上海市专项化学品制造行业VOCs排放特征及臭氧生成潜势研究
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摘要
选取上海市某工业区内专项化学品制造行业中有代表性的10家企业,使用苏玛罐对各企业有组织排放废气进行采样,通过GC-MS (气相色谱-质谱联用仪)对106种VOCs进行分析,研究了专项化学品制造行业的VOCs排放特征,并使用MIR (最大增量反应活性)法计算了各企业排放VOCs对臭氧生成的贡献.结果表明:OVOCs (含氧挥发性有机物)和芳香烃是专项化学品制造行业的VOCs特征组分,OVOCs与芳香烃质量分数之和为65. 0%～100. 0%; 8家企业排放的VOCs中质量分数最高的物种均为OVOCs,w(OVOCs)为55. 8%～99. 9%.异丙醇、四氢呋喃、丙酮、乙酸乙酯等OVOCs及苯、甲苯等芳香烃是专项化学品制造行业的特征物种. 10家企业排放VOCs的OFP (臭氧生成潜势)为1. 9～933. 5 mg/m3,OVOCs和芳香烃是专项化学品制造企业的主要活性组分,累计对OFP的贡献率在80. 1%～100. 0%之间.异丙醇、四氢呋喃、丙酮、乙酸乙酯、甲基异丁基酮、苯和甲苯等是专项化学品制造行业的关键活性物种.研究显示,专项化学品制造行业VOCs污染治理应重点控制OVOCs和芳香烃.
Ten special chemical manufacturing industries in an industrial area in Shanghai City were selected and from which organized exhaust gases were sampled using the Summa canisters. 106 VOCs compounds were analyzed by GC-MS(gas chromatography mass spectrometry) to study the VOCs emission characteristics. The MIR(maximum incremental reactive activity) method was used to estimate the contribution of the emission of VOCs from each company to ozone production. The results showed that OVOCs and aromatic hydrocarbons were the characteristic VOCs components in the special chemical manufacturing industry,with cumulative mass ratios ranging from 65. 0% to 100. 0%. Among 8 VOCs-emitting enterprises,OVOCs were the main components,accounting for 55. 8% to99. 9% of the total mass. OVOCs such as isopropanol,tetrahydrofuran,acetone and ethyl acetate,and aromatic hydrocarbons like benzene and toluene were characteristic VOCs of the special chemical manufacturing industries. The absolute amount of OFP(ozone generation potential) of VOCs emitted from each special chemical manufacturing industry was quite different,and the range of OFP was 1. 9-933. 5 mg/m3. OVOCs and aromatic hydrocarbons such as isopropyl alcohol,tetrahydrofuran,acetone,ethyl acetate,methyl isobutyl ketone,benzene and toluene were the main active components of the special chemical manufacturing industries. The cumulative contribution to OFP was between 80. 1% and 100. 0%. OVOCs and aromatic hydrocarbons should be focused on to control the pollution in the special chemical manufacturing industry.
Ten special chemical manufacturing industries in an industrial area in Shanghai City were selected and from which organized exhaust gases were sampled using the Summa canisters. 106 VOCs compounds were analyzed by GC-MS(gas chromatography mass spectrometry) to study the VOCs emission characteristics. The MIR(maximum incremental reactive activity) method was used to estimate the contribution of the emission of VOCs from each company to ozone production. The results showed that OVOCs and aromatic hydrocarbons were the characteristic VOCs components in the special chemical manufacturing industry,with cumulative mass ratios ranging from 65. 0% to 100. 0%. Among 8 VOCs-emitting enterprises,OVOCs were the main components,accounting for 55. 8% to99. 9% of the total mass. OVOCs such as isopropanol,tetrahydrofuran,acetone and ethyl acetate,and aromatic hydrocarbons like benzene and toluene were characteristic VOCs of the special chemical manufacturing industries. The absolute amount of OFP(ozone generation potential) of VOCs emitted from each special chemical manufacturing industry was quite different,and the range of OFP was 1. 9-933. 5 mg/m3. OVOCs and aromatic hydrocarbons such as isopropyl alcohol,tetrahydrofuran,acetone,ethyl acetate,methyl isobutyl ketone,benzene and toluene were the main active components of the special chemical manufacturing industries. The cumulative contribution to OFP was between 80. 1% and 100. 0%. OVOCs and aromatic hydrocarbons should be focused on to control the pollution in the special chemical manufacturing industry.
