Species distribution of As, Se and Pb in coal-fired flue gas and influence of elements S and Cl on them
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摘要: 基于化学热力学平衡分析方法，计算分析了燃煤烟气中重金属As、Se、Pb的形态分布规律，研究了S、Cl等元素对As、Se、Pb的形态分布规律的影响。结果表明，氧化性气氛下，As以As2O5、As4O6、AsO等氧化物的形式存在；Se主要以SeO2形式存在；Pb在1000 K以下主要是固态PbSO4，1200 K以上为气态PbO。还原性气氛下，As在较低温度时为固态As2S2，900-1400 K以As2、AsS、AsN气体共存，2000 K以上全部转化为气态AsO。Se在1100 K以下主要以气态H2Se存在，1100 K开始生成SeS和Se2气体，1800 K时主要是气态Se和少量气态SeO；Pb在中低温时主要是PbS，1800 K以上气态Pb为主要存在形态。S在还原性气氛下增大了AsS（g）、PbS（g）、SeS（g）的比例，氧化性气氛下对As、Se、Pb形态分布基本无影响；Cl无论在氧化还是还原气氛下对As、Se影响均较小，但对Pb的形态分布影响较大。Abstract: Based on chemical thermodynamics equilibrium analysis, species distribution of As, Se and Pb in coal-fired flue gas was calculated and analyzed, and effect of S, Cl on them was studied. The results show that As exists in the form of As2O5, As4O6 and AsO in oxidizing atmosphere, Se mainly exists in the form of SeO2, and Pb is mainly solid PbSO4 below 1000 K and gaseous PbO above 1200 K. In reducing atmosphere, As is solid As2S2 at lower temperature; As2, AsS and AsN coexist at 900-1400 K, and all of As is changed into gas AsO above 2000 K. Se exists mainly as gaseous H2Se below 1100 K, SeS and Se2 are generated at 1100 K, gaseous Se and a small amount of gaseous SeO at 1800 K. Pb mainly exists as PbS and gaseous Pb above 1800 K at middle and low temperature. The ratio of AsS(g), PbS(g) and SeS(g) increases in the reducing atmosphere, but the distribution of As, Se and Pb is not affected in the oxidizing atmosphere. Cl has little effect on As and Se in both oxidizing and reducing atmosphere, but has a great influence on species distribution of Pb.
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Key words:
- coal-fired flue gas /
- chemical thermodynamic equilibrium calculation /
- As /
- Se /
- Pb /
- speciation distribution
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图 1 还原性气氛与氧化性气氛下As与煤的形态分布
(a): reducing atmosphere; (b): oxidizing atmosphere
Figure 1 Calculation results of species distribution of As and coal in reducing and oxidizing atmosphere
图 2 还原性气氛与氧化性气氛下Se与煤的形态分布
Figure 2 Calculation results of species distribution of Se and coal in reducing and oxidizing atmosphere
(a): reducing atmosphere; (b): oxidizing atmosphere
图 3 还原性气氛与氧化性气氛下Pb与煤的形态分布
Figure 3 Calculation results of species distribution of Pb and coal in reducing and oxidizing atmosphere
(a): reducing atmosphere; (b): oxidizing atmosphere
图 4 还原性气氛下不同S含量对As形态分布的影响
Figure 4 Effects of different concentrations of S on species distribution of As in reducing atmosphere
(a): As + coal + S; (b): As+ coal + 5S; (c): As+ coal + 10S
图 5 氧化性气氛下不同S含量对As形态分布的影响
Figure 5 Effects of different concentrations of S on species distribution of As in oxidizing atmosphere
(a): As + coal + S; (b): As+ coal + 5S; (c): As+ coal + 10S
图 6 还原性气氛下不同S含量对Se形态分布的影响
