Characteristics of sewage sludge medium-low temperature gasification and heavy metal migration in a fluidized bed reactor

doi:10.16085/j.issn.1000-6613.2018-1231

Abstract

Abstract:

The sewage sludge air gasification experiment was carried out by a self-built fluidized bed thermal experimental device, and the characteristics of medium-low temperature gasification and heavy metal migration were studied systematically. Among the main parameters affecting the sludge gasification characteristics in fluidized bed, the most important factor affecting the cold gas efficiency and carbon conversion rate is temperature, the second one is air equivalent ratio. The effects of air ratio and fluidization number on the gasification characteristics are weaker. Compared with higher temperature gasification, the output of tar in medium-low temperature gasification increased significantly. With the increase of secondary air and air ratio, the tar yield of medium-low temperature decreased monotonously. With the gasification temperature rises from 600℃ to 850℃, the cold gas efficiency and carbon conversion rate are all increasing. In the process of the air equivalent ratio rising from 0.2 to 0.4, the cold gas efficiency increases firstly and then decreases, and reaches the maximum at 0.3, while the carbon conversion rate increases monotonously. In the rising process of gasification temperature, the mobility in fly ash, gas and tar increased monotonously. With the increase of equivalent ratio, the mobility of Ni and Cu decreased, while Cr increases, and Cd, Zn, As and Pb almost did not change.

Key words: sewage sludge, fluidized bed, medium-low temperature gasification, heavy metals

摘要：

利用自行搭建的流化床热态实验装置，系统研究了污泥的中低温气化及重金属迁移特性。研究表明，对冷煤气效率和碳转化率影响最大的是气化温度，其次是空气当量比，而一二次风配比和流化数影响较弱。污泥中低温气化的焦油产率较之高温气化明显增加。随着二次风占比和空气当量比的提高，焦油产率单调下降。气化温度由600℃升至850℃，冷煤气效率和碳转化率均呈升高趋势；空气当量比由0.2升至0.4，冷煤气效率呈先升高后下降的趋势，在0.3时达到最大值，而碳转化率则呈单调升高趋势。随着气化温度的升高，污泥中重金属转移至产气、焦油及飞灰的迁移率升高。随着空气当量比的升高，Ni、Cu的迁移率降低，Cr升高，Cd、Zn、As和Pb等其他重金属的迁移率几乎不变。

关键词: 城市污泥, 流化床, 中低温气化, 重金属

CLC Number:

TK123

Wei ZHANG, Xiaoping CHEN, Qing WANG, Xujun YANG, Lian SONG, Ge ZHU, Jiliang MA, Daoyin LIU, Cai LIANG. Characteristics of sewage sludge medium-low temperature gasification and heavy metal migration in a fluidized bed reactor[J]. Chemical Industry and Engineering Progress, 2019, 38(04): 2011-2021.

张伟, 陈晓平, 王清, 杨叙军, 宋联, 朱葛, 马吉亮, 刘道银, 梁财. 城市污泥流化床中低温空气气化及重金属迁移特性[J]. 化工进展, 2019, 38(04): 2011-2021.

