Name: combustion chemistry of fuels: quantitative speciation data obtained from an atmospheric high-temperature flow reactor with coupled molecular-beam mass spectrometer
Uploaded: 2018-02-19T14:00:00
Description: Watch this Scientific Journal Video about Combustion Chemistry of Fuels: Quantitative Speciation Data Obtained from an Atmospheric High-temperature Flow Reactor with Coupled Molecular-beam Mass Spectr

这些实验是在德国斯图加特的燃烧技术研究所、德意志姆霍兹 Luft Raumfahrt (DLR) 的质谱学系进行的。这项工作还得到了亥姆霍兹能源联盟 "合成液态烃"、卓越中心 "替代燃料" 和 DLR 项目 "未来燃料" 的支持。作者希望感谢帕特里克乐 Clercq 和他在喷气燃料方面卓有成效的讨论。

1. 分子束质谱仪 (MBMS) 和流化反应器系统的建立
<ol><li>加热烤箱到指定的起始温度, 这是最高温度在指定的测量系列。对于射流 A-1 与Φ = 1 的典型条件, 总氧化低于850°c (~ 1100 K)。适当的起动温度的选择取决于被调查的燃料的化学性质和计量 (Φ)。</li>
	<li>为中间物种检测准备飞行时间测量光谱仪。该谱仪与分子束对齐, 从而为不稳定物种提供可靠的检测。 注: 质量分辨率适用于 C/小时系统中元素...

