碱性水热法高效降解全氟/多氟烷基化合物

doi:10.19965/j.cnki.iwt.2024-0666

摘要/Abstract

摘要：

全氟/多氟烷基化合物（Per- and polyfluoroalkyl substances，PFAS）是一种持久性有机污染物，化学性质稳定，难以降解。目前水和土壤等环境介质中均能检出PFAS，且PFAS能由食物链累积至人体，毒害生殖和免疫等系统，因此如何高效降解PFAS受到广泛关注。碱性水热法（Hydrothermal alkaline treatment，HALT）利用亚临界水（170~350 ℃，2~22 MPa）在强碱性条件下产生·OH，再利用·OH攻击PFAS中的羧基或磺酸基，实现PFAS的脱羧基或磺酸基、水解脱氟，是一种高效、低能耗和低成本的PFAS处理工艺。总结了HALT对PFAS的降解、脱氟效果，以及反应条件（如碱浓度、反应温度、催化剂和环境基质等）对HALT降解PFAS的影响；阐述了HALT工艺降解PFAS的脱羧-羟基化-消除-水解路径；综述了HALT工艺处理水性成膜泡沫废水、修复受PFAS污染的土壤和水体、再生吸附PFAS饱和的活性炭和处理蓄积PFAS的宽叶香蒲等实际工程的效果；展望了HALT工艺的未来研究方向，为推动HALT处理PFAS的发展提供一定的理论指导和技术参考。

关键词: 全氟/多氟烷基化合物, 碱性水热法, 脱氟, 降解路径

Abstract:

Per- and polyfluoroalkyl substances(PFAS) are persistent organic pollutants that are chemically stable and difficult to degrade. These compounds can be detected in environmental media, such as water and soil, and have the potential to accumulate in the human body through the food chain, posing risks to reproductive and immune systems. Consequently, efficient PFAS degradation has gained widespread attention. Hydrothermal alkaline treatment (HALT) utilizes subcritical water (170-350 ℃,2-22 MPa) under strongly alkaline conditions to generate hydroxyl radicals (·OH). These radicals attack the carboxyl or sulfonic groups in PFAS to facilitate decarboxylation or desulfonation, hydrolytic defluorination, and rapid complete degradation. HALT represents an efficient, low-energy, and cost-effective technique for PFAS treatment. This paper summarized effects of HALT on PFAS degradation and defluorination, explored the influence of reaction conditions (such as alkali concentration, temperature, catalysts, and environmental matrices), and elucidated the decarboxylation-hydroxylation-elimination-hydrolysis pathway. Additionally, the practical engineering outcomes of HALT in treating aqueous film-forming foam wastewater, remediating PFAS-contaminated soil and water bodies, regenerating PFAS-saturated activated carbon, and processing Typha latifolia with accumulated PFAS were reviewed. Lastly, the paper anticipated future research directions for HALT, aiming to provide theoretical guidance and technical references to advance the development of HALT dealing with PFAS.

Key words: per- and polyfluoroalkyl substances, hydrothermal alkaline treatment, defluorination, degradation pathway

中图分类号:

X703

张强, 彭宇华, 张静, 马军. 碱性水热法高效降解全氟/多氟烷基化合物[J]. 工业水处理, 2025, 45(3): 1-9.

Qiang ZHANG, Yuhua PENG, Jing ZHANG, Jun MA. Hydrothermal alkaline treatment for efficient degradation of per- and polyfluoroalkyl substances[J]. Industrial Water Treatment, 2025, 45(3): 1-9.

