低共熔溶剂用于高温煤焦油脱氮的影响因素机理与前景

Influencing factors mechanisms and prospects of high-temperature coal tar denitration with deep eutectic solvents

  • 摘要: 高温煤焦油作为我国能源体系中的关键组成部分,其含有的含氮化合物不仅会导致燃烧污染和催化剂中毒,还会给储存与炼化工艺带来严重危害;但是这类含氮化合物又是医药、农药和功能材料等领域的重要原料。因此,开发绿色高效的高温煤焦油脱氮技术,实现高效分离与回收,兼具环境与资源双重意义。当前存在的分离高温煤焦油中含氮化合物的方法有溶剂萃取、酸碱精制、离子液体萃取等,存在着环境负担重、生产成本高等不足。低共熔溶剂(DESs)作为一种由氢键供体和氢键受体构成的新型绿色溶剂,以其可设计性强、合成简便、成本低、毒性低和可生物降解等突出优势,成为高温煤焦油脱氮领域的研究热点。因此,系统综述了近年来低共熔溶剂在高温煤焦油脱氮领域中的研究进展,重点解析了关键操作参数、溶剂酸度、黏度以及水含量等理化性质对含氮化合物分离效果的影响规律:含氮化合物的脱除率随温度上升而下降;随时间延长而上升,最终趋于稳定,时间过长反而会下降;随剂油比上升而上升;DESs酸度是决定选择性的重要因素,酸性DESs对碱性氮化物具有更强的选择性,而中性或弱碱性DESs更适用于非碱性含氮化合物;降低DESs黏度可以提高含氮化合物脱除效率;DESs中引入适度水分可以提高含氮化合物脱除率。萃取结束,通过反萃取法、抗溶剂沉淀法以及蒸馏/蒸发法等方法回收的DESs仍具有较理想的分离能力,对降低实际生产成本作用重大。随后,针对各影响因素分析了优化分离条件的方法,并从分子层面深入探讨了氢键相互作用与空间位阻效应等微观机制,指出氢键作用是低共熔溶剂实现选择性分离和对含氮化合物解析的核心驱动力,同时空间位阻效应也对脱氮效率有着较为重要的影响。最后,基于现有研究瓶颈,指出低共熔溶剂在特定含氮化合物的高选择性、复杂真实高温煤焦油体系中的适配性、从实验室放大至工业规模等方面仍面临挑战,并对未来面向产业化应用的低共熔溶剂分子定向设计、中试实验模拟、多过程协同优化和全生命周期可持续性评价等研究方向进行了展望。

     

    Abstract: High-temperature coal tar is a critical component of China’s energy system. However, the nitrogen-containing compounds present in high-temperature coal tar not only contribute to combustion pollution and catalyst poisoning but also pose serious hazards to the environment and refining processes. Nonetheless, if efficiently separated and recovered, these nitrogen-containing substances can serve as valuable raw materials in fields such as pharmaceuticals, agrochemicals, and functional materials. Therefore, the development of green and efficient denitrogenation technologies holds dual significance for both environmental protection and resource utilization.Current methods for separating nitrogen-containing compounds from high-temperature coal tar include solvent extraction, acid-base purification, and ionic liquid extraction, which suffer from drawbacks such as significant environmental impact and high production costs. Deep eutectic solvents (DESs), a new class of green solvents composed of hydrogen bond donors and acceptors, have gained increasing attention as promising agents for high-temperature coal tar denitrogenation due to their tunability, ease of synthesis, low cost, low toxicity, and biodegradability. The article provides a systematic review of recent years advances in the application of DESs for high-temperature coal tar denitrogenation. It emphasizes the influence patterns of key operational parameters, viscosity, and water content on separation efficiency of nitrogen-containing compounds:The removal efficiency of nitrogen-containing compounds decreases with increasing temperature; it increases with prolonged duration before stabilising, but declines if left for excessively long periods; it rises with higher agent-to-oil ratios. The acidity of DESs is a key factor determining selectivity: acidic DESs exhibit greater selectivity towards basic nitrogen compounds, while neutral or weakly basic DESs are more suitable for non-basic nitrogen compounds. Reducing DES viscosity enhances nitrogen compound removal efficiency; Introducing moderate moisture into DESs improves nitrogen compound removal rates. Following extraction completion, recovered DESs via counter-extraction, antisolvent precipitation, or distillation/evaporation retain satisfactory separation capabilities, significantly reducing operational costs. Subsequently,methods for optimising separation conditions were analysed for each of the influencing factors.The review further explores the underlying microscopic mechanisms, such as hydrogen bonding interactions and steric hindrance effects.It was pointed out that hydrogen bonding is the central driving force for the selective separation and resolution of nitrogen-containing compounds through deep eutectic solvents, and that spatial potential resistance also has a important influence on the efficiency of denitrogenation. Finally, based on current research bottlenecks, the article outlines persistent challenges in the highly selective separation of specific nitrogen compounds,the adaptability of DESs to complex real high-temperature coal tar systems and the process for scaling up from laboratory to industrial applications. Prospects for future research directions are also discussed,including targeted molecular design of DESs,pilot-scale experimental simulation,optimization of integrated processes and sustainability assessment over the full life cycle.

     

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