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工业过程二恶英的排放特征及其控制技术

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王得梁, 谢雯静, 赵文博, 何钰晴, 徐菁, 黄亚妮, 郝艳芬, 梁勇, 王璞. 工业过程二恶英的排放特征及其控制技术[J]. 环境化学, 2023, 42(5): 1449-1465. doi: 10.7524/j.issn.0254-6108.2022070704
引用本文: 王得梁, 谢雯静, 赵文博, 何钰晴, 徐菁, 黄亚妮, 郝艳芬, 梁勇, 王璞. 工业过程二恶英的排放特征及其控制技术[J]. 环境化学, 2023, 42(5): 1449-1465. doi: 10.7524/j.issn.0254-6108.2022070704
shu
WANG Deliang, XIE Wenjing, ZHAO Wenbo, HE Yuqing, XU Jing, HUANG Yani, HAO Yanfen, LIANG Yong, WANG Pu. Dioxin emission characteristics and control technologies in industrial processes[J]. Environmental Chemistry, 2023, 42(5): 1449-1465. doi: 10.7524/j.issn.0254-6108.2022070704
Citation: WANG Deliang, XIE Wenjing, ZHAO Wenbo, HE Yuqing, XU Jing, HUANG Yani, HAO Yanfen, LIANG Yong, WANG Pu. Dioxin emission characteristics and control technologies in industrial processes[J]. Environmental Chemistry, 2023, 42(5): 1449-1465. doi: 10.7524/j.issn.0254-6108.2022070704
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工业过程二恶英的排放特征及其控制技术

  • 1.

    江汉大学省部共建精细爆破国家重点实验室，武汉，430056

  • 2.

    工业烟尘污染控制湖北省重点实验室，环境与健康学院，江汉大学，武汉，430056

  • 3.

    国民核生化灾害防护国家重点实验室，北京，102205

    • 通讯作者: Tel：13466359131，E-mail：puwang@jhun.edu.cn
  • 基金项目:
    江汉大学省部共建精细爆破国家重点实验室自主研究课题（PBSKL2022103）和国家自然科学基金（41977327）资助.

Dioxin emission characteristics and control technologies in industrial processes

  • 1.

    State Key Laboratory of Precision Blasting, Jianghan University ，Wuhan, 430056, China

  • 2.

    Hubei Key Laboratory of Industrial Fume & Dust Pollution Control, School of Environment and Health, Jianghan University, Wuhan, 430056, China

  • 3.

    State Key Laboratory of NBC Protection for Civilian, Beijing , 102205, China

    • Corresponding author: WANG Pu, puwang@jhun.edu.cn
  • Fund Project: the State Key Laboratory of Precision Blasting, Jianghan University (PBSKL2022103) and National Natural Science Foundation of China（41977327）.

  • 摘要: 工业排放是环境中二恶英（PCDD/Fs）最主要的人为排放源. 2010年我国九部委联合发布PCDD/Fs污染防治指导意见，之后出台多项政策要求对主要行业持久性有机污染物（POPs）开展污染防治. 在一系列防治措施下，PCDD/Fs的工业排放水平有所下降，整体取得良好成效. 本文针对固体废弃物焚烧、钢铁生产、有色金属生产和水泥窑协同处置四类主要行业的PCDD/Fs排放研究进展进行综述，阐述了不同行业PCDD/Fs排放量、排放特征及其变化趋势，比较分析了目前四类主要行业针对PCDD/Fs排放的控制技术及其效果，并对烟气中PCDD/Fs污染控制技术的发展方向进行了展望. 本文可为更加深入地了解工业排放PCDD/Fs的研究现状以及污染控制技术提供参考.
    Abstract: Industrial emissions are the main sources of anthropogenic polychlorinated dibenzo-p-dioxin and dibenzofurans (PCDD/Fs) in the environment. In 2010, nine ministries and commissions of China jointly issued the Guidance on the Strengthening of Dioxin Pollution Prevention, and then issued many policy documents for pollution prevention and control of persistent organic pollutants (POPs) in major industries. Under a series of control measures, the industrial emission of PCDD/Fs has been reduced in recent years. In this review, we summarized the research progress on PCDD/Fs emission in solid waste incineration, iron and steel smelting, non-ferrous metal smelting and coordinated disposal of cement kiln. The emission levels , emission characteristics and temporal trend of PCDD/Fs from these different industries were discussed, the control technologies and their effects to PCDD/Fs emission in four major industries were also evaluated. The development about PCDD/Fs control measures in flue gas was finally prospected. This review may enhance understanding the industrial emissions of PCDD/Fs and their control effects.
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  • 图 1  四类工业大气PCDD/Fs排放量示意图[3-4,30,35,61,63-65]

    Figure 1.  Atmosphere PCDD/Fs emission form four types of industrial [3-4,30,35,61,63-65]

