过硫酸盐高级氧化原位修复地下水中卤代烃污染研究进展

doi:10.16085/j.issn.1000-6613.2023-1229

摘要/Abstract

摘要：

近年来，地下水卤代烃污染问题日益突出，在多种修复技术中，过硫酸盐（PS）高级氧化技术由于其氧化能力强、反应适用pH范围广、半衰期长且氧化范围广，在水处理界引起了广泛关注。本文先对地下水卤代烃的赋存类型进行了分类，指出国内污染场地检出的卤代烃大部分为重非水相液体（DNAPLs），然后对收集的155个污染地区的卤代烃检出类型和频次进行了统计。对于PS高级氧化技术对卤代烃的降解机制，本文作了详细的分析，大体上分为自由基途径和非自由基途径。由于单一的PS活性不高，因此需要将其活化才能起到较好的氧化效果。在此，总结了金属基催化剂和碳基催化剂的种类和特点。最后讨论了具体应用时PS浓度、无机阴离子、反应初始pH和地下水中天然有机物对反应的影响。与传统的地下水卤代烃修复技术相比，过硫酸盐高级氧化技术可以成为高效清洁的替代技术。

关键词: 地下水污染, 卤代烃污染, 过硫酸盐高级氧化, 自由基, 非自由基途径, 催化剂

Abstract:

The groundwater contamination by halogenated hydrocarbons has gained increasing attention in recent years. Among various available remediation technologies, persulfate (PS)-based advanced oxidation processes have become a promising option in the water treatment community due to their high oxidation capacity, wide range of applicable pH, and long half-life with a wide range of oxidation. In this review, the types of halogenated hydrocarbons commonly detected in groundwater were classified, and dense non-aqueous phase liquids (DNAPLs) were the most frequently detected type of halogenated hydrocarbons in domestically contaminated sites. Next, statistics were presented regarding the types and frequencies of halogenated hydrocarbons identified in a total of 155 sampled contaminated areas. Additionally, this review included a detailed analysis of the degradation mechanism of PS-based advanced oxidation processes, which was categorized into two pathways: free radical and non-free radical. Given the low activity of single PS, activation was required to achieve optimal oxidation performance, and this review summarized the properties and characteristics of metal-based and carbon-based catalysts. Lastly, the effects of various factors on the reaction in specific applications were discussed, including PS concentration, inorganic anions, initial pH of the reaction, and the presence of natural organic matter in groundwater. PS-based advanced oxidation processes had the potential to be an efficient and environmentally friendly alternative to conventional groundwater halogenated hydrocarbon remediation technologies.

Key words: groundwater contamination, halogenated hydrocarbon contamination, persulfate-based advanced oxidation process, free radicals, non-free radical pathways, catalysts

中图分类号:

何弈雪, 秦先超, 马伟芳. 过硫酸盐高级氧化原位修复地下水中卤代烃污染研究进展[J]. 化工进展, 2024, 43(7): 4072-4088.

HE Yixue, QIN Xianchao, MA Weifang. Research progress on in situ remediation of halogenated hydrocarbon contamination in groundwater by persulfate-based advanced oxidation process[J]. Chemical Industry and Engineering Progress, 2024, 43(7): 4072-4088.

图/表 8

表1 两类非水相液体对比表

类型	相对密度	主要迁移运动	主要存在区域	常见有机物
LNAPLs	>1.0	垂向迁移	包气带	苯、甲苯、原油、汽油、柴油、煤油、热煤油、一氟代烷烃、一氯代烷烃等
DNAPLs	<S1.0	水平迁移	包气带、地下水层	氯代溶剂、煤焦油、重矿物油、杂酚油、多环芳烃、多氯联苯等

表2 两类非水相液体各相存在特征表

相态	LNAPLs	DNAPLs
自由相	（1）受重力、毛细作用垂直迁移；（2）在水力梯度下水平运移；（3）受水力梯度影响更大；（4）主要污染源	（1）受重力、毛细作用垂直迁移；（2）在水力梯度下水平运移；（3）主要污染源
残留相	（1）残留于运移路径；（2）受吸附和毛细作用以薄膜或液滴赋存于孔隙，难以在重力作用下继续迁移	（1）残留于运移路径；（2）受吸附和毛细作用以薄膜或液滴赋存于孔隙，难以在重力作用下继续迁移；（3）可在雨水冲刷或外力作用下垂向迁移
气相	极少量LNAPLs卤代烃挥发进入地下水，并在浓度梯度下迁移形成污染羽	（1）一些DNAPLs卤代烃挥发进入地下水，并在浓度梯度下迁移形成污染羽；（2）包气带中的气相卤代烃，可在雨水冲刷或外力作用下垂向迁移
溶解相	（1）溶于地下水并随地下水流动形成污染羽；（2）泄漏量足够大时，部分能够缓慢向下迁移到达地下水层，积聚后向周边水平运移	（1）溶于地下水并随地下水流动形成污染羽；（2）缓慢向下迁移，到达低渗层后，少量垂直迁移，大部分积聚后向周边水平运移

