生活垃圾焚烧飞灰处理技术研究进展

doi:10.16085/j.issn.1000-6613.2024-0075

化工进展 ›› 2024, Vol. 43 ›› Issue (7): 4102-4117.DOI: 10.16085/j.issn.1000-6613.2024-0075

• 资源与环境化工 • 上一篇

生活垃圾焚烧飞灰处理技术研究进展

孔祥蕊¹^,²(), 董玥岑², 张蒙雨³, 王彪⁴, 尹水娥³, 陈冰³, 陆家纬³, 张媛³, 冯乐乐⁴(), 王洪涛², 徐海云³()

^1.中国城市建设研究院有限公司，北京 100120
^2.清华大学环境学院，北京 100084
^3.中城院（北京）环境科技股份有限公司，北京 100120
^4.中国矿业大学安全工程学院，江苏徐州 221116

收稿日期:2024-01-11 修回日期:2024-03-01 出版日期:2024-07-10 发布日期:2024-08-14
通讯作者: 冯乐乐,徐海云
作者简介:孔祥蕊（1996—），女，博士，研究方向为固体废物处置。E-mail：kongxiangrui121@mail.tsinghua.edu.cn。
基金资助:
国家自然科学基金面上项目(42177177);国家重点研发计划(2020YFC1910102)

Treatment technologies of fly ash from municipal solid waste incineration

KONG Xiangrui¹^,²(), DONG Yuecen², ZHANG Mengyu³, WANG Biao⁴, YIN Shui′e³, CHEN Bing³, LU Jiawei³, ZHANG Yuan³, FENG Lele⁴(), WANG Hongtao², XU Haiyun³()

^1.China Urban Construction Design & Research Institute Co. , Ltd. , Beijing 100120, China
^2.School of Environment, Tsinghua University, Beijing 100084, China
^3.CUCDE Environmental Technology Co. , Ltd. , Beijing 100120, China; School of Safety Engineering, China University of Mining and Technology, Xuzhou 2221116, Jiangsu, China

Received:2024-01-11 Revised:2024-03-01 Online:2024-07-10 Published:2024-08-14
Contact: FENG Lele, XU Haiyun

摘要/Abstract

摘要：

焚烧是我国生活垃圾最主要的处置手段，焚烧飞灰含有二英和重金属，属于危险废物，处理方式比较受限，但处理需求量大。推动生活垃圾焚烧飞灰无害化处置与资源化利用处理技术的发展，积极补齐城镇生活垃圾处理设施短板，符合国家节能减排与绿色发展的要求。本文系统分析了我国典型地区生活垃圾焚烧飞灰基础特性、二英和重金属产生特征，综述了飞灰二英的主要处理技术，包括高温烧结、高温熔融/玻璃化、水泥回转窑热处理、低温催化热解、水热处理技术、机械化学降解技术，对比了飞灰中重金属的主要处理方法，包括固化稳定化、固热处理、金属分离技术，并对飞灰处理技术的工程化应用进行总结与展望，以期为我国生活垃圾焚烧飞灰减量化、无害化、资源化技术发展提供理论支撑。

关键词: 生活垃圾, 焚烧, 飞灰, 二英, 重金属

Abstract:

Incineration is the primary method of municipal solid waste disposal in China, and the resulting fly ash contains dioxins and heavy metals, classifying it as hazardous waste. The treatment methods are relatively limited, but the demand for effective disposal is substantial. Promoting the development of technologies for the harmless disposal and resource utilization of municipal solid waste incineration fly ash, actively addressing the shortcomings in municipal solid waste treatment facilities, all align with the national requirements for energy conservation, emission reduction, and green development. This study systematically analyzed the basic characteristics of municipal solid waste incineration fly ash in typical regions of China, focusing on the generation of dioxins and heavy metals. It provided an overview of the main technologies for treating dioxins in fly ash, including sintering, melting/vitrification, cement kiln co-treatment, low-temperature pyrolysis, and mechanochemical techniques. The major methods for treating heavy metals in fly ash were compared, encompassing solidification/stabilization, thermal treatment, and heavy metal extraction technologies. The study gave a summary and outlook on the application of fly ash treatment technologies, aiming to guide the development of reduction, harmlessness, and resource utilization technologies for municipal solid waste incineration fly ash in China.

