二 恶英生成抑制剂及其阻滞机理研究现状与展望

doi:10.16085/j.issn.1000-6613.2019-0671

摘要/Abstract

摘要：

固体废物焚烧过程产生的二英类物质具剧毒性且可在环境中造成持久性污染，国内外学者一直致力于探究高效的二英类物质源头减量化技术以保护公众健康。本文综述了近年来二英类物质从头合成的生成阻滞研究现状，对比分析了实验研究中常采用的含硫类抑制剂、含氮类抑制剂、含OH基抑制剂及复合抑制剂对二英类物质的抑制效果及其阻滞机理，进而剖析二英生成抑制剂的研发思路进展。在当前以抑制氯源和催化剂活性为主的抑制途径基础上，依据二英类物质的从头合成机理，探讨了通过阻滞碳源或氧气与反应物接触进而阻滞从头合成反应的抑制新途径，并展望了未来新型阻滞剂研发的方向，以期为二英类物质的源头减量和污染控制提供理论支持。抑制剂工业化应用和推广仍处于尝试阶段，在实际规模的焚烧厂应用时抑制效果不稳定，未来仍需进一步开展中试和现场试验以验证抑制作用实效及其影响因素。

关键词: 二英类物质, 废物处理, 源头减量, 过程控制, 催化, 抑制机理

Abstract:

PCDD/Fs formed in the incineration of municipal solid waste are highly toxic and can cause persistent environmental pollution. Efficient source reduction technologies for PCDD/Fs pollution control have been explored to protect human health. The paper reviewed the research progresses in developing inhibitors on de novo formation of PCDD/Fs in recent years. The inhibitory effects and suppressing mechanisms of the inhibitors widely used in laboratory tests were summarized, including sulfur-containing inhibitors, nitrogen-containing inhibitors, OH-containing inhibitors and complex inhibitors. The research and developing ideas were discussed and new potential pathways were proposed based on the formation mechanisms of PCDD/Fs, which is to prevent carbon source or oxygen from synthesis from de novo synthesis in addition to limiting chlorine source and the activity of the catalyst. The possible directions for new highly efficient inhibitors and their pilot verification were discussed, which provides the scientific basis for the source reduction and pollution control of PCDD/Fs. The industrial application of inhibitors is still in trial stage and unstable inhibitory effects have been reported in a few tests in full-scale incineration plants. Further studies and tests in pilot and full-scale incinerators are required to verify the inhibitory effects of the inhibitors and their influencing factors in the future.

Key words: PCDD/Fs, waste treatment, source reduction, process control, catalysis, inhibiting pathways

中图分类号:

X705

章骅,杨瑞,邵立明,何品晶. 二恶英生成抑制剂及其阻滞机理研究现状与展望[J]. 化工进展, 2020, 39(4): 1485-1492.

Hua ZHANG,Rui YANG,Liming SHAO,Pinjing HE. Progresses in the inhibitors for suppressing de novo formation ofPCDD/Fs: a review[J]. Chemical Industry and Engineering Progress, 2020, 39(4): 1485-1492.

