洁净煤技术

2019, v.25;No.124(06) 1-9

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以煤为原料的合成氨企业挥发性有机物排放特征研究
Study on the emission characteristics of volatile organic compounds(VOCs)from coal-based ammonia plant

刘丹;张鑫;张凤莲;孙永刚;王璐;郝郑平;
LIU Dan;ZHANG Xin;ZHANG Fenglian;SUN Yonggang;WANG Lu;HAO Zhengping;Caofeidian District Branch,Tangshan Bureau of Ecological Environment;National Engineering Laboratory for VOCs Pollution Control Material & Technology,University of Chinese Academy of Sciences;Research Center for Environmental Material and Pollution Control Technology,University of Chinese Academy of Sciences;State Key Laboratory of High-efficiency Coal Utilization and Green Chemical Engineering,Ningxia University;CNPC Fuel Oil C

摘要(Abstract):

为摸清合成氨工业生产过程中VOCs排放来源,核算行业排放量,笔者主要对煤化工中合成氨工业过程进行工艺全过程的排放特征的研究,研究内容包括生产过程中的有组织排放、车间逸散及厂界无组织排放等,用得出的排放因子进行排放量估算。研究表明,合成氨有组织排放以芳香烃和含氧有机物为主,硫回收工艺废气、尿素合成工艺废气、低温甲醇洗工艺段中CO_2闪蒸气废气、CO_2闪蒸排放气、尾气洗涤塔放空气中分别检出VOCs 36、19、26、21、20种。苄基氯、异丙醇、2-丁酮是合成氨VOCs排放的特征污染物。生产过程中产生的大量苄基氯可能是由α-氢侧键的芳香烃化合物转化而来的。合成氨的车间无组织排放特征与其所对应的生产过程排放特征具有一致性。从气化炉车间、尿素包装车间及酚氨回收车间中分别检出19、32、15种挥发性有机物。气化炉车间排放的VOCs主要为苄基氯,占比为23.16%;尿素包装车间主要为2-丁酮、乙酸乙酯、1,2,4-三甲基苯,占比达到49.58%;酚氨回收车间主要为醋酸乙烯酯,占比高达56.60%,这与酚氨回收的工艺过程中所使用的助溶剂有关。合成氨的厂界无组织各监测点的挥发性有机污染物特征均为:芳香烃>卤代烃>含氧有机物>烷烃,与各监测点所对应的生产过程排放特征具有一致性。运用排放因子法计算合成氨过程的总排放因子为75.02 g/t合成氨,硫回收13.66 g/t合成氨、尿素合成14.45 g/t合成氨、CO_2闪蒸气废气21.42 g/t合成氨、CO_2闪蒸排放气13.01 g/t合成氨、尾气洗涤塔放空气12.49 g/t合成氨。按此排放因子计算2015年内蒙某典型以煤为原料的合成氨生产过程中VOCs的排放量约为22.51 t。
It lays a foundation for finding out the VOCs emission sources in the production process of synthetic ammonia industry and accounting the industrial emissions. In this paper,the emission characteristics of synthetic ammonia industrial in coal chemical industry were studied. The research included the organized emission in the production process,the workshop emission and the unorganized emission in the plant boundary. The emission was estimated by the emission factors. The results show that the aromatics and oxygen-containing organics are the main emissions of synthetic ammonia. 36,19,26,21 and 20 VOCs species are detected in the sulfur recovery process,urea synthesis process,CO_2 flash gas in low-temperature methanol washing process,the exhaust gas of CO_2 flash and washing tower,respectively.Benzyl chloride,isopropanol and 2-butanone are the characteristic pollutants of VOCs emission in synthetic ammonia. A large amount ofbenzyl chloride produced in the production process may be converted from aromatic compounds with α-hydrogen side bond. the unorgan-ized emission characteristics of synthetic ammonia workshop are consistent with the emission characteristics of the corresponding productionprocess. 19,32 and 15 VOCs species are detected in gasifier workshop,urea packaging workshop and phenol Ammonia Recovery Workshoprespectively. The VOCs discharged from the gasifier workshop are mainly benzyl chloride,accounting for 23.16%,the urea packaging work-shop is mainly 2-butanone,ethyl acetate,1,2,4-trimethylbenzene,accounting for 49.58%,the phenol ammonia recovery workshop ismainly vinyl acetate,accounting for 56.60%,which is related to the auxiliary solvent used in the process of phenol ammonia recovery. Thecharacteristics of VOCs at unorganized monitoring points in the plant boundary of synthetic ammonia are:aromatic hydrocarbon > halogena-ted hydrocarbon > oxygenated organic matter > alkane,which is consistent with the emission characteristics of production process corre-sponding to each monitoring point.The total emission factors of synthetic ammonia process calculated by emission factor method are 75.02 g/tsynthetic ammonia,13.66 g/t synthetic ammonia with sulfur recovery,14.45 g/t synthetic ammonia with urea synthesis,21.42 g/t syntheticammonia with CO_2 flash gas,13.01 g/t synthetic ammonia with CO_2 flash exhaust gas and 12.49 g/t synthetic ammonia with tail gas scrub-ber vent gas. According to this emission factor,the VOCs emission of a typical coal based synthetic ammonia production process in InnerMongolia was about 22.51 t in 2015.

关键词(KeyWords): 合成氨;挥发性有机物;排放特征;排放因子;煤化工
synthetic ammonia;volatile organic compounds;emission characteristics;emission factors;coal chemical industry

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作者(Author): 刘丹;张鑫;张凤莲;孙永刚;王璐;郝郑平;
LIU Dan;ZHANG Xin;ZHANG Fenglian;SUN Yonggang;WANG Lu;HAO Zhengping;Caofeidian District Branch,Tangshan Bureau of Ecological Environment;National Engineering Laboratory for VOCs Pollution Control Material & Technology,University of Chinese Academy of Sciences;Research Center for Environmental Material and Pollution Control Technology,University of Chinese Academy of Sciences;State Key Laboratory of High-efficiency Coal Utilization and Green Chemical Engineering,Ningxia University;CNPC Fuel Oil C

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