https://www.iwt.cn/CN/Y2025/V45/I3/1

图/表 7

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PFAS来源	包含PFAS的种类	PFAS浓度	NaOH浓度/（mol·L^-1）	反应温度/℃	反应时间	催化剂	降解率/%	脱氟率/%	参考文献
	PFOS	50 mg/L	5	350	90 min		>99	80	〔29〕
宽叶香蒲	多种PFAS		1	300	2 h		>99	>86	〔30〕
水性成膜泡沫（AFFF）	109种PFAS		5	350	30 min		>99	98	〔31〕
宽叶香蒲	GenX ADONA F-53B		0.01	300	2 h	Ca²⁺等	>99	>99	〔32〕
AFFF	40种PFAS		5	350	2 h	专用催化剂	>99	120.5	〔33〕
土壤和地下水	148种PFAS		5	350	90 min		>99	178	〔34〕
	PFCA	0.089 mol/L	2.67	120	24 h	DMSO	>99	90	〔35〕
AFFF	多种PFAS	5 mg/L	5	350	10 min		>99		〔36〕
颗粒活性炭（GAC）	PFOS	1.6 g/L	5	350	400 min		>99	96	〔37〕
生物炭	PFOA	100 mg/L	0.25	240	4 h	Fe	>99	99	〔38〕
地下水	62种PFAS		1	350	90 min		>90	>90	〔39〕
磁性生物炭（MAC）	多种PFAS	770 mg/L	1	350	240 min		97	101	〔40〕

PFAS来源	包含PFAS的种类	PFAS浓度	NaOH浓度/（mol·L^-1）	反应温度/℃	反应时间	催化剂	降解率/%	脱氟率/%	参考文献
	PFOS	50 mg/L	5	350	90 min		>99	80	〔29〕
宽叶香蒲	多种PFAS		1	300	2 h		>99	>86	〔30〕
水性成膜泡沫（AFFF）	109种PFAS		5	350	30 min		>99	98	〔31〕
宽叶香蒲	GenX ADONA F-53B		0.01	300	2 h	Ca²⁺等	>99	>99	〔32〕
AFFF	40种PFAS		5	350	2 h	专用催化剂	>99	120.5	〔33〕
土壤和地下水	148种PFAS		5	350	90 min		>99	178	〔34〕
	PFCA	0.089 mol/L	2.67	120	24 h	DMSO	>99	90	〔35〕
AFFF	多种PFAS	5 mg/L	5	350	10 min		>99		〔36〕
颗粒活性炭（GAC）	PFOS	1.6 g/L	5	350	400 min		>99	96	〔37〕
生物炭	PFOA	100 mg/L	0.25	240	4 h	Fe	>99	99	〔38〕
地下水	62种PFAS		1	350	90 min		>90	>90	〔39〕
磁性生物炭（MAC）	多种PFAS	770 mg/L	1	350	240 min		97	101	〔40〕

工艺	HALT	热再生
温度/℃	350	800
介质	亚临界水	N₂
m（H₂O）∶m（GAC）	2	0.3
处理单位质量GAC所需加热水的能量/（kW·h·kg^-1）	0.63	2.04
处理单位质量GAC所需加热GAC的能量/（kW·h·kg^-1）	0.08	0.18
处理单位质量GAC所需能量总计/（kW·h·kg^-1）	0.71	2.2
能量总计（回收60%的热）	0.3	—

工艺	HALT	热再生
温度/℃	350	800
介质	亚临界水	N₂
m（H₂O）∶m（GAC）	2	0.3
处理单位质量GAC所需加热水的能量/（kW·h·kg^-1）	0.63	2.04
处理单位质量GAC所需加热GAC的能量/（kW·h·kg^-1）	0.08	0.18
处理单位质量GAC所需能量总计/（kW·h·kg^-1）	0.71	2.2
能量总计（回收60%的热）	0.3	—

[1]	孙志强,袁东,韩广业,荆明阳,高灿柱,刘汝涛,牛启桂. 臭氧处理分散染料生产废水的效率与机理研究[J]. 工业水处理, 2020, 40(1): 29-32, 111.
[2]	杨铸, 傅文燕. 阴离子交换树脂的间接脱氟方法研究[J]. 工业水处理, 1996, 16(6): 16-18.

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