<ol>
	<li>Moore, R. H., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Biofuel+blending+reduces+particle+emissions+from+aircraft+engines+at+cruise+conditions.">Biofuel blending reduces particle emissions from aircraft engines at cruise conditions.</a> Nature. 543 (7645), 411-415 (2017).</li><li>Braun-Unkhoff, M., Kathrotia, T., Rauch, B., Riedel, U. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=About+the+interaction+between+composition+and+performance+of+alternative+jet+fuels.">About the interaction between composition and performance of alternative jet fuels.</a> CEAS Aeronautical Journal. 7 (1), 83-94 (2016).</li><li>Egolfopoulos, F. N., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Advances+and+challenges+in+laminar+flame+experiments+and+implications+for+combustion+chemistry.">Advances and challenges in laminar flame experiments and implications for combustion chemistry.</a> Prog Energ Combust. 43, 36-67 (2014).</li><li>Lynch, P. T., Troy, T. P., Ahmed, M., Tranter, R. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Probing+combustion+chemistry+in+a+miniature+shock+tube+with+synchrotron+VUV+photo+ionization+mass+spectrometry.">Probing combustion chemistry in a miniature shock tube with synchrotron VUV photo ionization mass spectrometry.</a> Anal Chem. 87 (4), 2345-2352 (2015).</li><li>Pelucchi, M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=An+experimental+and+kinetic+modeling+study+of+the+pyrolysis+and+oxidation+of+n-C3C5+aldehydes+in+shock+tubes.">An experimental and kinetic modeling study of the pyrolysis and oxidation of n-C3C5 aldehydes in shock tubes.</a> Combust. Flame. 162 (2), 265-286 (2015).</li><li>Hanson, R. K., Davidson, D. F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Recent+advances+in+laser+absorption+and+shock+tube+methods+for+studies+of+combustion+chemistry.">Recent advances in laser absorption and shock tube methods for studies of combustion chemistry.</a> Prog Energ Combust. 44, 103-114 (2014).</li><li>Sung, C. -. J., Curran, H. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Using+rapid+compression+machines+for+chemical+kinetics+studies.">Using rapid compression machines for chemical kinetics studies.</a> Prog Energ Combust. 44, 1-18 (2014).</li><li>Kohse-H&#246;inghaus, K., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Cover+Picture:+Biofuel+Combustion+Chemistry:+From+Ethanol+to+Biodiesel.">Cover Picture: Biofuel Combustion Chemistry: From Ethanol to Biodiesel.</a> Angw Chem Int Edit. 49 (21), 3545 (2010).</li><li>K&#246;hler, M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=1-,+2-+and+3-Pentanol+combustion+in+laminar+hydrogen+flames+-+A+comparative+experimental+and+modeling+study.">1-, 2- and 3-Pentanol combustion in laminar hydrogen flames - A comparative experimental and modeling study.</a> Combust. Flame. 162 (9), 3197-3209 (2015).</li><li>Li, Y., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Experimental+Study+of+a+Fuel-Rich+Premixed+Toluene+Flame+at+Low+Pressure.">Experimental Study of a Fuel-Rich Premixed Toluene Flame at Low Pressure.</a> Energ Fuel. 23 (3), 1473-1485 (2009).</li><li>Yang, B., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Identification+of+combustion+intermediates+in+isomeric+fuel-rich+premixed+butanol-oxygen+flames+at+low+pressure.">Identification of combustion intermediates in isomeric fuel-rich premixed butanol-oxygen flames at low pressure.</a> Combust. Flame. 148 (4), 198-209 (2007).</li><li>Reuter, C. B., Won, S. H., Ju, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Flame+structure+and+ignition+limit+of+partially+premixed+cool+flames+in+a+counterflow+burner.">Flame structure and ignition limit of partially premixed cool flames in a counterflow burner.</a> P Combust Inst. 36 (1), 1513-1522 (2017).</li><li>Reuter, C. B., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Experimental+study+of+the+dynamics+and+structure+of+self-sustaining+premixed+cool+flames+using+a+counterflow+burner.">Experimental study of the dynamics and structure of self-sustaining premixed cool flames using a counterflow burner.</a> Combust. Flame. 166, 125-132 (2016).</li><li>Bufferand, H., Tosatto, L., La Mantia, B., Smooke, M. D., Gomez, A. