我国污染场地化学氧化修复技术应用特征及再利用潜在腐蚀风险分析

王珍霞; 宋久浩; 苑文仪; 李翔; 吴乃瑾; 李艺; 李培中

doi:10.13198/j.issn.1001-6929.2022.03.10

我国污染场地化学氧化修复技术应用特征及再利用潜在腐蚀风险分析

doi: 10.13198/j.issn.1001-6929.2022.03.10

王珍霞^{1, 2,},
宋久浩^{2, 3},
苑文仪¹,
李翔^{2, 3},
吴乃瑾^{2, 3},
李艺^{2, 3},
李培中^{2, 3, ,}

1.
上海第二工业大学资源与环境工程学院，上海　201209
2.
北京市科学技术研究院资源环境研究所，北京　100095
3.
工业场地污染与修复北京市重点实验室，北京　100095

基金项目: 国家重点研发计划项目(No.2018YFC1801400)；国家自然科学基金项目(No.41907159)

详细信息

作者简介:
王珍霞（1997-），女，江苏盐城人，zhenxia_wang@126.com

通讯作者:
李培中(1982-)，男，安徽临泉人，副研究员，博士，主要从事场地污染调查与修复研究，liepi_li@163.com

中图分类号: X53
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- 文章访问数: 456
- HTML全文浏览量: 81
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- 被引次数: 0
出版历程
- 收稿日期: 2021-10-29
- 修回日期: 2022-01-25
- 网络出版日期: 2022-05-17

Application Characteristics and Potential Corrosion Risks of Chemical Oxidation Remediation Technology for Contaminated Sites in China

WANG Zhenxia^{1, 2
,},
SONG Jiuhao^{2, 3},
YUAN Wenyi¹,
LI Xiang^{2, 3},
WU Naijin^{2, 3},
LI Yi^{2, 3},
LI Peizhong^{2, 3
, ,}

1.
School of Resources and Environmental Engineering, Shanghai Polytechnic University, Shanghai 201209, China
2.
Institute of Resource and Environment, Beijing Academy of Science and Technology, Beijing 100095, China
3.
Beijing Key Lab of Industrial Land Contamination and Remediation, Beijing 100095, China

Funds: National Key Research and Development Program of China (No.2018YFC1801400)；National Natural Science Foundation of China (No.41907159)

摘要

摘要: 化学氧化修复技术在国内有机污染场地修复中所占比例逐年快速增加，但是残留氧化剂、副产物等产生的再利用潜在腐蚀风险问题也引起了研究人员的关注. 首先，通过实际调研和网络检索对国内137个实际修复案例进行研究分析，总结出我国化学氧化法修复技术应用的4个主要特征，包括主要应用于中小型污染地块、水土协同修复且介质复杂、过硫酸盐占比过大且副产物较多、修复周期短且修复药剂过量现象严重；然后，针对应用最多的过硫酸盐氧化法修复技术，通过资料文献分析和国内外案例场地调研信息，梳理出修复后场地再利用过程中可能产生的残留氧化剂腐蚀、副产物盐分腐蚀及环境条件变化导致的微生物侵蚀等3种主要的腐蚀风险机理，以及定性及定量的腐蚀风险测试方法；最后，结合化学氧化过程及pH、氧化还原条件、盐分和微生物环境条件等发生短期、中期和长期的影响因素，提出了可将化学氧化修复后潜在腐蚀过程风险划分为三阶段的概念模型，以期为化学氧化修复技术实际应用及效果评估提供参考.
- 污染场地 /
- 化学氧化 /
- 过硫酸盐 /
- 环境残留 /
- 腐蚀风险
Abstract: The proportion of chemical oxidation in the remediation of organically contaminated sites has increased rapidly in China, but the potential corrosion risk of residual oxidants and by-products to land reuse has attracted the attention of researchers. Through the actual investigation and literature research of 137 sites in China, four main characteristics of chemical oxidation remediation technology can be drawn: applications mainly in small and medium-sized contaminated site, soil and water co-remediation and complex remediation media, excessive persulfate application and various by-products, short repair cycle and overload of chemical oxidant. Then, for the most commonly used persulfate oxidation remediation technology, three main potential corrosion mechanisms were analyzed through literature review and field case studies. The residual oxidant corrosion, by-product salt corrosion and microbial erosion can occur during the redevelopment of the remediated sites. The qualitative and quantitative monitoring of corrosion risk was also investigated. Finally, a conceptual model that divides the potential post-remediation corrosion process into 3 different phases was proposed for chemical oxidation by persulfate based on the chemical oxidation process and the key factors in the short-term, mid-term and long-term, including pH, ORP, salt and microbial environmental conditions. This research can provide scientific references for the field application and effect verification of chemical oxidation remediation technology.
- contaminated site /
- chemical oxidation /
- persulfate /
- environmental residual /
- corrosion risk

HTML全文

图 1 我国化学氧化修复技术的工程化应用发展概况

Figure 1. The general situation of engineering application of chemical oxidation remediation technology in China