图1 近十年全国155个地下水卤代烃污染场地占比示意图

图2 近十年全国155个地下水卤代烃污染场地卤代烃检出频次图（前15种）

图3 卤代烃污染途径示意图

图4 活化过硫酸盐氧化降解卤代烃机理图

表3 不同方式活化过硫酸盐降解卤代烃总结表

污染物种类及浓度	催化剂种类及浓度	氧化剂种类及浓度	反应条件			反应活性物种	污染物降解率/%	参考文献
污染物种类及浓度	催化剂种类及浓度	氧化剂种类及浓度	时间	温度	pH	反应活性物种	污染物降解率/%	参考文献
TCE，0.15mmol/L	螯合Fe²⁺，0.3mmol/L	未区分，2.25mmol/L	3h	20℃	3	·SO $4 -$ 、·OH	97.5	[74]
氯苯，300mg/L	nZVI，6g/L	PDS，6g/L	20h	(20.5±4)℃	6.5	·SO $4 -$	>97	[73]
TCE，9.4mmol/L	nZVI，376mmol/L	PDS，376mmol/L	16h	(20.5±4)℃	6.5	·SO $4 -$ 、Fe⁰	96.3	[73]
TCE，0.1mmol/L	CuO，0.1g/L	PDS，2.5mmol/L	3h	25℃	11	PDS（电子转移）	57.42	[38]
TCE，5μmol/L	CuO，200mg/L	PDS，40μmol/L	40min	20℃	5.8	未提及	约66	[39]
三氯乙烷，0.15mmol/L	CuO，0.2g/L	PMS，0.4mmol/L	2h	25℃	7	·SO $4 -$ 、·OH、metal-PMS表面配合物	43	[78]
	Co₃O₄，0.2g/L	PMS，0.4mmol/L			7		47
	片状CuO，0.25g/L	PMS，0.5mmol/L			5		97.5
TCE，20mg/L	S-Fe₂MnO₄，0.2g/L	PMS，0.2g/L	10min	—	7.2	·SO $4 -$ 、·OH、•O $2 -$ 、¹O₂、 metal-PMS表面配合物	92.4	[63]
TCE，0.15mmol/L	负载生物炭的nZVI，5mmol/L	PDS，4.5mmol/L	5min	25℃	6.2	·SO $4 -$ 、·OH	100	[72]
TCE，0.16mmol/L	负载沸石的nZVI，84mg/L	PDS，1.5mmol/L	2h	(22±2)℃	7	·SO $4 -$ 、·OH	98.8	[82]

表3 不同方式活化过硫酸盐降解卤代烃总结表

污染物种类及浓度	催化剂种类及浓度	氧化剂种类及浓度	反应条件			反应活性物种	污染物降解率/%	参考文献
污染物种类及浓度	催化剂种类及浓度	氧化剂种类及浓度	时间	温度	pH	反应活性物种	污染物降解率/%	参考文献
TCE，0.15mmol/L	螯合Fe²⁺，0.3mmol/L	未区分，2.25mmol/L	3h	20℃	3	·SO $4 -$ 、·OH	97.5	[74]
氯苯，300mg/L	nZVI，6g/L	PDS，6g/L	20h	(20.5±4)℃	6.5	·SO $4 -$	>97	[73]
TCE，9.4mmol/L	nZVI，376mmol/L	PDS，376mmol/L	16h	(20.5±4)℃	6.5	·SO $4 -$ 、Fe⁰	96.3	[73]
TCE，0.1mmol/L	CuO，0.1g/L	PDS，2.5mmol/L	3h	25℃	11	PDS（电子转移）	57.42	[38]
TCE，5μmol/L	CuO，200mg/L	PDS，40μmol/L	40min	20℃	5.8	未提及	约66	[39]
三氯乙烷，0.15mmol/L	CuO，0.2g/L	PMS，0.4mmol/L	2h	25℃	7	·SO $4 -$ 、·OH、metal-PMS表面配合物	43	[78]
	Co₃O₄，0.2g/L	PMS，0.4mmol/L			7		47
	片状CuO，0.25g/L	PMS，0.5mmol/L			5		97.5
TCE，20mg/L	S-Fe₂MnO₄，0.2g/L	PMS，0.2g/L	10min	—	7.2	·SO $4 -$ 、·OH、•O $2 -$ 、¹O₂、 metal-PMS表面配合物	92.4	[63]
TCE，0.15mmol/L	负载生物炭的nZVI，5mmol/L	PDS，4.5mmol/L	5min	25℃	6.2	·SO $4 -$ 、·OH	100	[72]
TCE，0.16mmol/L	负载沸石的nZVI，84mg/L	PDS，1.5mmol/L	2h	(22±2)℃	7	·SO $4 -$ 、·OH	98.8	[82]

