低能量电子轰击电离源质谱技术的研究及应用测试
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摘要
发酵工业中尾气O_2与尾气CO_2的浓度变化反映了发酵过程中一些重要的生理代谢特征参数,发酵尾气的监测对发酵过程具有重要的指导意义。然而,传统监测手段速度慢、精度低、通用性差,无法对发酵尾气进行实时准确监测。在过程质谱方面,传统70 eV的电子轰击电离源会产生大量碎片离子,不同物质的碎片离子有可能存在重叠,增加了定性分析的难度,并造成监测结果不准确。为实现发酵尾气的实时在线准确监测,研制了一台用于在线分析的基于电子轰击电离的四极杆过程质谱仪,通过研究低电离能量下灯丝发射电流与电子接收极之间的相互关系,提高了电子轰击电离源在低电离能模式下的电离效率,并对CO_2、O_2和N_2进行了测试。结果表明,在电子能量22 eV、电子接收极电压-22 V、灯丝发射电流为20～25 mA的条件下,对体积分数高于0.023%的CO_2与体积分数高于0.021%的O_2定量检测相对误差均小于1%。本仪器与方法在工业过程快速实时在线监测领域具有较好的应用前景。
The changes of concentrations of O_2 and CO_2 in the tail gas of fermentation industry reflect some important physiological and metabolic parameters in the fermentation process. Monitoring of the tail gas of fermentation has important significance for guiding the fermentation process. However, traditional monitoring methods are time-consuming with low precision and poor versatility, and are not suitable to monitor fermentation tail gas accurately in real time. In the process mass spectrometry, the traditional 70 eV electron impact ionization source will produce a large number of fragment ions, which may overlap with different substances, thus increasing the difficulty of qualitative analysis and causing inaccurate monitoring results. In order to realize real-time, on-line accurate monitoring of fermentation tail gas, a quadrupole process mass spectrometry based on electron impact ionization was developed for on-line analysis. Through investigation of the relationship between emission current of filament and the electron receiving pole at low ionization energy, the ionization efficiency of the electron impact ionization source under low ionization energy mode was improved, and CO_2, O_2 and N_2 were tested. Experimental results showed that under the conditions including electron energy of 22 eV, electron receiving voltage of 22 V and filament emission current of 20-25 mA, the relative errors of quantitative detection of CO_2 with volume fraction of higher than 0.023% and O_2 with volume fraction of higher than 0.021% were all less than 1%. The instrument and the developed method had ideal application prospect in the rapid real-time, on-line monitoring of industrial processes.
The changes of concentrations of O_2 and CO_2 in the tail gas of fermentation industry reflect some important physiological and metabolic parameters in the fermentation process. Monitoring of the tail gas of fermentation has important significance for guiding the fermentation process. However, traditional monitoring methods are time-consuming with low precision and poor versatility, and are not suitable to monitor fermentation tail gas accurately in real time. In the process mass spectrometry, the traditional 70 eV electron impact ionization source will produce a large number of fragment ions, which may overlap with different substances, thus increasing the difficulty of qualitative analysis and causing inaccurate monitoring results. In order to realize real-time, on-line accurate monitoring of fermentation tail gas, a quadrupole process mass spectrometry based on electron impact ionization was developed for on-line analysis. Through investigation of the relationship between emission current of filament and the electron receiving pole at low ionization energy, the ionization efficiency of the electron impact ionization source under low ionization energy mode was improved, and CO_2, O_2 and N_2 were tested. Experimental results showed that under the conditions including electron energy of 22 eV, electron receiving voltage of 22 V and filament emission current of 20-25 mA, the relative errors of quantitative detection of CO_2 with volume fraction of higher than 0.023% and O_2 with volume fraction of higher than 0.021% were all less than 1%. The instrument and the developed method had ideal application prospect in the rapid real-time, on-line monitoring of industrial processes.
