氧化钙调理污泥气化过程中重金属的迁移转化规律

doi:10.11949/j.issn.0438-1157.20161018

化工学报 ›› 2017, Vol. 68 ›› Issue (1): 272-280.DOI: 10.11949/j.issn.0438-1157.20161018

氧化钙调理污泥气化过程中重金属的迁移转化规律

卢更^1,2, 刘欢¹, 胡红云¹, 张强¹, 易琳琳¹, 姚洪¹

1 华中科技大学能源与动力工程学院, 煤燃烧国家重点实验室, 湖北武汉 430074;
2 华中科技大学中欧清洁与可再生能源学院, 湖北武汉 430074

收稿日期:2016-07-20 修回日期:2016-09-09 出版日期:2017-01-05 发布日期:2017-01-05
通讯作者: 刘欢
基金资助:
国家自然科学基金项目（51506064，51661145010，51606075）；中央高校基本科研业务费（HUST：2016YXMS038）。

Fate of heavy metals in CaO-conditioned sludge gasification

LU Geng^1,2, LIU Huan¹, HU Hongyun¹, ZHANG Qiang¹, YI Linlin¹, YAO Hong¹

1 State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, Wuhan 430074, Hubei, China;
2 China-EU Institute for Clean and Renewable Energy, Huazhong University of Science and Technology, Wuhan 430074, Hubei, China

Received:2016-07-20 Revised:2016-09-09 Online:2017-01-05 Published:2017-01-05
Contact: 10.11949/j.issn.0438-1157.20161018
Supported by:
supported by the National Natural Science Foundation of China (51506064, 51661145010, 51606075) and the Fundamental Research Funds for the Central Universities (HUST: 2016YXMS038).

摘要/Abstract

摘要：

以CaO为主要成分的石灰常用于污泥的调理和稳定。为探究其对污泥气化过程中重金属迁移转化规律的影响，在沉降炉-固定床反应器和固定床上于600、800、1000℃进行了污泥的热解及气化实验，并分析了不同污泥样品、热解焦和气化灰中典型重金属（Mn、Zn、Cu、Cr、Ni）的含量及形态分布。结果表明，CaO的加入将稀释调理污泥中的重金属，并使Mn、Zn、Cr向稳定态转化；CaO会使重金属离子与OH-结合生成沉淀，继而在气化反应中分解成氧化物。在气化过程中，CaO会提高重金属的残留率，也会吸收其氯化物、硫酸盐等在高温下分解生成的HCl、SO₂等酸性气体，促使氧化物的生成和抑制重金属的释放。

关键词: 污泥, 气化, 调理剂CaO, 生物能源, 重金属

Abstract:

Lime, which is mainly presented as CaO, is often used in sludge conditioning and stabilization.To study the effects of CaO on the fate of heavy metals in pyrolysis and sludge gasification process, the sludge pyrolysis and gasification experiments were conducted with a drop-tube furnace and a fixed-bed system.The content and speciation of typical heavy metals(Mn, Zn, Cu, Cr, Ni) were also analyzed.Samples included different sludges(raw sludge, CaO conditioned sludge), their corresponding pyrolysis chars and gasification ashes.The results indicated that after CaO conditioning, the content of heavy metals reduced due to the dilution effect.Mn, Zn, Cr transformed to stable state.Some heavy metals ions reacted with OH-to form precipitate which then decomposed to produce oxide during sludge gasification process.In addition, CaO can increase the residual rate of heavy metals in solids, and also absorb HCl, SO₂ and other acid gases from decomposition of chloride or sulfate to promote the formation of oxides at high temperatures.Subsequently, eutectic was generated in the reactions between these oxides and compounds such as Al₃O₂, SiO₂, Fe₂O₃ and CaO, thus suppressing the release of heavy metals.

Key words: sludge, gasification, conditioner CaO, biological energy, heavy metals

中图分类号:

TK16

卢更, 刘欢, 胡红云, 张强, 易琳琳, 姚洪. 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, ZHANG Qiang, YI Linlin, YAO Hong. Fate of heavy metals in CaO-conditioned sludge gasification[J]. CIESC Journal, 2017, 68(1): 272-280.

