兰州市典型企业VOCs排放特征及反应活性分析
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摘要
基于兰州市大气VOCs排放清单,选取石化厂、乙烯厂、涂料厂3个典型企业采集VOCs样品,分析其无组织排放特征,并采用MIR (最大增量反应活性)法和LOH(·OH反应速率)法综合评价其化学反应活性,识别各企业的VOCs活性优势物种,同时探究不同企业特征VOCs比值.结果表明:不同排放源φ(VOCs)差异较大,范围为20. 8×10~(-9)～6 520. 3×10~(-9).从VOCs物种构成上来看,涂料厂芳香烃占比最高,而石化厂、乙烯厂均以烷烃物种最为丰富,石化厂不同工艺VOCs物种构成略有差异.从活性上看,涂料厂VOCs活性最高,其LOH和OFP (臭氧生成潜势)分别为2 676. 9 s-1和72 519. 0×10~(-9),约为其他行业的18～1 000倍,间/对-二甲苯、乙苯、邻二甲苯等物种活性较大;其次为石化厂,其LOH和OFP分别为273. 2 s-1和4 039. 1×10~(-9),正戊烷、异戊烷、乙烯、丙烯等物种活性贡献率高,其中柴油工艺对石化厂VOCs活性贡献率最大;乙烯厂的OFP最低,其LOH和OFP分别为4. 6s-1和69. 7×10~(-9),其VOCs活性主要来自乙烯、丙烯、正丁烯等烯烃物种.各工业源BTEX (苯、甲苯、乙苯及3种二甲苯异构体的合称)分布具有一定的差异,对于指示不同VOCs来源有一定的参考价值,但不同源比值的重叠性也表明并非全部VOCs来源可以通过特征物种比值来区分.研究显示,控制工业源特别是涂料与石化工业VOCs的排放有助于控制兰州市O3的生成.
Based on the emission inventory of the VOCs in Lanzhou City,petrochemical plants,coating plants and ethylene plants were selected to analyze the fugitive emission characteristics of VOCs using off-line monitoring instruments. The atmospheric chemical reactivity of VOCs and their OFP(ozone formation potential) were evaluated by using MIR(maximum increment reactivity) and LOHmethods(·OH radical reactivity). Also,we studied the diagnostic ratios of the different enterprises. The results showed that the φ(VOCs) varied from 20. 8×10~(-9) to 6,520. 3 × 10~(-9) in those VOC sources,among which the coating plants were the highest,the lowest was in ethylene plants. As for the compositions of VOCs,aromatics were the most abundant species in coating factories,while alkanes were in petrochemical plants and ethylene plants. Moreover,the processes of petrochemical plants were also slightly different. The photochemical reactivity of VOCs in the coating plants was higher than that in the other industries of this study,with which LOHand OFP were 2,676. 9 s-1 and 72,519. 0×10~(-9),respectively. It was about 18 to 1,000 times that of other industries. Moreover,the aromatic hydrocarbons such as m,p-xylene,ethylbenzene and o-xylene accounted for the highest ratio. The petrochemical industry was followed with the LOHand OFP being 273. 2 s-1 and 4,039. 1×10~(-9),and the major contribution came from diesel. N-pentane,isopentane,ethylene and propylene were dominant species for ozone formation in the petrochemical plants. The contribution of ethylene plants was the lowest in the study,with the LOHand OFP values of 4. 6 s-1 and 69. 7×10~(-9). Its photochemical reactivity mainly came from olefin species such as ethylene,propylene and n-butene. BTEX(the combination of benzene,toluene,ethylbenzene and three xylenes) ratios showed that some but not all VOC sources could be distinguished by those diagnostic ratios. The research indicated that the control of the industrial emission sources,especially the coatings and petrochemical plants,would be favorable for controlling ozone formation.