引文
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16 Kang M,Zou X,Lu Y,Wang H,Shen C,Jiang H,Chu Y.Chem.Res.Chin.Univ.,2016,32(4):565-569
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23 XIE Yuan-Yuan,HUA Lei,HOU Ke-Yong,CHEN Ping,CUI Hua-Peng,ZHAO Wu-Duo,CHEN Wen-Dong,LI Jing-Hua,LI Hai-Yang.Chinese J.Anal.Chem.,2012,40(12):1883-1889谢园园,花磊,侯可勇,陈平,崔华鹏,赵无垛,陈文东,李京华,李海洋.分析化学,2012,40(12):1883-1889
24 Sun W Q,Shu J N,Zhang P,Li Z,Li N N,Liang M,Yang B.Atmos.Meas.Tech.,2015,8(8):5877-5894
25 Betancourt A M,Coutinho L H,Bernini R B,De Moura C E,Rocha A B,De Souza G G.J.Chem.Phys.,2016,144(11):114305
26 Wang J,Yang B,Li Y,Tian Z,Zhang T,Qi F,Nakajima K.Int.J.Mass Spectrom.,2007,263(1):30-37
27 Ehrhardt H,Jung K,Knoth G,Schlemmer P.Zeitschrift Für Physik D Atoms Molecules & Clusters,1986,1(1):3-32
28 Straub H C,Renault P,Lindsay B G,Smith K A,Stebbings R F.J.Geophys.Res.Planet.,1998,108(1):109-116
29 Straub H C,Renault P,Lindsay B G,Smith K A,Stebbings R F.Phys.Rev.A,1995,52(2):1115-1124
30 Davies S,Rees J A,Seymour D L.Vacuum,2014,101(3):416-422
31 HUANG Ze-Jian,JIANG You,YUE Jun-Rong,GONG Xiao-Yun,LIU Mei-Ying,FANG Xiang.Journal of Chinese Mass Spectrometry Society,2018,39(4):399-406黄泽建,江游,岳君容,龚晓云,刘梅英,方向.质谱学报,2018,39(4):399-406
32 Beckeyand H D,Comes F J ,OU Xia-Min.Analytical Instrumentation,1975,(1):53-61Beckeyand H D,Comes F J,欧夏民.分析仪器,1975,(1):53-61
33 HUANG Chao,ZHAO Xue-Hong,ZHANG Jian-Chao,WANG Yan.Journal of Chinese Mass Spectrometry Society,2011,32(2):71-76黄超,赵学玒,张建超,汪曣.质谱学报,2011,32(2):71-76
2 Xiao J,Shi Z,Gao P,Feng H,Duan Z,Mao Z.Bioprocess.Biosyst.Eng.,2006,29(2):109-117
3 LI liang,ZHANG Si-Liang,ZHUANG Ying-Ping,CHU Ju.Analytical Instrumentation,2012,(4):103-105黎亮,张嗣良,庄英萍,储炬.分析仪器,2012,(4):103-105
4 Xu J,Liu N,Qiao K,Vogg S,Stephanopoulos G.Proc.Natl.Acad.Sci.USA,2017,114(27):E5308-E5316
5 Nevares I,Martínezmartínez V,Martínezgil A,Martín R,Laurie V F,Del M.Food Chem.,2017,229(15):588-596
6 Marrufo-Curtido A,Carrascón V,Bueno M,Ferreira V,Escudero A.Food Chem.,2018,248:37-45
7 Heinzle E,Oeggerli A,Dettwiler B.Anal.Chim.Acta,1990,238(1):101-115
8 CHEN Jie,CHU Ju,ZHUANG Ying-Ping,ZHANG Si-Liang,LUO Jia-Li,BAI Hua.Chinese Journal of Antibiotics,2004,29(1):4-7谌颉,储炬,庄英萍,张嗣良,罗家立,白骅.中国抗生素杂志,2004,29(1):4-7
9 Beuermann T,Egly D,Geoerg D,Klug K I,Storhas W,Methner F J.J.Biosci.Bioeng.,2012,113(3):399-405
10 Georgia Ch L,George K.J.Chromatogr.Sci.,2013,51(8):764-779
11 ZHANG Jin-Wei,ZHANG Fei,GU Hai-Tao.Journal of Chinese Mass Spectrometry Society,2012,33(5):315-320张进伟,张飞,顾海涛.质谱学报,2012,33(5):315-320
