Influence of cerium doping on Cu–Ni/activated carbon low-temperature CO-SCR denitration catalysts

Abstract

In this study, to evaluate the effects of two methods for activation of nitric acid, air thermal oxidation and Ce doping were applied to a Cu–Ni/activated carbon (AC) low-temperature CO-SCR denitration catalyst. The Cu–Ni–Ce/AC_0,1 catalyst was prepared using the ultrasonic equal volume impregnation method. The physical and chemical structures of Cu–Ni–Ce/AC_0,1 were studied using scanning electron microscopy, Brunauer–Emmett–Teller analysis, Fourier-transform infrared spectroscopy, X-ray diffractometry, X-ray photoelectron spectroscopy, CO-temperature programmed desorption (TPD) and NO-TPD characterisation techniques. It was found that the denitration efficiency of 6Cu–4Ni–5Ce/AC₁ can reach 99.8% at a denitration temperature of 150 °C, a GHSV of 30 000 h⁻¹ and 5% O₂. Although the specific surface area of the AC activated by nitric acid was slightly lower than that activated by air thermal oxidation, the pore structure of the AC activated by nitric acid was more developed, and the number of acidic oxygen-containing functional groups was significantly increased. Ce metal ions were inserted into the graphite microcrystalline structure of AC, splitting it into smaller graphene fragments, whereby the dispersibility of Cu and Ni was improved. In addition, many reaction units were formed on the catalyst surface, which could adsorb more CO and NO reaction gases. With the increase in Ce doping, the relative proportions of Cu²⁺/Cuⁿ⁺, Ni³⁺/Niⁿ⁺ and surface adsorbed oxygen (Oα) in the Cu–Ni–Ce/AC_0,1 catalyst increased. In addition, after the introduction of Ce into Cu–Ni/AC, the amount of weak and medium acids significantly increased. This may be due to the Ce species or its influence on the Cu/Ni species. Further, the active sites of the acid were more exposed. According to the results of the study, a composite metal oxide CO-SCR denitration mechanism is proposed. Through the oxidation–reduction reaction between the metals, the reaction gas of CO and NO is adsorbed and the incoming O₂ is converted into (Oα), which promotes the conversion of NO into NO₂. The CO-SCR reaction is accelerated, and the rate of low-temperature denitration was increased. Overall, the results of this study will provide theoretical support for the research and development of low-temperature denitration catalysts for sintering flue gas in iron and steel enterprises.