Figures/Tables 18

References 31

1	中华人民共和国生态环境部 . 2017年中国环境状况公报[EB/OL]. .
	People's Republic of China Ministry of Ecology and Environment . 2017 China environmental bulletin [EB/OL]..
2	江子箫, 陈晓平, 蒋志坚, 等 . 城市污泥流化床燃烧过程中气态污染物排放特性[J]. 化工进展, 2018, 37(1):368-374.
	JIANG Zixiao , CHEN Xiaoping , JIANG Zhijian , et al . Emission characteristics of gaseous pollutants in fluidized bed combustion of municipal sludge[J]. Chemical Industry and Engineering Progress, 2018, 37(1): 368-374.
3	杨明沁, 解立平, 岳俊楠, 等．污水污泥气化焦油热解特性的研究[J]．化工进展, 2015, 34(5): 1472-1477．
	YANG Mingqin , XIE Liping , YUE Junnan , et al ．Research on pyrolysis characteristics of sewage sludge gasification tar [J]．Chemical Industry and Engineering Progress, 2015, 34(5): 1472-1477．
4	PETERSEN I , WERTHER J . Experimental investigation and modeling of gasification of sewage sludge in the circulating fluidized bed[J]. Chemical Engineering and Processing: Process Intensification, 2005, 44(7): 717-736.
5	KANG S , DONG J , KIM J, et al . Gasification and its emission characteristics for dried sewage sludge utilizing a fluidized bed gasifier[J]. Journal of Material Cycles and Waste Management, 2011, 13(3): 180-185.
6	ANDRÉS J M DE , NARROS A , RODRÍGUEZ M E . Air-steam gasification of sewage sludge in a bubbling bed reactor: effect of alumina as a primary catalyst[J]. Fuel Processing Technology, 2011, 92(3): 433-440.
7	刘渊源 . 城市污水污泥在流化床中的焚烧特性及重金属排放特性研究[D]. 杭州: 浙江大学, 2004.
	LIU Yuanyuan . Incineration characteristics and heavy metal emission characteristics of municipal sewage sludge in fluidized bed [D]. Hangzhou: Zhejiang University, 2004.
8	刘淑静, 李爱民, 袁维波 . 温度对污泥焚烧残渣中重金属形态分布及残渣综合毒性的影响[J]. 安全与环境学报, 2008, 8(1):43-47.
	LIU Shujing , LI Aimin , YUAN Weibo . Influence of temperature on the morphological distribution of heavy metals and the comprehensive toxicity of residue in sludge incineration residue [J]. Journal of Safety and Environment, 2008, 8(1): 43-47.
9	卢更, 刘欢, 胡红云, 等 . 氧化钙调理污泥气化过程中重金属的迁移转化规律[J]. 化工学报, 2017, 68(1): 272-280.
	LU Geng , LIU Huan , HU Hongyun , et al ．Transport and transformation rules of heavy metals during calcium sludge gasification[J]. CIESC Journal, 2017, 68(1): 272-280．
10	陈晓平, 卜昌盛, 马吉亮, 等 . 一种飞灰等温等速取样装置: CN103162993A[P]. 2013.
	CHEN Xiaoping , BU Changsheng , Jiliang MA , et al . An isothermal isothermal sampling device for fly ash: CN103162993A[P]. 2013.
11	马隆龙, 吴创之, 孙立 . 生物质气化技术及其应用[M]. 北京: 化学工业出版社, 2003.
	Longlong MA , WU Chuangzhi , SUN Li . Biomass gasification technology and its application[M]. Beijing: Chemical Industry Press, 2003.
12	中国科学院数学研究所数理统计组 . 正交实验法[M]. 北京: 人民教育出版社, 1975.
	Mathematical Statistics Section of Institute of Mathematics, Chinese Academy of Sciences . Orthogonal experiment[M]. Beijing: People’s Education Press, 1975.
13	刘彦鹏, 王勤辉, 骆仲泱, 等 . 不同煤种下循环流化床灰渣特性的试验研究[J]. 锅炉技术, 2004, 35(3): 18-22.
	LIU Yanpeng , WANG Qinhui , LUO Zhongyang , et al . Experimental study on the characteristics of circulating fluidized bed ash under different coal species[J]. Boiler Technology, 2004, 35(3): 18-22.
14	CHAMBERLAND A , LABRECQUE R , BRIDGWATER A V , et al . Parametric study of an oxygen-blown fluidised-bed reactor for wood gasification[M]// Research in Thermochemical Biomass Conversion. Springer Netherlands, 1988:1125-1140.
15	MANYÀ J J , SÁNCHEZ J L , GONZALO A , et al . Air gasification of dried sewage sludge in a fluidized bed: effect of the operating conditions and in-bed use of alumina[J]. Energy & Fuels, 2005, 19(2): 629-636.
16	CALVO L F , GARCÍA A I , OTERO M . An experimental investigation of sewage sludge gasification in a fluidized bed reactor[J]. The Scientific World Journal, 2013(5): 306-403.
17	米铁, 张春林, 刘武标, 等．流化床作为生物质气化反应器试验研究[J]. 化学工程, 2003, 31(5): 26-30．
	MI Tie , ZHANG Chunlin , LIU Wubiao , et al . Fluidized bed as biomass gasification reactor experimental study[J]. Chemical Engineering, 2003, 31(5): 26-30.
18	谢军, 吴创之, 阴秀丽, 等 . 中型流化床中二次风对生物质气化的影响[J]. 太阳能学报, 2007, 28(8):852-856.
	XIE Jun , WU Chuangzhi , YIN Xiuli , et al . The influence of two winds on biomass gasification in a medium fluidized bed[J]. Journal of Solar Energy, 2007, 28(8): 852-856.
19	刘凌沁 . 生物质气化试验与Aspen Plus模拟研究[D]. 南京: 东南大学, 2016.
	LIU Lingqin . Biomass gasification experiment and Aspen Plus simulation study[D]. Nanjing: Southeast University, 2016.
20	SHARMA A M , KUMAR A , PATIL K N , et al . Fluidization characteristics of a mixture of gasifier solid residues, switchgrass and inert material[J]. Powder Technology, 2013, 235(2):661-668.
21	伏启让 . 生物质流化床富氧气化试验与模拟研究[D]. 南京: 东南大学, 2015.
	FU Qirang . Experiment and simulation study of biomass fluidized bed oxygen enriched gasification[D]. Nanjing: Southeast University, 2015.
22	秦育红 . 生物质气化过程中焦油形成的热化学模型[D]. 太原: 太原理工大学, 2009.
	QIN Yuhong . Thermochemical model of tar formation in biomass gasification process[D]. Taiyuan: Taiyuan University of Technology, 2009.
23	陈汉平, 杨海平, 李斌, 等 . 生物质流化床气化焦油析出特性的研究[J]. 燃料化学学报, 2009, 37(4): 433-437.
	CHEN Hanping , YANG Haiping , LI Bin , et al . Study on the characteristics of tar emission from biomass fluidized bed gasification [J]. Acta Fuel Acta Sinica, 2009, 37(4): 433-437.
24	王云峰 . 流化床污水污泥空气气化焦油特性研究[D]. 天津: 天津工业大学, 2017.
	WANG Yunfeng . Characteristics of tar in fluidized bed sewage sludge air gasification[D]. Tianjin: Tianjin University of Technology, 2017.
25	MARANI D , BRAGUGLIA C M , MININNI G , et al . Behaviour of Cd, Cr, Mn, Ni, Pb and Zn in sewage sludge in-cineration by fluidised bed furnace[J]. Waste Management, 2003, 23(2): 117-124.
26	曾小强, 陈晓平, 梁财, 等 . 温度对污泥流化床焚烧飞灰重金属迁移的影响[J]. 东南大学学报(自然科学版), 2015, 45(1):97-102.
	ZENG Xiaoqiang , CHEN Xiaoping , LIANG Cai , et al . Influence of temperature on heavy metal migration in fly ash from sludge fluidized bed incineration[J]. Journal of Southeast University (Natural Science Edition), 2015, 45(1): 97-102.
27	董隽, 池涌, 汤元君,等 . 生活垃圾流化床热处置中重金属迁移分布研究[J]. 燃料化学学报, 2016, 44(1): 120-128.
	DONG Jun , CHI Yong , TANG Yuanjun , et al . Study on migration and distribution of heavy metals in fluidized bed heat treatment of domestic waste[J]. Acta Fuel Chemistry, 2016, 44(1): 120-128.
28	BARTON R G , CLARK W D , SEEKER W R . Fate of metals in waste combustion systems[J]. Combustion Science & Technology, 1990, 74(1-6): 327-342.
29	吴桢芬, 苏有勇, 王华, 等 . 气氛对垃圾焚烧中重金属迁移特性的影响[J]. 环境工程学报, 2011, 5(7): 1623-1626.
	WU Zhenfen , SU Youyong , WANG Hua , et al . Influence of atmosphere on the migration characteristics of heavy metals in MSW incineration [J]. Journal of Environmental Engineering, 2011, 5(7): 1623-1626.
30	FRANDSEN F , DAM-JOHANSEN K , RASMUEESN P . Trace elements from combustion and gasification of coal: an equilibrium approach[J]. Progress in Energy of Combustion and Science, 1994, 20(2): 115-138.
31	YU J , SUN L , XIANG J , et al . Vaporization of heavy metals during thermal treatment of model solid waste in a fluidized bed incinerator[J]. Chemosphere, 2012, 86(11): 1122.