Figure 6 Effects of different concentrations of S on species distribution of Se in reducing atmosphere
(a): Se + coal + S; (b): Se+ coal + 5S; (c): Se+ coal + 10S
图 7 氧化性气氛下不同S含量对Se形态分布的影响
Figure 7 Effects of different concentrations of S on species distribution of Se in oxidizing atmosphere
(a): Se + coal + S; (b): Se+ coal + 5S; (c): Se+ coal + 10S
图 8 还原性气氛下不同S含量对Pb形态分布的影响
Figure 8 Effects of different concentrations of S on species distribution of Pb in reducing atmosphere
(a): Pb + coal + S; (b): Pb + coal + 5S; (c): Pb + coal + 10S
图 9 氧化性气氛下不同S含量对Pb形态分布的影响
Figure 9 Effects of different concentrations of S on species distribution of Pb in oxidizing atmosphere
(a): Pb + coal + S; (b): Pb + coal + 5S; (c): Pb + coal + 10S
图 10 还原性气氛下不同Cl含量对As形态分布的影响
(a): As + coal + Cl; (b): As + coal + 5Cl; (c): As + coal + 10Cl
Figure 10 Effects of different concentrations of Cl on species distribution of As in reducing atmosphere
图 11 氧化性气氛下不同Cl含量对As形态分布的影响
Figure 11 Effects of different concentrations of Cl on species distribution of As in oxidizing atmosphere
(a): As + coal + Cl; (b): As + coal + 5Cl; (c): As + coal + 10Cl
图 12 还原性气氛下不同Cl含量对Se形态分布的影响
Figure 12 Effects of different concentrations of Cl on species distribution of Se in reducing atmosphere
(a): Se + coal + Cl; (b): Se + coal + 5Cl; (c): Se + coal + 10Cl
图 13 氧化性气氛下不同Cl含量对Se形态分布的影响
Figure 13 Effects of different concentrations of Cl on species distribution of Se in oxidizing atmosphere
(a): Se + coal + Cl; (b): Se + coal + 5Cl; (c): Se + coal + 10Cl
图 14 还原性气氛下不同Cl含量对Pb形态分布的影响
Figure 14 Effects of different concentrations of Cl on species distribution of Pb in reducing atmosphere
(a): Pb + coal + Cl; (b): Pb + coal + 5Cl; (c): Pb + coal + 10Cl
图 15 氧化性气氛下不同Cl含量对Pb形态分布的影响
Figure 15 Effects of different concentrations of Cl on species distribution of Pb in oxidizing atmosphere
(a): Pb + coal + Cl; (b): Pb + coal + 5Cl; (c): Pb + coal + 10Cl
表 1 输入煤初始条件
Table 1 Initial condition of coal input
Element C H O N S Cl As Se Pb Quantity/mol 64.04 37.5 176.35 659.2 0.178 0.845×10-3 3.19×10-3 7.06×10-3 5.22×10-3 Content 76.85% 3.75% 2.20% 1.37% 0.57% 30 μg/g 2.39 μg/g 5.58 μg/g 10.81 μg/g 
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[1] 徐静颖, 卓建坤, 姚强.燃煤有机污染物生成排放特性与采样方法研究进展[J].化工学报, 2019, 70(8):2823-2834. http://www.cnki.com.cn/Article/CJFDTotal-HGSZ201908002.htmXU Jing-ying, ZHUO Jian-kun, YAO Qiang. Research progress on formation, emission characteristics and sampling methods of organic compounds from coal combustion[J]. J Chem Ind Eng, 2019, 70(8):2823-2834. http://www.cnki.com.cn/Article/CJFDTotal-HGSZ201908002.htm [2] 王丽.超低排放机组中汞、砷和硒等重金属的迁移特性研究[D].杭州: 浙江大学, 2018.WANG Li. Study on the partitioning characteristics of Hg, As, Se and other hazardous elements in ultra low emission coal fired power plants[D]. Hangzhou: Zhejiang University, 2018. [3] 郭欣, 郑楚光, 陈丹. 300MW煤粉锅炉砷排放特征的实验研究[J].