Study of acidified ignitable liquid residues in fire debris by solid‐phase microextraction with gas chromatography and mass spectrometry

The detection and identification of ignitable liquid residues in fire debris can be meaningful in fire investigations. However, background pyrolysis products and weathering hinder the identification and classification steps. In addition to those processes, the acidification of the ignitable liquids before the combustion process could make those tasks even more difficult. Nevertheless, there are no systematic studies assessing the extraction, analysis, and composition of acidified ignitable liquid residues obtained from fire debris. In this work, a method for the study of acidified ignitable liquid residues in fire debris by solid‐phase microextraction with gas chromatography and mass spectrometry is proposed. This methodology has been evaluated, first with simulated solutions (gasoline/sulfuric acid mixtures set on fire under controlled conditions), and then with analysis of samples from real fire debris obtained from 18 chemical ignition Molotov cocktails made with sulfuric acid and three different ignitable liquids (two types of gasoline and diesel fuel). In addition, the extensive modifications observed in chromatograms of acidified ignitable liquid residues regarding neat and weathered samples were studied. These alterations were produced by the combustion and acidification processes. As a consequence, tert‐butylated compounds are proposed as diagnostic indicators for the identification of acidified gasoline in fire debris, even in strongly weathered samples.     

Light intensity and image visualization of GDI injector sprays according to nozzle hole arrangements

The light intensity measurement and image visualization of multi-hole injection spray due to different hole arrangements and hole numbers were investigated. The light intensities and behavior characteristics of the GDI spray were analyzed through the axial and diagonal spray penetration, cone angle, and spray area from the spray images by using the image visualization system and image analysis system. The atomization performance of GDI injectors was analyzed by the local and overall Sauter mean diameter (SMD) measurement.     

An experimental study of fuel injection strategies in CAI gasoline engine

Combustion of gasoline in a direct injection controlled auto-ignition (CAI) single-cylinder research engine was studied. CAI operation was achieved with the use of the negative valve overlap (NVO) technique and internal exhaust gas re-circulation (EGR). Experiments were performed at single injection and split injection, where some amount of fuel was injected close to top dead centre (TDC) during NVO interval, and the second injection was applied with variable timing. Additionally, combustion at variable fuel-rail pressure was examined.Investigation showed that at fuel injection into recompressed exhaust fuel reforming took place. This process was identified via an analysis of the exhaust-fuel mixture composition after NVO interval. It was found that at single fuel injection in NVO phase, its advance determined the heat release rate and auto-ignition timing, and had a strong influence on NO_X emission. However, a delay of single injection to intake stroke resulted in deterioration of cycle-to-cycle variability. Application of split injection showed benefits of this strategy versus single injection. Examinations of different fuel mass split ratios and variable second injection timing resulted in further optimisation of mixture formation. At equal share of the fuel mass injected in the first injection during NVO and in the second injection at the beginning of compression, the lowest emission level and cyclic variability improvement were observed.     

适用于汽油参比燃料TRF的多环芳香烃生成机理

构造了一个包括287种组分和1569个反应的汽油参比燃料TRF(toluene reference fuel)燃烧过程中多环芳香烃(PAHs)生成机理的详细化学反应动力学模型,引入四种PAH生长路径将多环芳香烃的生成机理发展到芘A4(C20H12)水平,并通过对PAH产率的分析,指出乙炔(C2H2)、丙炔(C3H3)、乙烯基乙炔(C4H4)以及含有奇数碳原子的环戊二烯自由基(C5H5)和茚基(C9H7)等物质对PAHs生成和生长起到重要作用.该机理可以较准确计算基础燃料(PRF)和TRF火焰的着火延迟期、燃烧火焰中小分子(PAH前驱体C2H2、C3H4等)和PAHs的物质浓度.通过与实验数据的比较表明,该机理在不同温度、压力、化学计量比下具有较好的性能.由此分析,该机理对碳烟前驱物PAHs的预测性能是可靠的.     