编号	温度	当量比	一二次风配比	流化数	一次风 /m³·h^-1	二次风 /m³·h^-1	加料量/kg·h^-1	冷煤气效率(X)	碳转化率(Y)
1	1(600℃)	1(0.20)	1(9∶1)	1(2.0)	1.77	0.20	3.09	12.1	31.5
2	1	2(0.25)	2(8∶2)	2(2.5)	2.21	0.55	3.48	21.2	46.0
3	1	3(0.30)	3(7∶3)	3(3.0)	2.65	1.14	3.98	22.5	51.0
4	1	4(0.35)	4(6∶4)	4(3.5)	3.09	2.06	4.64	20.2	47.0
5	1	5(0.40)	5(5∶5)	5(4.0)	3.53	3.53	5.57	17.6	49.6
6	2(650℃)	1	2	3	2.30	0.57	4.53	23.4	35.0
7	2	2	3	4	2.68	1.15	4.83	28.6	47.5
8	2	3	4	5	3.06	2.04	5.36	29.9	48.0
9	2	4	5	1	1.53	1.53	2.76	27.9	49.0
10	2	5	1	2	1.92	0.21	1.68	17.5	52.5
11	3(700℃)	1	3	5	2.68	1.15	6.04	31.9	49.0
12	3	2	4	1	1.34	0.89	2.82	32.8	48.5
13	3	3	5	2	1.68	1.68	3.52	38.3	53.0
14	3	4	1	3	2.01	0.22	2.01	31.2	57.5
15	3	5	2	4	2.35	0.59	2.31	24.5	63.5
16	4(750℃)	1	4	2	1.48	0.99	3.89	39.1	53.5
17	4	2	5	3	1.78	1.78	4.48	40.9	56.5
18	4	3	1	4	2.07	0.23	2.42	50.1	55.5
19	4	4	2	5	2.37	0.59	2.67	33.8	64.5
20	4	5	3	1	1.19	0.51	1.33	18.8	68.5
21	5(850℃)	1	5	4	1.76	1.76	5.55	52.5	73.2
22	5	2	1	5	2.02	0.22	2.82	55.5	77.5
23	5	3	2	1	1.01	0.25	1.32	60.5	78.7
24	5	4	3	2	1.26	0.54	1.62	38.1	82.9
25	5	5	4	3	1.51	1.01	1.98	15.9	79.6
X
K ₁	93.5	159.1	166.4	152.3
K ₂	127.4	179.1	163.5	154.3
K ₃	158.9	201.4	140.0	134.0
K ₄	182.7	151.2	138.0	175.8
K ₅	222.6	94.5	177.3	168.7
极差R	129.2	106.8	39.2	41.8
Y
K ₁	225.1	242.2	274.5	276.2
K ₂	232.0	276.0	287.7	287.9
K ₃	271.5	286.2	298.9	279.6
K ₄	298.5	300.9	276.6	286.7
K ₅	391.9	313.7	281.3	288.6
极差R	166.8	71.5	22.3	12.4

