污泥与煤泥混烧对重金属固留特性的影响

doi:10.16085/j.issn.1000-6613.2022-1489

摘要/Abstract

摘要：

针对污泥与煤泥混烧时重金属（Pb、As、Cu、Cr、Cd）的迁移特性以及在混烧条件下矿物质对重金属固留效果的影响，利用电热管式炉并结合电感耦合等离子体质谱（ICP-MS）、X 射线衍射（XRD）等表征分析手段，研究不同燃烧条件下污泥与煤泥单独燃烧及多比例混烧过程。结果表明：污泥单独燃烧时，As的挥发率随温度升高而上升，Pb、Cu、Cd、Cr的挥发率在700℃时达到顶峰，在700~900℃时随着温度升高而下降。对于煤泥，Pb、Cr的挥发率随温度升高逐渐上升，Cu的挥发率随温度升高呈现先下降后上升的趋势，700℃时达到最低点，Cd的挥发率则相反。对于污泥-煤泥耦合燃烧过程，污泥-煤泥在5∶5掺混比条件下重金属固留率相比于2∶8及8∶2掺混比条件有所提升，5∶5掺混比条件下900℃燃烧温度时污泥-煤泥中矿物质交互作用对Pb、As、Cu、Cr和Cd实际残留率相比理论值分别提高了148.9%、5.8%、28.6%、112%和75.7%。混烧过程中重金属的固留主要受到矿物组分之间所发生的交互作用的影响。其中，对于单组分燃烧条件，SiO₂、Al₂O₃、Fe₂O₃易与重金属反应生成难挥发化合物并在灰渣中赋存；而混烧过程可以促进硅铝酸盐及含铁化合物的分解，进而在大量生成SiO₂等化合物的基础上，促进重金属残留率的提升。

关键词: 污泥, 煤泥, 混烧, 重金属, 交互作用, 固留特性

Abstract:

To investigate the migration characteristics of heavy metals (Pb, As, Cu, Cr, Cd) and the influence of minerals on the heavy metal retention effect in the mixed combustion conditions, the combustion of sludge and coal slime alone and the co-combustion in multiple proportions were studied under different combustion conditions using an electric tube furnace and by means of ICP and XRD characterization analysis. The results showed that when sludge was burned alone, the volatilization rate of As increased with the increase of temperature, and the volatilization rates of Pb, Cu, Cd and Cr peaked at 700℃ and decreased with the increase of temperature at 700—900℃. For the combustion of coal slime, the volatilization rates of Pb and Cr gradually increased with the increase of temperature, the volatilization rate of Cu showed a trend of decreasing and then increasing with the increase of temperature and reached the lowest point at 700℃, while the volatilization rate of Cd was the opposite. For the coupled sludge-coal slurry combustion process, the retention rate of heavy metals in sludge-coal slurry at 5∶5 blending ratio was higher than that at 2∶8 and 8∶2 blending ratios, and the actual residual rates of Pb, As, Cu, Cr and Cd from mineral interactions in sludge-coal slurry at 900℃ combustion temperature at 5∶5 blending ratio increased by 148.9%, 5.8%, 28.6%, 112% and 75.7%, respectively, compared with the theoretical values. The retention of heavy metals in the mixed firing process was mainly influenced by the interaction between mineral components, in which, for single-component combustion conditions, SiO₂, Al₂O₃, and Fe₂O₃ were prone to react with heavy metals to form compounds that were difficult to volatilize and fused in the ash, while the mixed firing process could promote the decomposition of silica-aluminate and iron-containing compounds to form SiO₂ and other compounds in large quantities, which enhanced the heavy metal residual rate.

Key words: sewage sludge, coal slime, co-combustion, heavy metals, interaction, retention characteristics

中图分类号:

X705

郑昕, 贾里, 王彦霖, 张靖超, 陈世虎, 乔晓磊, 樊保国. 污泥与煤泥混烧对重金属固留特性的影响[J]. 化工进展, 2023, 42(6): 3233-3241.

