Removal of Perfluorooctanoic Acid from Water by Nanosecond Pulsed Dielectric Blocking Discharge Plasma

doi:10.12422/j.issn.1006-396X.2024.01.001

Abstract

Abstract:

The efficient removal of perfluorooctanoic acid (PFOA) from contaminated water remains a challenge due to the very stable carbon?fluorine bonds in perfluorinated compounds.In this experiment,nanosecond pulsed dielectric barrier discharge (DBD) plasma was used to degrade PFOA,a difficult?to?degrade organic pollutant in water,and the effects of discharge parameters such as discharge atmosphere,discharge power,gas flow rate,and liquid flow rate,as well as the reaction conditions,on the removal rate of PFOA were investigated in the reaction.The experimental results showed that under the conditions of the discharge atmosphere of argon,discharge power of 11.84 W,gas flow rate of 3.33 L/min,and liquid flow rate of 0.28 L/min,DBD had a better degradation effect on PFOA,and the removal rate could reach more than 94.0% after 60 min of reaction.Combined with emission spectroscopy and free radical burst analysis,it was determined that e^-,?OH,H₂O₂, and O₃ were the main active species to break the molecular structure of PFOA and realize the efficient degradation of the reactants,and thus could provide an effective solution for the removal of PFOA in water.

Key words: Plasma, Perfluorooctanoic acid, Oxidative degradation, Active substances

摘要：

由于全氟化合物中有很稳定的碳氟键，因此如何高效地去除受污染水体中全氟辛酸（PFOA）是一项挑战。采用纳秒脉冲介质阻挡放电等离子体（DBD）对水中难降解有机污染物PFOA进行降解处理，考察了放电气氛、放电功率等放电参数以及气体流量和液体流量等反应条件对PFOA去除率的影响。结果表明，在放电气氛为Ar、放电功率为11.84 W、气体流量为3.33 L/min、液体流量为0.28 L/min的条件下，DBD对PFOA具有较好的降解效果，反应60 min后PFOA去除率可达94.0%以上。结合发射光谱和自由基猝灭分析，确定破坏PFOA的分子结构、实现反应物高效降解的主要活性物种是e^-、?OH、H₂O₂、O₃。该技术可为PFOA去除提供有效的解决方法。

关键词: 等离子体, 全氟辛酸, 氧化降解, 活性物质

CLC Number:

TQ203.9

Lan YANG, Ruijuan LIU, Shusu SHEN, Shiyu MIAO, Xiaoqiang AN, Huachun LAN. Removal of Perfluorooctanoic Acid from Water by Nanosecond Pulsed Dielectric Blocking Discharge Plasma[J]. Journal of Petrochemical Universities, 2024, 37(1): 1-10.

杨兰, 刘瑞娟, 沈舒苏, 苗时雨, 安晓强, 兰华春. 纳秒脉冲介质阻挡放电等离子体去除水中全氟辛酸研究[J]. 石油化工高等学校学报, 2024, 37(1): 1-10.

Figures/Tables 12

Fig.1 Schematic diagram of the experimental setup and detection system for plasma treatment of perfluorinated compounds

Fig.2 Effect of plasma discharge power on PFOA removal and Kobs

Table 1 Comparison of PFOA degradation rate andenergy yield under different discharge power conditions

放电功率/W	降解率/%	能量产率/ （μg $⋅$ kJ^-1）
11.82	38.0	71.44
13.02	68.0	116.06
15.84	96.0	134.68
21.16	100.0	105.02

Table 1 Comparison of PFOA degradation rate andenergy yield under different discharge power conditions

放电功率/W	降解率/%	能量产率/ （μg $⋅$ kJ^-1）
11.82	38.0	71.44
13.02	68.0	116.06
15.84	96.0	134.68
21.16	100.0	105.02

Table 2 Comparison of the effectiveness of plasma degradation of PFOA

降解方法	ρ（PFOA）/（mg $⋅$ L^-1）	溶液体积 /mL	降解时间 /min	放电功率 /W	降解率 /%	能量产率/（μg $⋅$ kJ^-1）	参考文献
DBD等离子体/PMS/O₃	5	150	120	3.00	94.80	33.30	[22]
电晕等离子体	50	50	240	-	-	16.11	[23]
DBD等离子体/Fe⁺	40	150	80	150.00	77.35	96.92	[24]
DBD等离子体	40	200	60	15.84	96.00	134.68	本文

Table 2 Comparison of the effectiveness of plasma degradation of PFOA

降解方法	ρ（PFOA）/（mg $⋅$ L^-1）	溶液体积 /mL	降解时间 /min	放电功率 /W	降解率 /%	能量产率/（μg $⋅$ kJ^-1）	参考文献
DBD等离子体/PMS/O₃	5	150	120	3.00	94.80	33.30	[22]
电晕等离子体	50	50	240	-	-	16.11	[23]
DBD等离子体/Fe⁺	40	150	80	150.00	77.35	96.92	[24]
DBD等离子体	40	200	60	15.84	96.00	134.68	本文

Fig.3 Effect of different atmospheres on PFOA removal and Kobs

Table 3 Parameters of oxygen,nitrogen and argon gas

气体	离解能/eV	电离能/eV
O₂	5.17	12.07
N₂	9.52	15.50
Ar	-	15.75

Fig.4 Effect of argon and solution flow rate on PFOA removal rate

Fig.5 Effect of solution pH and conductivity on PFOA removal rate

Fig.6 Emission spectra of Ar plasma at 200~900 nm

Fig.7 Effect of NaNO3,IPA and BQ on PFOA removal efficiency and K

Fig.8 Changes of fluoride ion mass fraction of each component with time during PFOA degradation process

Fig.9 Schematic diagram of plasma discharge generating reactive species and inferred PFOA degradation pathway

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