Experimental and theoretical studies on effective synergistic low-temperature removal of NO and typical volatile organic compounds (VOCs) from flue gas based on Cu@VWTi catalyst

Abstract

The transition metal-modified VWTi structural catalysts hold great promise for simultaneously removing nitrogen oxides (NOx) and volatile organic compounds (VOCs) from industrial flue gases. A series of Cu@VWTi catalysts were prepared to investigate their synergistic low-temperature removal performance towards NO and typical VOCs, including toluene, benzene, chlorobenzene (CB), p-chlorotoluene (p-CT), and dichloromethane (DCM). The copper-enhanced samples prepared via ultrasound-assisted impregnation exhibited irregular globular and varying crystallinity. The catalysts displayed a typical anatase crystal structure with high TiO2 content or high dispersion of V and W species along with a certain adjustment effect on the morphology. Various controlling factors affecting the synergistic removal of NO and VOCs were evaluated. It was observed that the presence of VOCs in flue gas has weak impact on NO removal, except for the waste incineration using the Cu@VWTi catalyst. However, a high initial NO concentration had an adverse effect on VOCs removal. Impressively, the optimized copper-doped catalyst (5wt% Cu loaded of smelting plant and coal-fired power plant used catalyst) exhibited excellent performance for p-CT, toluene and DCM removal of 95.0%, 99.6% and 100% at 300 °C, respectively. The toluene and p-CT conversion efficiencies were highest over the catalyst used in the smelting plant after Cu loading, surpassing the benzene conversion efficiency. Cu@VWTi demonstrated excellent performance for p-CT, toluene, and DCM removal at 250 °C. Although 5wt% Cu loading on the catalysts significantly enhanced the stability and anti-jamming of VOCs removal, as well as their tolerance to both SO2 and water vapor. The enhanced mechanism of Cu decoration attributed to the enhanced intensity of acid sites and the stable relative proportion of Oads/Olatt species in the used 5% Cu loaded catalyst due to the redox cycles of Cu and V species. Compared with Brønsted acid, which primarily adsorbs NH4+, Lewis acid mainly adsorbs gas phase acid and forms coordinated NH3 in gas phase. The bonding between toluene and the Cu site was enhanced with an adsorption energy of -130.9 kJ·mol-1, as well as the cracking adsorption of the CH2Cl2 on the Ti site with a bonding energy of -436.7 kJ·mol-1, both indicating strong chemical adsorption. The first step of dechlorination and demethylation was thermodynamically and kinetically favorable for DCM and toluene decomposition.