引文
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[22] HE Qiusheng,YAN Yulong,LI Hongyan,et al.Characteristics and reactivity of volatile organic compounds from non-coal emission sources in China[J]. Atmospheric Environment,2015,115:153-162.
[23] ZHONG Z M,SHA Q,ZHENG J,et al.Sector-based VOCs emission factors and source profiles for the surface coating industry in the Pearl River Delta Region of China[J]. Science of the Total Environment,2017,583:19-28.
[24] YUAN Bin,SHAO Min,LU Sihua,et al.Source profiles of volatile organic compounds associated with solvent use in Beijing,China[J].Atmospheric Environment,2010,44(15):1919-1926.
[25] LI Jing,ZHAI Chongzhi,YU Jiayan,et al.Spatio temporal variations of ambient volatile organic compounds and their sources in Chongqing,a mountainous megacity in China[J]. Science of the Total Environment,2018,627:1442-1452.
[26] CARTER W P L. Development of the SAPRC-07 chemical mechanism[J]. Atmospheric Environment,2010,44(40):5324-5335.
[27]田亮,魏巍,程水源,等.典型有机溶剂使用行业VOCs成分谱及臭氧生成潜势[J].安全与环境学报,2017,17(1):314-320.TIAN Liang,WEI Wei,CHENG Shuiyuan,et al.Source profiles and ozone formation potential of volatile organic compounds from the use of solvents in typical industry[J]. Journal of Safety and Environment,2017,17(1):314-320.
[28]何梦林,王旎,陈扬达,等.广东省典型电子工业企业挥发性有机物排放特征研究[J].环境科学学报,2016,36(5):1581-1588.HE Menglin, WANG Ni, CHEN Yangda, et al. Emission characteristics of volatile organic compounds(VOCs)from electronic manufacturing factory of Guangdong Province[J]. Acta Scientiae Circumstantiae,2016,36(5):1581-1588.
[29]赵锐,黄络萍,张建强,等.成都市典型溶剂源使用行业VOCs排放成分特征[J].环境科学学报,2018,38(3):1147-1154.ZHAO Rui,HUANG Luoping,ZHANG Jianqiang,et al. Emissions characteristics of volatile organic compounds(VOCs)from typical industries of solvent use in Chengdu City[J]. Acta Scientiae Circumstantiae,2018,38(3):1147-1154.
[30]韩博,吴建会,王凤炜,等.天津滨海新区工业源VOCs及恶臭物质排放特征[J].中国环境科学,2011,31(11):1776-1781.HAN Bo,WU Jianhui,WANG Fengwei,et al. Characterization of VOCs and odorous compounds from industrial sources in Binhai New Area,Tianjin[J]. China Environmental Science,2011,31(11):1776-1781.
[31] BARLETTA B,MEINARDI S,ROWLAND F S,et al. Volatile organic compounds in 43 Chinese cities[J]. Atmospheric Environment,2005,39(32):5979-5990.
[32] MONOD A,SIVE B C,AVINO P,et al.Monoaromatic compounds in ambient air of various cities:a focus on correlations between the xylenes and ethylbenzene[J]. Atmospheric Environment,2001,35(1):135-149.
[2] COCKER D R,MADER B T,KALBERER M,et al. The effect of water on gas-particle partitioning of secondary organic aerosol:II.mxylene and 1,3,5-trimethylbenzene photooxidation systems[J].Atmospheric Environment,2001,35(35):6073-6085.
[3] LIU W T,HSIEH H C,CHEN S P,et al. Diagnosis of air quality through observation and modeling of volatile organic compounds(VOCs)as pollution tracers[J].Atmospheric Environment,2012,55(3):56-63.