下载: 全尺寸图片幻灯片

图 2 过硫酸盐在不同环境介质中滞留时间的对比

Figure 2. The comparison of residence time of persulfate in different environmental media

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图 3 某污染场地原位化学氧化后土壤和地下水中硫酸盐浓度的变化情况

Figure 3. The Changes of sulfate concentration in soil and groundwater after in-situ chemical oxidation in a contaminated site

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图 4 不同投加药剂对反应体系pH的影响^[40]

Figure 4. The influence of different agents on pH of reaction system^[40]

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图 5 混凝土腐蚀产物SEM显微图像和腐蚀产物EDX光谱分析^[34,48]

Figure 5. SEM microscopic images of concrete and EDX spectroscopic analysis of corrosion products^[34,48]

下载: 全尺寸图片幻灯片

图 6 金属表面微生物腐蚀的电子传递方式^[59]

注：Med(ox)表示介导的氧化态；Med(red)表示介导的还原态；CytC表示导电蛋白；Pili表示生物导电纳米线；Fe(ox)表示铁的氧化态.

Figure 6. The electron transfer mode of microbial corrosion on the metal surface^[59]

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图 7 不同腐蚀阶段的作用机理及腐蚀速率^[12,34]

Figure 7. The mechanism of action and corrosion rate in different corrosion stages^[12,34]

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表 1 近期国内污染场地的过硫酸盐化学氧化修复应用和pH变化

Table 1. The recent application of persulfate chemical oxidation and change of pH in contaminated sites in China

污染物	药剂及用量	降解效果	土壤环境变化	数据来源
二氯乙烯、氯乙烯	1%过硫酸钠+0.1%氢氧化钠	20 d后达标	pH较高，在11左右	文献[42]
石油烃、苯系物和多环芳烃	4 t过硫酸钠+氢氧化钠	去除率在99.5%以上	pH较高，在10以上，硫酸盐含量升高	文献[43]
苯并[a]芘和二苯并[a,h]蒽	2%过硫酸盐+0.3%硫酸亚铁	6 d后去除率在90%以上	pH为7.8~8.1	文献[44]
1,1-二氯乙烷和三氯甲烷	1.5%过硫酸钠+0.03%氢氧化钠、 4%过硫酸钠+0.05%氢氧化钠	4 h后去除率在98%以上	pH在10左右，硫酸盐含量升高	文献[45]
多环芳烃	2%过硫酸钠+2%生石灰	3 d后达标	硫酸盐和碱使土壤盐碱化，限制绿化用土	文献[46]
多环芳烃	2 mmol/g过硫酸盐+0.2 mmol/g硫酸亚铁	3 d后去除率在90%以上	处理后的土壤pH接近4	文献[47]
石油烃	3%过硫酸盐+4%氧化钙	2 d后去除率达68.7%	CaO会提高反应体系的pH，最大为12.42	文献[40]

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表 2 基于盐分对混凝土侵蚀模拟试验的情况总结

Table 2. The summary of the simulation test of concrete corrosion by salt

试验对象	盐分种类	试验条件	暴露时间	试验结果	数据来源
混凝土	硫酸钠	硫酸钠溶液浓度分别为5%、10%、30%，实验室干湿循环加速试验	120 d	硫酸钠溶液浓度为30%时，试块减重达到180 g	文献[49]
球墨铸铁管	碳酸盐	自然条件下沙质土壤	17 a	HCO₃⁻浓度越高，腐蚀风险概率越大	文献[50]
混凝土建筑	硫酸盐	不同硫酸盐浓度但浓度持续偏高的河流	28 d	SO₄²⁻对不同类型混凝土存在不同程度的损害行为	文献[51]
混凝土	硫酸盐	硫酸钠溶液浓度为5%，实验室干湿循环加速试验	1 522、2 022、 2 572 d	提出了混凝土在微观水平上受到外部硫酸盐侵蚀的化学-力学(C-M)有限元模型	文献[52]
混凝土	硫酸盐	硫酸盐溶液浓度分别为5%、10%，实验室加速试验	800 d	混凝土中的硫酸盐侵蚀由硫酸盐离子和水泥水化产物间的一系列复杂反应形成，使材料内部产生膨胀和微裂纹	文献[53]
混凝土	硫酸盐	硫酸盐溶液浓度分别为0%、2.1%、15%，在干湿循环条件下进行混凝土侵蚀试验	360、720 d	高浓度条件下呈现两阶段演化模型；类场暴露条件下呈现三阶段演化模型	文献[34]
混凝土	硫酸盐、硝酸盐等	0.01 mol/L 硫酸钠+0.01 mol/L 碳酸氢钠和0.01 mol/L氯化钠+0.01 mol/L硝酸钠		阴离子能降低电荷转移电阻，阴离子的腐蚀性表现为SO₄²⁻> HCO₃⁻>NO₃⁻	文献[54]
混凝土	硫酸钠	硫酸钠溶液浓度为10%，室内加速试验	120 d	存在明显质量损失，其范围为6%~23%	文献[48]

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