer. Mn incorporation generates a negligible difference on the chemical shift in ³¹P and ²⁷Al MAS NMR, while an effect on the intensity of resonance peaks is revealed. ²⁹Si MAS NMR study has demonstrated that Mn incorporation favors the Si island formation, which may give rise to the stronger acidic sites. The thermal analysis (TG–DSC) on template removal in a diluted oxygen atmosphere, leading to the formation of CO₂, NO and H₂O, showed, besides a low temperature endothermic weight loss due to the desorption of water, two weight losses (200–400 and 400–600 °C) for SAPO-34 and MnAPSO-34, suggesting two different chemical location environments of template molecules in these two molecular sieves. The quantity of template removed at higher temperature range is much higher in MnAPSO-34, indicating stronger template–framework interaction and stronger acidity after calcination. The acid difference caused by Mn incorporation has also been evidenced by ammonia adsorption evaluated by FT-IR. Chloromethane transformation was carried out over MnAPSO-34 and SAPO-34 and the catalytic performance showed that both molecular sieves are very active and selective catalyst for light olefins production. MnAPSO-34 demonstrated higher activity and light olefins selectivity.