图/表 4

表1 二英类物质从头合成抑制的研究进展

抑制剂种类	抑制剂用量	飞灰^⑥	反应条件^⑦	抑制率	抑制作用机理	参考文献
S^①	S/Cl=0.5 S/Cl=1 S/Cl=2 S/Cl=3	实际静电除尘飞灰经甲苯索提两次去除PCDD/Fs，干燥后用于实验，3g	10% O₂+15% H₂O+N₂，1L/min，300℃，60min	32.1% 44.3% 54.2% 30.1%	S与CuO/CuCl₂反应生成 Cu₂SO₄/CuSO₄，钝化铜的催化能力，阻滞PCDD/Fs从头合成，部分S单质在300℃可被氧化生成SO₂/SO₃，进而阻滞PCDD/Fs生成	[39]
SO₂^①	50% SO₂+ 5% O₂+ 45% N₂	0.44g实际飞灰（甲苯索提24h）+0.428mmol NaCl+1.998 mmol C+0.064mmol CuCl₂·2H₂O	50% SO₂+5% O₂+45% N₂，20mL/min，340℃，1h	21.1%	CuCl₂被SO₂转化为硫酸盐，硫酸盐在热力学上更加稳定，催化能力弱	[37,52]
SO₂^①	150μL/L （S/Cl=0.25）	100g模拟飞灰：3.2% C+0.09% Cu（加入CuO，以Cu计）+石英基质，600μL/L Cl₂	10% O₂+10% H₂O+N₂，400mL/min，350℃，30min	90.3%	CuO被转化为CuSO₄，催化能力减弱	[53]
SO₃^①	135μL/L （S/Cl=0.225）	100g模拟飞灰：3.2% C+0.09% Cu（加入CuO，以Cu计）+石英基质，600μL/L Cl₂	10% O₂+10% H₂O+N₂，400mL/min，350℃，30min	90.5%	CuO被转化为CuSO₄，催化能力减弱	[53]
(NH₄)₂SO₄^①,②	0.1g	2g模拟飞灰：3.1% C+96.7%石英砂+0.2% CuCl₂·2H₂O	10% O₂+90% N₂，350℃，60min	93.0%	(NH₄)₂SO₄可减少气相中氯气的生成进而阻断氯与有机物反应，减少PCDD/Fs的生成	[40]
CH₄N₂S^①,②	0.06g	2g模拟飞灰：3.0% C+91.8% SiO₂+5% NaCl+0.2% CuCl₂·2H₂O	1.12% O₂+N₂，300mL/min，350℃，50min	99.8%	胺既可与金属结合降低金属的催化性能，亦可胺化有机物，从而抑制氯化反应生成PCDD/Fs	[41]
(NH₄)₂S₂O₃^①,②	0.06g	2g模拟飞灰：3.0% C+91.8% SiO₂+5% NaCl+0.2% CuCl₂·2H₂O	1.12% O₂+N₂，300mL/min，350℃，50min	85.4%	胺既可与金属结合降低金属的催化性能，亦可胺化有机物，从而抑制氯化反应生成PCDD/Fs	[41]
CO(NH₂)₂^②	0.1g	2g模拟飞灰：3.1% C+96.7%石英砂+0.2% CuCl₂·2H₂O	10% O₂+90% N₂，350℃，60min	55.0%	分解形成氨气，氨气的强还原性可将Cl₂转化为氯化能力较差的物质	[40]
氟化氢铵^②	$C u / H F 2 - = 1$	5g模拟飞灰：10% CuCl₂·2H₂O+20% 活性炭+石英基质	20% O₂+80% N₂,1L/min，400℃，60min	61.1%^⑤	$C u C l 2 + N H 4 H F 2 → C u F 2 + N H 3 + 2 H C l$	[46]
溴化铵^②	$C u / B r - = 1$			35.8%^⑤	$C u C l 2 + ? 2 N H 4 B r → ?? C u B r 2 + 2 N H 3 + 2 H C l$	[46]
NH₄H₂PO₄^②	$C u / H 2 P O 4 - = 1$			98.1%^⑤	$C u C l 2 + ? 2 N H 4 H 2 P O 4 → C u (P O 3) 2 + 2 H C l + 2 N H 3 + 2 H 2 O$	[46]
(NH₄)₂SO₄^①,②	$C u / S O 4 2 - = 1$			88.8%^⑤	$C u C l 2 + (N H 4) 2 S O 4 → C u S O 4 + 2 N H 3 + 2 H C l$	[46]
NH₃^②	350μL/L 1000μL/L	10g模拟飞灰：石墨粉+CuCl₂·2H₂O（Cl为1%）	2.5% O₂+97.5% Ar，2L/min，15min升温至300℃，再恒温120min	25.9% 55.5%	供碳能力对PCDD/Fs形成极为重要，同时NH₃对HCl也有很好的结合作用，通过凝结成NH₄Cl的途径能够去除97%的HCl	[54]
NaOH^③	2% 5%	5g实际飞灰，收集于静电除尘器，未添加活性炭及石灰	10% O₂+90% N₂,50mL/min，300℃，30min	19.0% 96.0%	NaOH与金属氯化物快速反应降低其催化能力和供氯能力	[50]
NaHCO₃^③	2% 5%	5g实际飞灰，收集于静电除尘器，未添加活性炭及石灰	10% O₂+90% N₂,50mL/min，300℃，30min	25.0% 50.0%	NaHCO₃与金属氯化物快速反应降低其催化能力和供氯能力	[50]
Ca(OH)₂^③	2% 5%	5g实际飞灰，收集于静电除尘器，未添加活性炭及石灰	10% O₂+90% N₂,50mL/min，300℃，30min	27.0% 67.0%	Ca(OH)₂与金属氯化物快速反应降低其催化能力和供氯能力	[50]
H₂O^③	10%	2g模拟飞灰：3.2% C+0.09% Cu （加入CuCl₂，以Cu计）+石英基质	10% O₂+10% H₂O+N₂，360mL/min，300℃，30min	10%~40%	$H 2 O + 2 C u C l 2 → C u C l 2 ? C u O + 2 H C l$	[55]
H₂O₂+SO₂^④	6% H₂O₂,0.1mmol/min	0.44g实际飞灰（甲苯索提24h）+0.428mmol NaCl+1.998 mmol C+0.064mmol CuCl₂·2H₂O	50% SO₂+5% O₂+45% N₂，20mL/min，340℃，60 min	77.2%	$C u C l 2 + H 2 O 2 → C u O + C l 2 + H 2 O$ $C u C l 2 + H 2 O ? + S O 2 + 1 / 2 O 2 → C u S O 4 + ? 2 H C l$	[37]
H₂O₂+H₂SO₄^④	9.5% H₂O₂,0.1mmol/min		50% SO₂+5% O₂+45% N₂，20mL/min，340℃，60 min	85.3%	$C u C l 2 + H 2 O 2 → C u O + C l 2 + H 2 O$ H₂SO₄的强氧化性催生了·OH，加快反应	[37]
(NH₂)₂CO+S^④	5%(NH₂)₂CO+5% S	10g模拟垃圾：72%褐煤+12.0%垃圾+6.0%聚氯乙烯	空气10% O₂+90% N₂，2L/min，400℃，30min	93.0%	同时发挥S及尿素的抑制作用，阻滞二英类物质的生成	[56]

