利用实验和分子模拟方法研究硝酸铵与氯化物杂质的分解机理。,Journal of Hazardous Materials

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利用实验和分子模拟方法研究硝酸铵与氯化物杂质的分解机理。
Journal of Hazardous Materials ( IF 12.2 ) Pub Date : 2019-04-22 , DOI: 10.1016/j.jhazmat.2019.04.068
Rong Xia ₁ , Jingyao Wang ₂ , Zhe Han ₂ , Zhenhua Li ₁ , M Sam Mannan ₂ , Benjamin Wilhite ₂

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硝酸铵（AN）分解引起的着火/爆炸会带来重大的安全隐患，在包含氯化钾（KCl）在内的各种盐的存在下，这种危险会加剧。在这项工作中，使用先进的反应化学筛选工具（ARSST）通过实验测量了KCl质量分数范围内AN分解的关键热参数。根据实验结果和以往的文献综述，提出了AN / KCl分解机理，该机理包括四个独立的途径，即（i）直接AN主分解途径，（ii）通过氯自由基的间接AN主分解途径，（iii）直接纯AN侧分解路径和（iv）通过氯自由基的间接AN侧分解路径。使用高斯软件通过密度泛函理论（DFT）估算了所提出机制中每个反应步骤的活化能。计算化学模型很好地说明了实验数据。计算和实验结果均证实氯自由基通过间接途径（ii）和（iv）降低了AN分解的反应势垒。由于这些间接分解途径比主要途径（i），（iii）放热更多，因此添加KCl不仅会加速AN分解，还会增加反应放热。

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Mechanism study of ammonium nitrate decomposition with chloride impurity using experimental and molecular simulation approach.

Fire/explosion due to ammonium nitrate (AN) decomposition poses significant safety hazards which are exacerbated in the presence of salts including potassium chloride (KCl). In this work, key thermal parameters of AN decomposition over a range of KCl mass fraction were experimentally measured using advanced reactive chemical screening tool (ARSST). Based on experimental findings and past literature review, AN/KCl decomposition mechanism was proposed consisting of four separate pathways, specifically, (i) direct AN main decomposition pathway, (ii) indirect AN main decomposition pathway via chlorine radical, (iii) direct pure AN side decomposition pathway and (iv) indirect AN side decomposition pathway via chlorine radical. Gaussian software was used to estimate activation energies for each reaction step involved in the proposed mechanism via density function theory (DFT). The computational chemistry model explained experimental data with good agreement. Both computational and experimental findings confirm that chlorine radical reduce reaction barrier of AN decomposition via indirect pathways (ii) and (iv). As these indirect decomposition pathways are more exothermic than the primary paths (i), (iii), KCl addition not only accelerates AN decomposition but also increases reaction heat release.

更新日期：2019-05-16

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