FeS/过硫酸盐体系元素价态转化及其降解有机物机制

doi:10.16085/j.issn.1000-6613.2019-1605

摘要/Abstract

摘要：

由于FeS表面的还原性Fe(Ⅱ)和S(-Ⅱ)都可以作为电子供体，可有效促进有机化合物的还原转化与过硫酸盐的活化，FeS活化过硫酸盐体系在土壤地下水有机污染原位修复中显示出巨大的应用发展潜力。本文综述了FeS活化过硫酸盐产生活性自由基的内在机理及影响体系反应效率的关键因素；总结了活化过程中FeS表面元素转化机制和转化提高途径；较系统地梳理了FeS活化过硫酸盐体系对卤代烃、石油烃、多环芳烃类复杂有机化合物的降解过程机制。最后对研究中存在的问题及在场地污染修复应用中应重点关注的问题进行了展望，应重视修复中产生的过硫酸根、硫酸根及降解中间产物对环境的影响，在实际应用中需要根据不同的环境条件评估FeS/过硫酸盐体系的有效性，并且制定不同的修复策略。

关键词: 硫化铁, 过硫酸盐, 自由基, 有机污染, 元素价态转化, 场地修复

Abstract:

Since Fe() and S(-Ⅱ) on the surface of FeS can be used as electron donors, it can effectively promote the reduction of organic compounds and the activation of persulfate. FeS activating persulfate shows great potential for application in the in situ remediation of organically polluted soil and groundwater. In this paper, the mechanism of FeS activated persulfate and its surface element conversion mechanism were reviewed. The key factors affecting the reaction efficiency and the ways to improve the reaction efficiency were summarized. Degradation mechanism of complex different types of organic pollutants such as petroleum hydrocarbons, halogenated hydrocarbons and polycyclic aromatic hydrocarbons by FeS/persulfate system was systematically established. Finally, the problems existing in the research and the issues that should be paid attention to in the application of site pollution restoration were prospected. The impacts of persulfate, sulfate and degradation intermediates produced in the restoration should be considered. The effectiveness of the FeS/persulfate system needs to be evaluated for different environmental conditions. And for different conditions, different repair strategies are required.

Key words: ferrous sulfide, persulfate, radicals, organic pollution, surface element valence transition, site remediation

中图分类号:

X131.2

钱思佳, 蒲生彦, 杨顺美. FeS/过硫酸盐体系元素价态转化及其降解有机物机制[J]. 化工进展, 2020, 39(7): 2817-2827.

Sijia QIAN, Shengyan PU, Shunmei YANG. Valence transition of ferrous sulfide/persulfate system and mechanism of degrading different organic species[J]. Chemical Industry and Engineering Progress, 2020, 39(7): 2817-2827.