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Experimental+and+computational+study+of+methane+counterflow+diffusion+flames+perturbed+by+trace+amounts+of+either+jet+fuel+or+a+6-component+surrogate+under+non-sooting+conditions.">Experimental and computational study of methane counterflow diffusion flames perturbed by trace amounts of either jet fuel or a 6-component surrogate under non-sooting conditions.</a> Combust. Flame. 156 (8), 1594-1603 (2009).</li><li>Lefkowitz, J. K., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+chemical+kinetic+study+of+tertiary-butanol+in+a+flow+reactor+and+a+counterflow+diffusion+flame.">A chemical kinetic study of tertiary-butanol in a flow reactor and a counterflow diffusion flame.</a> Combust. Flame. 159 (3), 968-978 (2012).</li><li>Dryer, F. L., Haas, F. M., Santner, J., Farouk, T. I., Chaos, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Interpreting+chemical+kinetics+from+complex+reaction-advection-diffusion+systems:+Modeling+of+flow+reactors+and+related+experiments.">Interpreting chemical kinetics from complex reaction-advection-diffusion systems: Modeling of flow reactors and related experiments.</a> Prog Energ Combust. 44, 19-39 (2014).</li><li>Zhao, H., Yang, X., Ju, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Kinetic+studies+of+ozone+assisted+low+temperature+oxidation+of+dimethyl+ether+in+a+flow+reactor+using+molecular-beam+mass+spectrometry.">Kinetic studies of ozone assisted low temperature oxidation of dimethyl ether in a flow reactor using molecular-beam mass spectrometry.</a> Combust. Flame. 173, 187-194 (2016).</li><li>O&#223;wald, P., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Combustion+of+butanol+isomers+-+A+detailed+molecular+beam+mass+spectrometry+investigation+of+their+flame+chemistry.">Combustion of butanol isomers - A detailed molecular beam mass spectrometry investigation of their flame chemistry.</a> Combust. Flame. 158 (1), 2-15 (2011).</li><li>Herrmann, F., O&#223;wald, P., Kohse-H&#246;inghaus, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Mass+spectrometric+investigation+of+the+low-temperature+dimethyl+ether+oxidation+in+an+atmospheric+pressure+laminar+flow+reactor.">Mass spectrometric investigation of the low-temperature dimethyl ether oxidation in an atmospheric pressure laminar flow reactor.</a> P Combust Inst. 34 (1), 771-778 (2013).</li><li>Li, Y., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Experimental+and+kinetic+modeling+study+of+tetralin+pyrolysis+at+low+pressure.">Experimental and kinetic modeling study of tetralin pyrolysis at low pressure.</a> P Combust Inst. 34 (1), 1739-1748 (2013).</li><li>O&#223;wald, P., K&#246;hler, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=An+atmospheric+pressure+high-temperature+laminar+flow+reactor+for+investigation+of+combustion+and+related+gas+phase+reaction+systems.">An atmospheric pressure high-temperature laminar flow reactor for investigation of combustion and related gas phase reaction systems.</a> Rev Sci Instum. 86 (10), 105109 (2015).</li><li>O&#223;wald, P., Whitside, R., Sch&#228;ffer, J., K&#246;hler, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=An+experimental+flow+reactor+study+of+the+combustion+kinetics+of+terpenoid+jet+fuel+compounds:+Farnesane,+p-menthane+and+p-cymene.">An experimental flow reactor study of the combustion kinetics of terpenoid jet fuel compounds: Farnesane, p-menthane and p-cymene.</a> Fuel. 187, 43-50 (2017).</li><li>Kathrotia, T., Naumann, C., O&#223;wald, P., K&#246;hler, M., Riedel, U. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Kinetics+of+Ethylene+Glycol:+The+first+validated+reaction+scheme+and+first+measurements+of+ignition+delay+times+and+speciation+data.">Kinetics of Ethylene Glycol: The first validated reaction scheme and first measurements of ignition delay times and speciation data.</a> Combust. Flame. 179, 172-184 (2017).</li><li>Hansen, N., Cool, T. A., Westmoreland, P. R., Kohse-H&#246;inghaus, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Recent+contributions+of+flame-sampling+molecular-beam+mass+spectrometry+to+a+fundamental+understanding+of+combustion+chemistry.">Recent contributions of flame-sampling molecular-beam mass spectrometry to a fundamental understanding of combustion chemistry.</a> Prog Energ Combust. 35 (2), 168-191 (2009).