参考文献 34

[1]	TYAGI V K, LO S. Sludge:a waste or renewable source for energy and resources recovery?[J]. Renewable and Sustainable Energy Reviews, 2013, 25:708-728.
[2]	NIPATTUMMAKUL N, AHMED I, KERDSUWAN S, et al. High temperature steam gasification of wastewater sludge[J]. Applied Energy, 2010, 87(12):3729-3734.
[3]	REED G P, PATERSON N P, ZHUO Y, et al. Trace element distribution in sewage sludge gasification:source and temperature effects[J]. Energy & Fuels, 2005, 19(1):298-304.
[4]	MARRERO T W, MCAULEY B P, SUTTERLIN W R, et al. Fate of heavy metals and radioactive metals in gasification of sewage sludge[J]. Waste Management, 2004, 24(2):193-198.
[5]	WERLE S, DUDZIAK M. Analysis of organic and inorganic contaminants in dried sewage sludge and by-products of dried sewage sludge gasification[J]. Energies, 2014, 7(1):462-476.
[6]	王兴栋, 张斌, 余广炜, 等. 不同粒径污泥热解制备生物炭及其特性分析[J]. 化工学报, 2016, 67(11):4808-4816. WANG X D, ZHANG B, YU G W, et al. Preparation of biochar with different particle sized sewage sludge and its characteristics[J]. CIESC Journal, 2016, 67(11):4808-4816.
[7]	李爱民, 曲艳丽, 姚伟, 等. 污泥焚烧底灰中重金属残留特性的实验研究[J]. 环境污染治理技术与设备, 2002, (11):20-24. LI A M, QU Y L, YAO W, et al. An experimental study on remains property of heavy metals in the bottom ash[J]. Techniques and Equipment for Environmental Pollution Control, 2002, (11):20-24.
[8]	刘敬勇, 孙水裕, 陈涛. 污泥焚烧过程中Cd的迁移与转化特征[J]. 中国科学:化学, 2013, (1):94-103. LIU J Y, SUN S Y, CHEN T. Partitioning and transformation of Cd during sewage sludge incineration process[J]. Scientia Sinica Chimica, 2013, (1):94-103.
[9]	LI L, XU Z, ZHANG C, et al. Quantitative evaluation of heavy metals in solid residues from sub-and super-critical water gasification of sewage sludge[J]. Bioresource Technology, 2012, 121:169-175.
[10]	XIAO Z, YUAN X, LI H, et al. Chemical speciation, mobility and phyto-accessibility of heavy metals in fly ash and slag from combustion of pelletized municipal sewage sludge[J]. Science of the Total Environment, 2015, 536:774-783.
[11]	李润东, 刘连芳, 李爱民. 添加剂对污泥流化床焚烧过程重金属迁移特性影响[J]. 热力发电, 2004, (10):11-14+54-93. LI R D, LIU L F, LI A M. The influence of additives upon heavy metalls migration behavior in the fluidized bed incineration process of sludges[J]. Thermal Power Generation, 2004, (10):11-14+54-93.
[12]	刘敬勇, 孙水裕, 陈涛. 固体添加剂对污泥焚烧过程中重金属迁移行为的影响[J]. 环境科学, 2013, 34(3):1166-1173. LIU J Y, SUN S Y, CHEN T. Effects of adsorbents on partitioning and fixation of heavy metals in the incineration process of sewage sludge[J]. Environmental Science, 2013, 34(3):1166-1173.
[13]	HU H, LIU H, SHEN W, et al. Comparison of CaO's effect on the fate of heavy metals during thermal treatment of two typical types of MSWI fly ashes in China[J]. Chemosphere, 2013, 93(4):590-596.
[14]	张强, 刘欢, 刘鹏, 等. 调理剂对深度脱水污泥热解特性的影响[J]. 化工学报, 2014, 65(4):1396-1402. ZHANG Q, LIU H, LIU P, et al. Pyrolysis characteristic of deep dewatered sludge[J]. CIESC Journal, 2014, 65(4):1396-1402.
[15]	LIU H, ZHANG Q, XING H, et al. Product distribution and sulfur behavior in sewage sludge pyrolysis:synergistic effect of Fenton peroxidation and CaO conditioning[J]. Fuel, 2015, 159:68-75.
[16]	LIU H, ZHANG Q, HU H, et al. Influence of residual moisture on deep dewatered sludge pyrolysis[J]. International Journal of Hydrogen Energy, 2014, 39(3):1253-1261.
[17]	CHEN D, HU H, XU Z, et al. Findings of proper temperatures for arsenic capture by CaO in the simulated flue gas with and without SO2[J]. Chemical Engineering Journal, 2015, 267:201-206.
[18]	GARCÍA-DELGADO M, RODRÍGUEZ-CRUZ M S, LORENZO L F, et al. Seasonal and time variability of heavy metal content and of its chemical forms in sewage sludges from different wastewater treatment plants[J]. Science of the Total Environment, 2007, 382(1):82-92.