Based on the emission inventory of the VOCs in Lanzhou City,petrochemical plants,coating plants and ethylene plants were selected to analyze the fugitive emission characteristics of VOCs using off-line monitoring instruments. The atmospheric chemical reactivity of VOCs and their OFP(ozone formation potential) were evaluated by using MIR(maximum increment reactivity) and LOHmethods(·OH radical reactivity). Also,we studied the diagnostic ratios of the different enterprises. The results showed that the φ(VOCs) varied from 20. 8×10~(-9) to 6,520. 3 × 10~(-9) in those VOC sources,among which the coating plants were the highest,the lowest was in ethylene plants. As for the compositions of VOCs,aromatics were the most abundant species in coating factories,while alkanes were in petrochemical plants and ethylene plants. Moreover,the processes of petrochemical plants were also slightly different. The photochemical reactivity of VOCs in the coating plants was higher than that in the other industries of this study,with which LOHand OFP were 2,676. 9 s-1 and 72,519. 0×10~(-9),respectively. It was about 18 to 1,000 times that of other industries. Moreover,the aromatic hydrocarbons such as m,p-xylene,ethylbenzene and o-xylene accounted for the highest ratio. The petrochemical industry was followed with the LOHand OFP being 273. 2 s-1 and 4,039. 1×10~(-9),and the major contribution came from diesel. N-pentane,isopentane,ethylene and propylene were dominant species for ozone formation in the petrochemical plants. The contribution of ethylene plants was the lowest in the study,with the LOHand OFP values of 4. 6 s-1 and 69. 7×10~(-9). Its photochemical reactivity mainly came from olefin species such as ethylene,propylene and n-butene. BTEX(the combination of benzene,toluene,ethylbenzene and three xylenes) ratios showed that some but not all VOC sources could be distinguished by those diagnostic ratios. The research indicated that the control of the industrial emission sources,especially the coatings and petrochemical plants,would be favorable for controlling ozone formation.
引文
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[7] LIU Y,SHAO M,FU L,et al. Source profiles of volatile organic compounds(VOCs)measured in China:part I[J]. Atmospheric Environment,2008,42(25):6247-6260.
[8]陈颖.我国工业源VOCs行业排放特征及未来趋势研究[D].广州:华南理工大学,2011:29-40.
[9]王伯光,邵敏,张远航,等.机动车排放中挥发性有机污染物的组成及其特征研究[J].环境科学研究,2006,19(6):75-80.WANG Boguang,SHAO Min,ZHANG Yuanhang,et al. A study of volatile organic compounds and its emission factors from city vehides[J].Research of Environmental Sciences,2006,19(6):75-80.
[10]李勤勤,张志娟,李杨,等.石油炼化无组织VOCs的排放特征及臭氧生成潜力分析[J].中国环境科学,2016,36(5):1323-1331.LI Qinqin,ZHANG Zhijuan,LI Yang,et al. Characteristics and ozone formation potential of fugitive volatile organic compounds(VOCs)emitted from petrochemical industry in Pearl River Delta[J]. Research of Environmental Sciences,2016,36(5):1323-1331.
[11] WEI W,CHENG S,LI G,et al. Characteristics of volatile organic compounds(VOCs)emitted from a petroleum refinery in Beijing,China[J].Atmospheric Environment,2014,89(2):358-366.
[12]景盛翱,王红丽,朱海林,等.典型工业源VOCs治理现状及排放组成特征[J].环境科学,2018,39(7):3090-3095.JING Shengao,WANG Hongli,ZHU Hailin,et al. Treatment status and emission characteristics of volatile organic compounds from typical industrial sources[J]. Environmental Science,2018,39(7):3090-3095.
[13]王刚,魏巍,米同清,等.典型工业无组织源VOCs排放特征[J].中国环境科学,2015,35(7):1957-1964.WANG Gang,WEI Wei,MI Tongqing,et al.Characteristics of VOCs emitted from typical industrial fugitive[J]. China Environmental Science,2015,35(7):1957-1964.
[14]张远航,邵可声,唐孝炎,等.中国城市光化学烟雾污染研究[J].北京大学学报(自然科学版),1998,34(S1):392-400.
[15] TANG X,LI J,DONG Z X,et al. Photochemical pollution in Lanzhou,China:a case study[J]. Journal of Environmental Sciences,1989,58(1):384-395.
[16]姜允迪,王式功,祁斌,等.兰州城区臭氧浓度时空变化特征及其与气象条件的关系[J].兰州大学学报(自然科学版),2000,36(5):118-125.JIANG Yundi,WANG Shigong,QI Bin,et al. Temporal and spatial variations of ozone concentration and its relations with meteorological factors[J]. Journal of Lanzhou University(Natural Sciences),2000,36(5):118-125.