Key words: municipal solid waste, incineration, fly ash, dioxins, heavy metals

中图分类号:

X799.3

孔祥蕊, 董玥岑, 张蒙雨, 王彪, 尹水娥, 陈冰, 陆家纬, 张媛, 冯乐乐, 王洪涛, 徐海云. 生活垃圾焚烧飞灰处理技术研究进展[J]. 化工进展, 2024, 43(7): 4102-4117.

KONG Xiangrui, DONG Yuecen, ZHANG Mengyu, WANG Biao, YIN Shui′e, CHEN Bing, LU Jiawei, ZHANG Yuan, FENG Lele, WANG Hongtao, XU Haiyun. Treatment technologies of fly ash from municipal solid waste incineration[J]. Chemical Industry and Engineering Progress, 2024, 43(7): 4102-4117.

图/表 8

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69	HAGENMAIER Hanspaul, KRAFT Michael, BRUNNER Hermann, et al. Catalytic effects of fly ash from waste incineration facilities on the formation and decomposition of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans[J]. Environmental Science & Technology, 1987, 21(11): 1080-1084.
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地点	炉型	集中粒径/μm	CaO/%	SiO₂/%	K₂O/%	Al₂O₃/%	Fe₂O₃/%	Na₂O/%	Cl/%	SO₃/%	参考文献
国内
浙江	流化床	—	29.38	32.79	—	10.97	10.88	—	17.44	—	[13]
山东	炉排炉	—	45.52	1.28	10.85	0.56	1.05	13.73	16.17	5	[12]
山东	炉排炉	—	52.67	1.14	7.93	0.69	0.63	13.62	11.09	5.58
山东	炉排炉	—	61.49	2.67	5.07	0.56	1.92	1.18	17.7	5.97
浙江	炉排炉	—	74.11	2.91	1.74	0.68	1.13	0.34	11.56	4.66
浙江	炉排炉	—	45.11	1.53	1.81	0.26	28.2	—	2.82	3.31
上海	炉排炉	—	57.88	1.76	4.61	0.26	0.88	1.37	25.01	4.62
四川	炉排炉	—	61.86	2.07	4.98	0.48	0.9	0.81	15.93	10
江苏	炉排炉	—	56	3.71	5.12	1.19	2.75	1.6	19.92	5.27
浙江	炉排炉	75～2000	34.39	3.42	7.71	2.58	1.85	11.38	24.31	5.33	[14]
浙江	流化床	5～75	44.07	9.82	3.19	9.85	5.47	3.99	10.32	2.89	[14]
上海	炉排炉	38～75	41.38	3.44	6.15	0.66	0.52	13.4	26.07	5.31	[15]
山东	炉排炉	—	52.42	2.84	5.3	0.88	0.92	5.09	22.26	6.3	[16]
北京	炉排炉	—	42.81	6.78	6.41	2.96	0.96	6.19	14.83	5.01	[17]
北京	炉排炉	56.38	32.46	3.27	8.46	0.802	0.649	11.34	35.21	4.38	[18]
河南	炉排炉	108.8	38.4	6.6	6.09	2.25	1.75	9.44	26.62	4.74
贵州	炉排炉	64.84	52.13	2.52	5.17	1.06	1.14	10.06	21.78	3.22
辽宁	炉排炉	55.16	36.72	3.17	7.01	0.727	0.65	16.47	27.23	4.59
天津	流化床	70.95	38.16	8.59	3.88	7.61	1.68	12.27	16.37	2.99
重庆	炉排炉	2～100	55.08	3.97	4.23	1.2	2.28	2.74	16.95	6.92	[19]
天津	炉排炉	2～100	52.7	6.34	3.42	2.7	2.77	2.52	10.51	7.06	[19]
天津	炉排炉	—	41.7	2.27	7.69	0.72	0.49	12.9	24.2	7.54	[20]
山西	流化床	—	30.09	17.91	2.35	11.9	4.4	1.26	5.23	5.45	[21]
云南	炉排炉	10～176	36.727	21.926	1.383	8.525	9.349	1.969	2.658	3.779	[22]
江苏	炉排炉	—	42.71	5.63	6.16	2.47	—	—	23.41	10.6	[23]
辽宁	炉排炉	—	45.25	2.12	8.15	2.36	0.75	9.94	21.48	8.55	[7]
广东	炉排炉	50～280	30.57	15.92	4.18	5.74	2.26	4.49	14.1	6.91	[24]
广东	炉排炉	2～100	26.87	5.22	10.04	—	—	9.84	20.96	11	[25]
国外
瑞典	流化床	—	40.6	6	2.4	4.5	1.7	6.2	12	8.7	[26]
新加坡	炉排炉	—	58.79	4.71	4.66	—	2.63	—	20.94	3.96	[27]
丹麦	炉排炉	—	21	4.9	13.3	2.3	1.1	17.5	8.9	22.5	[26]
韩国	炉排炉	—	41.64	3.22	6.65	1.38	0.57	9.41	—	—	[28]