    下载: 全尺寸图片 幻灯片

    表 1  我国PCDD/Fs的主要排放源及其排放量

    Table 1.  Main emission sources of dioxins and their emissions in China

    排放源
    Emission source    		排放因子/（ng·t−1 I-TEQ）
    Emission factor    		年排放量/（g TEQ）
    Annual emission    		参考文献
    References
    大气Atmosphere总量Total
    固体废弃物焚烧生活垃圾—125.8338[3]
    危险废物—57.27243.27
    医疗废物—427.41176.3
    总计（2004）—610.471757.57
    生活垃圾1728——[24]
    27—225——[25]
    12200217—[23]
    56—607——[60]
    危险废物70—3270——[60]
    工业废物302500103—[23]
    医疗废物97800272—[23]
    780—473930——[26]
    1923.60.466—[20]
    总计（2013）—1280—[61]
    总计（2016）—2469—[4]
    钢铁生产铁矿石烧结—1522.51523.4[3]
    钢铁冶炼—150.91125.4
    铸铁生产—10.797
    炼焦239.2252.6
    总计（2004）—1923.312998.4
    铁矿石烧结1582.95——[30]
    772.2—827.9——[37]
    1330—7610[38]
    180±220[36]
    电弧炉1245.85——[30]
    270±23[36]
    3160——[37]
    177—869——[38]
    炼焦160.09——[30]
    28.9（WHO）——[62]
    总计（2011）—6817—[63]
    总计（2012）—618—[64]
    总计（2015）—1216.83—[35]
    总计（2016）—5333—[4]
    总计（2018）—2240—[30]
    有色金属生产铜生产—4031133.8[3]
    铝生产—133.5365.5
    铅生产—13.417.4
    其他—12.9951.85
    总计（2004）—562.891568.55
    铜生产38.5、651（WHO）——[49]
    14.2——[50]
    铝生产1240.2——
    铅生产3140.0——
    锌生产166.0——
    再生铜241719—1707200——[37]
    1480237.5—[65-66]
    24451.3——[50]
    再生铝147819—434840——[37]
    84.8—2720——[38]
    再生铅4297——[37]
    镁生产412（WHO）——[49]
    废旧导线回收5569（WHO）——[49]
    水泥窑协同处置水泥窑（2004）—365.3365.3[3]
    水泥窑50000.02g—[57-58]
    水泥窑0.01—1.35 mg——[55]
    上述四类总计（2004）—3461.976437.22[3]
    所有污染源总计（2004）—5042.410236.8[3]
    　　注：“—”：表示未提及；其他：包锌、黄铜和青铜、镁等未提及的有色金属生产；
    排放源
    Emission source    		排放因子/（ng·t−1 I-TEQ）
    Emission factor    		年排放量/（g TEQ）
    Annual emission    		参考文献
    References
    大气Atmosphere总量Total
    固体废弃物焚烧生活垃圾—125.8338[3]
    危险废物—57.27243.27
    医疗废物—427.41176.3
    总计（2004）—610.471757.57
    生活垃圾1728——[24]
    27—225——[25]
    12200217—[23]
    56—607——[60]
    危险废物70—3270——[60]
    工业废物302500103—[23]
    医疗废物97800272—[23]
    780—473930——[26]
    1923.60.466—[20]
    总计（2013）—1280—[61]
    总计（2016）—2469—[4]
    钢铁生产铁矿石烧结—1522.51523.4[3]
    钢铁冶炼—150.91125.4
    铸铁生产—10.797
    炼焦239.2252.6
    总计（2004）—1923.312998.4
    铁矿石烧结1582.95——[30]
    772.2—827.9——[37]
    1330—7610[38]
    180±220[36]
    电弧炉1245.85——[30]
    270±23[36]
    3160——[37]
    177—869——[38]
    炼焦160.09——[30]
    28.9（WHO）——[62]
    总计（2011）—6817—[63]
    总计（2012）—618—[64]
    总计（2015）—1216.83—[35]
    总计（2016）—5333—[4]
    总计（2018）—2240—[30]
    有色金属生产铜生产—4031133.8[3]
    铝生产—133.5365.5
    铅生产—13.417.4
    其他—12.9951.85
    总计（2004）—562.891568.55
    铜生产38.5、651（WHO）——[49]
    14.2——[50]
    铝生产1240.2——
    铅生产3140.0——
    锌生产166.0——
    再生铜241719—1707200——[37]
    1480237.5—[65-66]
    24451.3——[50]
    再生铝147819—434840——[37]
    84.8—2720——[38]
    再生铅4297——[37]
    镁生产412（WHO）——[49]
    废旧导线回收5569（WHO）——[49]
    水泥窑协同处置水泥窑（2004）—365.3365.3[3]
    水泥窑50000.02g—[57-58]
    水泥窑0.01—1.35 mg——[55]
    上述四类总计（2004）—3461.976437.22[3]
    所有污染源总计（2004）—5042.410236.8[3]
    　　注：“—”：表示未提及；其他：包锌、黄铜和青铜、镁等未提及的有色金属生产；
    下载: 导出CSV

    表 2  PCDD/Fs的全过程控制方法

    Table 2.  Whole process control method of PCDD/Fs

    过程
    Process    		方法
    Method    		参考文献
    References
    生成前物料预处理、添加辅助燃料、配制垃圾衍生燃料等[69-70]
    生成中改进炉膛结构、调整工作参数（含氧量、气体湍流度、温度区间及停留时间、多段燃烧等）、含硫含氮抑制剂（硫脲、氨、含硫煤等）、烟气循环、烟气急冷等[69, 71-74]
    生成后活性炭吸附、除尘器拦截（袋式、静电等除尘器等）、选择性催化还原、光降解、等离子体降解、高级氧化等[72, 75-80]
    过程
    Process    		方法
    Method    		参考文献
    References
    生成前物料预处理、添加辅助燃料、配制垃圾衍生燃料等[69-70]
    生成中改进炉膛结构、调整工作参数（含氧量、气体湍流度、温度区间及停留时间、多段燃烧等）、含硫含氮抑制剂（硫脲、氨、含硫煤等）、烟气循环、烟气急冷等[69, 71-74]
    生成后活性炭吸附、除尘器拦截（袋式、静电等除尘器等）、选择性催化还原、光降解、等离子体降解、高级氧化等[72, 75-80]
    下载: 导出CSV

    表 3  不同行业烟气PCDD/Fs排放控制标准

    Table 3.  PCDD/Fs emission control standard for different industries

    行业
    Industry    		限值/（ng·m−3 TEQ）
    Limiting value    		开始时间
    Time    		参考文献
    References
    生活垃圾焚烧0.12014[82]
    危险废物焚烧0.52001[83]
    火葬场0.52015[84]
    炼钢工业（电炉、烧结、球团）0.52012[85-86]
    再生铜、铝、铅、锌0.52015[87]
    水泥窑协同处置固体废物0.12013[88]
    行业
    Industry    		限值/（ng·m−3 TEQ）
    Limiting value    		开始时间
    Time    		参考文献
    References
    生活垃圾焚烧0.12014[82]
    危险废物焚烧0.52001[83]
    火葬场0.52015[84]
    炼钢工业（电炉、烧结、球团）0.52012[85-86]
    再生铜、铝、铅、锌0.52015[87]
    水泥窑协同处置固体废物0.12013[88]
    下载: 导出CSV