表1 二英类物质从头合成抑制的研究进展

抑制剂种类	抑制剂用量	飞灰^⑥	反应条件^⑦	抑制率	抑制作用机理	参考文献
S^①	S/Cl=0.5 S/Cl=1 S/Cl=2 S/Cl=3	实际静电除尘飞灰经甲苯索提两次去除PCDD/Fs，干燥后用于实验，3g	10% O₂+15% H₂O+N₂，1L/min，300℃，60min	32.1% 44.3% 54.2% 30.1%	S与CuO/CuCl₂反应生成 Cu₂SO₄/CuSO₄，钝化铜的催化能力，阻滞PCDD/Fs从头合成，部分S单质在300℃可被氧化生成SO₂/SO₃，进而阻滞PCDD/Fs生成	[39]
SO₂^①	50% SO₂+ 5% O₂+ 45% N₂	0.44g实际飞灰（甲苯索提24h）+0.428mmol NaCl+1.998 mmol C+0.064mmol CuCl₂·2H₂O	50% SO₂+5% O₂+45% N₂，20mL/min，340℃，1h	21.1%	CuCl₂被SO₂转化为硫酸盐，硫酸盐在热力学上更加稳定，催化能力弱	[37,52]
SO₂^①	150μL/L （S/Cl=0.25）	100g模拟飞灰：3.2% C+0.09% Cu（加入CuO，以Cu计）+石英基质，600μL/L Cl₂	10% O₂+10% H₂O+N₂，400mL/min，350℃，30min	90.3%	CuO被转化为CuSO₄，催化能力减弱	[53]
SO₃^①	135μL/L （S/Cl=0.225）	100g模拟飞灰：3.2% C+0.09% Cu（加入CuO，以Cu计）+石英基质，600μL/L Cl₂	10% O₂+10% H₂O+N₂，400mL/min，350℃，30min	90.5%	CuO被转化为CuSO₄，催化能力减弱	[53]
(NH₄)₂SO₄^①,②	0.1g	2g模拟飞灰：3.1% C+96.7%石英砂+0.2% CuCl₂·2H₂O	10% O₂+90% N₂，350℃，60min	93.0%	(NH₄)₂SO₄可减少气相中氯气的生成进而阻断氯与有机物反应，减少PCDD/Fs的生成	[40]
CH₄N₂S^①,②	0.06g	2g模拟飞灰：3.0% C+91.8% SiO₂+5% NaCl+0.2% CuCl₂·2H₂O	1.12% O₂+N₂，300mL/min，350℃，50min	99.8%	胺既可与金属结合降低金属的催化性能，亦可胺化有机物，从而抑制氯化反应生成PCDD/Fs	[41]
(NH₄)₂S₂O₃^①,②	0.06g	2g模拟飞灰：3.0% C+91.8% SiO₂+5% NaCl+0.2% CuCl₂·2H₂O	1.12% O₂+N₂，300mL/min，350℃，50min	85.4%	胺既可与金属结合降低金属的催化性能，亦可胺化有机物，从而抑制氯化反应生成PCDD/Fs	[41]
CO(NH₂)₂^②	0.1g	2g模拟飞灰：3.1% C+96.7%石英砂+0.2% CuCl₂·2H₂O	10% O₂+90% N₂，350℃，60min	55.0%	分解形成氨气，氨气的强还原性可将Cl₂转化为氯化能力较差的物质	[40]
氟化氢铵^②	$C u / H F 2 - = 1$	5g模拟飞灰：10% CuCl₂·2H₂O+20% 活性炭+石英基质	20% O₂+80% N₂,1L/min，400℃，60min	61.1%^⑤	$C u C l 2 + N H 4 H F 2 → C u F 2 + N H 3 + 2 H C l$	[46]
溴化铵^②	$C u / B r - = 1$			35.8%^⑤	$C u C l 2 + ? 2 N H 4 B r → ?? C u B r 2 + 2 N H 3 + 2 H C l$	[46]