ZHENG Xin, JIA Li, WANG Yanlin, ZHANG Jingchao, CHEN Shihu, QIAO Xiaolei, FAN Baoguo. Effect of sewage sludge mixed with coal slime on heavy metal retention characteristics[J]. Chemical Industry and Engineering Progress, 2023, 42(6): 3233-3241.

图/表 18

表1 污泥和煤泥工业分析及元素分析

样品	工业分析/%				元素分析/%
样品	M_ad	A_ad	V_ad	FC_ad	C_d	H_d	N_d	O_d	S_d
污泥	2.44	47.33	46.31	3.92	24.78	3.002	4.33	27.77	1.469
太选煤泥	0.38	51.16	13.04	35.42	37.7	2.17	1.03	2.33	5.57

表2 污泥和煤泥中的重金属含量单位：mg/kg

样品	Pb	As	Cu	Cr	Cd
污泥	9.02	2.72	98.19	22.04	1.19
太选煤泥	19.65	2.2	71.6	10.93	0.16

表3 污泥和煤泥的灰分组成（质量分数，%）

样品	SiO₂	Al₂O₃	Fe₂O₃	P₂O₅	CaO	Cl
污泥	20.85	6.6	29.99	16.29	8.48	0.863
太选煤泥	44.82	27.38	12.2	0.53	2.72	0.941

图1 污泥在不同燃烧温度下XRD图Q—石英，SiO2；D—磷酸亚铁，Fe3(PO4)2；N—偏磷酸铁，Fe(PO3)3；H—氧化铁，Fe2O3；M—白云母，K{Al2[AlSi3O10](OH)2}；I—黄铅矿，Pb2OSO4；K—高岭土，Al2Si2O5(OH)4；G—LiNiFe2O4；Y—硅酸铬，Cr2SiO4；P—磷酸氧铅，Pb4O(PO4)2；V—CdO·Al2O3·3SiO2

图2 煤泥在不同燃烧温度下XRD图Q—石英，SiO2；D—磷酸亚铁，Fe3(PO4)2；K—高岭土，Al2Si2O5(OH)4；G—LiNiFe2O4；C-硅锰酸钙，CaMnSi；H—氧化铁，Fe2O3；A—砷酸铁，FeAsO4；D—硅碳氮，SiCN；R—SiAs2

图3 焚烧温度对Pb浓度及残留率变化的影响

图4 焚烧温度对As浓度及残留率变化的影响

图5 焚烧温度对Cu浓度及残留率变化的影响

图6 焚烧温度对Cr浓度及残留率变化的影响

图7 焚烧温度对Cd浓度及残留率变化的影响

图8 5∶5混烧条件下灰渣XRD图Q—石英，SiO2；K—高岭土，Al2Si2O5(OH)4；G—LiNiFe2O4；H—氧化铁，Fe2O3；U—斜硅铜矿，Cu5Si4O12(OH)2；O—砷化铁，FeAs3O9；L—氧化铅，Pb5O8；Z—硅酸锌，ZnSiO3；M—白云母，K{Al2[AlSi3O10](OH)2}

图9 2∶8掺混比条件灰渣XRD图Q—石英，SiO2；H—氧化铁，Fe2O3；M—白云母，K{Al2[AlSi3O10](OH)2}

图10 8∶2混烧条件下灰渣XRD图Q—石英，SiO2；H—氧化铁，Fe2O3；M—白云母，K{Al2[AlSi3O10](OH)2}；B—蓝晶石，Al2SiO5

图11 Pb在底渣中的理论残留率与实际残留率变化

图12 As在底渣中的理论残留率与实际残留率变化

图13 Cu在底渣中的理论残留率与实际残留率变化

图14 Cr在底渣中的理论残留率与实际残留率变化

图15 Cd在底渣中的理论残留率与实际残留率变化

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