垃圾焚烧飞灰重金属药剂稳定化研究进展

doi:10.16085/j.issn.1000-6613.2020-2508

摘要/Abstract

摘要：

生活垃圾焚烧飞灰中存有大量高毒性的重金属物质，若不规范处置容易对土壤、地下水造成严重污染，目前通常采用添加化学药剂的方法来稳定飞灰中的重金属。本文在梳理国内外文献的基础上，归纳评述了飞灰重金属的性质、固化稳定化填埋工艺以及目前已被研究或应用的飞灰重金属稳定药剂，包括硫化钠、磷酸、无定形硅材料、铁化合物等无机药剂以及硫脲、EDTA接聚体、壳聚糖、氨基硫代羧酸盐等有机螯合剂，阐明了药剂作用机制和存在的问题，总结了不同药剂作用下的重金属稳定效果，同时针对新形势下的飞灰重金属稳定化要求进行了探讨，提出今后的研究方向为：选择特征性重金属药剂复配稳定飞灰；以改性、成环方式改良氨基硫代羧酸盐类物质（DTC）物质或以交联接枝等方式开发新型螯合剂。

关键词: 垃圾焚烧飞灰, 重金属, 稳定化, 无机药剂, 有机螯合剂

Abstract:

There are abundant highly toxic heavy metals in municipal solid waste incineration fly ash. Without properly disposed, it will cause serious pollution to the soil and groundwater, thus, the addition of chemical agents to stabilize the heavy metals in fly ash is vital. On the basis of reviewing the literatures at home and abroad, the characteristics of heavy metals, the solidification technology in landfills, and the heavy metal stabilization agents including inorganic agents (sodium sulfide, phosphoric acid, amorphous silicon, iron compound) and organic chelating agents (thiourea, EDTA polymer, chitosan, thiosamine carboxylate) of fly ash that had been studied or applied are reviewed. The mechanism of action and existing problems of these agents are clarified, and the stabilization effects under different agents are summarized. The requirements of heavy metal stabilization under the new situation are discussed, and suggestions and prospects are put forward, namely, selecting compound distinctive agents, improving DTC substances by means of modification and ring formation or developing new agents via cross-linking and grafting.

Key words: waste incineration fly ash, heavy metal, stabilization, inorganic agent, organic chelating agent

中图分类号:

X705

朱子晗, 陈卫华, 华银锋, 张海涛, 赵由才, 郭燕燕, 戴世金. 垃圾焚烧飞灰重金属药剂稳定化研究进展[J]. 化工进展, 2021, 40(11): 6358-6368.

ZHU Zihan, CHEN Weihua, HUA Yinfeng, ZHANG Haitao, ZHAO Youcai, GUO Yanyan, DAI Shijin. Research progress and consideration on medicament stabilization of heavy metals in waste incineration fly ash[J]. Chemical Industry and Engineering Progress, 2021, 40(11): 6358-6368.

图/表 7

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序号	焚烧工艺	烟气净化工艺	重金属总量/mg·kg^-1						文献
序号	焚烧工艺	烟气净化工艺	Pb	Cd	Cu	Zn	Cr	Ni	文献
1	流化床	SNCR+SM+AC+BDC	1300~1500	40~45	1600~1700	5000~5600	350~390	80~100	［7］
2	流化床	SNCR+EPS+SM+AC+BDC	700~800	30~35	1400~1500	3700~3800	290~310	110~130
3	炉排炉	SNCR+DM+AC+BDC	1000~1500	100~150	400~500	4000~4100	50~100	10~25
4	炉排炉	SNCR+DM+AC+BDC+GGH	1500~1800	140~160	50~60	5200~5500	130~175	25~30
5	炉排炉	SNCR+SM+DM+AC+BDC	1500~2300	100~140	600~1000	4200~6000	100~425	40~90
6	炉排炉	SNCR+DM+AC+BDC+WC	1200~2700	120~210	310~390	—	—	—

序号	焚烧工艺	烟气净化工艺	重金属总量/mg·kg^-1						文献
序号	焚烧工艺	烟气净化工艺	Pb	Cd	Cu	Zn	Cr	Ni	文献
1	流化床	SNCR+SM+AC+BDC	1300~1500	40~45	1600~1700	5000~5600	350~390	80~100	［7］
2	流化床	SNCR+EPS+SM+AC+BDC	700~800	30~35	1400~1500	3700~3800	290~310	110~130
3	炉排炉	SNCR+DM+AC+BDC	1000~1500	100~150	400~500	4000~4100	50~100	10~25
4	炉排炉	SNCR+DM+AC+BDC+GGH	1500~1800	140~160	50~60	5200~5500	130~175	25~30
5	炉排炉	SNCR+SM+DM+AC+BDC	1500~2300	100~140	600~1000	4200~6000	100~425	40~90
6	炉排炉	SNCR+DM+AC+BDC+WC	1200~2700	120~210	310~390	—	—	—

