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    工业烟气CO催化还原NOx技术研究进展

    Research Progress on NOx Catalytic Reduction by CO in Industrial Flue Gas

    • 摘要: 工业烟气氮氧化物(NOx)的减排对于实现我国细颗粒物(PM2.5)和臭氧(O3)的协同控制至关重要。围绕以一氧化碳(CO)为还原剂的选择性催化还原(Selective Catalytic Reduction, SCR)技术,系统综述了研究现状,并展望了未来的应用前景。研究表明,CO-SCR脱硝技术的核心是气固相反应催化剂的研发。常见的CO-SCR催化剂可分为过渡金属氧化物和负载型贵金属材料,其表面的缺陷位(如氧空位)以及不饱和配位的阳离子中心等,是主要的氧化还原活性位点。在过渡金属氧化物中,Cu基、Co基、Mn基催化剂的研究较为广泛;而在负载型贵金属材料中,以Ir基为典型代表。工况波动导致的CO/NO比例变化、高浓度氧气(O2)、二氧化硫(SO2)和水(H2O)均会影响CO-SCR催化剂脱硝性能。因此,未来应重点关注在不同应用领域的催化剂研发需求,完善不同反应条件下CO-SCR微观模型,如钢铁烧结烟气选择性循环耦合CO-SCR脱硝等技术协同效果。此外,高昂的催化剂成本也是限制CO-SCR脱硝技术大规模应用的关键。

       

      Abstract: The reduction of nitrogen oxides (NOx) in industrial flue gas is crucial for achieving coordinated control of fine particulate matter (PM2.5) and ozone (O3) in China′s atmosphere. The most common NOx removal method for stationary sources is selective catalytic reduction (SCR) technology using NH3 as a reducing agent, referred to as NH3-SCR. However, the negative effects associated with NH3 introduction, such as secondary pollution caused by NH3 slip and higher carbon emissions, have gradually attracted widespread attention in recent years. This article provides a review and outlook on the research status and application prospects of selective catalytic reduction technology using carbon monoxide (CO) as a reducing agent (CO-SCR). Research has shown that developing high-performance catalysts is the key challenge for CO-SCR technology. CO-SCR catalysts can be broadly categorized into two types: transition metal oxides and supported noble metal materials. Typical catalysts, including Cu-, Co-, Mn-, and Ir-based catalysts, are reviewed in this article. The microscopic reaction process of CO-SCR involves three main steps: (1) the adsorption of reactant molecules, (2) the conversion of intermediate molecules, and (3) desorption and diffusion of product molecules. Among these steps, the preferential adsorption of NO molecules on the active site, followed by dissociation, is the rate-determining step. The interaction between NO and the substrate strongly depends on the surface state and tends to occur at oxygen vacancies on transition metal oxides, while it occurs at unsaturated coordination cation centers on supported noble metal materials. In addition, the impact of CO/NO, oxygen (O2), sulfur dioxide (SO2), and water vapor (H2O) on CO-SCR performance has also been discussed in detail. For example, on the surface of Ir-based catalysts, Ir0 (serving as the main active site) is unlikely to remain unchanged throughout the entire reaction process. It is anticipated that Ir0 will be converted to oxidized Irδ+ after donating electrons to the antibonding π* orbital of the NO molecule. If new electrons are not replenished promptly, the catalytic activity will gradually decrease as oxidized Irδ+ becomes the predominant species, which is the primary reason for the poor stability of the catalyst in the presence of O2. Interestingly, SO2 stabilizes the catalyst and facilitates the generation of Ir0 sites under O2-containing conditions. Therefore, future research should prioritize the development of catalysts tailored to specific applications, and refine the CO-SCR reaction model under diverse conditions, with a focus on synergistic technologies such as the selective circulation coupling of CO-SCR in steel sintering flue gas. Furthermore, the high cost of catalysts remains a crucial obstacle hindering the widespread adoption of CO-SCR technology.

       

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