球磨钒钛磁铁矿尾矿活化过硫酸盐去除2,4-二氯苯酚的研究

夏甫; 徐祥健; 路红丽; 郜普闯; 韩旭; 肖瀚; 王新港; 杨昱; 姜永海

doi:10.12153/j.issn.1674-991X.20220407

球磨钒钛磁铁矿尾矿活化过硫酸盐去除2,4-二氯苯酚的研究

doi: 10.12153/j.issn.1674-991X.20220407

夏甫^{1, 2,},
徐祥健^{1, 2, ,},
路红丽^{1, 2},
郜普闯^{1, 2},
韩旭^{1, 2},
肖瀚^{1, 2},
王新港^{1, 2},
杨昱^{1, 2},
姜永海^{1, 2}

1.
污染场地安全修复技术国家工程实验室，北京建工环境修复股份有限公司
2.
国家环境保护地下水污染模拟与控制重点实验室，中国环境科学研究院

基金项目: 污染场地安全修复技术国家工程实验室开放基金(NEL-SRT201704)；国家重点研发计划项目(2019YFC1806200)

详细信息

作者简介:
夏甫(1988—)，男，工程师，主要从事地下水原位化学氧化技术研究，239014113@qq.com

通讯作者:
徐祥健(1988—)，男，副研究员，主要从事地下水污染修复技术及材料研究，xuxjian406@126.com

中图分类号: X753
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- 被引次数: 0
出版历程
- 收稿日期: 2022-04-28
- 录用日期: 2023-03-22

Removal efficiency of 2,4-dichlorophenol by persulfate activated with ball-milling vanadium-titanium magnetite tailings

XIA Fu^{1, 2
,},
XU Xiangjian^{1, 2
, ,},
LU Hongli^{1, 2},
GAO Puchuang^{1, 2},
HAN Xu^{1, 2},
XIAO Han^{1, 2},
WANG Xingang^{1, 2},
YANG Yu^{1, 2},
JIANG Yonghai^{1, 2}

1.
National Engineering Laboratory for Site Remediation Technologies, Beijing Construction Engineering Group Environmental Remediation Co., Ltd.
2.
State Environmental Protection Key Laboratory of Simulation and Control of Groundwater Pollution, Chinese Research Academy of Environmental Sciences

摘要

摘要:
为探究球磨钒钛磁铁矿尾矿(B-VTMT)活化过硫酸盐(PS)去除地下水中有机污染物2,4-二氯苯酚(2,4-DCP)可行性，采用扫描电子显微镜、X射线衍射仪、X射线光电子能谱等表征手段对B-VTMT的形貌和组成进行测试分析，探讨B-VTMT投加量、PS初始浓度、初始pH、2,4-DCP初始浓度及地下水常见阴离子(Cl^–、NO₃ ^–、SO₄ ^2–)对2,4-DCP去除率的影响。结果表明：在B-VTMT投加量为0.5 g/L，PS浓度为5 mmol/L，2,4-DCP初始浓度为20 mg/L，初始pH为7.1，室温条件下39 h内2,4-DCP的去除率为45.4%。自由基淬灭和捕获试验证实，硫酸根自由基(SO₄ ^–·)和羟基自由基(·OH)是体系去除2,4-DCP的主要活性自由基，通过高效液相色谱-质谱仪(HPLC-MS)识别了8种中间产物，推测了2,4-DCP可能的降解路径。地下水中Cl^–提高了2,4-DCP的去除率，而NO₃ ^–和SO₄ ^2–降低了2,4-DCP的去除率。研究显示，B-VTMT作为PS的活化剂是一种很有前景的尾矿资源化利用方式。
- 钒钛磁铁矿尾矿 /
- 过硫酸盐 /
- 活化机制 /
- 影响因素
Abstract:
The removal feasibility of 2,4-dichlorophenol (2,4-DCP) in groundwater by persulfate (PS) activated with ball-milling vanadium-titanium magnetite tailings (B-VTMT) was investigated. The morphology and composition of B-VTMT were analyzed by scanning electron microscope, X-ray diffraction, and X-ray photoelectron spectroscopy. The effects of B-VTMT dosages, initial PS concentrations, initial pH, initial 2,4-DCP concentrations, and common anions in groundwater (Cl^–, NO₃ ^–, and SO₄ ^2–) on 2,4-DCP removal efficiency were explored. The experiment results indicated that: The removal efficiency of 2,4-DCP was 45.4% within 39 h at room temperature under the conditions of B-VTMT dosage of 0.5 g/L, initial PS concentration of 5 mmol/L, initial 2,4-DCP concentration of 20 mg/L and initial pH 7.1. Radical quenching experiments and electron spin-resonance (ESR) spectroscopy confirmed that sulfate radical (SO₄ ^–·) and hydroxyl radical (·OH) were the main free radicals of 2,4-DCP removal. Eight intermediates were identified by high performance liquid chromatography-mass spectrometry (HPLC-MS). The possible degradation pathways of 2,4-DCP were speculated. The presence of chloride ions promoted the 2,4-DCP removal efficiency, while nitrate ions and sulfate ions inhibited the 2,4-DCP removal efficiency. It was concluded that B-VTMT could effectively activate PS to remove 2,4-DCP in groundwater, which was a promising way of tailings resource utilization.
- vanadium-titanium magnetite tailings /
- persulfate /
- activation mechanism /
- influencing factors

