The effect of hydrothermal impregnation of Ni, Co, and Cu on HZSM-5 in the nitrogen oxide removal

Abstract

The selective catalytic reduction (SCR) of nitrogen oxides on M/ZSM-5 (M = Cu, Ni, Co) catalysts was investigated. The catalysts were prepared using hydrothermal impregnation of the metal chlorides and nitrates on ZSM-5. The catalysts were characterized by nitrogen absorption/desorption, X-ray diffraction, Fourier transform infrared (FTIR) spectroscopy, ultraviolet–visible diffusion reflection spectroscopy (UV–Vis DRS), temperature-programmed reduction (TPR), N2O chemisorption and ammonia temperature-programmed desorption. The performance tests for SCR of NO were carried out in a fixed-bed reactor from 250 to 400 °C. During the impregnation, part of the aluminum was eliminated from the zeolite framework due to the acidity of the metal salt solution and heating process as indicated by the reduction in the intensity of XRD peaks and variations in the positions of the FTIR vibrational bands. The Cu(Cl)/ZSM-5 catalyst exhibited NO conversions over 90% over the entire temperature range. The other catalysts showed comparable activities, but the catalysts prepared with chloride salt precursors demonstrated higher activity than those based on nitrate as the precursor. Moreover, the TPR reduction peaks of the metal ion in catalysts prepared with chloride precursor were lower, and their UV–Vis absorption bands revealed bathochromic transfers with higher intensities. Concurrent with these changes, the activity of the catalyst increased. The TPR profiles indicated that Cu and Ni both had an oxidation number of +2, whereas Co was present in the oxidation number of +2 and +3. The mass transfer limitation analysis showed that for particles in millimeter size range or larger significant intra-particle mass transfer limitation would be expected.