煤焦化过程苯系物的排放特征及稳定碳同位素组成

牟玲; 冯传阳; 李杨勇; 李晓帆; 刘添; 刘紫叶; 姜辛

PDF(829 KB)

中国环境科学 ›› 2023, Vol. 43 ›› Issue (6) : 2806-2813.

大气污染与控制

煤焦化过程苯系物的排放特征及稳定碳同位素组成

牟玲^1,2, 冯传阳¹, 李杨勇¹, 李晓帆¹, 刘添¹, 刘紫叶¹, 姜辛¹

作者信息 +

Emission characteristics and stable carbon isotope composition of BTEX in coal coking process

MU Ling^1,2, FENG Chuan-yang¹, LI Yang-yong¹, LI Xiao-fan¹, LIU Tian¹, LIU Zi-ye¹, JIANG Xin¹

Author information +

文章历史 +

摘要

选取山西省典型焦化厂开展不同生产工序苯系物(BTEX)样品采集,分析5种主要BTEX组分的排放特征及稳定碳同位素组成(δ¹³C),并对我国焦化行业BTEX排放量及不确定性进行了估算.结果表明:炼焦过程BTEX总排放因子为16649mg/t焦炭,其中焦炉烟气BTEX排放因子最高(7167mg/t),其次为出焦(6454,1825mg/t)、污水处理 (1096mg/t)和化产回收废气 (112.7mg/t);与燃煤不同,苯是炼焦过程排放的优势特征物种(86.12%),其次是甲苯(11.45%);炼焦过程排放BTEX的δ¹³C值为-27.10‰~-32.58‰,不同生产工序δ¹³C值无显著差异;煤焦化过程排放的苯/甲苯比值(B/T)和苯的δ¹³C值具有特异性,可作为区分炼焦与其他污染源的指示物;2020年我国焦化行业BTEX排放量为7844t,其中山西(22.27%)、陕西(10.39%)、河北(10.24%)和内蒙古(8.96%)贡献最大.

Abstract

Emission characteristics and stable carbon isotopic (δ¹³C) composition of BTEX emitted from different production processes in a typical coal coke plant were measured, and the total BTEX emissions during the coke production in China were estimated. The total emission factor (EF) of BTEX from coal coking process was 16655mg/t coke, among which the EF from coke oven flue gas was the highest (7167mg/t), followed by the flue gases from coke pushing (6454and 1825mg/t), sewage treatment (1096mg/t) and chemical byproduct recovery (112.7mg/t). The total emissions of BTEX from the coking in 2020 were 7844 tons in China, and Shanxi (22.27%), Shaanxi (10.39%), Hebei (10.24%) and Inner Mongolia (8.96%) made higher contributions. Benzene was the most abundant compound, accounting for 86.12% of the total BTEX, followed by Toluene (11.45%); and δ¹³C of BTEX from coal coking ranged from -27.10‰ to -32.58‰. There was no significant difference in the carbon isotope composition of BTEX emissions from different processes during the coal coke production, and the unique B/T (Benzene/ Toluene) ratio and δ¹³C value of benzene imply that it could be a good marker for distinguishing coking emissions from other sources in the ambient air.

导出引用

牟玲, 冯传阳, 李杨勇, 李晓帆, 刘添, 刘紫叶, 姜辛. 煤焦化过程苯系物的排放特征及稳定碳同位素组成[J]. 中国环境科学. 2023, 43(6): 2806-2813

MU Ling, FENG Chuan-yang, LI Yang-yong, LI Xiao-fan, LIU Tian, LIU Zi-ye, JIANG Xin. Emission characteristics and stable carbon isotope composition of BTEX in coal coking process[J]. China Environmental Science. 2023, 43(6): 2806-2813