    表 4  工业烟气PCDD/Fs控制技术

    Table 4.  Collaborative dioxin control technology for industrial flue gas

    工业类型
    Industrial Type    		空气污染控制装置
    Air pollution control devices（APCDs）    		进口
    Before    		出口
    After    		效率
    Efficiency    		参考文献
    Reference
    固体废弃物焚烧生活垃圾焚烧SDS+DS+AC+BF+SCR0.22530.002898.76%[89]
    SNCR+SDS+AC+BF—0.0365—[98]
    —0.076—0.153—[107]
    —0.007—0.095—[25]
    SDS+AC+BF+SCR—0.41—[108]
    —0.06—[108]
    热交换+SDS+AC+BF2.580.024699%[109]
    急冷+SDS+AC+BF—0.45—[94]
    SDS+AC+BF—0.078—[110]
    —0.008—0.1291.7%—99.3%[93]
    —0.026—[94]
    —0.099—[98]
    DS+AC+BF—0.0844—[38]
    WDS+AC+BF—0.082—[98]
    AC+BF—0.239—[38]
    CY+SDS+BF—0.54—[111]
    WDS+BF—0.50—[94]
    SDS+BF—1.33—[94]
    CY+ESP16.1370.94694.14%[112]
    CY+ESP+BF0.231.948-747%[112]
    0.4365.018-1051%[112]
    危险废物焚烧VS+CY+AC+BF1130.054（WHO）99.95%[90]
    SDS+AC+BF—0.01—11.91—[92]
    AC+BF—0.225—[38]
    医疗废弃物焚烧SDS+AC+BF+WDS5.320.0798.68%[91]
    DS+AC+BF—1.64—[38]
    SDS+AC+BF—0.07—12.21—[92]
    SDS+BF—0.07—
    钢铁生产电弧炉炼钢BF—0.17—[113]
    —0.148—0.757—[38]
    —0.34—[37]
    ESP+脱硫—0.003—0.557—[36]
    烧结ESP+WFGD2.3±0.560.99±0.53—[99]
    ESP+SFGD0.32—0.690.022—0.2—[99]
    WFGD+WESP—0.15—[103]
    钢铁生产烧结ESP+SCR—0.137—0.657—[38]
    ESP—0.233—[38]
    —0.005—0.48—[37]
    BF—0.006—0.057—[36]
    炼焦BF—(4.9—89.3)×10−3 （WHO）—[33]
    —0.00870—[38]
    —(0.0039—0.03)×10−3—[114]
    有色金属生产再生铜BF—0.310—[38]
    —0.84—[115]
    —0.004—0.37—[46]
    —0.009—1.29—[47]
    再生锌GS或ESP+BF—0.48—[103, 115]
    再生铅BF
    ESP+GS+BF    		—0.05—
    BF+WDS+DS—0.037—[37]
    再生铝AC+BF—0.1—[45]
    BF—(5.68—44)×10−3—[38]
    —2.05—[37]
    WDS—0.88—[37]
    水泥窑水泥窑协同处置ESP—5.9×10−3—[115，103]
    —（9.3—49.3）×10−3—[116]
    —0.01—0.19—[55]
    BF—0.076—[106]
    —(17.8—90.8) ×10−3—[116]
    —0.01—0.46—[55]
    WDS—0.04—[55]
    　　单位：ng·m−3 I-TEQ：“—”：未提及；WDS：湿法除尘器；CY：旋风除尘器；VS：文丘里洗涤器；WFGD：湿法脱硫；SFGD：半干法脱硫；WESP：湿法静电除尘；GS：重力沉降
    　　unit：ng·m−3 I-TEQ；“—”：Not Reported；WDS：Wet dust collector；CY：Cyclone dust collector；VS：Venturi scrubber；WFGD：Wet flue gas desulfurization；SFGD：Semi-dry desulphurization；WESP：Wet electrostatic precipitator；GS：Gravity settling
    工业类型
    Industrial Type    		空气污染控制装置
    Air pollution control devices（APCDs）    		进口
    Before    		出口
    After    		效率
    Efficiency    		参考文献
    Reference
    固体废弃物焚烧生活垃圾焚烧SDS+DS+AC+BF+SCR0.22530.002898.76%[89]
    SNCR+SDS+AC+BF—0.0365—[98]
    —0.076—0.153—[107]
    —0.007—0.095—[25]
    SDS+AC+BF+SCR—0.41—[108]
    —0.06—[108]
    热交换+SDS+AC+BF2.580.024699%[109]
    急冷+SDS+AC+BF—0.45—[94]
    SDS+AC+BF—0.078—[110]
    —0.008—0.1291.7%—99.3%[93]
    —0.026—[94]
    —0.099—[98]
    DS+AC+BF—0.0844—[38]
    WDS+AC+BF—0.082—[98]
    AC+BF—0.239—[38]
    CY+SDS+BF—0.54—[111]
    WDS+BF—0.50—[94]
    SDS+BF—1.33—[94]
    CY+ESP16.1370.94694.14%[112]
    CY+ESP+BF0.231.948-747%[112]
    0.4365.018-1051%[112]
    危险废物焚烧VS+CY+AC+BF1130.054（WHO）99.95%[90]
    SDS+AC+BF—0.01—11.91—[92]
    AC+BF—0.225—[38]
    医疗废弃物焚烧SDS+AC+BF+WDS5.320.0798.68%[91]
    DS+AC+BF—1.64—[38]
    SDS+AC+BF—0.07—12.21—[92]
    SDS+BF—0.07—
    钢铁生产电弧炉炼钢BF—0.17—[113]
    —0.148—0.757—[38]
    —0.34—[37]
    ESP+脱硫—0.003—0.557—[36]
    烧结ESP+WFGD2.3±0.560.99±0.53—[99]
    ESP+SFGD0.32—0.690.022—0.2—[99]
    WFGD+WESP—0.15—[103]
    钢铁生产烧结ESP+SCR—0.137—0.657—[38]
    ESP—0.233—[38]
    —0.005—0.48—[37]
    BF—0.006—0.057—[36]
    炼焦BF—(4.9—89.3)×10−3 （WHO）—[33]
    —0.00870—[38]
    —(0.0039—0.03)×10−3—[114]
    有色金属生产再生铜BF—0.310—[38]
    —0.84—[115]
    —0.004—0.37—[46]
    —0.009—1.29—[47]
    再生锌GS或ESP+BF—0.48—[103, 115]
    再生铅BF
    ESP+GS+BF    		—0.05—
    BF+WDS+DS—0.037—[37]
    再生铝AC+BF—0.1—[45]
    BF—(5.68—44)×10−3—[38]
    —2.05—[37]
    WDS—0.88—[37]
    水泥窑水泥窑协同处置ESP—5.9×10−3—[115，103]
    —（9.3—49.3）×10−3—[116]
    —0.01—0.19—[55]
    BF—0.076—[106]
    —(17.8—90.8) ×10−3—[116]
    —0.01—0.46—[55]
    WDS—0.04—[55]
    　　单位：ng·m−3 I-TEQ：“—”：未提及；WDS：湿法除尘器；CY：旋风除尘器；VS：文丘里洗涤器；WFGD：湿法脱硫；SFGD：半干法脱硫；WESP：湿法静电除尘；GS：重力沉降
    　　unit：ng·m−3 I-TEQ；“—”：Not Reported；WDS：Wet dust collector；CY：Cyclone dust collector；VS：Venturi scrubber；WFGD：Wet flue gas desulfurization；SFGD：Semi-dry desulphurization；WESP：Wet electrostatic precipitator；GS：Gravity settling
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  • 收稿日期:  2022-07-07
  • 录用日期:  2022-09-16
  • 刊出日期:  2023-05-27
王得梁, 谢雯静, 赵文博, 何钰晴, 徐菁, 黄亚妮, 郝艳芬, 梁勇, 王璞. 工业过程二恶英的排放特征及其控制技术[J]. 环境化学, 2023, 42(5): 1449-1465. doi: 10.7524/j.issn.0254-6108.2022070704
引用本文: 王得梁, 谢雯静, 赵文博, 何钰晴, 徐菁, 黄亚妮, 郝艳芬, 梁勇, 王璞. 工业过程二恶英的排放特征及其控制技术[J]. 环境化学, 2023, 42(5): 1449-1465. doi: 10.7524/j.issn.0254-6108.2022070704
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WANG Deliang, XIE Wenjing, ZHAO Wenbo, HE Yuqing, XU Jing, HUANG Yani, HAO Yanfen, LIANG Yong, WANG Pu. Dioxin emission characteristics and control technologies in industrial processes[J]. Environmental Chemistry, 2023, 42(5): 1449-1465. doi: 10.7524/j.issn.0254-6108.2022070704
Citation: WANG Deliang, XIE Wenjing, ZHAO Wenbo, HE Yuqing, XU Jing, HUANG Yani, HAO Yanfen, LIANG Yong, WANG Pu. Dioxin emission characteristics and control technologies in industrial processes[J]. Environmental Chemistry, 2023, 42(5): 1449-1465. doi: 10.7524/j.issn.0254-6108.2022070704
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工业过程二恶英的排放特征及其控制技术