</li><li>Qi, F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Combustion+chemistry+probed+by+synchrotron+VUV+photoionization+mass+spectrometry.">Combustion chemistry probed by synchrotron VUV photoionization mass spectrometry.</a> P Combust Inst. 34 (1), 33-63 (2013).</li><li>Biordi, J. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Molecular+beam+mass+spectrometry+for+studying+the+fundamental+chemistry+of+flames.">Molecular beam mass spectrometry for studying the fundamental chemistry of flames.</a> Prog Energ Combust. 3 (3), 151-173 (1977).</li><li>K&#246;hler, M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Speciation+data+for+fuel-rich+methane+oxy-combustion+and+reforming+under+prototypical+partial+oxidation+conditions.">Speciation data for fuel-rich methane oxy-combustion and reforming under prototypical partial oxidation conditions.</a> Chem Eng Sci. 139, 249-260 (2016).</li><li>O&#223;wald, P., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=In+situ+flame+chemistry+tracing+by+imaging+photoelectron+photoion+coincidence+spectroscopy.">In situ flame chemistry tracing by imaging photoelectron photoion coincidence spectroscopy.</a> Rev Sci Instum. 85 (2), 025101 (2014).</li><li>O&#223;wald, P., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Combustion+Chemistry+of+the+Butane+Isomers+in+Premixed+Low-Pressure+Flames.">Combustion Chemistry of the Butane Isomers in Premixed Low-Pressure Flames.</a> Zeitschrift f&#252;r Physikalische Chemie. 225, 1029 (2011).</li><li>Schenk, M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Detailed+mass+spectrometric+and+modeling+study+of+isomeric+butene+flames.">Detailed mass spectrometric and modeling study of isomeric butene flames.</a> Combust. Flame. 160 (3), 487-503 (2013).</li><li>Li, W., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Multiple+benzene-formation+paths+in+a+fuel-rich+cyclohexane+flame.">Multiple benzene-formation paths in a fuel-rich cyclohexane flame.</a> Combust. Flame. 158 (11), 2077-2089 (2011).</li><li>Bierkandt, T., Hemberger, P., Osswald, P., Kohler, M., Kasper, T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Insights+in+m-xylene+decomposition+under+fuel-rich+conditions+by+imaging+photoelectron+photoion+coincidence+spectroscopy.">Insights in m-xylene decomposition under fuel-rich conditions by imaging photoelectron photoion coincidence spectroscopy.</a> P Combust Inst. 36 (1), 1223-1232 (2017).</li><li>Taatjes, C. A., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Enols+Are+Common+Intermediates+in+Hydrocarbon+Oxidation.">Enols Are Common Intermediates in Hydrocarbon Oxidation.</a> Science. 308 (5730), 1887-1889 (2005).</li><li>Li, Y., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=An+experimental+study+of+the+rich+premixed+ethylbenzene+flame+at+low+pressure.">An experimental study of the rich premixed ethylbenzene flame at low pressure.</a> P Combust Inst. 32 (1), 647-655 (2009).</li><li>Yuan, W., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+comprehensive+experimental+and+kinetic+modeling+study+of+ethylbenzene+combustion.">A comprehensive experimental and kinetic modeling study of ethylbenzene combustion.</a> Combust. Flame. 166, 255-265 (2016).</li><li>Hansen, N., Skeen, S. A., Michelsen, H. A., Wilson, K. R., Kohse-Hoinghaus, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Flame+experiments+at+the+advanced+light+source:+new+insights+into+soot+formation+processes.">Flame experiments at the advanced light source: new insights into soot formation processes.</a> J Vis Exp. (87), e51369 (2014).</li><li>Qi, F., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Isomeric+identification+of+polycyclic+aromatic+hydrocarbons+formed+in+combustion+with+tunable+vacuum+ultraviolet+photoionization.">Isomeric identification of polycyclic aromatic hydrocarbons formed in combustion with tunable vacuum ultraviolet photoionization.</a> Rev Sci Instum. 77 (8), 084101 (2006).</li><li>Hansen, N., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=2D-imaging+of+sampling-probe+perturbations+in+laminar+premixed+flames+using+Kr+X-ray+fluorescence.">2D-imaging of sampling-probe perturbations in laminar premixed flames using Kr X-ray fluorescence.</a> Combust. Flame. 181, 214-224 (2017).</li></ol>

