Wang Defu, Huang Bangfu, Shi Zhe, Long Hongming, Li Lu, Yang Zhengyu, Dai Meng
Faculty of Metallurgy and Energy Engineering, Kunming University of Science and Technology Kunming 650093 China
Clean Metallurgy Key Laboratory of Complex Iron Resources Kunming 650093 China.
RSC Adv. 2021 May 21;11(30):18458-18467. doi: 10.1039/d1ra02352g. eCollection 2021 May 19.
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 catalyst was prepared using the ultrasonic equal volume impregnation method. The physical and chemical structures of Cu-Ni-Ce/AC 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/AC can reach 99.8% at a denitration temperature of 150 °C, a GHSV of 30 000 h and 5% O. 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 Cu/Cu , Ni/Ni and surface adsorbed oxygen (Oα) in the Cu-Ni-Ce/AC 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 O is converted into (Oα), which promotes the conversion of NO into NO. 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.
在本研究中,为评估两种硝酸活化方法的效果,将空气热氧化和铈掺杂应用于Cu-Ni/活性炭(AC)低温CO-SCR脱硝催化剂。采用超声等体积浸渍法制备了Cu-Ni-Ce/AC催化剂。利用扫描电子显微镜、Brunauer-Emmett-Teller分析、傅里叶变换红外光谱、X射线衍射、X射线光电子能谱、CO程序升温脱附(TPD)和NO-TPD表征技术研究了Cu-Ni-Ce/AC的物理和化学结构。结果发现,6Cu-4Ni-5Ce/AC在脱硝温度为150℃、空速为30000 h⁻¹和含5% O₂的条件下,脱硝效率可达99.8%。虽然硝酸活化的AC比表面积略低于空气热氧化活化的AC,但其孔结构更发达,酸性含氧官能团数量显著增加。铈金属离子插入AC的石墨微晶结构中,将其分裂成更小的石墨烯片段,从而提高了Cu和Ni的分散性。此外,催化剂表面形成了许多反应单元,能够吸附更多的CO和NO反应气体。随着铈掺杂量的增加,Cu-Ni-Ce/AC催化剂中Cu/Cu⁺、Ni/Ni²⁺和表面吸附氧(Oα)的相对比例增加。此外,将Ce引入Cu-Ni/AC后,弱酸和中强酸的量显著增加。这可能是由于Ce物种或其对Cu/Ni物种的影响。此外,酸的活性位点更易暴露。根据研究结果,提出了一种复合金属氧化物CO-SCR脱硝机理。通过金属之间的氧化还原反应,吸附CO和NO反应气体,并将进入的O₂转化为(Oα),促进NO转化为NO₂。加速了CO-SCR反应,提高了低温脱硝速率。总体而言,本研究结果将为钢铁企业烧结烟气低温脱硝催化剂的研发提供理论支持。