    通讯作者: Tel：13466359131，E-mail：puwang@jhun.edu.cn
  • 1. 江汉大学省部共建精细爆破国家重点实验室，武汉，430056
  • 2. 工业烟尘污染控制湖北省重点实验室，环境与健康学院，江汉大学，武汉，430056
  • 3. 国民核生化灾害防护国家重点实验室，北京，102205
  • 收稿日期:  2022-07-07
  • 录用日期:  2022-09-16
  • 网络出版日期:  2023-05-16
基金项目:
江汉大学省部共建精细爆破国家重点实验室自主研究课题（PBSKL2022103）和国家自然科学基金（41977327）资助.

摘要: 工业排放是环境中二恶英（PCDD/Fs）最主要的人为排放源. 2010年我国九部委联合发布PCDD/Fs污染防治指导意见，之后出台多项政策要求对主要行业持久性有机污染物（POPs）开展污染防治. 在一系列防治措施下，PCDD/Fs的工业排放水平有所下降，整体取得良好成效. 本文针对固体废弃物焚烧、钢铁生产、有色金属生产和水泥窑协同处置四类主要行业的PCDD/Fs排放研究进展进行综述，阐述了不同行业PCDD/Fs排放量、排放特征及其变化趋势，比较分析了目前四类主要行业针对PCDD/Fs排放的控制技术及其效果，并对烟气中PCDD/Fs污染控制技术的发展方向进行了展望. 本文可为更加深入地了解工业排放PCDD/Fs的研究现状以及污染控制技术提供参考.

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  • 二恶英（dioxins）是一类具有相似结构和性质的氯代芳香烃族杂环化合物的统称，包括多氯代二苯并-对-二恶英（polychlorinated dibenzo-p-dioxins，PCDDs）和多氯代二苯并呋喃（polychlorinated dibenzofurans，PCDFs），共有210个同族体. PCDD/Fs作为典型的非故意产生的持久性有机污染物（UP-POPs），其来源包括自然源和人为源两大类，前者包括火山爆发、森林火灾等一些自然过程，后者包括固体废弃物焚烧、钢铁生产、有色金属生产、含氯化学品生产和纸浆漂白等工业过程. 由于环境中的PCDD/Fs主要来源于人类活动，自然排放的PCDD/Fs极少，故针对PCDD/Fs的研究主要围绕人为源展开[1-2].

    研究显示，2004年我国PCDD/Fs大气排放量为5042 g毒性当量（TEQ），之后一段时间未见官方统计数据，但有研究指出2016年我国PCDD/Fs大气排放量为10366 g TEQ[3-4]，尽管不同研究中对排放因子和生产强度的选择差异较大，导致PCDD/Fs大气排放量的计算存在一定差异[5]，但金属生产、固体废弃物焚烧等工业污染源导致的PCDD/Fs排放量占大气总排放量的90%以上[4]. 因此积极削减工业源排放的PCDD/Fs是其污染防治的关键，也是我国履行《关于持久性有机污染物的斯德哥尔摩公约》，推动国内经济高质量发展和生态文明建设的必然选择.

