CO属于我国《环境空气质量标准》中的六大基本控制污染物之一，来源广泛。目前钢铁工业中转炉炼钢产生的含高浓度CO放散煤气，通常以“点天灯”的引燃方式进行直燃放散，造成严重的能源浪费与环境污染。CO催化燃烧技术被视为极具潜力的放散煤气高效脱除方法，对于钢铁企业节能减排与升级转型具有重要意义。本文以含高浓度CO（≥3%）的转炉放散煤气为研究对象，采用理论研究、多种催化剂表征手段、活性评价实验、原位谱学与同位素实验、数学建模以及量子化学模拟等方法，分别从理论与实验研究、动力学模型、微观反应机理定性与定量分析、工业应用等角度对CO催化燃烧反应过程开展了一系列研究。

（1）通过溶胶凝胶法制备CuO-CeO₂催化剂，并采用纯CuO、CeO₂作为对比催化剂，详细研究了反应气浓度变化对催化活性的影响规律，得到3种催化剂活性大小顺序为：CuO-CeO₂ > CuO > CeO₂，结合红外热像仪，确定了CO自持催化燃烧的稳燃极限与二维温度场分布，结果表明，CO自持催化燃烧临界浓度与催化剂活性相关，3种催化剂的稳燃极限大小顺序为：CeO₂（9.75%）> CuO（3.75%）> CuO-CeO₂（2%）。通过原位红外（in situ IR）实验与恒温催化燃烧反应耦合质谱瞬变实验，得到了不同反应阶段（低温诱导与高温自持）活性位的演变规律，即在低温诱导阶段，CO优先吸附在Cu⁺-[O_v]-Ce³⁺上形成Cu⁺-[C≡O]-Ce³⁺，然后与活性氧反应产生CO₂。高温自持阶段，CO更倾向于吸附在CuO_x物种Cu⁺上形成Cu⁺-CO，然后与晶格氧反应生成CO₂，气相氧气进入氧空位继续生成晶格氧，形成氧循环，均主要遵循M-K机理。在此基础上，建立了低温诱导阶段的本征反应动力学与高温自持阶段的飞温动力学模型，进一步验证了反应机理，实现了CO催化燃烧反应由低浓度CO向高浓度CO的拓展。

（2）通过液相沉积法合成具有规整形貌的正六面体Cu₂O催化剂，通过XRD、SEM、XPS等表征与活性评价实验，明确了催化燃烧与化学链燃烧过程中，催化剂形貌结构的演变规律及催化循环性能。结果表明，催化燃烧反应后的Cu₂O催化剂（Cu₂O-CC）表面形成Cu₂O-CuO表层与表面晶格氧稳定循环，正六面体结构保持良好；而化学链燃烧后的Cu₂O催化剂（Cu₂O-CLC）表面结构由于晶格氧不断消耗最终导致结构发生塌陷。同时采用in situ IR实验与稳态同位素（¹⁸O₂）瞬态切换实验，在Cu₂O模型催化剂上建立了反应活性氧物种及反应机理的定量化方法，得到Cu₂O催化剂中主要存在表面晶格氧、体相晶格氧与化学吸附氧，含量分别为1.79、8.46和0.81 mmol/g_cat。Cu₂O催化剂在催化燃烧与化学链燃烧过程中，M-K机理均占主导地位，对各自反应的贡献度分别为76.6%（表面晶格氧：69.4%，体相晶格氧：7.2%）和89.7%（表面晶格氧：45.4%，体相晶格氧：44.3%）；L-H机理占次要地位，对各自反应的贡献度分别为23.4%和10.6%，实现了反应机理由定性分析向定量分析的跨越。

（3）采用多种表征实验手段确定了CuO-CeO₂催化剂活性位类型及活性氧类型：CuO催化剂活性位主要是表面分散的CuO_x与颗粒CuO_x；CeO₂催化剂主要是分散的CeO₂与颗粒CeO₂；CuO-CeO₂催化剂上主要活性位是Cu-[O_v]-Ce固溶体、分散的CuO_x及颗粒CuO_x，Cu-Ce之间的协同作用使得Cu-Ce固溶体活性最高。进一步建立基于高真空原位红外定量分析仪的反应物及中间吸附物种的定量分析方法，定量描述CO吸附中间物种类型及数量。结果表明，CuO-CeO₂催化剂在较高真空度（<7.4 mbar）下，CO更容易达到单层饱和吸附，Cu⁰-CO、Cu⁺-CO（包含Cu-Ce固溶体）、Cu²⁺-CO饱和吸附量分别1.33、16.72、0.99 mmol/g，表明Cu⁺是CO吸附的主要位点；碳酸盐饱和吸附量为19.34 mmol/g，但碳酸盐较难分解，对反应的贡献有限。通过稳态同位素（¹⁸O₂）瞬变实验系统在线检测产物浓度及种类，定量揭示CuO-CeO₂催化剂在低温诱导阶段与高温自持阶段不同CO₂产物的生成速率，确定了不同阶段中M-K与L-H机理对反应的贡献度，CuO-CeO₂催化剂在低温诱导阶段，M-K机理对反应贡献度为77.55%，L-H机理占22.45%；在高温自持阶段，M-K机理占84.34%，L-H机理占15.66%。

