鲍卫仁,王倩,李挺,等. 催化剂对煤热解焦油品质的调控及其表面积炭行为的分析[J]. 煤炭学报,2024,49(2):1067−1082. DOI: 10.13225/j.cnki.jccs.2023.1600
引用本文: 鲍卫仁,王倩,李挺,等. 催化剂对煤热解焦油品质的调控及其表面积炭行为的分析[J]. 煤炭学报,2024,49(2):1067−1082. DOI: 10.13225/j.cnki.jccs.2023.1600
BAO Weiren,WANG Qian,LI Ting,et al. Analysis of catalytic control of tar quality during coal pyrolysis and the coke behavior on catalyst surface[J]. Journal of China Coal Society,2024,49(2):1067−1082. DOI: 10.13225/j.cnki.jccs.2023.1600
Citation: BAO Weiren,WANG Qian,LI Ting,et al. Analysis of catalytic control of tar quality during coal pyrolysis and the coke behavior on catalyst surface[J]. Journal of China Coal Society,2024,49(2):1067−1082. DOI: 10.13225/j.cnki.jccs.2023.1600

催化剂对煤热解焦油品质的调控及其表面积炭行为的分析

Analysis of catalytic control of tar quality during coal pyrolysis and the coke behavior on catalyst surface

  • 摘要: 以催化剂为核心和焦油提质为目的的低阶煤热解技术是保障国家能源安全和实现“双碳”目标的煤炭清洁高效转化技术。鉴于煤焦油品质调控和催化剂表面积炭行为的复杂性,阐述了金属、金属氧化物、天然矿物质、分子筛和炭基催化剂对煤和热解挥发物的催化作用及其对热解产物分布和组成的影响,并对比分析了各类催化剂的优缺点。探讨不同催化剂物理化学性质的区别及其与催化性能之间的关系,结合煤及热解挥发物中C—C、C—H、C=C、—OH、C=O、C—O和—COOH等化学键的断键行为,揭示了不同催化剂的作用机制。在此基础上,针对催化过程中存在的焦油产率低及提质效果差的问题,提出了利用金属尤其是过渡金属改性催化剂活化热解体系中的内部小分子氢供体和外部固体/气体氢供体对重质组分裂解碎片原位供氢的方法,实现焦油产率的提高及焦油品质的改善。同时,针对催化剂易积炭失活问题,分析了积炭的物理化学性质和组成以及积炭形成的原因。从催化剂设计及热解反应体系出发,分析了多种有效抑制积炭的途径,如多级孔与金属活性位点的组合效应、双金属改性调控Brønsted和Lewis酸性位点的比例、酸碱双功能催化剂的开发以及引入H2O、CH4、C2H6和CH3OH等富氢小分子调控挥发物组成等,以期为低阶煤催化热解技术的发展提供理论基础。

     

    Abstract: The low-rank coal pyrolysis technology with tar upgrading by catalyst is a clean and efficient coal conversion technology that ensures national energy security while also meeting the “carbon peaking and carbon neutrality” goals. The catalytic effects of metals, metal oxides, natural minerals, zeolites, and carbon-based catalysts on coal and pyrolysis volatiles are discussed due to the complexity in controlling tar quality and coke behavior. It also evaluates the effects of each type of catalysts on the distribution and composition of pyrolysis products, comparing their advantages and disadvantages. The differences in the physical and chemical properties of various catalysts, as well as their relationship with catalytic performance, are explored in detail, and the action mechanism of various catalysts is revealed by combining the bond breaking behavior of C—C, C—H, C=C, —OH, C=O, C—O and —COOH in coal and pyrolysis volatiles. Based on the studies above, aiming at the problems with low-tar yield and poor-tar quality during the catalytic process, it is proposed to use internal small molecule hydrogen donors and external solid/gaseous hydrogen donors activated by metal, particularly the transition metal modified catalysts, for in-situ hydrogen supply to heavy components cracking fragments in order to increase tar yield and improve tar quality during the catalytic process. Furthermore, to solve the problem of catalyst deactivation caused by coke, the chemical and physical characteristics and composition of coke, as well as the causes of coke formation, are examined in depth. Several effective strategies to coke inhibition are proposed, commencing with the design of the catalysts and the pyrolysis reaction system. Combining metal active sites with multi-level pores, bimetallic modification to control the ratio of Lewis and Brønsted acid sites, the synthesis of dual-functional catalysts with basic and acidic properties, and the introduction of hydrogen-rich small molecules such as H2O, CH4, C2H6, and CH3OH to control volatiles composition all contribute to effective coke suppression methods. The study can serve as a theoretical basis for the advancement of catalytic pyrolysis technology for low rank coal.

     

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