    2010年我国加强大气污染物防治，工业废气治理投资快速增长，并于2014年达到峰值[6]. 但截止2018年，我国除固体废弃物焚烧行业外的其他行业专门针对UP-POPs控制的措施十分有限，且相关工作多停留在实验室研究阶段[7]，与2010年的研究状况几近相似[8]. 减少工业污染源UP-POPs的排放仍然是我国POPs污染控制面临的最大挑战[7].

    尽管目前对PCDD/Fs的工业排放源已有大量研究报道，但对于不同工业的PCDD/Fs排放特征、污染控制措施及其成效评估的文献综述仍然相对较少，且近年来随着工业的发展，不同工业PCDD/Fs排放特征和排放量也发生了一定的变化，因此，有必要进一步对比以前和近年来PCDD/Fs排放特征、控制措施变化. 根据联合国环境规划署（UNEP）在2013年提出的《鉴别及量化PCDD/Fs类排放标准工具包》以及其他研究对不同行业PCDD/Fs的排放因子及排放量的核算结果[9-12]，本文选取固体废弃物焚烧、钢铁生产、有色金属生产和水泥窑协同处置固体废弃物这四类排放因子较大、生产强度较高的行业为主要研究对象，系统总结了固体废弃物焚烧、钢铁生产、有色金属生产和水泥窑协同处置四类重要工业源PCDD/Fs排放的相关研究进展，阐述了不同行业PCDD/Fs排放特征及及其变化趋势，比较分析了这四类重要行业针对PCDD/Fs排放采取的控制技术及其效果，在此基础上对工业生产过程中PCDD/Fs污染控制技术的发展方向进行了展望. 本文可为更加深入了解工业排放PCDD/Fs的研究现状及其污染控制技术提供参考.

    • 1.   不同工业烟气中PCDD/Fs排放特征（Emission characteristics of PCDD/Fs in flue gas of different industries）

    • 焚烧等工业热过程中的PCDD/Fs生成机理包括高温气相合成、低温异相催化前驱体反应和低温异相催化从头合成等. 异相反应被认为是热过程PCDD/Fs的主要生成机理，可通过分析样品中PCDFs/PCDDs比值是否大于1来判断某排放源的PCDD/Fs生成途径是从头合成还是前驱体反应占主导地位[13].

      • 1.1.   固体废弃物焚烧

    • 固体废弃物焚烧主要指生活垃圾、危险废物、医疗废弃物等固体废弃物的焚烧[3, 7]. 焚烧能减少70%—80%的质量以及90%的体积[14]，且焚烧产生的热能不仅能有效杀灭病原体，还可以用来发电[15-16]，因此焚烧逐渐成为固体废弃物集中处置的首选方法[17-18]. 2010—2020年，我国城市生活垃圾焚烧处理量从2317万t增长到14608万t（年增长率为53.0%），处理量和增长率均超过传统的填埋处理（9598万t下降为7772万t，年增长率为-19.0%）；危险废物产生量从1587万t增长到7282万t，年增长率为35.9%[6, 19].

      从PCDD/Fs指纹分布看，大部分固体废弃物焚烧产生的烟气中PCDD/Fs以7—8氯代同族体为主，少部分以4—5氯代同族体为主，且PCDFs/PCDDs比值通常显著大于1，其生成机理主要为从头合成[7, 20-22]. 从PCDD/Fs排放量，2004年我国固体废物焚烧大气PCDD/Fs排放量为610 g TEQ（占大气PCDD/Fs排放量12.1%），2016年为2469 g TEQ（占大气PCDD/Fs排放量23.8%）[3-4]，同2004年相比，2016年我国固体废弃物焚烧PCDD/Fs排放量增加1859 g TEQ（304.8%），排放占比升高11.7%. 在焚烧量相同的情况下，焚烧医疗废弃物和危险废弃物产生的PCDD/Fs要远高于生活垃圾焚烧的排放量[23].

      固体废弃物焚烧厂因规模、工艺和操作控制等差异较大，PCDD/Fs的排放水平有很大差别（0.5—3500 μg·t−1 TEQ）[11]. Ni等[24]在2009年的研究中指出，我国生活垃圾焚烧过程中PCDD/Fs的平均排放因子为1728 ng·t−1 TEQ，这与2013年UNEP提供的排放因子参考范围相一致[11]，2018年Zhu等[25]的研究结果显示排放因子有所下降（27—225 ng·t−1 I-TEQ），其均值为170 ng·t−1 I-TEQ，这可能与后来的焚烧厂采取更加完善的控制措施有关. 若以2020年我国生活垃圾焚烧量14608万 t[6]和Zhu等的排放因子[25]进行推测，我国2020年生活垃圾焚烧PCDD/Fs排放量达3.9—36.7 g TEQ. 对于医疗废弃物，Cao等[26]2009年的研究指出我国此类焚烧炉烟气中PCDD/Fs排放因子为0.78—474 μg·t−1 I-TEQ，据此估算的当年医疗废弃物焚烧产生的PCDD/Fs为4.87 g TEQ；若以2019年我国医疗废弃物产量（226万 t）[27]进行推测，PCDD/Fs年排放量可达1.76—1071 g I-TEQ.

      总体相比于2004年，2016年我国固体废弃物焚烧行业大气PCDD/Fs总排放量增加1859 g TEQ（304.8%），排放占比升高11.7%[3-4]. 同时，由于焚烧技术的推广，新冠疫情后医疗废弃物的产量急剧增加（增幅可达24.7%）[28]，危险废弃物处置量于2020年首次超过产生量[6, 19]，这可能直接导致固体废弃物焚烧PCDD/Fs排放量的增加，然而相关研究报道比较欠缺，相关工作有待进一步开展.