（4）通过浸渍涂覆法制备CuCe_0.75Zr_0.25O_δ/HC蜂窝陶瓷催化剂，针对转炉放散煤气浓度、温度特性，研究了不同反应气浓度与烟气温度变化对催化燃烧活性的影响规律。结果表明，随CO与O₂浓度增大，整体上均能促进CO催化燃烧反应的进行；而随CO₂浓度的增大，在一定程度上抑制了CO催化燃烧反应，主要是由于CO₂与CO/O₂的竞争吸附作用导致。同时开展了蜂窝陶瓷催化剂200 h的耐久性测评，活性保持良好，轻微的积碳可以通过空气高温再生活化。明晰了蜂窝陶瓷催化剂上CO催化燃烧反应机理，发现仍以M-K机理为主，以L-H机理为辅，与粉末催化剂上的反应机理一致。进一步开展了小试与中试平台上蜂窝陶瓷催化剂的活性评价实验，得到了不同CO浓度下的自持燃烧特性与温度场分布规律，为进一步的工业示范与应用提供了理论依据与数据支撑。

Carbon monoxide (CO) is one of the six major pollutants, controlled with the standard of environmental air quality in our country, and its sources are widespread. At present, the emission of high-concentration CO (≥3%) in off-gases produced in converter steelmaking industry is usually directly burned and released by igniting in a "sky lantern" manner, resulting in severe energy waste and environmental pollution. CO catalytic combustion technology is regarded as a highly promising method for efficient removal of off-gases. This technology has significant implications for energy conservation, emission reduction, and upgrading transformation in the steel industry. This study investigates the high-concentration CO in off-gases emitted from converters through the theoretical research, various catalyst characterization methods, activity evaluation experiments, in-situ spectroscopy and isotope experiments, mathematical modeling, and quantum chemistry numerical simulations methods. The research covers many aspects, such as theoretical and experimental research, kinetic models, qualitative and quantitative analysis of the microscopic reaction mechanism, and industrial applications.

(1) CuO-CeO₂ catalyst was prepared by the sol-gel method, with CuO and CeO₂ used as comparative catalysts. The influence of reactant gas concentration on catalytic activity was studied in detail, revealing the activity ranking of the three catalysts: CuO-CeO₂ > CuO > CeO₂. Using an infrared thermal imager, the stable combustion limit and two-dimensional temperature field distribution of CO self-sustaining catalytic combustion were obtained. The results demonstrated that the critical boundary concentration of CO self-sustaining catalytic combustion is related to catalyst activity, and the stable combustion limits of the three catalysts ranked as follows: CeO₂ (9.75%) > CuO (3.75%) > CuO-CeO₂ (2%). In-situ IR experiments and constant temperature catalytic combustion reaction coupled mass spectrometry transient experiments revealed the evolution of active sites at different reaction stages (low-temperature induction and high-temperature self-sustaining). At the low-temperature induction stage, CO preferentially adsorbs onto Cu⁺-[O_v]-Ce³⁺ to form Cu⁺-[C≡O]-Ce³⁺, which then reacts with active oxygen to generate CO₂. At the high-temperature self-sustaining stage, CO tends to adsorb onto Cu⁺ to form Cu⁺-CO on CuO_x species and reacts with lattice oxygen to produce CO₂. Oxygen enters the oxygen vacancy to continuously generate lattice oxygen, forming an oxygen cycle, mainly following the M-K mechanism. Intrinsic reaction kinetics of the low-temperature induction stage and the fly-temperature kinetics model of the high-temperature self-sustaining stage were established, further verifying the reaction mechanism and achieving the expansion of CO catalytic combustion reaction from low concentration CO to high concentration CO.