[4]唐孝炎,张远航,邵敏.大气环境化学[M]. 2版.北京:高等教育出版社,2006:232.
[5] SMITH M T,ZHANG L.Biomarkers of leukemia risk:benzene as a model[J]. Environmental Health Perspectives,1998,106(S4):937-946.
[6] SPONRING A,FILIPIAK W,AGER C,et al. Analysis of volatile organic compounds(VOCs)in the headspace of NCI-H1666 lung cancer cells[J].Cancer Biomark,2010,7(3):153-161.
[7] CAI Changjie,GENG Fuhai,TIE Xuexi,et al. Characteristics and source apportionment of VOCs measured in Shanghai,China[J].Atmospheric Environment,2010,44(38):5005-5014.
[8]乔月珍,王红丽,黄成,等.机动车尾气排放VOCs源成分谱及其大气反应活性[J].环境科学,2012,33(4):1071-1079.QIAO Yuezhen,WANG Hongli,HUANG Cheng,et al. Source profile and chemical reactivity of volatile organic compounds from vehicle exhaust[J]. Environmental Science,2012,33(4):1071-1079.
[9] KWANGSAM N,YONG P,MOON I,M,et al.Chemical composition of major VOC emission sources in the Seoul atmosphere[J].Chemosphere,2004,55(4):585-594.
[10] LIU Ying,SHAO Min,FU Linlin,et al. Source profiles of volatile organic compounds(VOCs)measured in China:part I[J].Atmospheric Environment,2008,42(25):6247-6260.
[11] WANG Hongli,JING Shengao,LOU Shengrong,et al. Volatile organic compounds(VOCs)source profiles of on-road vehicle emissions in China[J]. Science of the Total Environment,2017,607/608:253-261.
[12]区家敏,冯小琼,刘郁葱,等.珠江三角洲机动车挥发性有机物排放化学成分谱研究[J].环境科学学报,2014,34(4):826-834.OU Jiamin, FENG Xiaoqiong, LIU Yucong, et al. Source characteristics of VOCs emissions from vehicular exhaust in the Pearl River Delta Region[J].Acta Scientiae Circumstantiae,2014,34(4):826-834.
[13] CHOW J C,WSATON J G,KUHNS H,et al. Source profiles for industrial,mobile,and area sources in the big bend regional aerosol visibility and observational study[J]. Chemosphere,2004,54(2):185-208.
[14] ZHENG Junyu,YU Yufan,MO Ziwei,et al.Industrial sector-based volatile organic compound(VOC)source profiles measured in manufacturing facilities in the Pearl River Delta,China[J].Science of the Total Environment,2013,456/457(7):127-136.
[15]崔如,马永亮.电子产品加工制造企业挥发性有机物(VOCs)排放特征[J].环境科学,2013,34(12):4585-4591.CUI Ru, MA Yongliang. Characteristics of volatile organic compounds(VOCs)emission from electronic products processing and manufacturing factory[J]. Environmental Science,2013,34(12):4585-4591.
[16]李国昊,魏巍,程水源,等.炼焦过程VOCs排放特征及臭氧生成潜势[J].北京工业大学学报,2014,40(1):91-99LI Guohao,WEI Wei,CHENG Shuiyuan, et al. Emission characterization and ozone formation potential of VOCs during the coking process[J]. Journal of Beijing University of Technology,2014,40(1):91-99.
[17]周静博,李亚卿,洪纲,等.石家庄市制药行业VOCs排放特征分析及健康风险评价[J].生态毒理学报,2015,10(4):177-186.ZHOU Jingbo,LI Yaqing,HONG Gang,et al. Characteristics and health risk assessment of VOCs emitted from pharmaceutical industry of Shijiazhuang City[J]. Asian Journal of Ecotoxicolog,2015,10(4):177-186.
[18]张欣.天津石化行业挥发性有机物源排放成分谱研究[D].天津:天津工业大学,2016:9.