      • 1.2.   钢铁生产

    • 钢铁生产流程可分为长流程和短流程两种，其中长流程是指以铁矿石为原料，以烧结、球团、炼焦、高炉炼铁、转炉炼钢和轧钢等工序为整套流程的生产工艺；短流程则是以废钢和直接还原铁为原料，直接从电炉炼钢开始的生产工艺[29]. 我国长流程炼钢约占90%左右[30]，但因电炉炼钢过程中废钢原料中的塑料和油漆等有机物对该过程PCDD/Fs的产生有重要影响[31]，故本文中的钢铁生产主要是指长流程生产工艺和电炉炼钢.

      炼焦、烧结、电弧炉炼钢等钢铁生产过程中生成的PCDD/Fs均以7-8氯代同族体为主，且PCDFs/PCDDs比值大于1，其主要生成途径为从头合成[11, 32-34]. 从排放量来看，2004年我国钢铁行业大气PCDD/Fs排放量为1923 g TEQ，而针对2016年的研究则估算为5333 g TEQ，同2004年相比PCDD/Fs排放量增加177.3%[3-4]. 我国钢铁生产行业大气PCDD/Fs排放的90%以上集中在3个环节：铁矿石烧结（60%以上）、电弧炉炼钢（20%—30%）和炼焦（5%—10%）[35-36]，因此后续研究控制应重点关注这些主要过程.

      汤铃等[30]对我国966家钢铁企业（占我国粗钢产量96.4%）进行研究表明，2018年我国钢铁行业烧结和电炉工序的PCDD/Fs排放因子分别为1583、1246 ng I-TEQ·t−1，而炼焦等其它工序的排放因子小于300 ng I-TEQ·t−1；关于烧结和电炉排放PCDD/Fs的研究结果与Wang等[37-38]的结果基本一致（1330—7610 ng·t−1 I-TEQ和177—869 ng·t−1 I-TEQ），但远高于2020年杨艳艳等[36]的研究结果（（180±220）ng·t−1 I-TEQ和（270±230 ng·t−1 ）I-TEQ），这可能与后者所涉及的研究企业数量较少、生产工艺和污染控制措施较为先进等因素有关. 根据汤铃[30]等获得的排放因子和高炉炼铁物料平衡关系（每 t生铁需要1.6 t铁矿石和0.4 t焦炭）[39-41]，结合我国2020年生铁和粗钢产量（分别为88898、106477万 t）[6]，2020年我国烧结和电弧炉炼钢大气PCDD/Fs排放量分别为2252 g I-TEQ和133 g I-TEQ（焦炭和转炉炼钢分别为57 g I-TEQ、266 g I-TEQ），明显高于固体废弃物焚烧的PCDD/Fs估算值.

      总体来看，相比于2004年，2016年我国钢铁行业大气PCDD/Fs排放量增加3410 g TEQ（117.3%），排放占比升高13.3%[3-4]；同时结合现有数据对我国钢铁行业大气PCDD/Fs的排放进行计算，结果表明目前钢铁行业仍具有较高的大气PCDD/Fs排放水平，因此，针对该行业PCDD/Fs排放及其控制的研究仍需持续加强.

      • 1.3.   有色金属生产

    • 有色金属生产包括有色金属生产和再生有色金属生产，其中再生有色金属生产因原料中含废弃导线、电子部件和废旧塑料等，为PCDD/Fs的产生提供了丰富的氯源，经物料中的铜、铁等金属的催化后可生成大量PCDD/Fs（与有色金属生产相比可增加1—3个数量级）[37, 42-43]. 有色金属种类丰富，原料和生产工艺的不同对PCDD/Fs的排放特征和排放量有较大影响，但多数研究表明有色金属行业排放的PCDD/Fs主要源于铝、铜、铅生产过程[42, 44].

      从指纹分布来看，铜生产过程中产生的PCDD/Fs多以7—8氯代同族体为主，且高氯代单体比例同原料中废铜含量成正比；而铝、铅、镁生产过程中多以4—7氯代同族体为主，主要生成途径为从头合成[45-48]. 从排放量来看，2004年我国有色金属行业大气PCDD/Fs排放量为563 g I-TEQ[3]；近年来关于有色金属行业PCDD/Fs排放的研究数据较少，文献报道2013年再生铝生产过程中PCDD/Fs排放量为609 g I-TEQ[42]，高于2004年有色金属行业的总排放量，由此推测2004至2013年有色金属生产行业PCDD/Fs排放量可能呈现出一定的增加趋势.

      聂志强[49]对铜、镁冶炼以及废旧导线焚烧回收过程的研究表明，PCDD/Fs排放因子范围为38.5—5569 ng·t−1 TEQ；这与Yu等[38, 50]的研究结果基本一致（14.2—24451 ng·t−1 I-TEQ），但远低于Zou等[37]的研究结果（0.24—1.7 g·t−1 I-TEQ，其中二次铅生产的排放因子为4297 ng·t−1 I-TEQ）. 排放因子范围变化较大的原因可能与有色金属类型、生产原料、生产工艺和控制措施等有关. 目前有色金属产量以精炼铜、电解铝以及十种有色金属总产量来核算，因此难以对有色金属行业排放的PCDD/Fs进行相对精细的计算，但2004至2020年我国十类有色金属总产量从1430万t增加到6188万t[6, 51]，相关生产过程排放的PCDD/Fs总量可能出现相应增加.

      • 1.4.   水泥窑协同处置

    • 因固体废弃物中含有水泥生产所需的部分原料，同时水泥窑的工作温度较高（1600 ℃以上）、物料停留时间长（30 min以上），因此水泥窑常被开发用于固体废弃物的协同处置[52-53]. 但固体废弃物中的大量氯源和金属催化剂在高温过程中可能导致PCDD/Fs的产生[3]，因此水泥窑协同处置也是PCDD/Fs的排放源. 水泥窑协同处置过程中废弃物的类型、添加量、处理工艺等均会影响PCDD/Fs的排放特征和排放量[54].