[17] WEI W,CHENG S,LI G,et al.Characteristics of ozone and ozone precursors(VOCs and NOx)around a petroleum refinery in Beijing,China[J]. Journal of Environmental Sciences,2014,26(2):332-342.
[18] GOLDAN P D,KUSTER W C,WILLIAMS E,et al. Nonmethane hydrocarbon and oxy hydrocarbon measurements during the 2002New England air quality study[J].Journal of Geophysical Research Atmospheres,2004.doi:10. 1029/2003JD004455.
[19] HUSSAIN S,AZIZ H A,ISA M H,et al. Orthophosphate removal from domestic wastewater using limestone and granular activated carbon[J].Desalination,2011,271(1/2/3):265-272.
[20] AND P T M,HARLEY R A,MILFORD J B,et al. Evaluation of incremental reactivity and its uncertainty in southern California[J].Environmental Science&Technology,2003,37(8):1598-1608.
[21] ATKINSON R,BAULCH D L,COX R A,et al. Evaluated kinetic and photochemical data for atmospheric chemistry:supplement III[J].Atmospheric Environment,1989,21(2):115-150.
[22] CARTER W P. Development of ozone reactivity scales for volatile organic com-pounds[J].Air Waste,1994,44(7):881-899.
[23]贾晨辉.中国西部兰州盆地非甲烷烃大气污染特征及其化学行为[D].兰州:兰州大学,2018:38-52.
[24]张振林,王贤慧,王晓华,等.石油化工装置污染源分析[J].油气田环境保护,2007,17(3):29-32.ZHANG Zhenlin,WANG Xianhui,WANG Xiaohua,et al. Pollution sources analysis of production and control process for petrochemical plants[J]. Environmental Protection of Oil and Gas Fields,2007,17(3):29-32.
[25]邵敏,付琳琳,刘莹,等.北京市大气挥发性有机物的关键活性组分及其来源[J].中国科学:地球科学,2005,35(S1):123-130.
[26]余宇帆.珠江三角洲地区典型工业VOCs源排放成分谱研究[D].广州:华南理工大学,2012:63-67.
[27] SEINFELD J H.Atmospheric chemistry and physics of air pollution[M].New York:Wiley Interscience,1986:242-266.
[28] ATKINSON R. Atmospheric chemistry of VOCs and NOx[J].Atmospheric Environment,2000,34(12/13/14):2063-2101.
[29] 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.
[30] 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,2012,104/105(1):245-254.
[31] MILLER L,XU X,WHEELER A,et al. Spatial variability and application of ratios between BTEX in two Canadian cities[J].Scientific World Journal,2011,11(1/2/3/4):2536-2549.
[32] HE Q,YAN Y,LI H,et al.Characteristics and reactivity of volatile organic compounds from non-coal emission sources in China[J].Atmospheric Environment,2015,115:153-162.
[33] AN J L,WANG Y S,WU F K,et al.Characterizations of volatile organic compounds during high ozone episodes in Beijing,China[J]. Environmental Monitoring&Assessment,2012,184(4):1879-1889.
[34] LIN T Y,SREE U,TSENG S H,et al. Volatile organic compound concentrations in ambient air of Kaohsiung petroleum refinery in Taiwan[J].Atmospheric Environment,2004,38(25):4111-4122.
[35] CARTER W P L.Development of ozone reactivity scales for volatile organic compounds[J].Jair Waste Manass,1994,44(7):881-899.
[36] TIWARI V,HANAI Y,MASUNAGA S. Ambient levels of volatile organic compounds in the vicinity of petrochemical industrial area of Yokohama,Japan[J].Air Quality,Atmosphere&Health,2010,3(2):65-75.
[37]罗达通,高健,王淑兰,等.北京秋季大气挥发性有机物及相关污染物特征分析[J].中国科学院大学学报,2014,31(3):329-336.LUO Datong,GAO Jian,WANG Shulan,et al. Characteristics of volatile organic compounds andrelative pollutants observed in autumn in Beijing[J].Journal of University of Chinese Academy of Sciences,2014,31(3):329-336.
[38] WANG H L,NIE L,JING L I,et al.Characterization and assessment of volatile organic compounds(VOCs)emissions from typical industries[J].Science Bulletin,2013,58(7):724-730.
