六氟化硫在氧化与还原气氛中的辐照裂解

doi:10.19894/j.issn.1000-0518.240381

摘要/Abstract

摘要：

六氟化硫（SF₆）在电力行业被广泛用作灭弧绝缘气体，同时又是危险的温室气体。 SF₆的降解处理及资源化利用是必须研究的迫切课题。采用钴-60放射源的伽马射线辐照来降解SF₆，研究了在氧化（O₂）和还原（H₂）气氛中的降解效果，采用傅里叶变换红外光谱（FT-IR）分析SF₆分别与氧气和氢气形成的混合气体的辐照结果。氢气中辐照初期出现微弱的硫酰氟（SO₂F₂）吸收峰，该产物为辐照生成的SF₄与固体内壁吸附水反应后生成，水反应结束后，该峰强度不再变化。氧气中辐照，硫酰氟吸收峰随吸收剂量增加而增强，说明氧气参与了硫酰氟的形成过程；除此以外，形成了其他复杂的氧化产物，吸收峰随吸收剂量增加而增强。无论氧化气氛还是还原气氛中，SF₆降解速率均比纯SF₆辐解大大加快，但是氢气中降解速率最快。根据动力学拟合结果，纯SF₆气体以及氧气与氢气中SF₆辐解速率常数分别为1.70×10^-3、6.0×10^-3和13.3×10^-3 kGy^-1。

关键词: 六氟化硫, 伽马射线, 辐照, 氧气, 氢气, 裂解

Abstract:

SF₆ is widely used in the power industry as an arc extinguishing insulating gas and is also a hazardous greenhouse gas. The degradation and resource utilization of SF₆ is an urgent issue that must be studied. The gamma irradiation of cobalt-60 radioactive source was used to degrade SF₆， and the degradation effects in oxidizing or reducing atmospheres were studied. The irradiation results of the mixed gas formed by SF₆ with oxygen or hydrogen were analyzed by fourier fransform infrared （FT-IR） spectrometer. A weak absorption peak of sulfuryl fluoride （SO₂F₂） appeared in the early stage of irradiation in hydrogen， which was formed after the reaction of SF₄ with the adsorbed water on the inner wall of the solid. The intensity of the peak did not change after all the water reacted. The absorption peak of sulfuryl fluoride increased with the increase of absorption dose in oxygen， indicating that oxygen was involved in the formation of sulfuryl fluoride. In addition， other complex oxidation products were formed， and the peak intensities were enhanced with the increase of absorbed dose. Both oxidizing and reducing atmospheres accelerated the degradation of SF₆， but the degradation rate is the fastest in hydrogen. According to the kinetic fitting results， the rate constants of SF₆ in pure gas， oxygen and hydrogen are 1.70×10^-3， 6.0×10^-3 and 13.3×10^-3 L/mol， respectively. This work not only contributes to the utilization of SF₆ resources， but also is of great significance to the realization of China's green and environmentally friendly modern power industry and the realization of the goals of “carbon peak” and “carbon neutrality”.

Key words: Sulfur hexafluoride, Gamma rays, Irradiation, Oxygen, Hydrogen, Decomposition

中图分类号:

O644

陈英, 赵跃, 马凤翔, 朱峰, 赵梦惠, 刘和文, 许争杰, 徐霄筱, 程伟, 杭忱. 六氟化硫在氧化与还原气氛中的辐照裂解[J]. 应用化学, 2025, 42(6): 811-817.

Ying CHEN, Yue ZHAO, Feng-Xiang MA, Feng ZHU, Meng-Hui ZHAO, He-Wen LIU, Zheng-Jie XU, Xiao-Xiao XU, Wei CHENG, Chen HANG. Irradiation Cracking of Sulfur Hexafluoride in Oxidizing and Reducing Atmospheres[J]. Chinese Journal of Applied Chemistry, 2025, 42(6): 811-817.

图/表 7

图1 不同吸收剂量下H2/SF6混合气体FT-IR谱图A. Full spectra； B. Enlargement between 400~2000 cm-1

Fig.1 FT-IR spectra of H2/SF6 mixture gas at different absorbed doses

表1 SF6特征红外峰归属

Table 1 IR assignment of SF6

No.	Peak position/cm^-1	Assignment
g	948.1	ν₃ as.stretching
h	615.0	ν₄ deformation
a	1 716	ν₁+ν₃ combining
b	1 584	ν₂+ν₃ combining
c	1 388	ν₁+ν₄ combining
d	1 257	ν₂+ν₄ combining
e	1 137	ν₄+ν₅ combining
f	989	ν₂+ν₆ combining

图2 不同吸收剂量下H2/SF6混合气体红外光谱减去未辐照样品光谱得到的差谱图The curve marked with SF6 is the absorption spectrum of pure SF6

Fig.2 Differential spectra obtained from the infrared spectra of the H2/SF6 mixture at different absorption doses minus the spectrum of the unirradiated sample

图3 不同吸收剂量下O2/SF6混合气体红外光谱图A. Full spectra； B. Enlargement between 400~2000 cm-1

Fig.3 Infrared spectra of O2/SF6 mixture gas at different absorbed doses

图4 不同吸收剂量下O2/SF6混合气体红外光谱减去未辐照样品光谱得到的差谱图（A） The absorption spectra of pure SF6；（B） The enlargement of the framed section in A

Fig.4 Differential spectra obtained from the infrared spectra of the O2/SF6 mixture at different absorption doses minus the spectra of the unirradiated sample

图5 相同吸收剂量下O2/H2不同气氛SF6红外差谱分析SF6 and SO2 are the absorption spectra of pure SF6 and SO2， respectively. a and b are the differential spectra obtained by the spectra of H2/SF6 minus those of O2/SF6 absorbing 38 and 91 kGy， respectively

Fig.5 Infrared differential analysis of SF6 in different O2/H2 atmospheres of the same absorbed doses

图6 不同气氛中辐照后SF6质量分数的变化The irradiation results of pure SF6 were obtained in our previous work. Dashed lines are the fitting curves based on eq （3）

Fig.6 Changes in the mass fraction of SF6 after irradiation in different atmospheres

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