      从指纹分布特征看，除少数样品中PCDD/Fs以7—8氯代同族体为主外，大部分水泥窑协同处置过程产生的PCDD/Fs以4—6氯代同族体为主[53-56]，主要生成途径为从头合成. 从排放量看，2004年我国水泥生产过程PCDD/Fs排放量为365.3 g TEQ[3]. 张婧等[57]研究指出，不同炉型的水泥窑PCDD/Fs排放因子差别可达100倍，而我国主要采用的水泥立窑生产工艺，PCDD/Fs排放因子为5.0 μg·t−1 TEQ，远高于干法旋窑. Aykan[58]对协同处置危险废物和医疗废弃物的水泥窑进行研究，结果表明烟气中PCDD/Fs排放量为每年0.02 g. 2018年Zou等[55]研究指出，我国水泥窑协同处置过程PCDD/Fs排放因子为0.01—1.35 mg·t−1 I-TEQ. 尽管2020年我国水泥生产高达339736万 t[6]，但其中协同处置固体废弃物生产的水泥比例并不清晰，无法对该过程PCDD/Fs排放量进行计算[59]. 以水泥工业计划中提出的2015年建成10%的协同处置水泥厂的目标来推算[59]，水泥窑PCDD/Fs排放量将达到2397 g I-TEQ，这与钢铁生产行业的排放量几乎相当. 由于我国水泥窑协同处置固体废弃物的生产线投产较晚，相关研究的基础数据仍然较少，因此加强水泥窑协调处置固体废弃物过程中PCDD/Fs的排放监测研究十分必要，可为准确评估该行业PCDD/Fs排放量提供重要科学依据.

      • 1.5.   不同工业过程PCDD/Fs排放特征比较

    • 基于以上排放特征分析，固体废弃物焚烧、钢铁生产和铜生产排放的PCDD/Fs多以7—8氯代同族体为主，而水泥窑协同处置和铅、铝等有色金属生产过程中多以4—6/7氯代同族体为主；尽管不同行业的PCDD/Fs指纹分布特征有所不同，但均以呋喃类为主要同族体，表明其来源主要为从头合成机理[20, 34, 45, 54].

      从排放量分析（表1，图1），PCDD/Fs排放量依次为钢铁生产>固体废弃物焚烧>有色金属生产>水泥窑协同处置；依据现有文献数据进行估算，2020年PCDD/Fs排放量依次为钢铁生产>水泥窑协同处置>有色金属色生产>固体废弃物焚烧，但水泥窑协同处置的排放量存在较大不确定性，仍需要更多的研究结果进行支撑.

    2.   不同工业烟气PCDD/Fs污染控制技术（Control technology of PCDD/Fs in different industrial processes）

    • 相比于发达国家，我国PCDD/Fs污染控制工作起步较晚[67]. 根据PCDD/Fs的生成机理及其来源，PCDD/Fs的控制主要针对生成前、生成中和生成后三个过程开展相关工作[44]. 原料中的PCDD/Fs大多在高温下可直接分解，因此高温再生成是PCDD/Fs排放量的主要来源，故PCDD/Fs的控制减排主要通过控制运行的工作参数、添加抑制剂或增加末端空气污染控制装置（APCDs）等措施[68]（详见表2），本文主要针对工业烟气末端处理装置及其控制效果进行综述介绍.

      由于不同行业烟气中PCDD/Fs的排放特征和浓度有所差别，烟气温度、烟气量、烟气中粉尘和氮氧化物等常规污染物的种类和数量相差较大，因此不同行业APCDs存在一定差异，而PCDD/Fs多以协同净化为主[81]，且不同行业排放控制标准不尽相同（见表3），因此本文针对不同行业的措施效果分别进行综述.

      • 2.1.   固体废弃物焚烧

    • 固体废弃物焚烧作为PCDD/Fs主要的排放源，相关控制技术比较完善[7]. Wei等[89]研究发现，经过垃圾发酵等预处理措施和焚烧参数控制后，采用半干洗涤器（SDS）+干洗涤器（DS）+活性炭喷射（AC）+袋式除尘器（BF）+选择性催化还原（SCR）技术组成的APCDs对烟气中PCDD/Fs进行脱除，最终的排放水平可达0.0028 ng·m−3I-TEQ，远低于0.1 ng·m−3 I-TEQ的控制标准；许多研究也表明，通过良好的过程和末端控制，固体废弃物焚烧厂烟气中PCDD/Fs的排放基本都能满足相关标准要求[25, 90-91]. 值得注意的是，一些研究也报道了焚烧厂由于控制技术不达标或不稳定，造成存在PCDD/Fs超标排放的现象（排放水平最高可达8.12 ng·m−3 I-TEQ，均值为0.423 ng·m−3 I-TEQ）[20, 24-26, 92-95]. 基于已有文献报道（表4），目前固体废弃物焚烧行业的PCDD/Fs末端控制技术基本以AC+BF为主，配以SDS、DS、WS、SCR、SCNR等不同技术组成APCDs，可有效降低烟气中PCDD/Fs浓度[96-98].

      • 2.2.   钢铁生产

    • 钢铁生产流程较长，不同工序烟气理化性质差异较大，其中烧结因烟气温度高、含尘量大等原因不适合使用BF，而静电除尘器（ESP）使用较为普遍[99]. 2018年，我国烧结和炼钢的PCDD/Fs达标率仅为33.3%和66.7%[100-101]. 近期研究表明[36, 102]，截止2021年，我国钢铁行业排放烟气中PCDD/Fs的浓度范围为0.05—2.93 ng·m−3 I-TEQ，均值为0.42 ng·m−3 I-TEQ，同2005—2019年相比下降1—2个数量级，能够满足0.5 ng·m−3 I-TEQ的排放要求. 钢铁生产行业的PCDD/Fs末端控制技术以ESP或BF为主，配备SCR、湿法脱硫等脱硫脱硝技术组成的APCDs（表4），可对PCDD/Fs等污染物进行协同控制. 尽管排放烟气中PCDD/Fs的浓度能够达到0.5 ng·m−3 I-TEQ的排放要求，但其排放浓度仍普遍高于固体废弃物焚烧行业. 因此钢铁行业尤其是烧结、电炉炼钢等工序的PCDD/Fs排放形势仍较为严峻，相关污染控制研究工作需进一步加强.

