化学氧化技术异位处理地下水非水相有机污染物中试研究

doi:10.19657/j.geoscience.1000-8527.2019.02.17

摘要/Abstract

摘要：

选取某农药厂旧厂区为试验场地,考察化学氧化技术异位处理地下水非水相有机污染物的运行效果。基于小试研究,确定高锰酸钾、高铁酸钾、芬顿试剂以及次氯酸钠4种氧化剂在中试试验中的适宜投加量。中试结果表明,当进水流量为1.0 m³/h时,不同氧化剂对于常规水质指标及特征有机污染物的去除效果存在差异性。总体而言,四种氧化剂对于中长链石油烃类污染物(C₁₀—C₃₆)的去除率可达20%~70%,但对氯代烷烃类污染物的去除效果低于20%;高铁酸钾和次氯酸钠分别对于苯酚类和多环芳烃类污染物的去除效果较好(70%~100%);芬顿试剂对各类污染物均有显著氧化效果,其中对于短链石油烃(C₆—C₉,去除率20%~40%)、苯系物(去除率40%~90%)的去除效果高于其他三种氧化剂。研究不同氧化剂对于多组分有机污染地下水的处理效果,为将化学氧化技术应用于此类污染场地提供了理论和技术支持。

关键词: 化学氧化, 地下水处理, 非水相有机污染物

Abstract:

In this study, a former pesticide plant was selected to test the performance of the ex-situ chemical oxidation technology in eliminating non-aqueous organic contaminants from groundwater. Through laboratory-based experiment, the appropriate dosage of the four oxidants (i.e., potassium permanganate, potassium ferrate, Fenton’s reagent, and sodium hypochlorite) for the pilot-scale study were determined. The results (flow rate: 1.0 m³/h) show distinct variations in removal efficiency of the different oxidants on conventional pollutants and target organic pollutants. In general, the removal efficiency of the four oxidants for medium-and long-chain petroleum hydrocarbons (C₁₀-C₃₆) can reach 20% to 70%, while removal performance is poor (<20%) on chlorinated alkane pollutants. Potassium ferrate and sodium hypochlorite achieved better removal efficiency for phenolic compounds and PAHs (70%-100%); Fenton’s reagent has significant oxidation effects on most pollutants, among which the removal efficiency on short-chain petroleum hydrocarbons (C₆-C₉, 20%-40%), as well as benzene, toluene, ethylbenzene, o-and p-xylene (BTEX) (40%-90%) is higher than that of the other three oxidants. Our finding is useful to the application of chemical oxidation technology on similar contaminated sites.

Key words: chemical oxidation, groundwater treatment, non-aqueous phase liquid

中图分类号:

P641

盛益之, 张旭, 翟晓波, 李广贺. 化学氧化技术异位处理地下水非水相有机污染物中试研究[J]. 现代地质, 2019, 33(02): 422-430.

SHENG Yizhi, ZHANG Xu, ZHAI Xiaobo, LI Guanghe. Ex-situ Chemical Oxidation Treatment for Non-aqueous Liquid Contaminated Groundwater: A Pilot Study[J]. Geoscience, 2019, 33(02): 422-430.

图/表 8

图1 化学氧化中试装置设备图

Fig.1 Photograph and configuration of pilot-scale chemical oxidation equipment

表1 污染场地地下水水质特征

Table 1 Characteristics of groundwater quality at the contaminated site

测试指标	检出值(检出率/%)	测试指标
pH	8.55±0.17 (100)	苯/(μg/L)	2.68±0.71 (77)
SS/(mg/L)	224.83±47.97 (100)	甲苯/(μg/L)	3.73±2.10 (77)
浊度/(NTU)	159.20±47.65 (100)	乙苯/(μg/L)	0.16±0.03 (46)
COD/(mg/L)	155.44±30.33 (100)	二甲苯/(μg/L)	0.23±0.04 (62)
BOD/(mg/L)	10.60±9.71 (100)	1,2-二氯乙烷/(μg/L)	17.58±4.26 (100)
总磷/(mg/L)	4.05±0.80 (100)	2-甲基苯酚/(μg/L)	2.75±1.36 (54)
总氮/(mg/L)	18.39±2.62 (100)	3,4-甲基苯酚/(μg/L)	2.27±0.46 (77)
氨氮/(mg/L)	8.43±0.82 (100)	萘/(μg/L)	75.33±60.50 (77)
C₆—C₉/(μg/L)	28.94±9.50 (100)	2-甲基萘/(μg/L)	302.27±257.31 (62)
C₁₀—C₁₄/(μg/L)	695.73±231.20 (100)	芴/(μg/L)	1.38±0.44 (85)
C₁₅—C₂₈/(μg/L)	397.60±48.58 (100)	菲/(μg/L)	1.10±0.05 (31)
C₂₉—C₃₆/(μg/L)	66.83±20.23 (83)	邻苯二甲酸二甲酯/(μg/L)	23.54±15.65 (31)