将大气高温流反应器与分子束质谱检测系统相结合, 使各种操作条件下的定量形态数据得以实现。几项研究21,22,23,27显示实验的灵活性从与部分氧化现象相关的丰富的甲烷条件开始 (φ = 2.5), 调查现代喷气燃料化合物如 farnesane 的燃烧化学。这样的研究使动能反应建模能够覆盖更多的技术领域,如?...

从可再生资源的现代低排放燃料中了解燃烧过程对当今社会的生态和经济议题是一个挑战。它们有可能减少我们对矿物燃料的依赖, 抵消 CO2排放量, 并对有害污染物排放 (如烟尘及其毒性前体1) 产生积极影响。将这个快速增长的领域与它们在现代燃烧室系统中的应用结合起来, 对控制化学和物理过程的基本理解的需求大大增加了2。即使在今天, 由于基链反应而产生的复杂化学反应网络仍然没有得到充分的理解。为了分析甚至控制污染物形成或 (自动) 点火过程等现象, 化学反应网络的详细知识是拼图3的关键部分。
为了调查和理解这些化学反应网络, 实验和数值方法是强制性的。实验中, 燃烧化学通常是通过应用简化的和良好的控制流环境的实验来研究特定问题。单个子过程的高复杂性和动态性通过基础实验防止了技术燃烧室条件的精确再现, 同时允许跟踪指定的关键特性, 如温度、压力、热释放, 或化学物种。早期, 对不同的实验方法的需要变得明显, 每个解决一个具体的问题, 并提供了后续的一系列信息, 有助于整个全球的燃烧化学图片。为了涵盖各种条件, 并收集随后的信息集, 以描述技术系统中发生的复杂情况, 成功地开发了多种方法。完善的技术包括:
<ul><li>激波管4,5,6和快速压缩机7。这些设备提供了很大范围内的压力和温度控制。然而, 可接触反应时间和适当的分析技术是有限的。</li>
	<li>层流预混火焰3,8,9,10,11是理想的, 以获得高温条件结合一个简单的流场。由于反应区的空间维数随着压力的增大而减小, 在低压条件下, 预混火焰通常会被研究成形态。</li>
	<li>逆流扩散火焰12,13,14,15是研究湍流燃烧小火焰计算机制的理想选择。它们模拟了由于不均匀性在一个真正的湍流流中的应变, 但在分析形态技术中又受到高度限制。</li>
	<li>各种反应堆实验16、17、18 (静态、搅拌和插头流) 提供了对高压环境的访问, 而温度通常比火焰环境低。常见的方法有:<ul>
<li>静止电抗器广泛用于脉冲光解实验, 但一般受长期停留时间和低温的限制。</li>
		<li>喷射搅拌反应器,即完全搅拌反应器 (PSR) 的气体版本, 依赖于气相的有效混合, 并可在恒定的停留时间、温度和压力下稳定运行, 使模型易于建模。然而, 分子有时间迁移到热表面, 并接受不同的反应。</li>
		<li>许多流动反应器方法是已知的, 与塞式流动反应器 (PFR) 是描述化学反应的最普遍的方法在连续, 流动系统的圆筒几何。在稳定状态下, 采用固定停留时间作为其理想 PFRs 位置的函数来假设插头流条件。</li>
	</ul>
</li>
</ul>在实验燃烧动力学领域有价值的技术的补充, 高温层流反应器实验19,20采用分子束质谱 (MBMS) 技术进行跟踪本文详细介绍了物种开发的21、22 。层流条件, 工作在大气压和可接近的温度到 1800 K 是流动反应器的主要特征, 而敏感 MBMS 技术允许检测几乎所有在燃烧中存在的化学物质过程.这包括高度活性的物种, 如激进分子, 它们不能或几乎无法与其他检测方法进行跟踪。MBMS 技术广泛用于对常规和现代替代燃料火焰中的反应网络进行详细调查, 如醇类或醚23,24,25 , 并已证明是对现代动力学模型的发展具有重要意义。
图 1显示了使用取样探针 (a) 缩放帧的高温流反应器的示意图, 以及两张突出显示总体实验 (B) 和探头设置 (C) 的图片。该系统可分为两部分: 一是具有燃气供应和蒸发器系统的高温流反应器, 二是 MBMS 飞行时间检测系统。在运行中, 流管的出口直接安装在 MBMS 系统的取样喷嘴上。气体直接从反应器出口取样, 转移到高真空检测系统。在这里, 电离是通过电子电离和随后的飞行时间检测进行的。
该反应器有一个40毫米内径陶瓷 (Al2O3) 管的1497毫米长度放置在一个高温烤箱 (, Gero, 类型 HTRH 40-1000).总加热段长度为1000毫米。气体被预混, 并预先汽化进入反应器由一个回火法兰 (通常回火到 ~ 80 °c)。高度稀释 (约99体积% 在 Ar), 层流流动反应物混合物通过已知的温度剖面 (详细的温度特性将在下面给出)。气体组分的检测发生在反应器出口作为烤箱温度的作用。测量是在恒定的入口质量流, 而单调下降温度斜坡 (-200 k/小时) 适用于烤箱的范围内 1800 k 到 600 k 注意到, 当测量不同的温度时, 可能会取得类似的结果。等温烘箱温度和热惯性被认为是正确的。该系统的热稳定性仍需一段时间, 选择温度坡道作为平均时间的折衷 (可忽略) 小温度增量和每系列总测量时间。平均时间 (四十五年代) MBMS 对应于 2.5 K。在给定条件下, 所得到的居住时间约为2秒 (在 1000 K 处)。最后, 由于温度的再现性, 在目前的反应堆实验中, 可以说明±5 K 或更好的测温温度的相对精度。
图 2显示了汽化系统的示意图, 它优化以调查甚至复杂的碳氢化合物混合物, 如技术喷射燃料。所有输入流都以科里奥利质量流量计的高精度 (±0.5%) 计量。燃料的汽化由一个商业蒸发器系统在温度200°c 实现。所有供应线与预汽化燃料的温度通常为150摄氏度, 以防止液体燃料的凝结, 同时避免热降解的同时。完全和稳定的汽化是例行检查, 甚至可能发生在温度低于正常沸点的各自燃料。完全蒸发是由小燃料分数和低分压 (通常低于 100 Pa) 确保所需的。
气体是由一个石英锥在反应堆出口中心线上的环境压力 (约 960 hPa) 取样, 在图 1的缩放框架中更详细地看到。喷嘴尖端有一个50微米的孔, 它位于大约30毫米内的陶瓷管在反应区结束。注意, 取样位置是固定在入口上的。烤箱管的热膨胀只发生在出口, 这是不机械地连接到取样系统导致温度独立长度的反应段。由于分子束的形成, 当气体扩展到高真空 (两个不同的抽运阶段; 10-2和 10-4 Pa)25,26时, 所有反应立即被淬火。该样本被引导到电子撞击时间 (飞行时) 质谱仪 (质量分辨率 R = 3000) 的离子源, 能够根据适当的精度确定现有物种的确切质量, 以确定一个 c-/小时内的元素组成。i/o 系统。电子能量被设置为低值 (通常为 9.5-10.5 eV), 以尽量减少由于电离过程的碎片。注意, 稀释剂和参考种类氩仍然是可检测的由于广泛的能量分布电离电子 (1.4 eV FWHM)。Ar 可以用好的 S/N 来测量, 低电子能量不允许对主要种类 (H2O、co2、co、H2、O2和燃料) 配置文件进行足够的确定, 这些剖面在显著较低浓度下存在。.
除了在飞行中检测外, 一个残留气体分析仪 (RGA),即四极质谱仪, 被放置在电离室中, 以更高的电子能量 (70 eV) 监测上述六种, 同时对 MBMS 的测量。