[39] YAN Y,YANG C,PENG L,et al. Emission characteristics of volatile organic compounds from coal-,coal gangue-,and biomassfired power plants in China[J]. Atmospheric Environment,2016,143:261-269.
[2] CHENG H R,GUO H,SAUNDERS S M,et al. Assessing photochemical ozone formation in the Pearl River Delta with a photochemical trajectory model[J]. Atmospheric Environment,2010,44(34):4199-208.
[3] MIN S,ZHANG Y H,ZENG L M,et al.Ground-level ozone in the Pearl River Delta and the roles of VOC and NOxin its production[J].Journal of Environmental Management,2009,90(1):512-518.
[4] BALE A S,MEACHAM C A,BENIGNUS V A,et al. Volatile organic compounds inhibit human and rat neuronal nicotinic acetylcholine receptors expressed in Xenopus oocytes[J].Toxicology&Applied Pharmacology,2005,205(1):77-88.
[5] ZHENG J Y,SHAO M,CHE W W,et al.Speciated VOC emission inventory and spatial patterns of ozone formation potential in the Pearl River Delta,China[J].Environmental Science&Technology,2009,43(22):8580-8586.
[6] LIU Y,LU S S,CHANG C C,et al. Source apportionment of ambient volatile organic compounds in the Pearl River Delta,China:part II[J].Atmospheric Environment,2008,42(25):6261-6274.
[7] LIU Y,SHAO M,FU L,et al. Source profiles of volatile organic compounds(VOCs)measured in China:part I[J]. Atmospheric Environment,2008,42(25):6247-6260.
[8]陈颖.我国工业源VOCs行业排放特征及未来趋势研究[D].广州:华南理工大学,2011:29-40.
[9]王伯光,邵敏,张远航,等.机动车排放中挥发性有机污染物的组成及其特征研究[J].环境科学研究,2006,19(6):75-80.WANG Boguang,SHAO Min,ZHANG Yuanhang,et al. A study of volatile organic compounds and its emission factors from city vehides[J].Research of Environmental Sciences,2006,19(6):75-80.
[10]李勤勤,张志娟,李杨,等.石油炼化无组织VOCs的排放特征及臭氧生成潜力分析[J].中国环境科学,2016,36(5):1323-1331.LI Qinqin,ZHANG Zhijuan,LI Yang,et al. Characteristics and ozone formation potential of fugitive volatile organic compounds(VOCs)emitted from petrochemical industry in Pearl River Delta[J]. Research of Environmental Sciences,2016,36(5):1323-1331.
[11] WEI W,CHENG S,LI G,et al. Characteristics of volatile organic compounds(VOCs)emitted from a petroleum refinery in Beijing,China[J].Atmospheric Environment,2014,89(2):358-366.
[12]景盛翱,王红丽,朱海林,等.典型工业源VOCs治理现状及排放组成特征[J].环境科学,2018,39(7):3090-3095.JING Shengao,WANG Hongli,ZHU Hailin,et al. Treatment status and emission characteristics of volatile organic compounds from typical industrial sources[J]. Environmental Science,2018,39(7):3090-3095.
[13]王刚,魏巍,米同清,等.典型工业无组织源VOCs排放特征[J].中国环境科学,2015,35(7):1957-1964.WANG Gang,WEI Wei,MI Tongqing,et al.Characteristics of VOCs emitted from typical industrial fugitive[J]. China Environmental Science,2015,35(7):1957-1964.
[14]张远航,邵可声,唐孝炎,等.中国城市光化学烟雾污染研究[J].北京大学学报(自然科学版),1998,34(S1):392-400.
[15] TANG X,LI J,DONG Z X,et al. Photochemical pollution in Lanzhou,China:a case study[J]. Journal of Environmental Sciences,1989,58(1):384-395.
[16]姜允迪,王式功,祁斌,等.兰州城区臭氧浓度时空变化特征及其与气象条件的关系[J].兰州大学学报(自然科学版),2000,36(5):118-125.JIANG Yundi,WANG Shigong,QI Bin,et al. Temporal and spatial variations of ozone concentration and its relations with meteorological factors[J]. Journal of Lanzhou University(Natural Sciences),2000,36(5):118-125.
[17] WEI W,CHENG S,LI G,et al.Characteristics of ozone and ozone precursors(VOCs and NOx)around a petroleum refinery in Beijing,China[J]. Journal of Environmental Sciences,2014,26(2):332-342.