表2 污染场地地下水特征有机污染物现状评价

Table 2 Groundwater quality assessment of the targeted organic contaminants at the contaminated site

指标	Ⅲ类标准	荷兰干涉值	新泽西州标准	超标率/%	最大超标倍数
总石油烃/(μg/L)		600		69.2	7.2
苯/(μg/L)	10	30		23.1	11.7
甲苯/(μg/L)	700	1 000		0
乙苯/(μg/L)	300	150		0
二甲苯/(μg/L)	500	70		0
1,2-二氯乙烷/(μg/L)	30			23.1	1.4
苯酚/(μg/L)		2 000		0
3,4-甲基苯酚/(μg/L)			70	0
萘/(μg/L)	100		100	15.4	5.6
2-甲基萘/(μg/L)			30	30.1	48.3
芴/(μg/L)			280	0
菲/(μg/L)		5		0
邻苯二甲酸二甲酯/(μg/L)			6	0

图2 场地地下水UV254值与不同氧化剂反应条件下的变化 (a)高锰酸钾;(b)高铁酸铁;(c)芬顿;(d)次氯酸钠

Fig.2 Change of onsite groundwater UV254 value under the reaction with different oxidants

表3 常见氧化剂在地下水环境中的标准电极电势[8, 15-16]

Table 3 Standard electrode potential of common oxidants in groundwater environment

氧化剂	反应方程	标准电极电势/V
高锰酸盐	$MnO 4 -$ + 2H₂O + 3e → MnO₂ + 4OH^-(碱性条件)	0.59
高铁酸盐	$FeO 4 2 -$ + 4H₂O + 3e → Fe(OH)₃ + 5OH^- ( 碱性条件)	0.70
过氧化氢	$HO 2 -$ + 2e+ H₂O → 3OH^-(碱性条件)	0.88
次氯酸盐	ClO^- + H₂O + 2e → Cl^- + 2OH^-	0.90

表3 常见氧化剂在地下水环境中的标准电极电势[8, 15-16]

Table 3 Standard electrode potential of common oxidants in groundwater environment

氧化剂	反应方程	标准电极电势/V
高锰酸盐	$MnO 4 -$ + 2H₂O + 3e → MnO₂ + 4OH^-(碱性条件)	0.59
高铁酸盐	$FeO 4 2 -$ + 4H₂O + 3e → Fe(OH)₃ + 5OH^- ( 碱性条件)	0.70
过氧化氢	$HO 2 -$ + 2e+ H₂O → 3OH^-(碱性条件)	0.88
次氯酸盐	ClO^- + H₂O + 2e → Cl^- + 2OH^-	0.90

图3 不同氧化剂对地下水常规水质指标的去除效果

Fig.3 Removal efficiency of conventional water quality indies using different oxidants for onsite groundwater treatment

图4 不同氧化剂对场地地下水总石油烃类污染物的去除效果 (a)C6—C9;(b)C10—C14;(c)C15—C28;(d)C29—C36

Fig.4 Removal efficiency of petroleum hydrocarbons using different oxidants for onsite groundwater treatment

图5 不同氧化剂对场地地下水特征NAPLs类污染物的去除效果

Fig.5 Removal efficiency of target NAPLs using different oxidants for onsite groundwater treatment