环境科学, 2006, (4):631-634.GUO Xin, ZHENG Chu-guang, CHEN Dan. Characterization of arsenic emissions from a coal-fired power plant[D]. Environ Sci, 2006, (4): 631-634. [4] 徐文东, 曾荣树, 叶大年, QUEROL X.电厂煤燃烧后元素硒的分布及对环境的贡献[J].环境科学, 2005, (2):64-68. http://www.cnki.com.cn/Article/CJFDTotal-HJKZ200502013.htmXU Wen-dong, ZENG Rong-shu, YE Da-nian, Querol X. Distributions and environmental impacts of selenium in wastes of coal from a power plant[J]. Environ Sci, 2005, (2):64-68. http://www.cnki.com.cn/Article/CJFDTotal-HJKZ200502013.htm [5] 徐杰英.煤燃烧过程中痕量元素铅的反应机理研究[D].武汉: 华中科技大学, 2004.XU Jie-ying. Study on the reaction mechanism of trace element Pb in the coal combustion process[D]. Wuhan: Huazhong University of Science and Technology, 2004. [6] JIAO F, ZHANG L, SONG W. Effect of inorganic particulates on the condensation behavior of lead and zinc vapors upon flue gas cooling[J]. Proc Combust Inst, 2013, 34(2):2821-2829. https://www.sciencedirect.com/science/article/pii/S1540748912003549 [7] 郭富强, 刘清才, 蒋历俊, 任山, 王铸, 赵齐.粒径和燃烧温度对燃煤颗粒物微观形貌影响研究[C].中国环境科学学会, 2016: 61-65.GUO Fu-qiang, LIU Qing-cai, JIANG Li-jun, REN Shan, WANG Zhu, ZHAO Qi. Influence of burning temperature and particle size on particulate matter microstructure during pulverized coal combustion[C]. Chin Soc Environ Sci, 2016: 61-65. [8] 李耀拉.煤焦化痕量元素的迁移与热力学形态的模拟研究[D].武汉: 武汉科技大学, 2009.LI Yao-la. The transformation and thermodynamics simuation of morphology of trace elements during the coal-coking[D]. Wuhan: Wuhan University of Science and Technology, 2009. [9] 田贺忠, 曲益萍, 王艳, 程珂, 潘迪.中国燃煤大气硒排放及其污染控制[J].中国电力, 2009, 42(8):53-57. http://d.wanfangdata.com.cn/Periodical/zgdl200908013TIAN He-zhong, QU Yi-ping, WANG Yan, CHENG Ke, PAN Di. Emission and control of atmospheric selenium from coal combustion in China[J]. Electric Power, 2009, 42(8):53-57. http://d.wanfangdata.com.cn/Periodical/zgdl200908013 [10] 邓双, 张凡, 刘宇, 石应杰, 王红梅, 张辰, 王相凤, 曹晴.燃煤电厂铅的迁移转化研究[J].中国环境科学, 2013, 33(7):1199-1206. http://qikan.cqvip.com/Qikan/Article/Detail?id=46850231DENG Shuang, ZHANG Fan, LIU Yu, SHI Ying-jie, WANG Hong-mei, ZHANG Chen, WANG Xiang-feng, CAO Qing. Lead emission and speciation of coal-fired power plants in China[J]. Chin Environ Sci, 2013, 33(7):1199-1206. http://qikan.cqvip.com/Qikan/Article/Detail?id=46850231 [11] 王泉海, 邱建荣, 温存, 熊全军, 吴辉, 孔凡海, 张小平.氧燃烧方式下痕量元素形态转化的热力学平衡模拟[C].中国工程热物理学会, 2005: 642-646.WANG Quan-hai, QIU Jian-rong, WEN Cun, XIONG Quan-jun, WU Hui, KONG Fan-hai, ZHANG Xiao-ping. Thermodynamic equilibrium simulation of trace element speciation in oxygen combustion[C]. CSET, 2005: 642-646. [12] 闫蓓.电厂燃煤过程中砷的迁移转化及控制技术[D].