[18] GOLDAN P D,KUSTER W C,WILLIAMS E,et al. Nonmethane hydrocarbon and oxy hydrocarbon measurements during the 2002New England air quality study[J].Journal of Geophysical Research Atmospheres,2004.doi:10. 1029/2003JD004455.
[19] HUSSAIN S,AZIZ H A,ISA M H,et al. Orthophosphate removal from domestic wastewater using limestone and granular activated carbon[J].Desalination,2011,271(1/2/3):265-272.
[20] AND P T M,HARLEY R A,MILFORD J B,et al. Evaluation of incremental reactivity and its uncertainty in southern California[J].Environmental Science&Technology,2003,37(8):1598-1608.
[21] ATKINSON R,BAULCH D L,COX R A,et al. Evaluated kinetic and photochemical data for atmospheric chemistry:supplement III[J].Atmospheric Environment,1989,21(2):115-150.
[22] CARTER W P. Development of ozone reactivity scales for volatile organic com-pounds[J].Air Waste,1994,44(7):881-899.
[23]贾晨辉.中国西部兰州盆地非甲烷烃大气污染特征及其化学行为[D].兰州:兰州大学,2018:38-52.
[24]张振林,王贤慧,王晓华,等.石油化工装置污染源分析[J].油气田环境保护,2007,17(3):29-32.ZHANG Zhenlin,WANG Xianhui,WANG Xiaohua,et al. Pollution sources analysis of production and control process for petrochemical plants[J]. Environmental Protection of Oil and Gas Fields,2007,17(3):29-32.
[25]邵敏,付琳琳,刘莹,等.北京市大气挥发性有机物的关键活性组分及其来源[J].中国科学:地球科学,2005,35(S1):123-130.
[26]余宇帆.珠江三角洲地区典型工业VOCs源排放成分谱研究[D].广州:华南理工大学,2012:63-67.
[27] SEINFELD J H.Atmospheric chemistry and physics of air pollution[M].New York:Wiley Interscience,1986:242-266.
[28] ATKINSON R. Atmospheric chemistry of VOCs and NOx[J].Atmospheric Environment,2000,34(12/13/14):2063-2101.
[29] 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.
[30] 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,2012,104/105(1):245-254.
[31] MILLER L,XU X,WHEELER A,et al. Spatial variability and application of ratios between BTEX in two Canadian cities[J].Scientific World Journal,2011,11(1/2/3/4):2536-2549.
[32] HE Q,YAN Y,LI H,et al.Characteristics and reactivity of volatile organic compounds from non-coal emission sources in China[J].Atmospheric Environment,2015,115:153-162.
[33] AN J L,WANG Y S,WU F K,et al.Characterizations of volatile organic compounds during high ozone episodes in Beijing,China[J]. Environmental Monitoring&Assessment,2012,184(4):1879-1889.
[34] LIN T Y,SREE U,TSENG S H,et al. Volatile organic compound concentrations in ambient air of Kaohsiung petroleum refinery in Taiwan[J].Atmospheric Environment,2004,38(25):4111-4122.
[35] CARTER W P L.Development of ozone reactivity scales for volatile organic compounds[J].Jair Waste Manass,1994,44(7):881-899.
[36] TIWARI V,HANAI Y,MASUNAGA S. Ambient levels of volatile organic compounds in the vicinity of petrochemical industrial area of Yokohama,Japan[J].Air Quality,Atmosphere&Health,2010,3(2):65-75.
[37]罗达通,高健,王淑兰,等.北京秋季大气挥发性有机物及相关污染物特征分析[J].中国科学院大学学报,2014,31(3):329-336.LUO Datong,GAO Jian,WANG Shulan,et al. Characteristics of volatile organic compounds andrelative pollutants observed in autumn in Beijing[J].Journal of University of Chinese Academy of Sciences,2014,31(3):329-336.
[38] WANG H L,NIE L,JING L I,et al.Characterization and assessment of volatile organic compounds(VOCs)emissions from typical industries[J].Science Bulletin,2013,58(7):724-730.
[39] YAN Y,YANG C,PENG L,et al. Emission characteristics of volatile organic compounds from coal-,coal gangue-,and biomassfired power plants in China[J]. Atmospheric Environment,2016,143:261-269.
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