抗生素发酵制药工程中异味的特征与关键污染物识别

Profiling and identification of fermentation odorants from industrial production of antibiotics

抗生素原料药在生产过程中产生异味污染引发的民众投诉增多,逐渐成为发酵制药企业亟需解决的污染治理难点。以红霉素、四环素和泰乐菌素3种抗生素原料药的发酵生产过程为例,通过采用感官评价、电子鼻、气相离子迁移谱和气相质谱等多手段分析方法,解析发酵过程中产生的异味污染特征。结果表明:3种发酵尾气的气味特征、挥发性物质组分和含量差异较大;尾气中含有的挥发性物质有相同的组分,如乙醇、丙酮、2-戊酮、辛醛和苯甲醛,也各有特异性成分。未经处理的红霉素发酵尾气具有明显的土霉味,且臭气浓度值明显大于四环素和泰乐菌素发酵尾气。气味活度值(OAV)的计算结果表明:2-MIB和土臭素2种萜烯类物质是红霉素发酵最主要的异味污染物;而四环素和泰乐菌素的发酵异味是多种醛等含氧有机物和有机硫化物混合后形成的,因而气味特征较复杂。3种废气中,红霉素发酵尾气具有气量大、异味物质嗅阈值极低的特点,易造成异味污染且影响范围广,去除治理的技术难度也相对更大。本研究通过解析识别不同品种抗生素的发酵异味污染特征,以期为抗生素发酵异味污染治理和环境管理提供参考。

Complaints caused by odors from the fermentative production of antibiotics is challenging in China.Appropriate control of fermentation odorants has become an urgent environmental problem for the pharmaceutical factories.In this work,the characteristics of fermentation odor emitted from production of active pharmaceutical ingredients corresponding to erythromycin,tetracycline and tylosin was investigated,using different analytics including olfactory evaluation,electronic nose,gas chromatography-coupled ion mobility spectrometry(GC-IMS),and gas chromatography-mass spectrometry(GC-MS)analysis.The integrative results showed that there were significant differences in the odor characteristics and composition of volatiles among the distinct fermentation off-gas samples.The untreated off-gas derived from erythromycin fermentation had obviously musty flavor and the odor concentration was significantly higher than that of tetracycline and tylosin.Gosmin and 2-methylisoborneol(2-MIB)were identified as the key odorants during erythromycin fermentation,while the peculiar odor oriented from tetracycline and tylosin fermentation is probably owning to the mixing of oxygen-containing organic compounds such as aldehydes and organic sulfides.Among the three kinds of offgas,the one produced from erythromycin fermentation was more likely correlated with odor pollution and having difficulty in deodorization.This could be attributed from the characteristics of large emission load and very low odor threshold of odorants.By analyzing and identifying the odor pollution characteristics of different kinds derived from fermentation production of antibiotics,the findings could provide a reference for future treatment of odor pollution and safer environmental management of fermentative antibiotics production.