表4 不同反应条件下初始pH对反应结果的影响及原因表

卤代烃种类	活化方式 /催化剂类型	反应时间 /min	反应结果	原因	参考文献
TCE	螯合-Fe(Ⅱ)	180	当pH从3增加至11时，TCE降解率从97.5%逐步下降至40.3%	①pH升高，·OH占主导地位，反应活性降低； ②pH升高，螯合-Fe(Ⅱ)形态变得更加稳定，活性降低； ③pH升高,螯合-Fe(Ⅱ)生成沉淀	[74]
TCE	天然沸石负载nZVI	120	①pH为4和7时降解率几乎达到100%； ②pH为10时降解率下降至77.5%	①pH升高，·OH占主导地位，反应活性降低； ②pH升高，nZVI生成铁氧化物、氢氧化铁和氢氧化亚铁，活性降低	[82]
TCE	生物炭负载S-FeNi	60	反应降解率为pH 9.2（57.2%）<pH 7.2（75.3%）<pH 6.39（82.4%）<pH 5.2（88.6%）<pH 3.2（98.4%）	①pH升高，·OH占主导地位，反应活性降低； ②pH升高，S-FeNi@BC中的Fe（Ⅱ）释放量减少； ③pH升高，催化剂生成Fe（Ⅲ）沉淀； ④pH升高，S-FeNi@BC表面发生钝化	[77]
三氯乙烷（TCA）	（片状）Sh-CuO	120	①pH为3、4、9、11时降解率均低于80%； ②pH为5、7、8时降解率大于80%，且pH=5时达到最大降解率，为92.1%	①pH升高，·OH占主导地位，反应活性降低； ②pH升高，Sh-CuO结构变得更加稳定，活性降低； ③pH为3、4时，加剧了Sh-CuO的腐蚀	[78]
1,2-二氯乙烷（1,2-DCA）	碱活化	120	①pH为10和11时降解率低于采用未活化的PS参与反应时的降解率； ②pH为12和13时降解率几乎达到100%	①pH为10和11时，·OH占主导地位，反应活性降低； ②高pH下碱活化产生·OH和·SO₄^-以外的活性氧化剂	[97]
四氯乙烯（PCE）	Fe(Ⅱ)	30	①pH为3时降解率最高，为97.6%； ②pH为6.25~11时，降解率从80.4%下降至2.1%	①pH升高，·OH占主导地位，反应活性降低； ②pH升高，Fe(Ⅱ)生成铁氧化物、氢氧化铁和氢氧化亚铁，活性降低	[98]

表4 不同反应条件下初始pH对反应结果的影响及原因表

卤代烃种类	活化方式 /催化剂类型	反应时间 /min	反应结果	原因	参考文献
TCE	螯合-Fe(Ⅱ)	180	当pH从3增加至11时，TCE降解率从97.5%逐步下降至40.3%	①pH升高，·OH占主导地位，反应活性降低； ②pH升高，螯合-Fe(Ⅱ)形态变得更加稳定，活性降低； ③pH升高,螯合-Fe(Ⅱ)生成沉淀	[74]
TCE	天然沸石负载nZVI	120	①pH为4和7时降解率几乎达到100%； ②pH为10时降解率下降至77.5%	①pH升高，·OH占主导地位，反应活性降低； ②pH升高，nZVI生成铁氧化物、氢氧化铁和氢氧化亚铁，活性降低	[82]
TCE	生物炭负载S-FeNi	60	反应降解率为pH 9.2（57.2%）<pH 7.2（75.3%）<pH 6.39（82.4%）<pH 5.2（88.6%）<pH 3.2（98.4%）	①pH升高，·OH占主导地位，反应活性降低； ②pH升高，S-FeNi@BC中的Fe（Ⅱ）释放量减少； ③pH升高，催化剂生成Fe（Ⅲ）沉淀； ④pH升高，S-FeNi@BC表面发生钝化	[77]
三氯乙烷（TCA）	（片状）Sh-CuO	120	①pH为3、4、9、11时降解率均低于80%； ②pH为5、7、8时降解率大于80%，且pH=5时达到最大降解率，为92.1%	①pH升高，·OH占主导地位，反应活性降低； ②pH升高，Sh-CuO结构变得更加稳定，活性降低； ③pH为3、4时，加剧了Sh-CuO的腐蚀	[78]
1,2-二氯乙烷（1,2-DCA）	碱活化	120	①pH为10和11时降解率低于采用未活化的PS参与反应时的降解率； ②pH为12和13时降解率几乎达到100%	①pH为10和11时，·OH占主导地位，反应活性降低； ②高pH下碱活化产生·OH和·SO₄^-以外的活性氧化剂	[97]
四氯乙烯（PCE）	Fe(Ⅱ)	30	①pH为3时降解率最高，为97.6%； ②pH为6.25~11时，降解率从80.4%下降至2.1%	①pH升高，·OH占主导地位，反应活性降低； ②pH升高，Fe(Ⅱ)生成铁氧化物、氢氧化铁和氢氧化亚铁，活性降低	[98]

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