地点	炉型	集中粒径/μm	CaO/%	SiO₂/%	K₂O/%	Al₂O₃/%	Fe₂O₃/%	Na₂O/%	Cl/%	SO₃/%	参考文献
国内
浙江	流化床	—	29.38	32.79	—	10.97	10.88	—	17.44	—	[13]
山东	炉排炉	—	45.52	1.28	10.85	0.56	1.05	13.73	16.17	5	[12]
山东	炉排炉	—	52.67	1.14	7.93	0.69	0.63	13.62	11.09	5.58
山东	炉排炉	—	61.49	2.67	5.07	0.56	1.92	1.18	17.7	5.97
浙江	炉排炉	—	74.11	2.91	1.74	0.68	1.13	0.34	11.56	4.66
浙江	炉排炉	—	45.11	1.53	1.81	0.26	28.2	—	2.82	3.31
上海	炉排炉	—	57.88	1.76	4.61	0.26	0.88	1.37	25.01	4.62
四川	炉排炉	—	61.86	2.07	4.98	0.48	0.9	0.81	15.93	10
江苏	炉排炉	—	56	3.71	5.12	1.19	2.75	1.6	19.92	5.27
浙江	炉排炉	75～2000	34.39	3.42	7.71	2.58	1.85	11.38	24.31	5.33	[14]
浙江	流化床	5～75	44.07	9.82	3.19	9.85	5.47	3.99	10.32	2.89	[14]
上海	炉排炉	38～75	41.38	3.44	6.15	0.66	0.52	13.4	26.07	5.31	[15]
山东	炉排炉	—	52.42	2.84	5.3	0.88	0.92	5.09	22.26	6.3	[16]
北京	炉排炉	—	42.81	6.78	6.41	2.96	0.96	6.19	14.83	5.01	[17]
北京	炉排炉	56.38	32.46	3.27	8.46	0.802	0.649	11.34	35.21	4.38	[18]
河南	炉排炉	108.8	38.4	6.6	6.09	2.25	1.75	9.44	26.62	4.74
贵州	炉排炉	64.84	52.13	2.52	5.17	1.06	1.14	10.06	21.78	3.22
辽宁	炉排炉	55.16	36.72	3.17	7.01	0.727	0.65	16.47	27.23	4.59
天津	流化床	70.95	38.16	8.59	3.88	7.61	1.68	12.27	16.37	2.99
重庆	炉排炉	2～100	55.08	3.97	4.23	1.2	2.28	2.74	16.95	6.92	[19]
天津	炉排炉	2～100	52.7	6.34	3.42	2.7	2.77	2.52	10.51	7.06	[19]
天津	炉排炉	—	41.7	2.27	7.69	0.72	0.49	12.9	24.2	7.54	[20]
山西	流化床	—	30.09	17.91	2.35	11.9	4.4	1.26	5.23	5.45	[21]
云南	炉排炉	10～176	36.727	21.926	1.383	8.525	9.349	1.969	2.658	3.779	[22]
江苏	炉排炉	—	42.71	5.63	6.16	2.47	—	—	23.41	10.6	[23]
辽宁	炉排炉	—	45.25	2.12	8.15	2.36	0.75	9.94	21.48	8.55	[7]
广东	炉排炉	50～280	30.57	15.92	4.18	5.74	2.26	4.49	14.1	6.91	[24]
广东	炉排炉	2～100	26.87	5.22	10.04	—	—	9.84	20.96	11	[25]
国外
瑞典	流化床	—	40.6	6	2.4	4.5	1.7	6.2	12	8.7	[26]
新加坡	炉排炉	—	58.79	4.71	4.66	—	2.63	—	20.94	3.96	[27]
丹麦	炉排炉	—	21	4.9	13.3	2.3	1.1	17.5	8.9	22.5	[26]
韩国	炉排炉	—	41.64	3.22	6.65	1.38	0.57	9.41	—	—	[28]