保定: 华北电力大学, 2006.YAN Bei. Arsenical transform and control technology in the process of coal-fired power plant[D]. Baoding: North China Electric Power University, 2006. [13] FRANDSEN F, JOHANSEN K D, RASMUSSEN P. Trace elements from combustion and gasification of coal-An equilibrium approach[J]. Prog Energy Combust, 1994, 20(2):115-138. https://www.sciencedirect.com/science/article/pii/0360128594900078 [14] MALYKH N V, PERTSIKOV I Z. Study of the partitioning of trace elements during pulverized coal combustion[J]. Khimiya Tverdogo Tela, 1990, 24(4):50. https://www.researchgate.net/publication/234183120_The_partitioning_of_trace_elements_during_pulverized_coal_combustion [15] 冯荣.燃煤典型痕量元素化学热力学与动力学计算的研究与比较[D].武汉: 华中科技大学, 2004.FENG Rong. A thesis submitted in partial fulfillment of the requirements for the degree of master of engineering[D]. Wuhan: Huazhong University of Science and Technology, 2004. [16] YAN R. Parti oning of trace elements in the flue gas from coal combustion[D]. Doctoral Dissertation, 1999: 59-61. [17] 张宾.水泥窑协同处置固体废弃物过程中氯、硫、碱对重金属迁移的影响及作用机制研究[D].广州: 华南理工大学, 2019.ZHANG Bin. Study on the effects of chlorine, sulfur and alkali on the migration of heavy metals and related mechanisms during Co-processing solid waste in cement kiln[D]. Guangzhou: South China University of Technology, 2019. [18] 刘迎晖, 郑楚光, 游小清, 郭欣.燃煤过程中易挥发有毒痕量元素的相互作用[J].燃烧科学与技术, 2001, (4):243-247. http://www.cqvip.com/Main/Detail.aspx?id=12447617LIU Ying-hui, ZHENG Chu-guang, YOU Xiao-qing, GUO Xin. Interaction between most volatile toxic trace elements during coal combustion[J]. Combust Sci Technol, 2001, (4):243-247. http://www.cqvip.com/Main/Detail.aspx?id=12447617 [19] WU C, BISWAS P. An equilibrium analysis to determine the speciation of metals in an incinerator[J]. Combust Flame, 1993, 93(1):31-40. https://www.sciencedirect.com/science/article/pii/001021809390082E [20] 严玉朋, 黄亚继, 王昕晔, 张帅毅.城市生活垃圾焚烧中铅形态转化的热力学平衡[J].中南大学学报(自然科学版), 2016, 47(6):2166-2173. http://qikan.cqvip.com/Qikan/Article/Detail?id=669532658YAN Yu-peng, HUANG Ya-ji, WANG Xin-ye, ZHANG Shuai-yi. Thermodynamic equilibrium analysis of lead partitioning during MSW incineration[J]. J Central South Univ(Nat Sci Ed), 2016, 47(6):2166-2173. http://qikan.cqvip.com/Qikan/Article/Detail?id=669532658 [21] 胡济民, 王瑟澜, 徐浩然, 吴亭亭.城市生活垃圾焚烧过程中铅的迁移特性探究[J].华东理工大学学报(自然科学版), 2018, 44(6):800-806. http://www.cqvip.com/QK/90601X/201806/7001015232.htmlHU Ji-min, WANG Se-lan, XU Hao-ran, WU Ting-ting. Partitioning of Pb during municipal solid waste incineration[J]. J East Chin Univ Sci Technol (Nat Sci Ed), 2018, 44(6):800-806. http://www.cqvip.com/QK/90601X/201806/7001015232.html [22] 陈勇.垃圾焚烧中镉、铅迁移转化特性研究[D].北京: 清华大学, 2008.CHEN Yong. Study on the partitioning and speciation of Cd and Pb during municipal solid waste incineration[D]. Beijing: Tsinghua University, 2008. [23] 丁建.两种废物重金属分布形态的热力学平衡模拟[D].沈阳: 沈阳航空航天大学, 2013.DING Jian. Thermodynamics equilibrium analysis of heavy metals in two kinds of wastes during thermal treatment[D]. Shenyang: Shenyang Aerospace University, 2013. -
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