参考文献

1	DEVI P, DAS U, DALAI A K. In-situ chemical oxidation: principle and applications of peroxide and persulfate treatments in wastewater systems[J]. Science of the Total Environment, 2016, 571: 643-657.
2	TSITONAKI A, PETRI B, CRIMI M, et al. In situ chemical oxidation of contaminated soil and groundwater using persulfate: a review[J]. Critical Reviews in Environmental Science and Technology, 2010, 40(1): 55-91.
3	WALDEMER R H, TRATNYEK P G, JOHNSON R L, et al. Oxidation of chlorinated ethenes by heat-activated persulfate: kinetics and products[J]. Environmental Science & Technology, 2007, 41(3): 1010-1015.
4	YANG Yi, LU Xinglin, JIANG Jin, et al. Degradation of sulfamethoxazole by UV, UV/H₂O₂ and UV/persulfate (PDS): formation of oxidation products and effect of bicarbonate[J]. Water Research, 2017, 118: 196-207.
5	LIU Liyan, YAN Hao, YANG Chao, et al. Dewatering of drilling sludge by ultrasound assisted Fe(Ⅱ)-activated persulfate oxidation[J]. RSC Advances, 2018, 8(52): 29756-29766.
6	占昌朝, 陈义, 严平, 等. 微波促进Fe@MCM-48催化K₂S₂O₈降解甲基橙废水[J]. 环境工程学报, 2015, 9(7): 3134-3140.
6	ZHAN Changchao, CHEN Yi, YAN Ping, et al. Degradation of methyl orange wastewater by microwave assisted catalysis of potassium persulfate with Fe@MCM-48[J]. Chinese Journal of Environmental Engineering, 2015, 9(7): 3134-3140.
7	张忠磊, 陈海, 杨琦, 等. FeS/K₂S₂O₈去除水体系中的2,4-D[J]. 环境工程学报, 2014, 8(11): 4631-4635.
7	ZHANG Zhonglei, CHEN Hai, YANG Qi, et al. Removal of 2,4-dichlorophenoxyacetic acid from water by FeS/K₂S₂O₈[J]. Chinese Journal of Environmental Engineering, 2014, 8(11): 4631-4635.
8	FURMAN O S, TEEL A L, WATTS R J. Mechanism of base activation of persulfate[J]. Environmental Science & Technology, 2010, 44(16): 6423-6428.
9	SOLTANI T, B-K LEE. Enhanced formation of sulfate radicals by metal-doped BiFeO₃under visible light for improving photo-Fenton catalytic degradation of 2-chlorophenol[J]. Chemical Engineering Journal, 2017, 313: 1258-1268.
10	CHEN Xiao, Wenda OH, Teikthye LIM. Graphene- and CNTs-based carbocatalysts in persulfates activation: material design and catalytic mechanisms[J]. Chemical Engineering Journal, 2018, 354: 941-976.
11	RASTOGI A, AL-ABED S R, DIONYSIOU D D. Effect of inorganic, synthetic and naturally occurring chelating agents on Fe(Ⅱ) mediated advanced oxidation of chlorophenols[J]. Water Research, 2009, 43(3): 684-694.
12	YAN Ni, LIU Fei, HUANG Weiying. Interaction of oxidants in siderite catalyzed hydrogen peroxide and persulfate system using trichloroethylene as a target contaminant[J]. Chemical Engineering Journal, 2013, 219: 149-154.
13	JEONG H Y, KIM H, HAYES K F. Reductive dechlorination pathways of tetrachloroethylene and trichloroethylene and subsequent transformation of their dechlorination products by mackinawite (FeS) in the presence of metals[J]. Environmental Science & Technology, 2007, 41(22): 7736-7743.
14	PU Mengjie, MA Yongwen, WAN Jinquan, et al. Fe/S doped granular activated carbon as a highly active heterogeneous persulfate catalyst toward the degradation of Orange G and diethyl phthalate[J]. Journal of Colloid and Interface Science, 2014, 418: 330-337.
15	DONG Haoran, HOU Kunjie, QIAO Weiwei, et al. Insights into enhanced removal of TCE utilizing sulfide-modified nanoscale zero-valent iron activated persulfate[J]. Chemical Engineering Journal, 2019, 359: 1046-1055.
16	S-Y OH, KANG S-G, KIM D-W, et al. Degradation of 2,4-dinitrotoluene by persulfate activated with iron sulfides[J]. Chemical Engineering Journal, 2011, 172(2/3): 641-646.
