石油污染场地地下水异位修复短程处理工艺

doi:10.16085/j.issn.1000-6613.2025-0266

化工进展 ›› 2025, Vol. 44 ›› Issue (9): 5491-5502.DOI: 10.16085/j.issn.1000-6613.2025-0266

• 资源与环境化工 • 上一篇

石油污染场地地下水异位修复短程处理工艺

王浩¹^,²(), 李梦琪³, 王庆吉²(), 王凌匀⁴, 罗臻², 宋权威², 李兴春², 何绪文³

^1.北京大学环境科学与工程学院，北京 100871
^2.中国石油集团安全环保技术研究院有限公司，北京 102206
^3.中国矿业大学(北京)化学与环境工程学院，北京 100083
^4.长庆油田质量健康安全环保部，陕西西安 710018

收稿日期:2025-03-10 修回日期:2025-04-19 出版日期:2025-09-25 发布日期:2025-09-30
通讯作者: 王庆吉
作者简介:王浩（1991— ），男，博士，工程师，研究方向为水污染控制工程。E-mail：hao.wang@pku.edu.cn。
基金资助:
中国石油集团直属院所基础科学研究和战略储备技术研究基金(2022DQ03-A4);中国石油天然气股分有限公司基础前瞻性科技专项(2023ZZ1305)

Short-process treatment technology for ex-situ remediation of groundwater in oil-contaminated sites

WANG Hao¹^,²(), LI Mengqi³, WANG Qingji²(), WANG Lingyun⁴, LUO Zhen², SONG Quanwei², LI Xingchun², HE Xuwen³

^1.College of Environmental Sciences and Engineering, Peking University, Beijing 100871, China
^2.CNPC Research Institute of Safety and Environmental Technology, Beijing 102206, China
^3.School of Chemical and Environmental Engineering, China University of Mining & Technology-Beijing, Beijing 100083, China
^4.Quality, Health, Safety and Environmental Protection Department of Changqing Oilfield Company, Xi’an 710018, Shaanxi, China

Received:2025-03-10 Revised:2025-04-19 Online:2025-09-25 Published:2025-09-30
Contact: WANG Qingji

摘要/Abstract

摘要：

石油污染场地地下水污染物成分复杂，毒性大，水质水量波动大，且具有含油含浊、高盐高有机负荷的特点，宜采用抽出-处理模式进行污染地下水异位修复。本研究采用耐油抗污染膜材料直接过滤技术耦合臭氧催化氧化技术对污染地下水进行修复，结果表明耦合工艺能有效降低水中的有机物含量。当超滤膜和纳滤膜的运行压力分别为0.2MPa和0.7MPa、臭氧投加量和催化剂投加量分别为50mg/L和300g/L时，出水化学需氧量（COD）降低至200mg/L以下，COD去除率达到96%以上，可满足污染地下水的修复要求。污染的膜材料通过热碱洗方式进行清洗，膜通量恢复率达到96%以上。膜过滤预处理优先去除油类及大分子有机物，为臭氧氧化阶段减轻了污染负荷，减少了臭氧消耗，臭氧氧化阶段深度降解膜过滤阶段残留的溶解性有机物，提高了污染物总体去除率，两种技术达到了良好的协同作用，形成了无二次污染的地下水异位修复绿色短程处理技术。

关键词: 石油污染场地, 地下水, 抽出-处理, 抗污染膜, 臭氧催化氧化, 短程处理

Abstract:

The composition of groundwater pollutants in petroleum-contaminated sites is complex, exhibiting high toxicity and significant fluctuations in water quality and quantity. These sites are characterized by oil and turbidity, as well as high salinity and organic load, making implementing an extraction-treatment model for the ex-situ remediation of contaminated groundwater advisable. This study employed an oil-resistant, pollution-resistant membrane filtration technology in conjunction with catalytic ozonation to remediate contaminated groundwater. When the operating pressures of the UF membrane and NF membrane were 0.2MPa and 0.7MPa, respectively, with ozone dosage and catalyst dosage at 50mg/L and 300g/L, the effluent COD was reduced to below 200mg/L. The COD removal rate reached over 96%, meeting the remediation requirements for contaminated groundwater. The polluted membrane materials were cleaned using a thermal-alkaline washing method, resulting in a membrane flux recovery rate of over 96%. The membrane filtration pretreatment preferentially removed oils and macromolecular organic matter, effectively reducing the pollutant load and ozone consumption during the subsequent ozonation stage. The ozonation process further degraded residual soluble organic compounds remaining from the membrane filtration phase, thereby enhancing the overall pollutant removal efficiency. These two technologies demonstrate excellent synergistic effects, ultimately forming an environmentally friendly short-process ex-situ groundwater remediation system that generates no secondary pollution.

Key words: oil contaminated site, groundwater, extraction-treatment, anti-fouling membrane, catalytic ozonation, short-process treatment

中图分类号:

X703.1

王浩, 李梦琪, 王庆吉, 王凌匀, 罗臻, 宋权威, 李兴春, 何绪文. 石油污染场地地下水异位修复短程处理工艺[J]. 化工进展, 2025, 44(9): 5491-5502.

WANG Hao, LI Mengqi, WANG Qingji, WANG Lingyun, LUO Zhen, SONG Quanwei, LI Xingchun, HE Xuwen. Short-process treatment technology for ex-situ remediation of groundwater in oil-contaminated sites[J]. Chemical Industry and Engineering Progress, 2025, 44(9): 5491-5502.

图/表 18

表1 石油污染场地地下水水质

项目	数据
pH	7.1~8.9
浊度/NTU	190~320
含油量/mg·L^-1	20~200
COD/mg·L^-1	2100~4900
DOC/mg·L^-1	420~1800
电导率/mS·cm^-1	70~90

表2 膜材料具体性能参数

项目	Titan-UF-70	Titan-NF-500
形状	平板膜	平板膜
截留分子量	70kDa	500Da
运行pH范围	1~13.5	1~13.5
最大含油浓度	≤10000mg/L	—

图1 不同压力下UF膜、NF膜超纯水通量变化

图2 臭氧催化氧化反应装置

图3 不同压力条件下膜通量及膜比通量变化

图4 不同pH条件对膜过滤除油效果的影响

图5 连续运行时UF膜、NF膜产水含油量与COD变化

表3 膜污堵模型

n	膜污堵模型	线性公式
0	滤饼层污堵	$J s - 1 = 1 + K v V s$
1.0	中间污堵	$(l n J s) 0.5 = - K v V s$
1.5	标准污堵	$J s 0.5 = 1 +$ $K v$ / $2 V s$
2.0	完全污堵	$J s = 1 - K v V s$

表3 膜污堵模型

n	膜污堵模型	线性公式
0	滤饼层污堵	$J s - 1 = 1 + K v V s$
1.0	中间污堵	$(l n J s) 0.5 = - K v V s$
1.5	标准污堵	$J s 0.5 = 1 +$ $K v$ / $2 V s$
2.0	完全污堵	$J s = 1 - K v V s$

图6 UF膜污染模型拟合

图7 NF膜污染模型拟合

图8 UF膜、NF膜通量恢复情况

图9 UF膜表面扫描电镜图

图10 NF膜表面扫描电镜图

图11 不同臭氧氧化体系对COD和DOC的去除效果（图中柱状表示污染物含量，曲线表示污染物去除率）

图12 臭氧催化氧化工艺不同运行参数对污染物去除性能的影响（图中柱状表示污染物含量，曲线表示污染物去除率）

图13 石油污染地下水中各有机组分占比

图14 不同工艺对各有机组分的去除情况

图15 污染地下水不同处理阶段的紫外-可见分光光谱

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石油污染场地地下水异位修复短程处理工艺

Short-process treatment technology for ex-situ remediation of groundwater in oil-contaminated sites

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