地点	炉型	PCDDs/ng·g^-1	PCDFs/ng·g^-1	PCDDs/PCDFs比值	dl-PCBs/ng·g^-1	TEQ毒性当量/ng·g^-1	参考文献
国内
吉林	流化床	1.1	1.6	0.69	0.095	0.034	[36]
北京	炉排炉	10	31	0.32	0.5	0.55
山东	流化床	51	79	0.65	2.3	1.8
江苏	炉排炉	38	24	1.58	1.4	0.71
江苏	炉排炉	7.3	17	0.43	0.55	0.44
上海	炉排炉	39	16	2.44	0.37	0.56
上海	炉排炉	26	24	1.08	1.5	0.64
浙江	流化床	27	52	0.52	2.1	1.3
重庆	炉排炉	28	35	0.80	1.7	1
四川	炉排炉	3.3	8.1	0.41	0.18	0.21
福建	炉排炉	5.6	4.2	1.33	0.21	0.11
广东	流化床	100	73	1.37	9.3	2.5
广东	炉排炉	10	17	0.59	0.36	0.44
福建	炉排炉	59	34	1.74	2.9	1
浙江	流化床	2.384	9.21 4	0.26	—	0.234	[37]
浙江	流化床	0.717	0.951	0.75	—	0.058	[38]
浙江	炉排炉	0.32	1.118	0.29	—	0.048	[38]
国外
法国	炉排炉	99.48	92.55	1.07	—	6.83	[39]
日本	炉排炉	54	86	0.63	—	3.3	[40]
韩国	炉排炉	80	30	2.67	—	3.35	[28]

地点	炉型	PCDDs/ng·g^-1	PCDFs/ng·g^-1	PCDDs/PCDFs比值	dl-PCBs/ng·g^-1	TEQ毒性当量/ng·g^-1	参考文献
国内
吉林	流化床	1.1	1.6	0.69	0.095	0.034	[36]
北京	炉排炉	10	31	0.32	0.5	0.55
山东	流化床	51	79	0.65	2.3	1.8
江苏	炉排炉	38	24	1.58	1.4	0.71
江苏	炉排炉	7.3	17	0.43	0.55	0.44
上海	炉排炉	39	16	2.44	0.37	0.56
上海	炉排炉	26	24	1.08	1.5	0.64
浙江	流化床	27	52	0.52	2.1	1.3
重庆	炉排炉	28	35	0.80	1.7	1
四川	炉排炉	3.3	8.1	0.41	0.18	0.21
福建	炉排炉	5.6	4.2	1.33	0.21	0.11
广东	流化床	100	73	1.37	9.3	2.5
广东	炉排炉	10	17	0.59	0.36	0.44
福建	炉排炉	59	34	1.74	2.9	1
浙江	流化床	2.384	9.21 4	0.26	—	0.234	[37]
浙江	流化床	0.717	0.951	0.75	—	0.058	[38]
浙江	炉排炉	0.32	1.118	0.29	—	0.048	[38]
国外
法国	炉排炉	99.48	92.55	1.07	—	6.83	[39]
日本	炉排炉	54	86	0.63	—	3.3	[40]
韩国	炉排炉	80	30	2.67	—	3.35	[28]