      • 2.3.   有色金属生产

    • 有色金属生产通常采用的烟气PCDD/Fs控制技术见表4. 目前我国对再生有色金属生产行业烟气PCDD/Fs的排放限值为0.5 ng·m−3 TEQ [87]. 研究表明[47, 103]，有色金属生产厂采用以BF或ESP为主要控制技术时，烟气中PCDD/Fs排放水平为0.009—0.13 ng·m−3 I-TEQ，能够持续满足0.5 ng·m−3 TEQ的限值要求. 但部分工厂排放PCDD/Fs的水平接近甚至超过限值要求（表4），且有色金属生产厂PCDD/Fs排放超标率可达22.2%[101]. 这表明能否有效利用现有控制技术（如BF或ESP为主的烟气污染控制系统）对有色金属行业的PCDD/Fs污染控制具有重要影响.

      • 2.4.   水泥窑协同处置

    • 水泥窑协同处置行业针对烟气污染采取的控制技术和手段见表4. 水泥工业本身对排放的烟气中PCDD/Fs浓度水平并无明确限值，目前协同处置固体废物的水泥窑烟气中PCDD/Fs排放限值为0.1 ng·m−3 TEQ [88, 104]. 尽管水泥窑协同处置固体废物时原料中PCDD/Fs浓度较高，但经过高温分解处理后，烟气采用BF、BF+SNCR（选择性非还原催化）或ESP为主的APCDs进行净化，PCDD/Fs排放水平可达0.011—0.076 ng·m−3 I-TEQ[55, 103, 105-106]，均可使PCDD/Fs以较低浓度排放.

      • 2.5.   不同工业过程PCDD/Fs污染控制效果比较

    • 从表4中可以看出，目前固体废弃物焚烧行业多以BF或AC+BF为主要技术，配备SDS、DS等非ESP技术组成的APCDs对烟气进行深度净化；钢铁生产、有色金属生产、水泥窑协同处置行业则以BF或ESP为主要技术，配备SDS、脱硫脱硝等技术组成的APCDs对烟气进行处理. 当过程控制和末端控制均能得到有效保障时，烟气中PCDD/Fs的排放水多处于较低水平，但钢铁生产和有色金属生产的PCDD/Fs排放强度仍然明显高于其他行业.

    3.   结果与展望（Results and perspectives）

    • 本文系统的总结了固体废弃物焚烧、钢铁生产、有色金属生产和水泥窑协同处置等四类主要行业烟气中PCDD/Fs排放特征及污染控制的研究进展. 从排放特征来看，水泥窑协同处置行业排放的PCDD/Fs以4—6/7氯代同族体为主要单体，而固体废弃物焚烧、钢铁生产、有色金属生产等行业排放的PCDD/Fs以7—8氯代同族体为主，四类工业源的主要生成机理均为从头合成；从现有排放量数据来看，2004—2016年我国大气PCDD/Fs总排放量上升明显，PCDD/Fs排放量依次为：钢铁生产>固体废弃物焚烧>有色金属生产>水泥窑协同处置；依据现有文献数据进行估算，2020年PCDD/Fs排放量依次为钢铁生产>水泥窑协同处置>有色金属色生产>固体废弃物焚烧，但水泥窑协同处置固体废弃物产生PCDD/Fs的研究仍比较有限，相关工作亟需加强.

      从烟气中PCDD/Fs的控制技术来看，在传统污染控制装置基础上增加活性炭吸附、催化剂、抑制剂等可以有效降低PCDD/Fs的大气排放[117-119]. 但目前各类工业源的PCDD/Fs末端控制多以除尘器结合吸附脱除装置为主，并未实现PCDD/Fs的总量削减；此外由于记忆效应导致的PCDD/Fs排放水平变化以及飞灰中高浓度PCDD/Fs带来的固废处置问题也给现有技术升级带来较大难度[46, 89, 120-123]，因此，如何有效控制PCDD/Fs的排放总量仍然面临极大挑战. 末端控制技术方面，AC+BF吸附技术存在活性炭使用量大、价格高、活性炭吸附效率低、存在记忆效应、产生高毒性粉煤灰等缺点[108, 124-127]，近年来，生物质制备活性炭、活性炭改性处理、双袋式除尘器、喷射聚丙烯胺、协同处置粉煤灰、热等离子体、紫外光降解等技术逐渐得到开发，能够有效改善或避免吸附法存在的问题[76-80, 128-136]，然而诸多新技术尚停留在实验室阶段，且PCDD/Fs降解技术还存在反应时间长、去除效率不稳定等问题[137-140]. 因此尚无法在企业层面上推广应用.

      一些针对工业过程中PCDD/Fs生成的研究发现，传统硫脲、硫酸铵等含N或含S的抑制剂存在氨溢出、额外成本等问题，研发使用无氨溢出风险的氧化钙，或采用含N或P的污泥等作为抑制剂可降低污染控制成本，且具有良好的抑制PCDD/Fs生成的控制效果[141-145]，可能是未来控制某些工业过程中PCDD/Fs排放的重要技术手段.

      基于以上研究现状，本文对典型工业过程中PCDD/Fs排放特征及其污染控制研究做以下两方面展望：

      （1） 工业过程是PCDD/Fs人为排放的主要来源，尽管我国已经制定了相关行业的排放标准，排放总量也有所下降，但是部分行业仍然存在PCDD/Fs排放量增加的趋势，因此及时更新典型行业PCDD/Fs排放因子并完善排放清单，对于我国履行《斯德哥尔摩公约》和降低PCDD/Fs暴露风险具有重要意义.

      （2） 对工业排放PCDD/Fs的控制应遵循“源头-过程-末端”的全过程控制原则. 开发新技术新材料，通过对原料预处理等措施从源头上弱化PCDD/Fs生成条件；通过添加抑制剂等措施从过程中减少PCDD/Fs的生成；积极研发PCDD/Fs的催化降解技术，结合活性炭吸附等末端控制技术可实现PCDD/Fs排放总量的有效削减.

    参考文献 (145)

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