中图分类号： X531

参考文献

[1] Huang Y S, Hsieh C C. VOC characteristics and sources at nine photochemical assessment monitoring stations in western Taiwan[J]. Atmospheric Environment, 2020,240.
[2] Chen L G, Hu G C, Fan R F, et al. Association of PAHs and BTEX exposure with lung function and respiratory symptoms among a nonoccupational population near the coal chemical industry in Northern China[J]. Environment International, 2018,120:480-488.
[3] Garg A, Gupta N C. A comprehensive study on spatio-temporal distribution, health risk assessment and ozone formation potential of BTEX emissions in ambient air of Delhi, India[J]. Science of the Total Environment, 2019,659:1090-1099.
[4] Masih A, Lall A S, Taneja A, et al. Inhalation exposure and related health risks of BTEX in ambient air at different microenvironments of a terai zone in north India[J]. Atmospheric Environment, 2016,147:55-66.
[5] US EPA. Integrated Risk Information System (IRIS)[M]. Washington:US EPA, 1998.
[6] IARC IARC monographs programme on evaluation of carcinogenic risks to humans[M]. LYON:IARC, 2002.
[7] Wang Y, Cheng K, Tian H Z, et al. Analysis of reduction potential of primary air pollutant emissions from coking industry in China[J]. Aerosol and Air Quality Research, 2018,18(2):533-541.
[8] Mu L, Peng L, Liu X F, et al. Emission characteristics of heavy metals and their behavior during coking processes[J]. Environmental Science & Technology, 2012,46(11):6425-6430.
[9] Mu L, Peng L, Cao J, et al. Emissions of polycyclic aromatic hydrocarbons from coking industries in China[J]. Particuology, 2013,11(1):86-93.
[10] Mu L, Peng L, Liu X F, et al. Characteristics of polycyclic aromatic hydrocarbons and their gas/particle partitioning from fugitive emissions in coke plants[J]. Atmospheric Environment, 2014,83:202-210.
[11] Mu L, Peng L, Liu X F, et al. Emission characteristics and size distribution of polycyclic aromatic hydrocarbons from coke production in China[J]. Atmospheric Research, 2017,197:113-120.
[12] Wu R R, Bo Y, Li J, et al. Method to establish the emission inventory of anthropogenic volatile organic compounds in China and its application in the period 2008~2012[J]. Atmospheric Environment, 2016,127:244-254.
[13] Li J, Zhou Y, Simayi M, et al. Spatial-temporal variations and reduction potentials of volatile organic compound emissions from the coking industry in China[J]. Journal of Cleaner Production, 2019,214:224-235.
[14] Li R M, Yan Y L, Peng L, et al. Segment-based volatile organic compound emission characteristics from different types of coking plants in China[J]. Aerosol and Air Quality Research, 2021,21(1):200145.
[15] Qiu K Q, Yang L X, Lin J M, et al. Historical industrial emissions of non-methane volatile organic compounds in China for the period of 1980~2010[J]. Atmospheric Environment, 2014,86:102-112.
[16] Wei W, Wang S X, Hao J M, et al. Projection of anthropogenic volatile organic compounds (VOCs) emissions in China for the period 2010~2020[J]. Atmospheric Environment, 2011,45(38):6863-6871.
[17] Suthawaree J, Tajima Y, Khunchornyakong A, et al. Identification of volatile organic compounds in suburban Bangkok, Thailand and their potential for ozone formation[J]. Atmospheric Research, 2012,104:245-254.
[18] Yurdakul S, Civan M, Tuncel G. Volatile organic compounds in suburban Ankara atmosphere, Turkey:Sources and variability[J]. Atmospheric Research, 2013,120:298-311.
[19] Miller L, Xu X H, Wheeler A, et al. Spatial variability and application of ratios between BTEX in two Canadian cities[J]. Thescientific worldjournal, 2011,11:2536-2549.