17	YUAN Yanmei, TAO Hong, FAN Jinhong, et al. Degradation of p-chloroaniline by persulfate activated with ferrous sulfide ore particles[J]. Chemical Engineering Journal, 2015, 268: 38-46.
18	CHEN Hai, ZHANG Zhonglei, FENG Mingbao, et al. Degradation of 2,4-dichlorophenoxyacetic acid in water by persulfate activated with FeS (mackinawite)[J]. Chemical Engineering Journal, 2017, 313: 498-507.
19	WOLTHERS M, GAAST S J VAN DER, RICKARD D. The structure of disordered mackinawite[J]. American Mineralogist, 2003, 88(11/12): 2007-2015.
20	YUAN Songhu, LIAO Peng, ALSHAWABKEH A N. Electrolytic manipulation of persulfate reactivity by iron electrodes for trichloroethylene degradation in groundwater[J]. Environmental Science & Technology, 2014, 48(1): 656-663.
21	GHANBARI F, MORADI M. Application of peroxymonosulfate and its activation methods for degradation of environmental organic pollutants: Review[J]. Chemical Engineering Journal, 2017, 310: 41-62.
22	LIANG Chenju, SU Hsinwey. Identification of sulfate and hydroxyl radicals in thermally activated persulfate[J]. Industrial & Engineering Chemistry Research, 2009, 48(11): 5558-5562.
23	WANG Jianlong, WANG Shizong. Activation of persulfate (PS) and peroxymonosulfate (PMS) and application for the degradation of emerging contaminants[J]. Chemical Engineering Journal, 2018, 334: 1502-1517.
24	Yuchi LEE, Shanglien LO, CHIUEH Peite, et al. Microwave-hydrothermal decomposition of perfluorooctanoic acid in water by iron-activated persulfate oxidation[J]. Water Research, 2010, 44(3): 886-892.
25	WU Xiaoliang, GU Xiaogang, LU Shuguang, et al. Degradation of trichloroethylene in aqueous solution by persulfate activated with citric acid chelated ferrous ion[J]. Chemical Engineering Journal, 2014, 255: 585-592.
26	PENG Hongjiang, ZHANG Wei, LIU Lin, et al. Degradation performance and mechanism of decabromodiphenyl ether (BDE209) by ferrous-activated persulfate in spiked soil[J]. Chemical Engineering Journal, 2017, 307: 750-755.
27	LIU Haizhou, BRUTON T A, LI Wei, et al. Oxidation of benzene by persulfate in the presence of Fe(Ⅲ)- and Mn(Ⅳ)-containing oxides: stoichiometric efficiency and transformation products[J]. Environmental Science & Technology, 2016, 50(2): 890-898.
28	PENG Hongliang, XU Liya, ZHANG Wei, et al. Different kinds of persulfate activation with base for the oxidation and mechanism of BDE209 in a spiked soil system[J]. Science of the Total Environment, 2017, 574: 307-313.
29	YU Sixia, GU Xiaogang, LU Shuguang, et al. Degradation of phenanthrene in aqueous solution by a persulfate/percarbonate system activated with CA chelated-Fe(Ⅱ)[J]. Chemical Engineering Journal, 2018, 333: 122-131.
30	FAN Jinhong, GU Lin, WU Deli, et al. Mackinawite (FeS) activation of persulfate for the degradation of p-chloroaniline: surface reaction mechanism and sulfur-mediated cycling of iron species[J]. Chemical Engineering Journal, 2018, 333: 657-664.
31	LI Jun, WAN Yanjian, LI Yangju, et al. Surface Fe(Ⅲ)/Fe(Ⅱ) cycle promoted the degradation of atrazine by peroxymonosulfate activation in the presence of hydroxylamine[J]. Applied Catalysis B: Environmental, 2019, 256: 127782.
32	WANG Zhen, JIANG Jin, PANG Suyan, et al. Is sulfate radical really generated from peroxydisulfate activated by iron(Ⅱ) for environmental decontamination?[J]. Environmental Science & Technology, 2018, 52(19): 11276-11284.
33	ZHU Changyin, ZHU Fengxiao, LIU Cun, et al. Reductive hexachloroethane degradation by ·S₂O₈^- with thermal activation of persulfate under anaerobic conditions[J]. Environmental Science & Technology, 2018, 52(15): 8548-8557.