<table>
	<tbody>
		<tr>
			<td>Time-Of-Flight MBMS</td>
			<td>Kaesdorf</td>
			<td>n.a.</td>
			<td>custom design</td>
		</tr>
		<tr>
			<td>Molecular Beam Samling Interface</td>
			<td>self made</td>
			<td>n.a.</td>
			<td>custom design</td>
		</tr>
		<tr>
			<td>Laminar Flow Reactor</td>
			<td>Gero</td>
			<td>Type HTRH 40-1000</td>
			<td>custom design</td>
		</tr>
		<tr>
			<td>Quadrupole MS</td>
			<td>Hiden</td>
			<td>HAL/3F 301</td>
			<td>adapted to ionization chamber</td>
		</tr>
		<tr>
			<td>Vaporizer</td>
			<td>Bronkhorst</td>
			<td>CEM</td>
			<td>Vaporizer</td>
		</tr>
		<tr>
			<td>Mass Flow Meter</td>
			<td>Bronkhorst</td>
			<td>Mini Cori-Flow M12, M13, M14</td>
			<td>Flow Controller</td>
		</tr>
		<tr>
			<td>Jet A-1</td>
			<td>n.a.</td>
			<td>n.a.</td>
			<td>Standard Jet fuel of interest</td>
		</tr>
		<tr>
			<td>Metal syringe</td>
			<td>Hugo Sachs</td>
			<td>70-2252</td>
			<td>Fuel Supply</td>
		</tr>
		<tr>
			<td>Heating Hoses</td>
			<td>Hillesheim</td>
			<td>HMI series</td>
			<td>Gas Preheating</td>
		</tr>
		<tr>
			<td>Gas</td>
			<td>Linde</td>
			<td>Ar, O2</td>
			<td>Diluent, Oxidizer</td>
		</tr>
	</tbody>
</table>