地点	炉型	Pb/mg·kg^-1	Cr/mg·kg^-1	Cd/mg·kg^-1	Ni/mg·kg^-1	Cu/mg·kg^-1	Zn/mg·kg^-1	参考文献
国内
浙江	流化床	493.75	311.09	11.36	78.38	588.16	2265.04	[13]
山东	炉排炉	1239	89	184	22	563	4716	[12]
山东	炉排炉	922	42	152	11	376	4325
山东	炉排炉	720	85	65	25	400	2420
浙江	炉排炉	635	50	65	10	350	2985
浙江	炉排炉	710	480	25	125	750	4715
上海	炉排炉	1115	35	75	15	435	4650
四川	炉排炉	980	70	140	15	280	4490
江苏	炉排炉	720	140	75	55	575	2595
浙江	炉排炉	1310.8	147.7	127.8	46	901.2	4582	[14]
浙江	流化床	1343.5	296.5	60	53.6	1438.9	9411.2	[14]
上海	炉排炉	4039	140.4	267.1	—	694.4	7714.8	[15]
山东	炉排炉	2120	—	220	—	—	—	[16]
浙江	炉排炉	1830	229	191	44.1	757	7640	[50]
浙江	流化床	1604	767.8	71.75	299.7	4084	9782	[50]
山西	流化床	677.4	—	60.9	—	1070.2	1166.3	[21]
安徽	流化床	1063.35	468.04	77.38	145.61	2237.22	6305.25	[51]
江苏	炉排炉	1647.26	40.7	280.3	24.23	626.8	6803.43	[51]
西藏	炉排炉	1578	57.4	107.4	25.4	561	3842	[52]
黑龙江	流化床	715	307	107	114	1122	5664	[53]
黑龙江	炉排炉	1653	221	424	62	872	6532	[53]
江苏	炉排炉	2622	787	111	—	950	4803	[23]
辽宁	炉排炉	924	50	172	36	506	4516	[7]
广东	炉排炉	1700	—	—	40	860	4900	[25]
国外
瑞典	流化床	5730	190	90	30	5400	5780	[54]
瑞典	流化床	3630	23.1	62.7	—	6940	6860	[26]
挪威	炉排炉	2900	500	200	—	1200	15900	[49]
日本	流化床	1274	192	17	—	3517	5029	[55]
奥地利	炉排炉	2300	190	180	—	780	13000	[56]
瑞士	炉排炉	9540	650	227	—	3901	26770	[57]
丹麦	炉排炉	6250	126	280	—	1070	34690	[26]

生活垃圾焚烧飞灰处理技术研究进展

Treatment technologies of fly ash from municipal solid waste incineration

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处理技术	优点	缺点
高温烧结	减容效果好，运行条件与高温熔融相比简单	烧结过程会产生重金属烟气，产生二次飞灰，成本较高，能耗较高
高温熔融/玻璃化	减容效果好，降低重金属浸出	能耗高，工艺流程复杂，熔融过程会产生烟气
水泥回转窑热处理	技术较成熟，标准体系较完善	需要与水泥窑协同处置，前端水洗工艺增加成本，水泥产品出路
低温催化热解	能耗较低	技术不够成熟，流程比较复杂
水热处理	操作简单，工艺流程简单	能耗高，废液再处理，规模化比较困难
机械化学	反应条件温和，工艺流程简单	能耗高，规模化比较困难

