梁华根,王安虎,王圣,等. 磁性煤基复合催化剂/H2O2类芬顿体系高效降解喹啉[J]. 煤炭学报,2024,49(3):1657−1668. DOI: 10.13225/j.cnki.jccs.YH23.1213
引用本文: 梁华根,王安虎,王圣,等. 磁性煤基复合催化剂/H2O2类芬顿体系高效降解喹啉[J]. 煤炭学报,2024,49(3):1657−1668. DOI: 10.13225/j.cnki.jccs.YH23.1213
LIANG Huagen,WANG Anhu,WANG Sheng,et al. Preparation of magnetized coal-based CoFe@Coal-C nano-composites: Efficient Fenton-like degradation of quinoline[J]. Journal of China Coal Society,2024,49(3):1657−1668. DOI: 10.13225/j.cnki.jccs.YH23.1213
Citation: LIANG Huagen,WANG Anhu,WANG Sheng,et al. Preparation of magnetized coal-based CoFe@Coal-C nano-composites: Efficient Fenton-like degradation of quinoline[J]. Journal of China Coal Society,2024,49(3):1657−1668. DOI: 10.13225/j.cnki.jccs.YH23.1213

磁性煤基复合催化剂/H2O2类芬顿体系高效降解喹啉

Preparation of magnetized coal-based CoFe@Coal-C nano-composites: Efficient Fenton-like degradation of quinoline

  • 摘要: 为实现煤炭资源利用最大化和煤化工废水中喹啉的高效去除,以煤化程度最低的褐煤为原料,经过酸洗和采用聚乙烯吡咯烷酮进行表面修饰,再通过负载普鲁士蓝类似物(CoFe-PBA)和高温煅烧,制备了CoFe@Coal-C复合材料,用作非均相类芬顿反应催化剂,展现出优异的喹啉降解性能。结果表明,CoFe@Coal-C具有适当的比表面积和孔隙结构,为活性物种提供了传输通道,有利于电子扩散和相互作用。同时,CoFe@Coal-C还表现出典型的超顺磁特性,有利于从水溶液中分离和循环利用。考察了催化剂投加量、初始喹啉质量浓度、溶液pH、及水中共存物质对喹啉降解效率的影响,结果表明,在仅有H2O2存在和仅有催化剂存在的情况下,喹啉的去除率几乎可忽略不计,表明活性氧物种是导致喹啉质量浓度降低的主要因素,而催化剂是催化H2O2产生强氧化性活性氧物种的必要条件。在有H2O2存在、初始喹啉质量浓度为10.0 mg/L、催化剂投加量为0.6 g/L、pH为7的条件下,反应30 min后,CoFe@Coal-C复合材料对喹啉的降解效率达到99.2%。此外,相比纯CoFe合金和纯Coal-C,CoFe@Coal-C对喹啉的降解速率常数分别提高了1个和3个数量级,表明CoFe合金和Coal-C的协同作用是提高催化剂活性的关键。Cl、\mathrmHCO_3^- 、\mathrmSO_4^2- 和\mathrmH_2\mathrmPO_4^- 等共存阴离子,以及初始pH对CoFe@Coal-C/H2O2催化喹啉降解的性能几乎没有影响。自由基淬灭实验和电子顺磁共振光谱表明·OH是主要活性物种,通过高效液相色谱−质谱联用仪检测了喹啉降解的中间产物,并推测了喹啉降解的可能路径。研究表明磁性CoFe@Coal-C催化材料对洗煤废水中喹啉等有机污染物的去除非常高效,具有广阔的应用前景,为洗煤废水的高效治理和资源循环利用提供科学依据。

     

    Abstract: To maximize the utilization of coal resources and efficiently remove quinoline from coal chemical wastewater, a CoFe@Coal-C composite material is prepared using lignite as raw material, which is applied as the heterogeneous Fenton-like catalyst for quinoline degradation. First, lignite is treated by acid washing and polyvinylpyrrolidone modification, and then loaded with Prussian blue analogs (CoFe-PBA), and subsequently calcined at high temperature to finally obtain the product CoFe@Coal-C. The results show that the CoFe@Coal-C has an appropriate specific surface area and pore structure, which provides some transmission channels for active species and is conducive to charge transfer. At the same time, the CoFe@Coal-C also exhibits typical superparamagnetic properties, which is bene-ficial to its separation from aqueous solutions. The effects of different reaction systems, catalyst dosage, initial quino-line concentration, solution pH value, and coexisting substances in water on quinoline degradation efficiency are inves-tigated. In the presence of only H2O2 and only the catalyst, the removal rate of quinoline is almost negligible. Therefore, it can be considered that reactive oxygen species are the main factor leading to the decrease in quinoline concentration, and the catalyst is a necessary condition for catalyzing H2O2 to produce reactive oxygen species. Under the optimal experimental conditions (initial quinoline concentration is 10.0 mg/L, catalyst dosage is 0.6 g/L, pH = 7), the degradation efficiency of quinoline catalyzed by CoFe@Coal-C/H2O2 reaches up to 99.2% within 30 minutes. In addi-tion, compared with pure CoFe alloy and pure Coal-C, the degradation rate constant of quinoline over CoFe@Coal-C increases by 1 and 3 orders of magnitude respectively, indicating that the synergistic effect of CoFe alloy and Coal-C is the culprit for the improved catalyst activity. Coexisting anions (such as Cl, \mathrmHCO_3^- , \mathrmSO_4^2- , \mathrmH_2\mathrmPO_4^- , etc.) and the initial pH value have little effect on the performance of CoFe@Coal-C/H2O2 for quinoline degradation. Free radical quenching experiments and electron paramagnetic resonance spectroscopy show that ·OH is the main reactive oxygen species. The intermediate products of quinoline degradation are detected by high-performance liquid chromatography-mass spectrometry (HPLC-MS), and the possible degradation pathways are speculated. This study shows that the magnetic CoFe@Coal-C composite is an efficient catalyst for the removal of quinoline pollution in the coal wastewater. In addition, the present work provides a reference for the rational design of a high-performance het-erogeneous Fenton-like catalyst that can be used in various complex water environments.

     

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