combustion chemistry of fuels: quantitative speciation data obtained from an atmospheric high-temperature flow reactor with coupled molecular-beam mass spectrometer

这篇手稿描述了一个高温流反应器实验耦合到强大的分子束质谱 (MBMS) 技术。这个灵活的工具提供了一个详细的观察化学气相动力学的反应流在良好的控制条件。在层流反应器中提供的大量操作条件使我们能够获得特殊的燃烧应用, 而这些应用程序通常不能通过火焰实验实现。这些包括在高温条件下与气化过程有关的丰富环境, 过氧化化学控制低温氧化机制或研究复杂的技术燃料。所提出的设置允许测量的数量形态数据的反应模型验证燃烧, 气化和热解过程, 同时使系统的普遍理解的反应化学。动力学反应模型的验证一般是通过研究纯化合物的燃烧过程来进行的。流化反应器已被加强, 以适合技术燃料 (如喷射 A-1 的多组分混合物), 以允许对发生燃烧中间体如烟尘前体或污染物的现象学分析。实验设计提供的受控和可比较的边界条件可以预测污染物的形成趋势。冷反应物被送入预混进反应器中, 高度稀释 (在 Ar 中约99体积%), 以抑制自我维持的燃烧反应。层流反应物混合物经过已知的温度场, 而气体成分是确定在反应堆排气作为一个功能的烤箱温度。流动反应器在大气压下作以温度 1800 K 。测量本身是通过降低温度单调率为-200 克/小时。利用敏感的 MBMS 技术, 在反应过程中几乎所有的化学物种, 包括激进物种, 都获得和量化了详细的形态数据。

在图 3中显示了取样气体组成的典型质量谱。与给定的质量分辨率约3000的设置, 物种由 m/z = 260, 您可以在 c/c++ 系统中检测到。在质量校准过程中, 峰值被集成为每个质量-电荷 (m-/z) 比和反褶积算法, 以评估未解决的信号。在背景和碎片校正之后, 信号可以用适当的校准因子与已知协作 (典型的惰性气体氩) 的参考物种进行量化。获得校准因子的几个复杂...

Watch this Scientific Journal Video about Combustion Chemistry of Fuels: Quantitative Speciation Data Obtained from an Atmospheric High-temperature Flow Reactor with Coupled Molecular-beam Mass Spectr

Combustion Chemistry of Fuels: Quantitative Speciation Data Obtained from an Atmospheric High-temperature Flow Reactor with Coupled Molecular-beam Mass Spectrometer

燃料燃烧化学: 用耦合分子束质谱仪从大气高温流反应器中获得的定量形态数据

通过比较定量形态数据, 对新型生物燃料、燃料组分或喷气燃料的氧化燃烧化学进行了研究。这些数据可用于动态模型验证, 并能够实现燃料评估策略。这篇手稿描述了大气高温流反应器并证明了它的能力。

This manuscript describes a high-temperature flow reactor experiment coupled to the powerful molecular beam mass spectrometry (MBMS) technique. This ...

