基于烃池机理的生物质和多氢原料催化共热解制油过程协同效应和调控机制研究

Significant synergistic effects (promotion of hydrocarbon production in bio-oil & inhibition of coke formation on ZSM-5 zeolite catalyst) are found during catalytic fast co-pyrolysis (co-CFP) of biomass and hydrogen-rich materials for the production of hydrocarbon-rich bio-oil with the action of hydrocarbon pool, and it is necessary to carry out in-depth study to investigate the detailed synergistic reaction mechanism and regulatory mechanism during co-CFP process. In order to study the synergistic reaction mechanism on promotion of hydrocarbon production during co-CFP process, variable working condition test and isotope analysis are conducted to explore the sharing mechanism of C and H elements from biomass and hydrogen-rich materials under the action of hydrocarbon pool from macro- and micro-perspective, respectively. On the other hand, advanced measurement techniques are applied to investigate the concerted reaction behaviors of various intermediate active components (functional groups, molecular fragments and free radicals). As a result, the mechanism of promotion of hydrocarbon production during co-CFP process can be revealed all sidedly on the basis of above-mentioned experimental results. In order to study the synergistic reaction mechanism on inhibition of coke formation during co-CFP process, laboratory research is conducted and dynamical model is established to illuminate the action characteristics and dynamical mechanism of coke formation inhibition from macro-perspective. Meanwhile, coke component analysis and isotopic tracing experiment are carried out to reveal how the addition of hydrogen-rich materials causes coke formation inhibition from micro-perspective. At last, the regulatory mechanism of co-CFP process is studied in this project based on the concept of modified hydrogen to carbon effective ratio. With the purpose of facilitating hydrocarbon production in bio-oil, mechanism-based experiments are conducted to investigate the optimal numerical range and regulatory mechanism of modified hydrogen to carbon effective ratio of overall feedstocks under the action of hydrocarbon pool. Finally, the obtained results of mechanism-based experiments are used to guide the real co-CFP process for the production of hydrocarbon-rich bio-oil.

烃池作用下生物质和多氢原料催化共热解制取富烃生物油过程存在促进烃类生成和减缓ZSM-5分子筛结焦的协同效应，有必要对具体的协同作用机理和过程调控机制开展深入研究。本项目首先研究催化共热解过程促进烃类生成的协同作用机理，通过工况实验和同位素研究分别从宏观和微观层面解析烃池作用下不同原料中C、H元素在过程中的共用机制，借助先进测试技术考察过程中各种活性组分的协同反应行为，全面揭示促进烃类生成的途径；其次研究催化共热解过程减缓催化剂结焦的协同作用机理，通过小试研究和动力学建模从宏观角度阐明减缓结焦的作用规律和动力学机制，通过结焦组分分析和同位素实验从微观角度解析多氢原料的添加减缓ZSM-5结焦的作用机理；最后基于修正后的有效氢碳比的概念研究催化共热解过程调控机制，以提高生物油中烃类产率为目标，通过机理性实验研究烃池作用下修正后的有效氢碳比的最佳数值范围和调控机制，并指导实际催化共热解制油过程。

本项目以烃池作用下生物质和多氢原料催化共热解制取富烃生物油过程中的协同效应和调控机制为研究对象，采用ZSM-5分子筛为催化剂，针对过程中关键元素共用机制、官能团等活性组分协同反应行为、减缓ZSM-5分子筛结焦机理以及基于原料修正后的有效氢碳比（Modified H/Ceff）的过程调控机制等机理性和基础性科学问题展开了系统的理论和实验研究，掌握了该过程的基本原理和基本规律，发展出生物质和多氢原料催化共热解制油的理论和实践。烃池作用下生物质和多氢原料催化共热解制取富烃生物油过程存在促进烃类生成和减缓ZSM-5分子筛结焦的显著协同效应，本项目首先研究了催化共热解过程促进烃类生成的协同作用机理，通过工况实验和同位素研究分别从宏观和微观层面解析了烃池作用下不同原料中C、H元素在过程中的共用机制，借助先进表征分析技术考察了过程中各种活性组分的协同反应行为，全面揭示促进烃类生成的途径；其次研究了催化共热解过程减缓催化剂结焦的协同作用机理，阐明了减缓结焦的作用规律，并解析了多氢原料的添加减缓ZSM-5结焦的作用机理，提出了构造介微孔复合结构的改性方法以增强ZSM-5催化剂的抗结焦性能；最后基于修正后的有效氢碳比的概念研究了催化共热解过程调控机制，以提高生物油中烃类产率为目标，通过机理性实验研究了烃池作用下修正后的有效氢碳比的最佳数值范围和调控机制，研究发现：当总原料中氢不足时，原料的平均相对分子质量越小，总化学品碳产率越高；当总原料中氢充足时，原料的平均相对分子质量越大，总化学品碳产率越高。项目的预期研究成果不仅对生物质和多氢原料催化共热解过程具有重要的理论和学术价值，也能为生物质制取高品质液体燃料这一新能源领域提供重要的参考依据，有望有效缓解我国的能源和环境危机。