本研究通过离子交换和成型工艺(干燥、粘结、滚压和煅烧)成功制备了球形钴基催化剂(Co-BC),其中以ZSM-5分子筛为载体,Co (NO3)2为活性组分.该催化剂具有超低钴含量(0.94wt.%).通过能量色散谱仪(EDS)、X射线衍射仪(XRD)、电感耦合等离子体发射光谱(ICP)和X射线光电子能谱仪(XPS)表征证实Co-BC可高效活化PMS降解液相丙酮(羰基挥发性有机化合物(CVOCs)模型污染物).在丙酮初始浓度为5×10-6(pH=7)、PMS为7.5mmol/L、催化剂为10g/L条件下,2h内丙酮去除率达100%(伪一级动力学常数为0.077min−1).淬灭实验和ESR分析表明,其优异性能源于自由基(SO4•−、•OH、O2•−)和非自由基(1O2)的协同作用.Co-BC在宽pH值(3~11)范围内保持70%~100%的去除率,循环使用5次后仍达90%,且钴浸出量仅0.61mg/L (低于国标1mg/L限值),较粉末催化剂(9.86mg/L)显著降低,展现出优异的催化稳定性.
Abstract
A spherical Co-based catalyst (Co-BC) was successfully synthesized via ion-exchange and molding (drying, binding, rolling, calcination) using ZSM-5 as support and Co(NO3)2 as active component, with ultralow Co content (0.94wt.%). Multiple characterizations (EDS/XRD/ICP/XPS) demonstrated Co-BC's efficient PMS activation for aqueous acetone (CVOC model) degradation. Under the conditions of 5×10−6acetone (initial pH=7), 7.5mmol/L PMS dosage, 10g/L Co-BC dosage, the removal efficiency of acetone can reach 100% in 2hours, with a pseudo first order kinetic constant of 0.077min−1. Radical quenching experiment and electron spin-resonance spectrometer (ESR) characterization results indicated that the excellent performance was attributed to synergy of radicals (SO4•−, •OH, O2•−) and nonradical (1O2). Co-BC performed good removal efficiency (70%~100%) for acetone within a wide pH range (3~11). After being reused for 5times, Co-BC still exhibited a removal rate of 90% for acetone. The Co leaching amount from the Co-BC/PMS system was merely 0.61mg/L, well within the national wastewater discharge limit of 1mg/L and significantly lower than that (9.86mg/L) of the powder catalyst under identical conditions, demonstrating the superior catalytic performance and stability of Co-BC.
关键词
PMS激活 /
成型钴基催化剂 /
高效去除 /
工业应用 /
含羰基挥发性有机物
Key words
carbonyl-containing VOCs /
efficient removal /
industrial application /
PMS activation /
shaped Co-based ball catalyst
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基金
国家自然科学基金资助项目(52200126);中央高校基本科研业务费专项资金资助项目(2024MS054,2024MS061);国家杰出青年科学基金资助项目(52325004)
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