煤气化条件下采用新型高效炭基吸附剂联合脱除Hg/As/Se的研究

The proposed project focuses on the frontier field of simultaneous removal of mercury, arsenic and selenium from syngas of coal gasification. New carbon materials with three dimensional network structures have shown great promise for mercury, arsenic and selenium capture applications. The key for mercury, arsenic and selenium simultaneous capture is the mechanisms and structure-property relations of mercury, arsenic and selenium adsorption on adsorbents. However, the current researches mainly focus on experimental observation and data accumulation, and lack the detailed study of microcosmic reaction mechanism. The project integrates the quantum chemistry calculation into the combustion science in order to study the mercury, arsenic and selenium adsorption on new carbon materials, and understand the nature of the interaction and microcosmic mechanism at the molecular level. The adsorption mechanisms of mercury, arsenic and selenium on new carbon materials will be investigated. The effects of syngas composition on simultaneous removal of mercury, arsenic and selenium will be clarified. The influences of oxygen functional groups on mercury, arsenic and selenium adsorption will be revealed. The type of oxygen functional groups which improve the simultaneous removal of mercury, arsenic and selenium will be validated. The theoretical modeling will be compared and verified with the experimental results. The comprehensive theoretical model for screening and predicting the mercury, arsenic and selenium capture performance will be built. An effective method which used to improve the removal ability of new carbon materials by adjusting the oxygen functional groups will by proposed. The project will be performed by multi-disciplinary studies of combustion science and quantum chemistry. The results will provide base for the development of new carbon materials that satisfy the requirements of simultaneous removal of mercury, arsenic and selenium.

本项目针对煤气化合成气中汞、砷、硒联合脱除的前沿领域进行研究。新型高效炭基吸附剂是极具前景的汞、砷、硒联合脱除的三维网状结构多孔轻质炭材料。联合脱除的关键在于研究汞、砷、硒的吸附机理和影响机制。现有研究局限于实验现象观测和数据积累，缺乏对微观相互作用的深入研究。本项目将量子化学交叉融入到燃烧学中，对新型高效炭基吸附剂联合脱除汞、砷、硒的性能进行系统深入的研究，从分子水平上剖析相互作用的本质和微观机理。揭示汞、砷、硒在吸附剂表面的吸附机理；阐明合成气成分的影响机制；揭示含氧官能团的影响机理，确定起促进作用的含氧官能团种类；理论模拟与实验结果进行对比验证，以期构建较为完整的新型高效炭基吸附剂对汞、砷、硒联合脱除的理论框架，建立通过调整含氧官能团来提高吸附剂联合脱除能力的新方法。通过燃烧学、量子化学等的交叉研究，为汞、砷、硒的联合脱除机理、吸附剂的分子设计和分子模拟提供理论基础和实验数据。

本项目针对煤气化合成气中汞、砷、硒联合脱除的前沿领域进行研究。汞、砷、硒是合成气中典型的三种气态重金属，是合成气净化的关键瓶颈之一。多孔炭这类新型高效炭基吸附剂是极具前景的汞、砷、硒联合脱除的三维网状结构多孔轻质炭材料。联合脱除的关键在于研究汞、砷、硒的吸附机理和影响机制，并开发相应的高效联合脱除吸附剂。.本项目应用量子化学密度泛函理论，对汞/砷/硒在多孔炭表面的吸附机理进行了较为全面系统的理论研究，在分子水平上深入研究了多孔炭基吸附剂对汞/砷/硒的吸附过程和微观机制，并针对性开发了可脱除煤气化合成气中汞/砷/硒的多孔炭基吸附剂。.建立了簇模型来模拟多孔炭的固体表面，得到汞/砷/硒的吸附能、吸附构型和吸附活性位等。揭示了多种官能团和活性位对多孔炭的汞/砷/硒吸附性能的影响。从本质上深入揭示了吸附过程的机理，定量分析它们的成键特性以及这些键在化学反应中的变化，得出有关反应性的信息。.分别采用冷冻干燥法和水热法制备了介孔多孔炭和微孔多孔炭，结合低温等离子体技术构建了快速活化的富氧官能团多孔炭，揭示了不同氧官能团对汞吸附的影响。提出了烟气汞原位活化脱除路径，揭示了等离子体作用下多种烟气组分在多孔炭表面形成活性组分的过程，掌握了不同活性组分对汞吸附的作用，并阐明了烟气组分的影响机制。这在本学科领域是一个新的研究思路。.设计了多种负载型多孔炭基吸附剂，实现了合成气中汞的高效脱除。阐明了汞在多孔炭基吸附剂表面的吸附机理和稳定吸附产物，掌握了不同烟气组分对汞吸附的影响机制。实现了中温条件下对合成气中汞的高效脱除。.揭示了多种形态砷和硒在多孔炭表面的吸附过程和稳定吸附产物，得到了典型合成气组分对不同形态砷和硒的影响机制。在固定床实验系统上研究了多孔炭基吸附剂对汞/砷/硒的脱除能力。多孔炭基吸附剂具有高效的汞/砷/硒脱除能力，吸附产物稳定，为实现合成气中汞/砷/硒的联合脱除奠定了基础。.发表SCI论文9篇；申请发明专利3项；参加学术会议4次。