34	LIU Haizhou, BRUTON T A, DOYLE F M, et al. In situ chemical oxidation of contaminated groundwater by persulfate: decomposition by Fe(Ⅲ)- and Mn(Ⅳ)-containing oxides and aquifer materials[J]. Environmental Science & Technology, 2014, 48(17): 10330-10336.
35	CHEN Shaohua, XIONG Pan, ZHAN Wei, et al. Degradation of ethylthionocarbamate by pyrite-activated persulfate[J]. Minerals Engineering, 2018, 122: 38-43.
36	VICENTE F, SANTOS A, ROMERO A, et al. Kinetic study of diuron oxidation and mineralization by persulphate: effects of temperature, oxidant concentration and iron dosage method[J]. Chemical Engineering Journal, 2011, 170(1): 127-135.
37	RAO Yongfang, QU Liang, YANG Haisong, et al. Degradation of carbamazepine by Fe(Ⅱ)-activated persulfate process[J]. Journal of Hazardous Materials, 2014, 268: 23-32.
38	HUANG Yifong, HUANG Yaohui. Identification of produced powerful radicals involved in the mineralization of bisphenol A using a novel UV-Na₂S₂O₈/H₂O₂-Fe(Ⅱ, Ⅲ) two-stage oxidation process[J]. Journal of Hazardous Materials, 2009, 162(2/3): 1211-1216.
39	余浪. Fe²⁺激活过硫酸盐降解三氯苯甲醚的影响因素及机理研究[D]. 杭州: 浙江大学, 2016.
39	YU Lang. Study on influencing factors and mechanism of trichloroanisole degradation by persulfate activated with Fe²⁺ [D]. Hangzhou: Zhejiang University, 2016.
40	RAYAROTH M P, C-S LEE, ARAVIND U K, et al. Oxidative degradation of benzoic acid using Fe⁰- and sulfidized Fe⁰-activated persulfate: a comparative study[J]. Chemical Engineering Journal, 2017, 315: 426-436.
41	QI Chengdu, LIU Xitao, LIN Chunye, et al. Degradation of sulfamethoxazole by microwave-activated persulfate: kinetics, mechanism and acute toxicity[J]. Chemical Engineering Journal, 2014, 249: 6-14.
42	GORDON A D, SMIRNOV A, SHUMLAS S L, et al. Reduction of nitrite and nitrate on nano-dimensioned FeS[J]. Origins of Life and Evolution of Biospheres, 2013, 43(4/5): 305-322.
43	DENG Dayi, PENG Libin, GUAN Mengyun, et al. Impact of activation methods on persulfate oxidation of methyl tert-butyl ether[J]. Journal of Hazardous Materials, 2014, 264: 521-528.
44	LI Xiaodong, WU Bin, ZHANG Qian, et al. Mechanisms on the impacts of humic acids on persulfate/Fe²⁺-based groundwater remediation[J]. Chemical Engineering Journal, 2019, 378: 122142.
45	张良波, 许春红, 祝慧娜, 等. Fe²⁺/过硫酸钠体系降解盐酸四环素的研究[J]. 环境污染与防治, 2017, 39(7): 776-779， 783.
45	ZHANG Liangbo, XU Chunhong, ZHU Huina, et al. Study on degradation of tetracycline hydrochloride by Fe²⁺/sodium persulfate system[J]. Environmental Pollution & Control, 2017, 39(7): 776-779， 783.
46	张忠磊, 陈海, 杨琦, 等. FeS/K₂S₂O₈去除水体系中的2,4-D[J]. 环境工程学报, 2014, 8(11): 4631-4635.
46	ZHANG Zhonglei, CHEN Hai, YANG Qi, et al. Removal of 2,4-dichlorophenoxyacetic acid from water by FeS/K₂S₂O₈[J]. Chinese Journal of Environmental Engineering, 2014, 8(11): 4631-4635.
47	陈平, 王晨, 王瑶. 过渡金属强化FeS/过硫酸钾体系降解甲基橙废水[J]. 工业用水与废水, 2018, 49(4): 17-21.
47	CHEN Ping, WANG Chen, WANG Yao. Methyl orange wastewater degradation by transition metal strengthening FeS/potassium persulfate system[J]. Industrial Water & Wastewater, 2018, 49(4): 17-21.
48	马国峰, 鲁志颖, 贺春林. 硫化亚铁活化过硫酸钠降解酸性橙Ⅱ[J]. 沈阳大学学报(自然科学版), 2018, 30(1): 1-5.
48	MA Guofeng, LU Zhiying, HE Chunlin. FeS activated sodium persulfate degradation of acid orange Ⅱ[J]. Journal of Shenyang University (Natural Science), 2018, 30(1): 1-5.
49	陈平, 王晨, 王瑶. 羟胺强化FeS/过硫酸盐体系处理甲基橙废水[J]. 化学工程师, 2018, 32(2): 38-40， 48.