参考文献 32

[1]	HOU Y, ZHANG T Z. Evaluation of major polluting accidents in China—Results and perspectives[J]. Journal of Hazardous Materials, 2009,168(2/3):670-673. DOI URL
[2]	XUE P, ZENG W. Trends of environmental accidents and impact factors in China[J]. Frontiers of Environmental Science & Engineering in China, 2011,5(2):266-276.
[3]	YAO H, ZHANG T, LIU B, et al. Analysis of surface water pollution accidents in China: characteristics and lessons for risk management[J]. Environmental Management, 2016,57(4):868-878. URL PMID
[4]	SHENG Y, TIAN X, WANG G, et al. Bacterial diversity and biogeochemical processes of oil-contaminated groundwater, Bao-ding, North China[J]. Geomicrobiology, 2016,33(6):537-551.
[5]	ZHANG Q, WANG G, SUGIURA N, et al. Distribution of petroleum hydrocarbons in soils and the underlying unsaturated subsurface at an abandoned petrochemical site, North China[J]. Hydrological Processes, 2013,28(4):2185-2191. DOI URL
[6]	王平, 黄爽兵, 韩占涛, 等. 基于溶质运移模拟的某化工场地污染物对拟建水库污染风险预测[J]. 现代地质, 2015,29(2):307-315.
[7]	张丹, 张旭, 李广贺, 等. Fenton试剂快速氧化处理事故场地地下水中的硝基苯[J]. 环境工程学报, 2016,10(7):3439-3444.
[8]	NYER E K. Groundwater Treatment Technology[M]. 3rd ed. New York:Van Nostrand Reinhold, 2009: 104-119.
[9]	蔡婧怡, 陈宗宇, 蔡五田, 等. 某石化污染场地含水层自然降解BTEX能力评估[J]. 现代地质, 2015,29(2):383-389.
[10]	翟晓波, 盛益之, 张旭, 等. 混凝-气浮工艺处理有机物污染地下水现场中试试验[J]. 化工环保, 2018,38(1):33-39.
[11]	HE L, HUANG G H, ZENG G M, et al. An integrated simulation, inference, and optimization method for identifying groundwater remediation strategies at petroleum-contaminated aquifers in western Canada[J]. Water Research, 2008,42(10/11):2629-2639. DOI URL
[12]	TRUEX M, JOHNSON C, MACBETH T, et al. Performance assessment of pump-and-treat systems[J]. Ground Water Monitoring and Remediation, 2017,37(3):28-44. DOI URL
[13]	MACKAY D, MCHERRY J A. Groundwater contamination: pump-and-treat remediation[J]. Environmental Science & Technology, 1989,23(6):630-636. DOI URL
[14]	万鹏, 张旭, 李广贺, 等. 基于模拟-优化模型的某场地污染地下水抽水方案设计[J]. 环境科学研究, 2016,29(11):1608-1616.
[15]	TSAI T T, KAO C M, YEH T Y, et al. Chemical oxidation of chlorinated solvents in contaminated groundwater: review[J]. Practice Periodical of Hazardous Toxic & Radioactive Waste Mana-gement, 2008,12(12):116-126.
[16]	王东升, 李文涛, 杨晓芳, 等. 高铁酸盐: 一种绿色的多功能水处理剂[J]. 应用化学, 2016,33(11):1221-1233.
[17]	尹贞, 廖书林, 马强, 等. 化学氧化技术在地下水修复中的应用[J]. 环境工程学报, 2015,9(10):4910-4914.
[18]	田璐, 杨琦, 尚海涛. 高锰酸钾降解地下水中PCE的研究[J]. 环境工程学报, 2009,3(8):1355-1359.
[19]	JOUSSE E, ATTEIA O, HOHENER P, et al. Removal of NAPL from columns by oxidation, sparging, surfactant and thermal treatment[J]. Chemosphere, 2017,188:182-189. DOI URL PMID
[20]	国家环境保护总局. 水和废水监测分析方法[M].4版. 北京: 中国环境科学出版社, 2002: 1-295.
[21]	BROWN D G, GUPTA L, KIM T H, et al. Comparative assessment of coal tars obtained from 10 former manufactured gas plant sites in the Eastern United States[J]. Chemosphere, 2006,65(9):1562-1569. DOI URL PMID
[22]	COULON F, ORSI R, TURNER C, et al. Understanding the fate and transport of petroleum hydrocarbons from coal tar within Gasholders[J]. Environment International, 2009,35(2):248-252. URL PMID
[23]	VROM. Circular Values and Intervention Values for Soil Remediation Annex A: Target Values, Soil Remediation Intervention Values and Indictive Levels for Serious Contamination[M]. Amster dam: Ministry of Housing, Spatial Planning and Environment (VROM), 2010.
[24]	NJDEP. Ground Water Quality Standards Class II-A[S]. Trenton:New Jersey Department of Environmental Protection, 2018.
[25]	盛益之, 王广才, 张琦伟, 等. 某污染场地周边地下水环境质量评价[J]. 现代地质, 2012,26(3):601-606.
[26]	金伟, 范瑾初. 紫外吸光值(UV_(254))作为有机物替代参数的探讨[J]. 工业水处理, 1997,17(6):30-32. DOI URL
[27]	BOONRATTANAKIJ N, LU M, CANOTAI J. Iron crystallization in a fluidized-bed Fenton process[J]. Water Research, 2011,45(10):3255-3262. URL PMID
[28]	吴建新. 高铁酸盐处理制药废水的试验研究[J]. 中国给水排水, 2010,26(15):79-81.
[29]	周建红, 李军, 令玉林, 等. 高铁酸钾和次氯酸钠联用处理苯酚废水研究[J]. 工业水处理, 2013,33(10):27-29.
[30]	杨涛. 高锰酸钾、次氯酸钠复合预氧化与常规处理工艺联用处理微污染水源水的中试研究[J]. 辽宁化工, 2006,35(4):217-218.
[31]	赵丹, 阎秀兰, 廖晓勇, 等. 不同化学氧化剂对焦化污染场地苯系物的修复效果[J]. 环境科学, 2011,32(3):849-856.
[32]	BERGENDAHL J, HUBBARD S, GRASSO D. Pilot-scale Fenton’s oxidation of organic contaminants in groundwater using autochthonous iron[J]. Journal of Hazardous Materials, 2003,99(1):43-56. DOI URL PMID