Research

JoVE Journal

Chemistry

PTR-ToF-MS Coupled with an Automated Sampling System and Tailored Data Analysis for Food Studies: Bioprocess Monitoring, Screening and Nose-space Analysis

PTR-ToF-MS结合自动采样系统和食品研究定制数据分析：生物过程监测，筛选和鼻空间分析

Proton Transfer Reaction (PTR), combined with a Time-of-Flight (ToF) Mass Spectrometer (MS) is an analytical approach based on chemical ionization that ...

科研

化学

Non-equilibrium Microwave Plasma for Efficient High Temperature Chemistry

用于高效高温化学的非平衡微波等离子体

A flowing microwave plasma based methodology for converting electric energy into internal and/or translational modes of stable molecules with the purpose ...

A Practical Guide on Coupling a Scanning Mobility Sizer and Inductively Coupled Plasma Mass Spectrometer (SMPS-ICPMS)

A Practical Guide on Coupling a Scanning Mobility Sizer and Inductively Coupled Plasma Mass Spectrometer SMPS-ICPMS

耦合扫描流动性测定仪和电感耦合等离子体质谱仪（SMPS-ICPMS）的实用指南

A large variety of analytical methods are available to characterize particles in aerosols and suspensions. The choice of the appropriate technique depends ...

Fizzy Extraction of Volatile Organic Compounds Combined with Atmospheric Pressure Chemical Ionization Quadrupole Mass Spectrometry

挥发性有机化合物与大气压化学电离四极杆质谱联用

Chemical analysis of volatile and semivolatile compounds dissolved in liquid samples can be challenging. The dissolved components need to be brought to ...

Real-time Breath Analysis by Using Secondary Nanoelectrospray Ionization Coupled to High Resolution Mass Spectrometry

利用二次 Nanoelectrospray 电离耦合高分辨质谱的实时呼吸分析

Exhaled volatile organic compounds (VOCs) have aroused considerable interest, since they can serve as biomarkers for disease diagnosis and environmental ...

Continuous Flow Chemistry: Reaction of Diphenyldiazomethane with p-Nitrobenzoic Acid

Continuous Flow Chemistry: Reaction of Diphenyldiazomethane with p-Nitrobenzoic Acid

连续流动化学: Diphenyldiazomethane 与p硝基苯甲酸的反应

Continuous flow technology has been identified as instrumental for its environmental and economic advantages leveraging superior mixing, heat transfer and ...

Time-resolved Photophysical Characterization of Triplet-harvesting Organic Compounds at an Oxygen-free Environment Using an iCCD Camera

利用 iccd 摄像机对无氧环境下的三重收集有机化合物进行光物理表征

Here, we present a sensible method of the acquisition and analysis of time-resolved photoluminescence using an ultrafast iCCD camera. This system enables ...

A Continuous-flow Photocatalytic Reactor for the Precisely Controlled Deposition of Metallic Nanoparticles

一种用于金属纳米粒子精确控制沉积的连续流动光催化反应器

In this work, a novel photocatalytic reactor for the pulsed and controlled excitation of the photocatalyst and the precise deposition of metallic ...

Reducing Willow Wood Fuel Emission by Low Temperature Microwave Assisted Hydrothermal Carbonization

低温微波辅助热液碳化降低柳树燃料排放

Biomass is a sustainable fuel, as its CO2 emissions are reintegrated in biomass growth. However, the inorganic precursors in the biomass cause a negative ...

Integrated Cell Manipulation Platform Coupled with the Single-probe for Mass Spectrometry Analysis of Drugs and Metabolites in Single Suspension Cells

集成细胞操作平台与单悬架细胞中药物和代谢物质谱分析的单探针相结合

Single cell mass spectrometry (SCMS) enables sensitive detection and accurate analysis of broad ranges of cellular species on the individual-cell level. ...