NH₄H₂PO₄^②	$C u / H 2 P O 4 - = 1$			98.1%^⑤	$C u C l 2 + ? 2 N H 4 H 2 P O 4 → C u (P O 3) 2 + 2 H C l + 2 N H 3 + 2 H 2 O$	[46]
(NH₄)₂SO₄^①,②	$C u / S O 4 2 - = 1$			88.8%^⑤	$C u C l 2 + (N H 4) 2 S O 4 → C u S O 4 + 2 N H 3 + 2 H C l$	[46]
NH₃^②	350μL/L 1000μL/L	10g模拟飞灰：石墨粉+CuCl₂·2H₂O（Cl为1%）	2.5% O₂+97.5% Ar，2L/min，15min升温至300℃，再恒温120min	25.9% 55.5%	供碳能力对PCDD/Fs形成极为重要，同时NH₃对HCl也有很好的结合作用，通过凝结成NH₄Cl的途径能够去除97%的HCl	[54]
NaOH^③	2% 5%	5g实际飞灰，收集于静电除尘器，未添加活性炭及石灰	10% O₂+90% N₂,50mL/min，300℃，30min	19.0% 96.0%	NaOH与金属氯化物快速反应降低其催化能力和供氯能力	[50]
NaHCO₃^③	2% 5%	5g实际飞灰，收集于静电除尘器，未添加活性炭及石灰	10% O₂+90% N₂,50mL/min，300℃，30min	25.0% 50.0%	NaHCO₃与金属氯化物快速反应降低其催化能力和供氯能力	[50]
Ca(OH)₂^③	2% 5%	5g实际飞灰，收集于静电除尘器，未添加活性炭及石灰	10% O₂+90% N₂,50mL/min，300℃，30min	27.0% 67.0%	Ca(OH)₂与金属氯化物快速反应降低其催化能力和供氯能力	[50]
H₂O^③	10%	2g模拟飞灰：3.2% C+0.09% Cu （加入CuCl₂，以Cu计）+石英基质	10% O₂+10% H₂O+N₂，360mL/min，300℃，30min	10%~40%	$H 2 O + 2 C u C l 2 → C u C l 2 ? C u O + 2 H C l$	[55]
H₂O₂+SO₂^④	6% H₂O₂,0.1mmol/min	0.44g实际飞灰（甲苯索提24h）+0.428mmol NaCl+1.998 mmol C+0.064mmol CuCl₂·2H₂O	50% SO₂+5% O₂+45% N₂，20mL/min，340℃，60 min	77.2%	$C u C l 2 + H 2 O 2 → C u O + C l 2 + H 2 O$ $C u C l 2 + H 2 O ? + S O 2 + 1 / 2 O 2 → C u S O 4 + ? 2 H C l$	[37]
H₂O₂+H₂SO₄^④	9.5% H₂O₂,0.1mmol/min		50% SO₂+5% O₂+45% N₂，20mL/min，340℃，60 min	85.3%	$C u C l 2 + H 2 O 2 → C u O + C l 2 + H 2 O$ H₂SO₄的强氧化性催生了·OH，加快反应	[37]
(NH₂)₂CO+S^④	5%(NH₂)₂CO+5% S	10g模拟垃圾：72%褐煤+12.0%垃圾+6.0%聚氯乙烯	空气10% O₂+90% N₂，2L/min，400℃，30min	93.0%	同时发挥S及尿素的抑制作用，阻滞二英类物质的生成	[56]

图1 固体废物焚烧发电工艺简图

图2 从头合成PCDD/Fs的阻滞机理

图3 从头合成PCDD/Fs的可能抑制新途径

参考文献 62

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