[19]	冯素萍, 刘慎坦, 杜伟, 等. 利用BCR改进法和Tessier修正法提取不同类型土壤中Cu、Zn、Fe、Mn的对比研究[J]. 分析测试学报, 2009, (3):297-300. FENG S P, LIU S T, DU W, et al. Assessment of Cu, Zn, Fe, Mn species in different soils by modified BCR and Tessier extraction procedures[J]. Journal of Instrumental Analysis, 2009, (3):297-300.
[20]	ALVAREZ E A, MOCHON M C, JIMENEZ S J, et al. Heavy metal extractable forms in sludge from wastewater treatment plants[J]. Chemosphere, 2002, 47(7):765-775.
[21]	付念新, 张伟龙, 张林楠, 等. 铬酸钙盐在酸碱溶液中的溶解行为[J]. 沈阳工业大学学报, 2012, (6):639-643. FU N X, ZHANG W L, ZHANG L N, et al. Dissolution behavior of calcium chromates in acid or alkali solution[J]. Journal of Shenyang University of Technology, 2012, (6):639-643.
[22]	WONG J W C, SELVAM A. Speciation of heavy metals during co-composting of sewage sludge with lime[J]. Chemosphere, 2006, 63(6):980-986.
[23]	张幸福. 污泥焚烧过程中铬等重金属的迁移转化特性研究[D]. 杭州:浙江大学,2015. ZHANG X F. Study on migration and transformation of chromium and other heavy metals during sewage sludge incineration[D]. Hangzhou:Zhejiang University,2015.
[24]	HU H, XU Z, LIU H, et al. Mechanism of chromium oxidation by alkali and alkaline earth metals during municipal solid waste incineration[J]. Proceedings of the Combustion Institute, 2015, 35(2):2397-2403.
[25]	王文霞, 胡红云, 朱娟娟, 等. 垃圾焚烧底灰中铬的分布及浸出特性研究[J]. 工程热物理学报, 2014, (1):196-199. WANG W X, HU H Y, ZHU J J, et al. Chromium distribution and leaching behavior in municipal solid waste incineration bottom ash[J]. Journal of Engineering Thermophysics, 2014, (1):196-199.
[26]	JIAO F, ZHANG L, DONG Z, et al. Study on the species of heavy metals in MSW incineration fly ash and their leaching behavior[J]. Fuel Processing Technology, 2016, 152:108-115.
[27]	刘敬勇, 孙水裕, 罗光前. 造纸污泥焚烧中Zn/Cu/Ni/Mn的热力学平衡分布[J]. 应用基础与工程科学学报, 2012, (2):200-209. LIU J Y, SUN S Y, LUO G Q. Thermodynamic equilibrium distribution of Zn, Cu, Ni and Mn during incineration of paper mill sewage sludge[J]. Journal of Basic Science and Engineering, 2012, (2):200-209.
[28]	陈宗良. 污泥热处理过程中重金属的迁移特性研究[D]. 沈阳:沈阳航空航天大学, 2011. CHEN Z L. Transfer characteristics study of heavy metal in thermal treatment of sewage sludge[D]. Shenyang:Shenyang Aerospace University, 2011.
[29]	JUNG C H, MATSUTI T, TANAKA N. Behavior of metals in ash melting and gasification-melting of municipal solid waste[J]. Waste Management, 2005, 25(3):301-310.
[30]	李诗媛, 别如山, 吕响荣. 流化床中钙基吸收剂与HCl的反应机理[J]. 化工学报, 2005, 56(2):318-323. LI S Y, BIE R S, LÜ X R. Reaction kinetics of Ca-based sorbents with HCl in fluidized bed[J]. Journal of Chemical Industry and Engineering(China), 2005, 56(2):318-323.
[31]	VAN ZOMEREN A, COMANS R. Contribution of natural organic matter to copper leaching from municipal solid waste incinerator bottom ash[J]. Environmental Science & Technology, 2004, 38(14):3927-3932.
[32]	JIAO F, ZHANG L, SONG W, et al. Effect of inorganic particulates on the condensation behavior of lead and zinc vapors upon flue gas cooling[J]. Proceedings of the Combustion Institute, 2013, 34(2):2821-2829.
[33]	朱丽珺, 张金池, 俞元春, 等. 胡敏酸吸附重金属Cu2+ Pb2+ Cd2+的特征及影响因素[J]. 农业环境科学学报, 2008, (6):2240-2245. ZHU L J, ZHANG J C, YU Y C, et al. Characteristics and affecting factors of humic acid adsorbing heavy metals Cu2+ Pb2+ Cd2+[J]. Journal of Agro-Environment Science, 2008, (6):2240-2245.
[34]	HU H, LIU H, ZHANG Q, et al. Sintering characteristics of CaO-rich municipal solid waste incineration fly ash through the addition of Si/Al-rich ash residues[J]. Journal of Material Cycles and Waste Management, 2016, 18(2):340-347.