[19] WANG Hongli,XIANG Zhiyuan,WANG Lina,et al. Emissions of volatile organic compounds(VOCs)from cooking and their speciation:a case study for Shanghai with implications for China[J].Science of the Total Environment,2018,621:1300-1309.
[20]崔彤,程婧晨,何万清,等.北京市典型餐饮企业VOCs排放特征研究[J].环境科学,2015,5(5):1523-1529.CUI Tong,CHENG Jingchen,HE Wanqing,et al. Emission characteristics of VOCs from typical restaurants in Beijing[J].Environmental Science,2015,5(5):1523-1529.
[21]莫梓伟,陆思华,李悦,等.北京市典型溶剂使用企业VOCs排放成分特征[J].中国环境科学,2015,35(2):374-380.MO Ziwei,LU Sihua,LI Yue,et al. Emission characteristics of volatile organic compounds(VOCs)from typical solvent use factories in Beijing[J]. China Environmental Science,2015,35(2):374-380.
[22] HE Qiusheng,YAN Yulong,LI Hongyan,et al.Characteristics and reactivity of volatile organic compounds from non-coal emission sources in China[J]. Atmospheric Environment,2015,115:153-162.
[23] ZHONG Z M,SHA Q,ZHENG J,et al.Sector-based VOCs emission factors and source profiles for the surface coating industry in the Pearl River Delta Region of China[J]. Science of the Total Environment,2017,583:19-28.
[24] YUAN Bin,SHAO Min,LU Sihua,et al.Source profiles of volatile organic compounds associated with solvent use in Beijing,China[J].Atmospheric Environment,2010,44(15):1919-1926.
[25] LI Jing,ZHAI Chongzhi,YU Jiayan,et al.Spatio temporal variations of ambient volatile organic compounds and their sources in Chongqing,a mountainous megacity in China[J]. Science of the Total Environment,2018,627:1442-1452.
[26] CARTER W P L. Development of the SAPRC-07 chemical mechanism[J]. Atmospheric Environment,2010,44(40):5324-5335.
[27]田亮,魏巍,程水源,等.典型有机溶剂使用行业VOCs成分谱及臭氧生成潜势[J].安全与环境学报,2017,17(1):314-320.TIAN Liang,WEI Wei,CHENG Shuiyuan,et al.Source profiles and ozone formation potential of volatile organic compounds from the use of solvents in typical industry[J]. Journal of Safety and Environment,2017,17(1):314-320.
[28]何梦林,王旎,陈扬达,等.广东省典型电子工业企业挥发性有机物排放特征研究[J].环境科学学报,2016,36(5):1581-1588.HE Menglin, WANG Ni, CHEN Yangda, et al. Emission characteristics of volatile organic compounds(VOCs)from electronic manufacturing factory of Guangdong Province[J]. Acta Scientiae Circumstantiae,2016,36(5):1581-1588.
[29]赵锐,黄络萍,张建强,等.成都市典型溶剂源使用行业VOCs排放成分特征[J].环境科学学报,2018,38(3):1147-1154.ZHAO Rui,HUANG Luoping,ZHANG Jianqiang,et al. Emissions characteristics of volatile organic compounds(VOCs)from typical industries of solvent use in Chengdu City[J]. Acta Scientiae Circumstantiae,2018,38(3):1147-1154.
[30]韩博,吴建会,王凤炜,等.天津滨海新区工业源VOCs及恶臭物质排放特征[J].中国环境科学,2011,31(11):1776-1781.HAN Bo,WU Jianhui,WANG Fengwei,et al. Characterization of VOCs and odorous compounds from industrial sources in Binhai New Area,Tianjin[J]. China Environmental Science,2011,31(11):1776-1781.
[31] BARLETTA B,MEINARDI S,ROWLAND F S,et al. Volatile organic compounds in 43 Chinese cities[J]. Atmospheric Environment,2005,39(32):5979-5990.
[32] MONOD A,SIVE B C,AVINO P,et al.Monoaromatic compounds in ambient air of various cities:a focus on correlations between the xylenes and ethylbenzene[J]. Atmospheric Environment,2001,35(1):135-149.
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