ABSTRACT
Al-rich (Si/Al = 4-6) Cu-SSZ-13 has been recognized as one of the potential catalysts to replace the commercial Cu-SSZ-13 (Si/Al = 10-12) towards ammonia-assisted selective catalytic reduction (NH3-SCR). However, poor hydrothermal stability is a great obstacle for Al-rich zeolites to meet the catalytic applications containing water vapor. Herein, we demonstrate that the hydrothermal stability of Al-rich Cu-SSZ-13 can be dramatically enhanced via Pr-ion modification. Particularly, after high-temperature hydrothermal aging (HTA), CuPr1.2-SSZ-13-HTA with an optimal Pr content of 1.2 wt% exhibits a T80 (temperature window of NO conversion above 80%) window of 225-550 °C and a T90 window of 250-350 °C. These values are superior to those of Cu-SSZ-13-HTA (225-450 °C for T80 and no T90 window). The results of X-ray diffraction Rietveld refinement, electron paramagnetic resonance (EPR) and spectral characterization reveal that Pr ions mainly located in the eight-membered rings (8MRs) in SSZ-13 zeolite can inhibit the generation of inactive CuOx during hydrothermal aging. This finding is further supported by density functional theory (DFT) calculations, which suggest that the presence of Pr ions restrains the transformation from Cu2+ ions in 6MRs into CuOx, resulting in enhanced hydrothermal stability. It is also noted that an excessive amount of Pr ions in Cu-SSZ-13 would result in the production of CuOx that causes the decline of catalytic performance. The present work provides a promising strategy for creating a hydrothermally stable Cu-SSZ-13 zeolite catalyst by adding secondary metal ions.
ABSTRACT
With the continuous development of intensive mariculture, the application of the integrated bioremediation system of aquaculture wastewater (IBSAW) is increasingly promoted. However, the process and nutrients removal performance of the IBSAW need to be further optimized due to its immature technologies. In this study, exogenous compound bacteria (ECB) were added to IBSAW to investigate its pollutants removal efficiency and the relevant mechanisms. High-throughput sequencing and Geochip gene array were used to analyze the correlation between nutrients and bacteria, and the abundance of N and P cycling genes were quantified. Multivariable statistics, dimensionality reduction analysis, and network analysis were applied to explore the mechanisms of IBSAW operation. The results showed that the nutrients decreased significantly after adding ECB, with the brush treatment group significantly outperforming the ceramsite in removing NO3- and PO43-. Ceramsite has an advantage in removing NO2--N. The addition of ECB and different substrates significantly affected the composition of bacterial communities. The contents of nosZ and nirKS related to denitrification in the treatment groups were significantly higher than those in the control group, and the contents in the brush treatment group were significantly higher than that of ceramsite. The biomarkers Psychroserpens and Ruegeria on the biofilm of the brush treatment group were positively correlated with nirKS, while Mycobacterium, Erythrobacter and Paracoccus, Pseudohaliea in the ceramsite group were positively correlated with nirS and nirK, respectively. Therefore, it is speculated that the ECB significantly promoted the increase of denitrification bacteria by affecting the composition of bacterial communities, and the ECB combined with functional genera improved the efficiency of nutrients removal in the system. This study provided a reference for understanding the process and mechanism of nutrients removal, optimizing the wastewater purification technology of the IBSAW and improving the performance of the system.