编号	温度	当量比	一二次风配比	流化数	一次风 /m³·h^-1	二次风 /m³·h^-1	加料量/kg·h^-1	冷煤气效率(X)	碳转化率(Y)
1	1(600℃)	1(0.20)	1(9∶1)	1(2.0)	1.77	0.20	3.09	12.1	31.5
2	1	2(0.25)	2(8∶2)	2(2.5)	2.21	0.55	3.48	21.2	46.0
3	1	3(0.30)	3(7∶3)	3(3.0)	2.65	1.14	3.98	22.5	51.0
4	1	4(0.35)	4(6∶4)	4(3.5)	3.09	2.06	4.64	20.2	47.0
5	1	5(0.40)	5(5∶5)	5(4.0)	3.53	3.53	5.57	17.6	49.6
6	2(650℃)	1	2	3	2.30	0.57	4.53	23.4	35.0
7	2	2	3	4	2.68	1.15	4.83	28.6	47.5
8	2	3	4	5	3.06	2.04	5.36	29.9	48.0
9	2	4	5	1	1.53	1.53	2.76	27.9	49.0
10	2	5	1	2	1.92	0.21	1.68	17.5	52.5
11	3(700℃)	1	3	5	2.68	1.15	6.04	31.9	49.0
12	3	2	4	1	1.34	0.89	2.82	32.8	48.5
13	3	3	5	2	1.68	1.68	3.52	38.3	53.0
14	3	4	1	3	2.01	0.22	2.01	31.2	57.5
15	3	5	2	4	2.35	0.59	2.31	24.5	63.5
16	4(750℃)	1	4	2	1.48	0.99	3.89	39.1	53.5
17	4	2	5	3	1.78	1.78	4.48	40.9	56.5
18	4	3	1	4	2.07	0.23	2.42	50.1	55.5
19	4	4	2	5	2.37	0.59	2.67	33.8	64.5
20	4	5	3	1	1.19	0.51	1.33	18.8	68.5
21	5(850℃)	1	5	4	1.76	1.76	5.55	52.5	73.2
22	5	2	1	5	2.02	0.22	2.82	55.5	77.5
23	5	3	2	1	1.01	0.25	1.32	60.5	78.7
24	5	4	3	2	1.26	0.54	1.62	38.1	82.9
25	5	5	4	3	1.51	1.01	1.98	15.9	79.6
X
K ₁	93.5	159.1	166.4	152.3
K ₂	127.4	179.1	163.5	154.3
K ₃	158.9	201.4	140.0	134.0
K ₄	182.7	151.2	138.0	175.8
K ₅	222.6	94.5	177.3	168.7
极差R	129.2	106.8	39.2	41.8
Y
K ₁	225.1	242.2	274.5	276.2
K ₂	232.0	276.0	287.7	287.9
K ₃	271.5	286.2	298.9	279.6
K ₄	298.5	300.9	276.6	286.7
K ₅	391.9	313.7	281.3	288.6
极差R	166.8	71.5	22.3	12.4

当量比	迁移率/%
当量比	Cr	Ni	Cu	Zn	Cd	As	Pb
0.1	69.32	69.14	65.02	62.64	58.87	72.38	64.28
0.6	53.45	75.23	70.35	59.39	56.34	70.32	62.23

当量比	迁移率/%
当量比	Cr	Ni	Cu	Zn	Cd	As	Pb
0.1	69.32	69.14	65.02	62.64	58.87	72.38	64.28
0.6	53.45	75.23	70.35	59.39	56.34	70.32	62.23

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