[20] Liu C T, Zhang C L, Mu Y J, et al. Emission of volatile organic compounds from domestic coal stove with the actual alternation of flaming and smoldering combustion processes[J]. Environmental Pollution, 2017,221:385-391.
[21] Barletta B, Meinardi S, Simpson I J, et al. Ambient mixing ratios of nonmethane hydrocarbons (NMHCs) in two major urban centers of the Pearl River Delta (PRD) region:Guangzhou and Dongguan[J]. Atmospheric Environment, 2008,42(18):4393-4408.
[22] Yan Y, Yang C, Peng L, et al. Emission characteristics of volatile organic compounds from coal-, coal,gangue-, and biomass-fired power plants in China[J]. Atmospheric Environment, 2016,143:261-269.
[23] Shi J W, Deng H, Bai Z P, et al. Emission and profile characteristic of volatile organic compounds emitted from coke production, iron smelt, heating station and power plant in Liaoning Province, China[J]. Science of the Total Environment, 2015,515:101-108.
[24] Wang H L, Hao R, Fang L, et al. Study on emissions of volatile organic compounds from a typical coking chemical plant in China[J]. Science of the Total Environment, 2021,752:141927.
[25] Zhang Y, Wei C, Yan B. Emission characteristics and associated health risk assessment of volatile organic compounds from a typical coking wastewater treatment plant[J]. Science of the Total Environment, 2019,693:133417.
[26] Zhang Y X, Zang T T, Yan B, et al. Distribution characteristics of volatile organic compounds and contribution to ozone formation in a coking wastewater treatment plant[J]. International Journal of Environmental Research and Public Health, 2020,17(2):553.
[27] Kornilova A, Moukhtar S, Saccon M, et al. A method for stable carbon isotope ratio and concentration measurements of ambient aromatic hydrocarbons[J]. Atmospheric Measurement Techniques, 2015,8(6):2301-2313.
[28] Kornilova A, Huang L, Saccon M, et al. Stable carbon isotope ratios of ambient aromatic volatile organic compounds[J]. Atmospheric Chemistry and Physics, 2016,16(18):11755-11772.
[29] Rudolph J, Czuba E, Norman A L, et al. Stable carbon isotope composition of nonmethane hydrocarbons in emissions from transportation related sources and atmospheric observations in an urban atmosphere[J]. Atmospheric environment, 2002,36(7):1173-1181.
[30] Kawashima H, Murakami M. Measurement of the stable carbon isotope ratio of atmospheric volatile organic compounds using chromatography, combustion, and isotope ratio mass spectrometry coupled with thermal desorption[J]. Atmospheric Environment, 2014, 89:140-147.
[31] 王佳妮,张晗,洪振宇,等.热脱附-单体稳定同位素技术测定挥发性有机物[J]. 分析化学, 2016,44(9):1342-1347. Wang J N, Zhang H, Hong Z Y, et al. Determination of volatile organic compounds by thermal desorption-monomer stable isotope technique[J]. Chinese Journal of Analytical Chemistry, 2016,44(9):1342-1347.
[32] Li Y H, Yan Y L, Hu D M, et al. Source apportionment of atmospheric volatile aromatic compounds (BTEX) by stable carbon isotope analysis:A case study during heating period in Taiyuan, northern China[J]. Atmospheric Environment, 2020,225:117369.
[33] Von Eckstaedt C D V, Grice K, Ioppolo-Armanios M, et al. Compound specific carbon and hydrogen stable isotope analyses of volatile organic compounds in various emissions of combustion processes[J]. Chemosphere, 2012,89(11):1407-1413.
[34] Von Eckstaedt C V, Grice K, Ioppolo-Armanios M, et al. delta C-13 and delta D of volatile organic compounds in an alumina industry stack emission[J]. Atmospheric Environment, 2011,45(31):5477-5483.
[35] HJ 732-2014 固定污染源废气挥发性有机物的采样气袋法[S]. HJ 732-2014 Sampling air bag method for volatile organic compounds in waste gas from fixed pollution sources[S].
