基于NPSC的生物油间接加氢-选择催化过程中碳、氢迁移机制及其调控

This project is intended to use Ti/HZSM-5 to conduct the bio-oil upgrading by employing the non-thermal plasma synergistic catalysis method, and the mechanism of carbon and hydrogen transition in the catalyst coking process is explored. The waste-plastic pyrolysis vapors are used as the hydrogen-supply gas, and the indirect-hydrogenation of biomass pyrolysis vapors is carried out with the help of the non-thermal plasma activation. Combined with the selective-catalysis of Ti/HZSM-5, the mechanism of carbon and hydrogen transition in the mixed pyrolysis vapors is studied. A reaction kinetic model considering catalyst coking process and refined bio-oil preparation process was established to conduct the study on the regulation and optimization of bio-oil upgrading, so as to achieve high-efficient preparation of high-grade refined bio-oil. .Our research is of great importance not only for understanding the mechanism of carbon and hydrogen transition in the bio-oil indirect-hydrogenation and selective-catalysis under the action of non-thermal plasma, but also for the development and application of high-grade bio-fuel preparation technology.

本项目拟采用低温等离子体协同催化法，以Ti/HZSM-5为催化剂，进行生物油提质研究，探究催化剂结焦的碳、氢迁移机制；并以废塑料热解气作为供氢气体，借助低温等离子体的激励作用对生物质热解气进行间接加氢，结合Ti/HZSM-5的选择催化，研究混合热解气中碳、氢迁移转化机制；建立涵盖催化剂结焦及精制生物油制备过程的反应动力学模型，进行生物油提质的优化调控研究，实现高品位精制生物油的高效制备。.本课题的开展，不仅在基础研究方面，理解低温等离子体作用下的生物油“间接加氢-选择催化”过程中碳、氢迁移机制具有重要意义，同时对高品位生物燃料高效制备技术的开发应用具有重要价值。

由于催化剂易结焦失活，生物油常规催化裂解提质效率较低。本项目在生物油提质中引入低温等离子体技术，其中，低温等离子体与催化剂耦合协同的一段式组合较优；在HZSM-5上负载适量低价态钛物种有利于活性自由基生成，降低结焦，而低温等离子体放电辉光可以诱导TiO2产生光催化作用，减少焦炭类型，使焦炭同构化。优化了生物质微波热解过程，实现了生物油和生物焦同时高效制备；进一步开展了以聚乙烯热解气为加氢原料的生物质热解气间接加氢实验，随着热解气有效氢碳比升高，更多烯烃发生解离和顺排键构，造成催化剂上石墨碳增加；且脱氢碳和石墨碳始终共存，但总沉积碳明显减少，催化剂稳定性显著增强。低温等离子体耦合Ti/HZSM-5协同催化，显著提高了生物质热解气间接加氢效率；结合动力学建模计算，研究了不同金属改性催化剂的结焦特性，钛改性使碳物种聚合沉降难度增加；此外，本项目实现了利用低温等离子体对结焦催化剂进行空气气氛下的原位低温(300℃)快速(25min)再生，且再生后活性较高；进一步提出了精制生物油连续制备的反应模型和调控方法，丰富和发展了高品位精制生物油高效制备的技术路线。