49	CHEN Ping, WANG Chen, WANG Yao. Treatment of methyl orange wastewater by hydroxylamine enhanced FeS/persulfate system[J]. Chemical Engineer, 2018, 32(2): 38-40， 48.
50	WU Xiaoliang, GU Xiaogang, LU Shuguang, et al. Accelerated degradation of tetrachloroethylene by Fe() activated persulfate process with hydroxylamine for enhancing Fe() regeneration[J]. Journal of Chemical Technology and Biotechnology, 2016, 91(5): 1280-1289.
51	张剑桥. Cu²⁺强化Fe²⁺活化过硫酸盐降解苯酚的效能与机理研究[D]. 哈尔滨: 哈尔滨工业大学, 2016.
51	ZHANG Jianqiao. Efficiency and mechanism of phenol degradation in Cu²⁺enhanced Fe²⁺ activated persulfate system [D]. Harbin: Harbin Institute of Technology, 2016.
52	DONG Zhengyu, ZHANG Qian, CHEN Boryann, et al. Oxidation of bisphenol A by persulfate via Fe₃O₄-α-MnO₂ nanoflower-like catalyst: mechanism and efficiency[J]. Chemical Engineering Journal, 2019, 357: 337-347.
53	SHENG Bo, YANG Fei, WANG Yihao, et al. Pivotal roles of MoS₂ in boosting catalytic degradation of aqueous organic pollutants by Fe(Ⅱ)/PMS[J]. Chemical Engineering Journal, 2019, 375: 121989.
54	HAN Donghui, WAN Jinquan, MA Yongwen, et al. New insights into the role of organic chelating agents in Fe(Ⅱ) activated persulfate processes[J]. Chemical Engineering Journal, 2015, 269: 425-433.
55	LIANG Chenju, LIANG Chingping, CHEN Chinchin. pH Dependence of persulfate activation by EDTA/Fe(Ⅲ) for degradation of trichloroethylene[J]. Journal of Contaminant Hydrology, 2009, 106(3/4): 173-182.
56	HAN Donghui, WAN Jinquan, MA Yongwen, et al. Enhanced decolorization of Orange G in a Fe(Ⅱ)-EDDS activated persulfate process by accelerating the regeneration of ferrous iron with hydroxylamine[J]. Chemical Engineering Journal, 2014, 256: 316-323.
57	LIANG Chenju, BRUELL C J, MARLEY M C, et al. Persulfate oxidation for in situ remediation of TCE. Ⅱ. Activated by chelated ferrous ion[J]. Chemosphere, 2004, 55(9): 1225-1233.
58	PARDO F, ROSAS J M, SANTOS A, et al. Remediation of a biodiesel blend-contaminated soil with activated persulfate by different sources of iron[J]. Water Air and Soil Pollution, 2015, 226(2): 17.
59	KHAN J A, HE Xuexiang, SHAH N S, et al. Kinetic and mechanism investigation on the photochemical degradation of atrazine with activated H₂O₂, S₂O₈^2- and HSO₅^-[J]. Chemical Engineering Journal, 2014, 252: 393-403.
60	HUANG Kunchang, ZHAO Zhiqiang, HOAG G E, et al. Degradation of volatile organic compounds with thermally activated persulfate oxidation[J]. Chemosphere, 2005, 61(4): 551-560.
61	ZHANG Meng, SHI Qin, SONG Xiaozhe, et al. Recent electrochemical methods in electrochemical degradation of halogenated organics: a review[J]. Environmental Science and Pollution Research, 2019, 26(11): 10457-10486.
62	USMAN M, FAURE P, HANNA K, et al. Application of magnetite catalyzed chemical oxidation (Fenton-like and persulfate) for the remediation of oil hydrocarbon contamination[J]. Fuel, 2012, 96(1): 270-276.
63	吴昊孙丽娜, 李玉双, 等. 活化过硫酸钠去除长期污染土壤中的TPH[J]. 环境工程学报, 2016, 10(9): 5231-5237.
63	WU Hao, SUN Lina, LI Yushuang, et al. Application of persulfate to remediatiate long-term TPH contaminated soils[J]. Chinese Journal of Environmental Engineering, 2016, 10(9): 5231-5237.
64	ZHOU Zhou, LIU Xitao, SUN Ke, et al. Persulfate-based advanced oxidation processes (AOPs) for organic-contaminated soil remediation: a review[J]. Chemical Engineering Journal, 2019, 372: 836-851.
65	LIANG Chenju, CHEN Yanjyun, CHANG Kengjung. Evaluation of persulfate oxidative wet scrubber for removing BTEX gases[J]. Journal of Hazardous Materials, 2009, 164(2/3): 571-579.