[36] Turner N, Jones M, Grice K, et al. delta C-13 of volatile organic compounds (VOCS) in airborne samples by thermal desorption-gas chromatography-isotope ratio-mass spectrometry (TD-GC-IR-MS)[J]. Atmospheric Environment, 2006,40(18):3381-3388.
[37] Von Eckstaedt C V, Grice K, Ioppolo-Armanios M, et al. Delta D and delta 13C analyses of atmospheric volatile organic compounds by thermal desorption gas chromatography isotope ratio mass spectrometry[J]. Journal of chromatography A, 2011,1218(37):6511-6517.
[38] USEPA, AP42Compilation of air pollutant emission factors[M]. Washington:USEPA, 2008.
[39] Mu L, Li X, Liu X, et al. Characterization and emission factors of carbonaceous aerosols originating from coke production in China[J]. Environmental Pollution, 2021,268:115768.
[40] Chen W H, Yang W B, Yuan C S, et al. Fates of chlorinated volatile organic compounds in aerobic biological treatment processes:The effects of aeration and sludge addition[J]. Chemosphere, 2014,103:92-98.
[41] Fatone F, Di Fabio S, Bolzonella D, et al. Fate of aromatic hydrocarbons in Italian municipal wastewater systems:An overview of wastewater treatment using conventional activated-sludge processes (CASP) and membrane bioreactors (MBRs)[J]. Water Research, 2011,45(1):93-104.
[42] Elbir T, Cetin B, Cetin E, et al. Characterization of volatile organic compounds (VOCs) and their sources in the air of Izmir, Turkey[J]. Environmental Monitoring and Assessment, 2007,133(1-3):149-160.
[43] Guo H, Lee S C, Louie P K K, et al. Characterization of hydrocarbons, halocarbons and carbonyls in the atmosphere of Hong Kong[J]. Chemosphere, 2004,57(10):1363-1372.
[44] Guo H, Wang T, Louie P. Source apportionment of ambient non-methane hydrocarbons in Hong Kong application of a principal component analysis/absolute principal component scores (PCA/APCS) receptor model[J]. Environmental-Pollution-1987, 2004,129(3):489-498.
[45] Goldstein A H, Shaw S L. Isotopes of volatile organic compounds:an emerging approach for studying atmospheric budgets and chemistry[J]. Chemical reviews, 2003,103(12):5025-5048.
[46] Suto N, Kawashima H. Measurement report:Source characteristics of water-soluble organic carbon in PM_2.5 at two sites in Japan, as assessed by long-term observation and stable carbon isotope ratio[J]. Atmospheric Chemistry and Physics, 2021,21(15):11815-11828.
[47] Mastral A M, Callén M S. A Review on Polycyclic Aromatic Hydrocarbon (PAH) emissions from energy generation[J]. Environmental Science & Technology, 2000,34(15):3051-3057.
[48] Mcrae C, Snape C E, Fallick A E. Variations in the stable isotope ratios of specific aromatic and aliphatic hydrocarbons from coal conversion processes[J]. Analyst, 1998,123(7):1519-1523.
[49] Buczynska A J, Geypens B, Van Grieken R, et al. Stable carbon isotopic ratio measurement of polycyclic aromatic hydrocarbons as a tool for source identification and apportionment-A review of analytical methodologies[J]. Talanta, 2013,105:435-450.
[50] 国家统计局.中国统计年鉴[M]. 北京:中国统计出版社, 2021. National Bureau of Statistics of China. China statistical yearbook[M]. Beijing:China Statistical Publishing House, 2021.
[51] Streets D G, Bond T C, Carmichael G R, et al. An inventory of gaseous and primary aerosol emissions in Asia in the year 2000[J]. Journal of Geophysical Research:Atmospheres, 2003,108(D21):8809.
[52] Bond T C, Bhardwaj E, Dong R, et al. Historical emissions of black and organic carbon aerosol from energy-related combustion, 1850~2000[J]. Global Biogeochemical Cycles, 2008,21(2):1-16.