Pervaporation separation of n-heptane/thiophene mixtures by polyethylene glycol membranes: Modeling and experimental

Gasoline desulfurization by membrane processes is a newly emerged technology, which has provided an efficient new approach for sulfur removal and gained increasing attention of the membrane and petrochemical field. A deep understanding of the solution/diffusion of gasoline molecules on/in the membrane can provide helpful information in improving or optimizing membrane performance. In this study, a desulfurization mechanism of polyethylene glycol (PEG) membranes has been investigated by the study of sorption and diffusion behavior of typical sulfur and hydrocarbon species through PEG membranes. A solution–diffusion model based on UNIFAC and free volume theory has been established. Pervaporation (PV) and sorption experiments were conducted to compare with the model calculation results and to analyze the mass transport behavior. The dynamic sorption curves for pure components and the sorption experiments for binary mixtures showed that thiophene, which had a higher solubility coefficient than n-heptane, was the preferential sorption component, which is key in the separation of thiophene/hydrocarbon mixtures. In all cases, the model calculation results fit well the experimental data. The UNIFAC model was a sound way to predict the solubility of solvents in membranes. The established model can predict the removal of thiophene species from hydrocarbon compounds by PEG membranes effectively.     

气相色谱/质谱/质谱法分析石油基引燃物

应用Ｖａｒｉａｎ ３８００ ＧＣ／Ｓａｔｕｒｎ ２０００ ＭＳ 气相色谱／质谱联用分析仪（简称ＧＣ／ＭＳ／ＭＳ）对以汽油、煤渍和紫油为引燃物，燃烧聚丙稀化纤地毯和土壤时的模拟现场物品进行了引燃物的检出。发现采用ＧＣ／ＭＳ／ＭＳ方法比用ＧＣ／ＭＳ方法可以较彻底地排队由于柱注失、地毯燃物分解产物、土壤背景产物和地毯增塑剂等引起的干扰，而且可以提高检测灵敏度。详细考察了以不同质荷比的离子作母离子时对ＧＣ     

磁化作用对汽油动态挥发性影响的研究

用热重（TG）分析和自行设计的原位动态挥发实验，研究了在不同条件下汽油的挥发性，结果表明，磁化空气或磁化汽油都可提高汽油的挥发性，而汽油和空气共同磁化，可更大幅度地提高汽油的挥发性。     

汽油族组成的近红外光谱快速测定

以荧光指示剂吸附色谱法（FIA）测定汽油族组成结果为基础，采用近红外光谱和化学计量学方法建立了快速、准确测定催化裂化馏出口汽油族组成（饱和烃、烯烃和芳烃）的分析模型；试验表明，该法分析速度快、重复性好、成本低，特别适用于生产中间控制分析。     

Analysis of petroleum fractions by on-line micro HPLC-HRGC coupling,involving increased efficiency in using retention gaps by partially concurrent solvent evaporation

Two-dimensional chromatography of gasoline by on-line coupled HPLC-HRGC, as described in this paper, allows separate GC analysis of paraffins and aromatics. The GC system contains a retention gap of only 10 m length for introducing HPLC fractions of 100 μl volume. This becomes possible through evaporation of part of the solvent during introduction of the HPLC eluent. This “partially concurrent solvent evaporation” technique allows transfer of large volumes of HPLC eluent into relatively short retention gaps, maintaining the full efficiency of the solvent effects in reconcentrating the bands of the early eluted solutes.     

Determination of the sulfur components of gasoline streams by capillary column gas chromatography with sulfur chemiluminescence detection

A method using a sulfur chemiluminescence detector (SCD) has been developed for the qualitative and quantitative determination of sulfur components in stabilized gasoline-range process streams, including blended gasolines containing between 1 and > 4000 ppm total sulfur. The detection limit per sulfur component was approximately 50 ppb. On-column injection was employed for optimum precision and accuracy. A new probe material was found which did not soften under FID operating conditions. A new method, using a hydrogen sulfide permeation tube, was developed for rapid alignment of the probe in the FID.