电晕放电与介质阻挡放电净化氰化氢的机理

doi:10.11949/0438-1157.20231039

摘要/Abstract

摘要：

利用电晕放电以及介质阻挡放电两种低温等离子体产生方式净化氰化氢（HCN），同时对二者的反应机理进行探讨。结果表明，在电晕放电中当输入能量比（SIE）达到8.3 kJ/L，HCN净化效率为76%，在介质阻挡放电中当SIE为11.9 kJ/L时，HCN净化效率为94%；通过Gaussian 软件利用密度泛函理论（DFT）引入外电场，计算分析了两种不同放电方式在HCN净化过程中的差异，在引入外电场之后HCN分子的分子结构以及体系能量均发生了变化，在不同的放电方式中，HCN转化的中间产物—OCN在电晕放电中主要转化为CO₂与N₂，而在介质阻挡放电中HCN更容易与体系中—OH结合生成H₂O与—CN，—CN会在介质阻挡放电中的高电子、粒子密度的作用下聚合为C₃N₄。

关键词: 氰化氢, 电晕放电, 介质阻挡放电, 密度泛函理论

Abstract:

Two low-temperature plasma generation methods, corona discharge and dielectric barrier discharge(DBD), are used to purify hydrogen cyanide (HCN), and the reaction mechanisms of the two are discussed. The results show that the purification efficiency of HCN is 76% when the specific input energy (SIE) is 8.3 kJ/L in corona discharge, and 94% when SIE is 11.9 kJ/L in dielectric barrier discharge. By using density functional theory (DFT) to introduce external electric field, Gaussian software is used to calculate and analyze the differences between the two different discharge modes in the HCN purification process. After the introduction of external electric field, the molecular structure and system energy of HCN molecules have changed. In corona discharge, OCN, the intermediate product of HCN conversion, is mainly converted into CO₂ and N₂, while in dielectric barrier discharge HCN is more easily combined with OH in the system to form H₂O and —CN, and —CN will be polymerized into C₃N₄ under the action of high electron and particle density in DBD.

Key words: hydrogen cyanide, corona discharge, dielectric barrier discharge, density functional theory

中图分类号:

X 511

张欣, 薛宇, 马懿星, 王学谦, 王郎郎, 谢妮霏, 陈怡, 周晓霞. 电晕放电与介质阻挡放电净化氰化氢的机理[J]. 化工学报, 2024, 75(2): 675-684.

Xin ZHANG, Yu XUE, Yixing MA, Xueqian WANG, Langlang WANG, Nifei XIE, Yi CHEN, Xiaoxia ZHOU. Purification mechanism of hydrogen cyanide by corona discharge and dielectric barrier discharge[J]. CIESC Journal, 2024, 75(2): 675-684.

图/表 7

表1 不同方法净化HCN的优缺点对比

Table 1 Comparison of advantages and disadvantages of different methods for purifying HCN

处理技术	脱除效果/%	操作温度	优点	缺点
吸收法	90~98	常温	技术成熟	吸附容量有限，回收处理难
吸附法	80~90	60℃以下	能耗低，处理效率高	吸附剂脱附过程复杂
燃烧法	60~70	700℃	过程简单	运行成本高，易产生二次污染
催化氧化法	75~98	250℃以上	应用广泛，处理彻底	贵金属成本较高，催化剂易中毒
催化水解法	95~99	200℃以下	能耗低，简化处理方式	工业化应用还在实验中
等离子体净化法（本文）	74~94	低温(60℃以下)	同时处理多种污染物，处理效率高	仍然处于实验与理论研究阶段，无法进行工业实际应用

图1 实验装置

Fig.1 Schematic diagram of experimental device

图2 不同放电形式HCN的净化效果

Fig.2 Purification effect of HCN in different discharge forms

图3 等离子体外电场对HCN分子体系的影响

Fig.3 The effect of plasma external electric field on the HCN molecular system

图4 电晕放电的反应路径及能垒

Fig.4 Reaction path and energy base of corona discharge

图5 介质阻挡放电反应路径及能垒

Fig.5 Reaction path and energy base of dielectric barrier discharge

表2 电晕放电与介质阻挡放电反应方程式及能垒

Table 2 Reaction equations and energy barriers of corona discharge and dielectric barrier discharge

序号	化学方程式	反应能垒/(kJ/mol)
电晕放电
①	HCN+O₂ $\overset{}{̿}$ OH+OCN	264.9
②	OH+HCN $\overset{}{̿}$ H₂O+CN	64.5
③	OCN+·O $\overset{}{̿}$ CO₂+N	132.5
④	2OCN $\overset{}{̿}$ 2CO+N₂	164.9
⑤	2NO+O₂ $\overset{}{̿}$ 2NO₂	326.9
⑥	2CO+O₂ $\overset{}{̿}$ 2CO₂	196.3
介质阻挡放电
①	HCN+O₂ $\overset{}{̿}$ OH+OCN	249.7
②	2OCN $\overset{}{̿}$ 2CO+N₂	158.9
③	OCN+·O $\overset{}{̿}$ N+CO₂	56.9
④	OH+HCN $\overset{}{̿}$ H₂O+CN	46.3
⑤	CNC₃N₄	423.6
⑥	H₂O+HCN $\overset{}{̿}$ NH₃+CO	284.0
⑦	2NH₃ $\overset{}{̿}$ 2N₂+3H₂	234.6

表2 电晕放电与介质阻挡放电反应方程式及能垒

Table 2 Reaction equations and energy barriers of corona discharge and dielectric barrier discharge

序号	化学方程式	反应能垒/(kJ/mol)
电晕放电
①	HCN+O₂ $\overset{}{̿}$ OH+OCN	264.9
②	OH+HCN $\overset{}{̿}$ H₂O+CN	64.5
③	OCN+·O $\overset{}{̿}$ CO₂+N	132.5
④	2OCN $\overset{}{̿}$ 2CO+N₂	164.9
⑤	2NO+O₂ $\overset{}{̿}$ 2NO₂	326.9
⑥	2CO+O₂ $\overset{}{̿}$ 2CO₂	196.3
介质阻挡放电
①	HCN+O₂ $\overset{}{̿}$ OH+OCN	249.7
②	2OCN $\overset{}{̿}$ 2CO+N₂	158.9
③	OCN+·O $\overset{}{̿}$ N+CO₂	56.9
④	OH+HCN $\overset{}{̿}$ H₂O+CN	46.3
⑤	CNC₃N₄	423.6
⑥	H₂O+HCN $\overset{}{̿}$ NH₃+CO	284.0
⑦	2NH₃ $\overset{}{̿}$ 2N₂+3H₂	234.6

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