HTML全文

图 1 反应前B-VTMT的SEM-EDS光谱

Figure 1. SEM-EDS spectra of fresh B-VTMT before reaction

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图 2 反应后B-VTMT的SEM-EDS光谱

Figure 2. SEM-EDS spectra of B-VTMT after reaction

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图 3 反应前后B-VTMT的XRD图谱

Figure 3. XRD patterns of B-VTMT before and after reaction

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图 4 B-VTMT活化PS对2,4-DCP的去除率

Figure 4. Removal efficiency of 2,4-DCP by PS activated with B-VTMT

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图 5 反应体系各影响因素对2,4-DCP去除率的影响

Figure 5. Effect of the influencing factors in the reaction system on the 2,4-DCP removal efficiency

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图 6 B-VTMT反应前后C 1s，Fe 2p和Ti 2p的XPS光谱

Figure 6. XPS patterns of C 1s, Fe 2p and Ti 2p of B-VTMT before and after reaction

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图 7 淬灭剂浓度对2,4-DCP去除率的影响

Figure 7. Effect of quenching agents concentrations on the 2,4-DCP removal efficiency

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图 8 B-VTMT活化PS体系反应时间为5和20 min的ESR光谱图

Figure 8. ESR spectrum in system of PS activated with B-VTMT at the reaction time of 5 and 20 min

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图 9 HPLC-MS测试所得中间产物

Figure 9. Intermediate products obtained by HPLC-MS test

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图 10 2,4-DCP可能降解路径

Figure 10. Possible degradation pathway of 2,4-DCP

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图 11 常见阴离子浓度对2,4-DCP降解效果的影响

Figure 11. Effect of common anion concentrations on the degradation efficiency of 2,4-DCP

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表 1 VTMT主要化学成分

Table 1. Main chemical components of VTMT %　

成分含量成分含量

SiO₂ 41.63 Al₂O₃ 10.98
Fe 14.80 MnO 0.21
CaO 13.16 V₂O₅ 0.11
TiO₂ 5.05 烧失量 2.07
MgO 9.94

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表 2 反应前后体系中铁、锰、钛和钒金属离子浓度

Table 2. Iron, manganese, titanium and vanadium ion concentrations before and after reaction μg/L　

金属离子反应前反应后

Fe 26.28 967.54
Mn 0.40 1.04
Ti 5.13 112.44
V 未检出未检出

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