12 YANG Jin-Cheng,ZHANG Jin-Wei.Automation in Petro-Chemical Industry,2015,51(6):1-5杨金城,张进伟.石油化工自动化,2015,51(6):1-5
13 Fischer M,Wohlfahrt S,Varga J,Saraji-Bozorgzad M,Matuschek G,Denner T,Zimmermann R.J.Therm.Anal.Calorim.,2014,116(3):1461-1469
14 Adam T,Zimmermann R.Anal.Bioanal.Chem.,2007,389(6):1941-1951
15 WU Qing-Hao,HUA Lei,HOU Ke-Yong,CUI Hua-Peng,CHEN Ping,ZHAO Wu-Duo,WANG Wei-Guo,LI Jing-Hua,LI Hai-Yang.Chinese J.Anal.Chem.,2011,39(10):1465-1469吴庆浩,花磊,侯可勇,崔华鹏,陈平,赵无垛,王卫国,李京华,李海洋.分析化学,2011,39(10):1465-1469
16 Kang M,Zou X,Lu Y,Wang H,Shen C,Jiang H,Chu Y.Chem.Res.Chin.Univ.,2016,32(4):565-569
17 Sémon E,Arvisenet G,Guichard E.J.Mass Spectrom.,2018,53(1):65-77
18 LI Zi-Xiao,ZHAO Xue-Hong,LI Wei-Kang,SUN Yun,DU Kang,WANG Yan,HU Xiao-Guang,JIANG Xue-Hui.Journal of Chinese Mass Spectrometry Society,2016,37(4):351-358李子晓,赵学玒,李维康,孙运,杜康,汪曣,胡晓光,蒋学慧.质谱学报,2016,37(4):351-358
19 Xie Y,Ping C,Lei H,Hou K,Wang Y,Wang H,Li H.J.Am.Soc.Mass Spectrom.,2016,27(1):144-152
20 Huang Y,Li J,Tang B,Zhu L,Hou K,Li H.Int.J.Anal.Chem.,2015,2015(1):1-7
21 Xu J,Yang P,Qiang Y,Zhu Y,Zhuo J.Energy Fuels,2017,31(1):730-737
22 LI Qing-Yun,HUA Lei,JIANG Ji-Chun,HOU Ke-Yong,QI Ya-Chen,TIAN Di,WANG Hai-Yan,LI Hai-Yang.Chinese J.Anal.Chem.,2015,43(10):1531-1537李庆运,花磊,蒋吉春,侯可勇,齐雅晨,田地,王海燕,李海洋.分析化学,2015,43(10):1531-1537
23 XIE Yuan-Yuan,HUA Lei,HOU Ke-Yong,CHEN Ping,CUI Hua-Peng,ZHAO Wu-Duo,CHEN Wen-Dong,LI Jing-Hua,LI Hai-Yang.Chinese J.Anal.Chem.,2012,40(12):1883-1889谢园园,花磊,侯可勇,陈平,崔华鹏,赵无垛,陈文东,李京华,李海洋.分析化学,2012,40(12):1883-1889
24 Sun W Q,Shu J N,Zhang P,Li Z,Li N N,Liang M,Yang B.Atmos.Meas.Tech.,2015,8(8):5877-5894
25 Betancourt A M,Coutinho L H,Bernini R B,De Moura C E,Rocha A B,De Souza G G.J.Chem.Phys.,2016,144(11):114305
26 Wang J,Yang B,Li Y,Tian Z,Zhang T,Qi F,Nakajima K.Int.J.Mass Spectrom.,2007,263(1):30-37
27 Ehrhardt H,Jung K,Knoth G,Schlemmer P.Zeitschrift Für Physik D Atoms Molecules & Clusters,1986,1(1):3-32
28 Straub H C,Renault P,Lindsay B G,Smith K A,Stebbings R F.J.Geophys.Res.Planet.,1998,108(1):109-116
29 Straub H C,Renault P,Lindsay B G,Smith K A,Stebbings R F.Phys.Rev.A,1995,52(2):1115-1124
30 Davies S,Rees J A,Seymour D L.Vacuum,2014,101(3):416-422
31 HUANG Ze-Jian,JIANG You,YUE Jun-Rong,GONG Xiao-Yun,LIU Mei-Ying,FANG Xiang.Journal of Chinese Mass Spectrometry Society,2018,39(4):399-406黄泽建,江游,岳君容,龚晓云,刘梅英,方向.质谱学报,2018,39(4):399-406
32 Beckeyand H D,Comes F J ,OU Xia-Min.Analytical Instrumentation,1975,(1):53-61Beckeyand H D,Comes F J,欧夏民.分析仪器,1975,(1):53-61
33 HUANG Chao,ZHAO Xue-Hong,ZHANG Jian-Chao,WANG Yan.Journal of Chinese Mass Spectrometry Society,2011,32(2):71-76黄超,赵学玒,张建超,汪曣.质谱学报,2011,32(2):71-76