(2) A regular hexahedral Cu₂O model catalyst was prepared by the liquid-phase deposition method. The evolution of catalyst morphology, and the catalytic cycling performance during the catalytic combustion and chemical chain combustion processes, was investigated using XRD, SEM, XPS, and other characterization methods and activity evaluation experiments. The results showed that, after the catalytic combustion reaction, the Cu₂O-CC catalyst surface forms a Cu₂O-CuO surface layer and a stable surface lattice oxygen cycle, maintaining a good hexahedral structure, while the Cu₂O-CLC catalyst surface structure collapses due to continuous consumption of lattice oxygen during chemical chain combustion. In-situ IR experiments and steady-state isotope (¹⁸O₂) transient switching experiments established a quantitative method for determining reactive oxygen species and reaction mechanisms on a simple model catalyst, revealing the presence of surface lattice oxygen, bulk lattice oxygen, and chemisorbed oxygen in the Cu₂O catalyst, with contents of 1.79, 8.46, and 0.81 mmol/g_cat, respectively. In the catalytic combustion and chemical chain combustion processes of the Cu₂O catalyst, the M-K mechanism dominates, contributing 76.6% (surface lattice oxygen: 69.4%, bulk lattice oxygen: 7.2%) and 89.7% (surface lattice oxygen: 45.4%, bulk lattice oxygen: 44.3%) to each respective reaction. The L-H mechanism plays a secondary role, contributing 23.4% and 10.6% to each respective reaction, realizing a transition from qualitative analysis to quantitative analysis of the reaction mechanism.

(3) Various characterization techniques were employed to determine the types of active sites and oxygen species on CuO-CeO₂ catalysts: For CuO catalysts, the main active sites were surface-dispersed CuO_x and particulate CuO_x; for CeO₂ catalysts, the main active sites were dispersed CeO₂ and particulate CeO₂; on CuO-CeO₂ catalysts, the primary active sites were Cu-[O_v]-Ce solid solutions, dispersed CuO_x, and particulate CuO_x, with the synergistic interaction between Cu and Ce rendering the Cu-Ce solid solution the most active. A quantitative analysis method based on a high-vacuum in situ analyzer was established for determining the types and amounts of reactants and intermediate adsorbates, suggesting that under a relatively high vacuum (<7.4 mbar), CO is more likely to reach monolayer saturation adsorption on CuO-CeO₂ catalysts, with Cu0-CO, Cu⁺-CO (including Cu-Ce solid solutions), and Cu²⁺-CO saturation adsorption capacities of 1.33, 16.72, and 0.99 mmol/g, respectively, indicating that Cu⁺ is the primary adsorption site for CO. The saturation adsorption capacity of carbonates was 19.34 mmol/g, but carbonates are difficult to decompose and have a limited contribution to the reaction. Further, by monitoring product concentrations and types online during steady-state isotope (¹⁸O₂) transient experiments, the formation rates of different CO₂ products during the low-temperature induction stage and high-temperature self-sustaining stage on CuO-CeO₂ catalysts were quantitatively revealed, and the contributions of the M-K and L-H mechanisms to the reaction at different stages were determined. In the low-temperature induction stage, the contribution of M-K and L-H mechanism is 77.55% and 22.45%, respectively. While in the high-temperature self-sustaining stage, the contribution of  M-K and L-H mechanism contributed 84.34% and 15.66%, respectively.

(4) CuCe_0.75Zr_0.25O_δ/HC honeycomb ceramic catalysts were prepared using an impregnation-coating method, and the effects of different reaction gas concentrations and flue gas temperature variations on catalytic combustion activity were investigated in light of the concentration and temperature characteristics of blast furnace off-gas. The results showed that increasing CO and O₂ concentrations generally promoted CO catalytic combustion, while an increased CO₂ concentration somewhat inhibited the reaction, primarily due to the competitive adsorption between CO₂ and CO/O₂. The catalyst demonstrated a 200-hour durability evaluation, maintaining good activity with only slight carbon deposition that could be reactivated through high-temperature air regeneration. The reaction mechanism on the honeycomb ceramic catalyst was found to be still dominated by the M-K mechanism and supplemented by the L-H mechanism, which validates the reaction mechanism observed on powder catalysts. Moreover, activity evaluation experiments were conducted on pilot and semi-industrial scale platforms for honeycomb ceramic catalysts. The results obtained the self-sustaining combustion characteristics and temperature field distribution patterns at different CO concentrations, providing data support and theoretical basis for further industrial demonstrations and applications.