氧化钙调理污泥气化过程中重金属的迁移转化规律

Fate of heavy metals in CaO-conditioned sludge gasification

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献 34

相关文章 15

编辑推荐

Metrics

本文评价

[1]	陈哲文, 魏俊杰, 张玉明. 超临界水煤气化耦合SOFC发电系统集成及其能量转化机制[J]. 化工学报, 2023, 74(9): 3888-3902.
[2]	韩晨, 司徒友珉, 朱斌, 许建良, 郭晓镭, 刘海峰. 协同处理废液的多喷嘴粉煤气化炉内反应流动研究[J]. 化工学报, 2023, 74(8): 3266-3278.
[3]	刘春雨, 周桓宇, 马跃, 岳长涛. CaO调质含油污泥干燥特性及数学模型[J]. 化工学报, 2023, 74(7): 3018-3027.
[4]	屈园浩, 邓文义, 谢晓丹, 苏亚欣. 活性炭/石墨辅助污泥电渗脱水研究[J]. 化工学报, 2023, 74(7): 3038-3050.
[5]	周必茂, 许世森, 王肖肖, 刘刚, 李小宇, 任永强, 谭厚章. 烧嘴偏转角度对气化炉渣层分布特性的影响[J]. 化工学报, 2023, 74(5): 1939-1949.
[6]	陈宇豪, 陈晓平, 马吉亮, 梁财. 市政污泥回转窑焚烧气态污染物排放特性研究[J]. 化工学报, 2023, 74(5): 2170-2178.
[7]	葛泽峰, 吴雨青, 曾名迅, 查振婷, 马宇娜, 侯增辉, 张会岩. 灰化学成分对生物质气化特性的影响规律[J]. 化工学报, 2023, 74(5): 2136-2146.
[8]	张兰河, 赖青燚, 王铁铮, 关潇卓, 张明爽, 程欣, 徐小惠, 贾艳萍. H₂O₂对SBR脱氮效率和污泥性能的影响[J]. 化工学报, 2023, 74(5): 2186-2196.
[9]	仇鹏, 韩洋, 许建良, 王辅臣, 代正华. 用于预测气流床煤气化的EDC模型参数研究[J]. 化工学报, 2023, 74(1): 428-437.
[10]	罗欣宜, 冯超, 刘晶, 乔瑜. 污泥不同热处理工艺产物磷的浸出回收实验研究[J]. 化工学报, 2022, 73(9): 4034-4044.
[11]	沈嘉辉, 王侃宏, 郁达伟, 胡大洲, 魏源送. 游离氨调理污泥厌氧消化优化产甲烷过程与强化有机物释放[J]. 化工学报, 2022, 73(9): 4147-4155.
[12]	戚新刚, 路利波, 陈渝楠, 葛志伟, 郭烈锦. 造纸黑液超临界水气化制氢与高附加值化学品回收研究进展[J]. 化工学报, 2022, 73(8): 3338-3354.
[13]	刘振宇. 煤地下气化低效的化学反应工程根源：滞留层及通道中的传质与反应[J]. 化工学报, 2022, 73(8): 3299-3306.
[14]	朱莲峰, 王超, 张梦娟, 刘方正, 贾鑫, 安萍, 许光文, 韩振南. 水蒸气/氧流化床两段煤气化制备低焦油合成气工艺实验[J]. 化工学报, 2022, 73(8): 3720-3730.
[15]	张劢, 田瑶, 郭之旗, 王叶, 窦广进, 宋浩. 光催化-生物杂合系统设计优化用于燃料和化学品绿色合成[J]. 化工学报, 2022, 73(7): 2774-2789.