处理技术	优点	缺点
固化稳定化	成本低，流程简单	对多种重金属的固化效果普适性较差，长期容易浸出，对二𫫇英没有去除效果，增大体积
固热处理	减容效果好，对多种重金属的适用性强	能耗高，成本高，工艺流程复杂，产生烟气和二次飞灰
金属热分离	对多种金属的分离效率均较高	能耗高，处理后飞灰与添加剂分离问题，产生烟气处理
金属化学浸出与电化学分离	国外技术较成熟，分离回收效率高	工艺流程复杂，增加废水处理工艺流程复杂，国内技术不成熟，缺乏政策支持

处理技术	工程实验条件	工程实验效果	参考文献
高温烧结	处理量为100t/d的回转窑，将飞灰与烧结剂按照2∶1质量比混合，窑内温度1200℃，回转窑长度为45m，混合物在45min内缓慢迁移通过回转窑，配备脱酸塔、活性炭、袋式除尘器	烟气中PCDD/Fs 0.019~0.025ng I-TEQ/m³，低于国际标准，烧结产物中PCDD/Fs从原始飞灰的2.593~2.704μg I-TEQ/kg，降至0.002~0.008μg I-TEQ/kg，在二次飞灰中发现14.3μg I-TEQ/kg高浓度，PCDD/Fs的破坏率较低（8.9%），烧结产物的重金属浸出浓度远低于标准限值	[98]
高温熔融/玻璃化	使用柴油炉，柴油消耗量为5L/h，熔化温度为1230~1350℃、飞灰进料速率为20~25kg/h，反应时间为15~20 min，研究温度为1260℃、1320℃和1350℃	在1260~1350℃高温下原始飞灰与水洗飞灰的体积减量率为75%~80%，烟气中PCDD/Fs浓度约为0.053ng TEQ/m³，远低于国家标准限值，二次飞灰中的主要组分是NaCl和KCl，熔渣中重金属浸出浓度低于标准	[99]
水泥回转窑热处理	飞灰经过水洗、脱氯预处理、干燥，使用气动输送机将飞灰送入窑入口的烟道气室，最大输送能力为8t/h，水泥窑为干法回转窑，配有五级旋风预热器和预分解器，熟料生产能力为2500t/d	水泥窑热处理能够保证飞灰中二𫫇英含量显著降低，并通过指纹图谱技术揭示了水泥窑生产并未受到影响，熟料中二𫫇英含量远低于国家标准，且来源于窑内其他杂质而非飞灰二𫫇英的转移	[100]
低温催化热解	低温热分解+水洗处理+蒸发结晶分盐工艺技术，每年处理飞灰量5万吨，在350～400℃绝氧的环境下进行二𫫇英解毒处理，解毒后的飞灰进行多级逆流漂洗，在MVR蒸发结晶单元将废水中的钠盐、钾盐分离	最高可将二𫫇英降从2500ng/kg降低至50ng/kg以下，二𫫇英降解效率大于99%，分离的钠盐、钾盐满足工业钠盐、钾盐产品标准	[101]
固化稳定化	200t/d生活垃圾焚烧飞灰模袋填埋示范工程，添加螯合剂实现飞灰中重金属固化稳定，对于充灌进模袋内的飞灰增加二次螯合工艺，采用飞灰膏体制备-管道泵送-模袋充灌工艺一体化技术	固结后模袋体内的飞灰含水率、重金属浸出指标均满足标准要求，与常规吨袋填埋相比，飞灰模袋填埋库容率增加25%左右	[102]
金属化学浸出与电化学分离	瑞士的FLUWA和FLUREC工艺，飞灰通过多级淋洗，使用酸性和中性的洗涤水进行浸出，结合电沉积回收金属	FLUWA工艺可以提取约60%～80%的Zn、80%～95%的Cd、50%～85%的Pb和Cu，FLUREC工艺从富含重金属的滤液中回收高纯度Zn（回收率>99.995%）	[57,97]

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