案例	基本情况	项目	重金属
案例	基本情况	项目	As	Cd	Cr	Cu	Pb	Zn	Hg	Ni		文献
1	宁波垃圾焚烧厂，工艺为炉排炉、半干袋式过滤器等	总量 /mg·kg^-1	156.85±6.20	254.79±4.48	98.34±6.65	545.43±18.16	2073.64±43.30	7787.15±65.81	—		—	［13］
1	宁波垃圾焚烧厂，工艺为炉排炉、半干袋式过滤器等	浸出浓度 /mg·L^-1	0.630±0.030	1.020±0.040	0.390±0.010	2.180±0.020	8.290±0.190	31.150±0.420	—		—	［13］
2	金山垃圾焚烧厂，工艺为机械炉排炉、烟气处理和烟气再热装置等	总量 /mg·kg^-1	65.10±4.52	64.76±5.05	132.89±10.77	603.41±31.52	2375.15±186.63	3487.65±278.64	100.78±8.52	23.58±1.39		［14］
2	金山垃圾焚烧厂，工艺为机械炉排炉、烟气处理和烟气再热装置等	浸出浓度 /mg·L^-1	0.022±0.003	0.101±0.023	0.123±0.025	13.876±1.734	9.983±0.865	5.413±0.352	0.149±0.010	ND		［14］
3	天津垃圾发电厂，工艺为链条锅炉、喷雾干燥、活性炭喷射和袋式除尘	总量 /mg·kg^-1	80.00±0.20	80.20±3.52	89.50±0.30	444.50±1.37	716.09±10.31	4795.28±20.04	0.31±0.01	445.09±11.16		［15］
3	天津垃圾发电厂，工艺为链条锅炉、喷雾干燥、活性炭喷射和袋式除尘	浸出浓度 /mg·L^-1	0.038±0.003	0.449±0.024	ND	0.680±0.172	0.530±0.062	4.602±0.921	ND	0.560±0.052		［15］
4	重庆市某生活垃圾焚烧厂布袋除尘器	总量 /mg·kg^-1	—	85.17	108.47	553.21	1086.86	5846.16	—	68.73		［16］
4	重庆市某生活垃圾焚烧厂布袋除尘器	浸出浓度 /mg·L^-1	—	0.280	0.500	0.210	3.350	0.85	—	0.790
填埋标准	GB 16889—2008	浸出浓度 /mg·L^-1	0.3	0.15	4.5	40	0.25	100	0.05	0.5

案例	基本情况	项目	重金属
案例	基本情况	项目	As	Cd	Cr	Cu	Pb	Zn	Hg	Ni		文献
1	宁波垃圾焚烧厂，工艺为炉排炉、半干袋式过滤器等	总量 /mg·kg^-1	156.85±6.20	254.79±4.48	98.34±6.65	545.43±18.16	2073.64±43.30	7787.15±65.81	—		—	［13］
1	宁波垃圾焚烧厂，工艺为炉排炉、半干袋式过滤器等	浸出浓度 /mg·L^-1	0.630±0.030	1.020±0.040	0.390±0.010	2.180±0.020	8.290±0.190	31.150±0.420	—		—	［13］
2	金山垃圾焚烧厂，工艺为机械炉排炉、烟气处理和烟气再热装置等	总量 /mg·kg^-1	65.10±4.52	64.76±5.05	132.89±10.77	603.41±31.52	2375.15±186.63	3487.65±278.64	100.78±8.52	23.58±1.39		［14］
2	金山垃圾焚烧厂，工艺为机械炉排炉、烟气处理和烟气再热装置等	浸出浓度 /mg·L^-1	0.022±0.003	0.101±0.023	0.123±0.025	13.876±1.734	9.983±0.865	5.413±0.352	0.149±0.010	ND		［14］
3	天津垃圾发电厂，工艺为链条锅炉、喷雾干燥、活性炭喷射和袋式除尘	总量 /mg·kg^-1	80.00±0.20	80.20±3.52	89.50±0.30	444.50±1.37	716.09±10.31	4795.28±20.04	0.31±0.01	445.09±11.16		［15］
3	天津垃圾发电厂，工艺为链条锅炉、喷雾干燥、活性炭喷射和袋式除尘	浸出浓度 /mg·L^-1	0.038±0.003	0.449±0.024	ND	0.680±0.172	0.530±0.062	4.602±0.921	ND	0.560±0.052		［15］
4	重庆市某生活垃圾焚烧厂布袋除尘器	总量 /mg·kg^-1	—	85.17	108.47	553.21	1086.86	5846.16	—	68.73		［16］
4	重庆市某生活垃圾焚烧厂布袋除尘器	浸出浓度 /mg·L^-1	—	0.280	0.500	0.210	3.350	0.85	—	0.790
填埋标准	GB 16889—2008	浸出浓度 /mg·L^-1	0.3	0.15	4.5	40	0.25	100	0.05	0.5

药剂种类	反应条件	药剂添加量及重金属稳定效果	文献
硫化钠	—	投加量为2%时，Pb和Cd的螯合率达到80%左右	［23］
磷酸	水灰比为30%~40%，搅拌时间20min	投加比为5%时，Cd的螯合率仅为33%，浸出浓度远超填埋场标准限值，而Pb、Cr则达到要求，螯合率均超过75%	［35］
磷酸	水灰比为30%左右，搅拌时间20min	投加量为5%时，Pb的螯合率超过80%，浸出浓度满足填埋场标准	［26］
磷酸钠	水灰比为20%	投加量为4%时，Pb、Cd的螯合率分别超过50%和45%，但浸出浓度均未满足填埋场标准的要求	［36］
磷酸氢二钠		Pb的螯合率高于磷酸钠，Cd的螯合率相反
磷酸二氢钠		Pb、Cd的稳定效果优于磷酸氢二钠，但浸出浓度未满足填埋场标准的要求
硫酸亚铁	水灰比为100%	投加量为4%时，Pb的稳定效果最佳，但浸出浓度仍为1.3mg·L^-1；对于Cd的稳定效果较差	［37］
重过磷酸钙	水灰比为25%左右，搅拌时间10min	投加量为5%时，Pb、Cd的浸出浓度分别为1.366mg·L^-1和0.166mg·L^-1	［38］
硅灰	水灰比50%，600℃热处理1h	投加量为10%时，Pb、Cd的浸出浓度分别为0.44mg·L^-1和0.05mg·L^-1	［39］