Molecular structure-driven mechanistic insights into the thermally inert refining processes for anthracite conversion

IF 6.3 3区工程技术 Q1 ENGINEERING, CHEMICAL

Journal of the Taiwan Institute of Chemical Engineers Pub Date : 2025-09-12 DOI:10.1016/j.jtice.2025.106393

Na Li , Jiancheng Hong , Meilin Zhu , Caizhu Liu , Shu Yan , Huining Wan , Jianbo Wu , Yuhua Wu , Hui Zhang , Hongcun Bai

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Abstract

Background

Anthracite, characterized by its high structural order and carbon content, offers unique potential for fabrication of advanced carbon materials. However, the molecular mechanisms governing its thermally inert refining processes (TIRP) remain unclear, particularly the dynamic evolution of polyaromatic networks and CC/C—X bonds cleavage-reorganization during thermal treatment.

Methods

This study investigates Rujigou anthracite from Ningxia, China through an integrated approach combining material characterization, controlled thermal treatment experiments, and molecular modeling calculations.

Significant Findings

Accurately reproduced the ordered 3D configuration, carbonization behavior, and oriented aromatic stacking of RJG-OM during TIRP at the atomic scale. Integrated micro/macro-scale analysis revealed a three-stage TIRP mechanism: bond cleavage without new fragments below 330 °C; aromatic collapse and carbon rearrangement at 330∼810 °C; volatile release and aromatic expansion dominating skeleton reorganization above 810 °C. Heteroatom removal involved triphase C=O evolution N-6→N-5 conversion. The release of oxygen from C=O primarily occurs through decarboxylation-induced growth, pyrolysis equilibrium, and high-temperature restructuring. The transformation of nitrogen-containing heterocycles from N-6 to N-5 follows a hydrogenation-ring opening-reconstruction pathway, accompanied by a nearly linear increase in N-5 content and a synchronous decrease in N-6/NOx levels.

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分子结构驱动的无烟煤转化热惰性精炼过程的机理研究

煤无烟煤结构有序、含碳量高，具有制造先进碳材料的独特潜力。然而，控制其热惰性精炼过程（TIRP）的分子机制仍不清楚，特别是在热处理过程中多芳网络和CC/ C-X键裂解-重组的动态演变。方法采用材料表征、控制热处理实验和分子模拟计算相结合的方法，对宁夏如吉沟无烟煤进行研究。重要发现：在原子尺度上准确再现了RJG-OM在TIRP过程中的有序三维构型、碳化行为和取向芳族堆积。综合微观/宏观尺度分析揭示了TIRP的三个阶段机制：330℃以下无新碎片的键解理；330 ~ 810℃时芳香崩塌和碳重排；在810℃以上，挥发性释放和芳香膨胀主导骨架重组。杂原子的去除涉及三相C=O演化N-6→N-5转化。C=O的氧释放主要通过脱羧诱导的生长、热解平衡和高温重构发生。含氮杂环从N-6向N-5的转变遵循加氢-开环-重构的途径，N-5含量几乎呈线性增加，N-6/NOx水平同步降低。

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来源期刊

Journal of the Taiwan Institute of Chemical Engineers 工程技术-工程：化工

CiteScore

9.10

自引率

14.00%

发文量

362

审稿时长

35 days

期刊介绍： Journal of the Taiwan Institute of Chemical Engineers (formerly known as Journal of the Chinese Institute of Chemical Engineers) publishes original works, from fundamental principles to practical applications, in the broad field of chemical engineering with special focus on three aspects: Chemical and Biomolecular Science and Technology, Energy and Environmental Science and Technology, and Materials Science and Technology. Authors should choose for their manuscript an appropriate aspect section and a few related classifications when submitting to the journal online.