양자전이 비행시간형 질량분석기를 활용한 미량 다 성분 악취분석 및 원인물질 연구

Abstract

In various industrial sites and living environments, odorous substances generate multiple components and cause odors even in trace amounts. Above all, it is important to identify odor-causing substances through quantitative analysis of odor-causing substances. However, the analysis of trace odor substances of multi-component has different sampling and storage methods for each substance, and it is difficult to analyze with different pretreatment and detection methods. In order to simplify this difficult analysis procedure, sample injection devices such as ATD (automatic thermal desorption) and cryogenic concentrators and GC-MS have been used, but low molecular weight and highly volatile substances are easily lost by oxidation or decomposition, making it difficult to analyze. In addition, concentration media such as liquid nitrogen or liquid oxygen are required during the low-temperature concentration process, and it is not economical because it takes a lot of time and manpower due to the complex analysis processes. Recently, proton transfer reaction-mass spectrometer (PTR-MS) and selected flow tube-mass spectrometer (SIFT-MS), which contain a quadrupole separator, are analytes that can be directly injected into equipment without sample pretreatment and quantitatively measured in real time. However, these quadrupole separation methods have limitations in multi-component simultaneous analysis because they have the disadvantage that many substances with the same mass act as obstacles due to low resolution (1 m/z). On the other hand, multi-component simultaneous quantitative analysis is possible with high resolution (5500 m/Δm, FWHM) and high sensitivity (detection limits for m/z 181, 5 pptv in average over 60 sec) through time-of-flight mass separation. In this study, 84 substances that frequently cause odors in industrial sites were selected, and simultaneous quantitative analysis was confirmed in PTR-ToF-MS (PTR-TOF 6000×2, Ionicon Analyticik Ges.m.b.H., Austria). The main variable values for quantitative analysis were obtained through comparative experiments of 34 standard substances with research data from other researchers. The analysis method using PTR-ToF-MS was verified by applying it to each process and exhaust gas analysis at industrial wastewater consignment treatment facilities. Specifically, two main characteristic data required for PTR-ToF-MS analysis are important: proton transfer reaction rate constant and yield ratio of target ion. The proton transfer reaction rate constant and yield ratio were measured directly by other researchers and obtained by theoretical calculation. In addition, in this study experiment, 34 standard substance experimental data were compared and utilized. As a result of quantitative analysis of 34 standard substances with PTR-ToF-MS, both showed linearity in correlation between each substance concentration and cps (count per second), and detection sensitivity (sensitivity, cps/ppbv) showed a value of 197 cps/ppbv (detected contract of 5 pptv) for toluene. In addition, preparing 6 substances of BTEX standard substances, the comparative quantitative analysis of ATD-GC-MS and PTR-ToF-MS showed a correlation of 0.994 (r2) or more. However, PTR-ToF-MS can detect high-resolution mass separation, but there are fundamental limitations in individual quantities for isomers and isobaric. This limitation was confirmed to be overcome through separation by ATD-GC-MS, and simultaneous quantitative analysis of 84 odorous substances was possible. This analysis method using PTR-ToF-MS and ATD-GC-MS was used to identify odor-causing substances by measuring odor gases for each process of two types of industrial wastewater consignment treatment facilities that frequently cause odor complaints. The gas generated in each wastewater treatment process is treated in a wet scrubber and then discharged to the exhaust. As a result of examining the substances that cause odor in the final outlet gas, company A was found to be pentanal, acetaldehyde, methylmercaptane, hexanol, and butanal company B was found to be decanal, nonanal, acetaldehyde, butanal, 4-octen-3-one. In both companies, most of the substances that cause odors were substances with low water solubility and could cause odors even in very small amounts. In conclusion, the existing odor substance analysis method is complex and uneconomical because sample collection, pretreatment and device detection methods differ from substance to substance, whereas PTR-ToF-MS enables multi-component simultaneous quantitative analysis in real time relatively easily without pretreatment. This method can be the basis for simplifying the quality management system of odor analysis. In addition, it can be used to identify and evaluate odor-causing substances and is expected to be one of the more economical and efficient analysis approaches to solving odor problems.