[1]	葛全倩, 徐迈, 梁铣, 王凤武. MOFs材料在光电催化领域应用的研究进展[J]. 化工进展, 2023, 42(9): 4692-4705.
[2]	白志华, 张军. 二乙烯三胺五亚甲基膦酸/Fenton体系氧化脱除NO[J]. 化工进展, 2023, 42(9): 4967-4973.
[3]	徐沛瑶, 陈标奇, KANKALA Ranjith Kumar, 王士斌, 陈爱政. 纳米材料用于铁死亡联合治疗的研究进展[J]. 化工进展, 2023, 42(7): 3684-3694.
[4]	徐伟, 李凯军, 宋林烨, 张兴惠, 姚舜华. 光催化及其协同电化学降解VOCs的研究进展[J]. 化工进展, 2023, 42(7): 3520-3531.
[5]	孙千千, 刘阵, 李瑞, 张溪, 杨明德, 吴玉龙. 低温水热耦合亚铁离子活化过硫酸盐提高剩余污泥的脱水性能[J]. 化工进展, 2023, 42(2): 595-602.
[6]	章萍萍, 丁书海, 高晶晶, 赵敏, 俞海祥, 刘玥宏, 谷麟. 碳量子点修饰半导体复合光催化剂降解水中有机污染物[J]. 化工进展, 2023, 42(10): 5487-5500.
[7]	王庆宏, 姜晨旭, 王鑫, 余美琪, 朱帅, 李一鸣, 陈春茂. 天然矿物催化氧化水中难降解有机污染物研究进展[J]. 化工进展, 2023, 42(1): 417-434.
[8]	刘怡璇, 林跃朝, 马伟芳. 可见光催化降解水中卤代有机污染物的研究进展[J]. 化工进展, 2022, 41(S1): 571-579.
[9]	伊学农, 李京梅, 高玉琼. 紫外-高铁酸盐体系氧化降解水中的萘普生[J]. 化工进展, 2022, 41(8): 4562-4570.
[10]	潘杰, 王明新, 高生旺, 夏训峰, 韩雪. 氮硫掺杂生物炭/过一硫酸盐体系降解水中磺胺异唑[J]. 化工进展, 2022, 41(8): 4204-4212.
[11]	段毅, 邹烨, 周书葵, 杨柳. 过渡金属单原子催化剂活化H₂O₂/PMS/PDS降解有机污染物的研究进展[J]. 化工进展, 2022, 41(8): 4147-4158.
[12]	徐虎, 郭泓凯, 柴昌盛, 郝相忠, 杨子元, 徐卫军. 碳纤维类材料用于电芬顿体系电极的研究现状[J]. 化工进展, 2022, 41(7): 3707-3718.
[13]	徐天缘, 郑茜, 王连娟, 陈婷, 魏鑫鹏. 焦粉高效活化过硫酸盐对苯胺的降解性能[J]. 化工进展, 2022, 41(6): 3314-3323.
[14]	李坡, 张珊珊, 施锦秋, 高航, 王明新. 活化过硫酸盐修复苯胺污染地下水及其环境风险[J]. 化工进展, 2022, 41(5): 2753-2760.
[15]	寇悦, 陈宇, 叶黄凡, 王庆宏, 陈春茂. 炼化含盐污水处理全过程有机污染物降解特征[J]. 化工进展, 2022, 41(4): 2202-2208.