Contributions of Flow Analysis for Quality Control of Automotive Fuels: A Review

Automotive fuels require strict quality control to assure best energy use with minimal environmental pollution. Fuels can be modified before consumption by inadequate transport, storage, and handling, as well as illegal adulteration. Continuous monitoring is of paramount importance to reduce such irregularities, thus requiring reliable analytical methods, which should be simple, fast, and minimize both reagent consumption and waste generation. The potential for in-situ monitoring is also highly desirable. Flow analysis plays an important role in this sense, by means of automated sample processing in closed systems, under highly reproducible conditions. In spite of this potential, application for routine fuel analysis is yet limited and wide dissemination is desirable. This review focuses on analytical approaches for in-line sample pretreatment and determination of organic and inorganic contaminants in automotive fuels by flow analysis. Applications in gasoline, diesel oil, biodiesel, and ethanol fuels are critically discussed.     

Characteristics of soot particles formed by diesel pyrolysis

This experiment involving diesel fuel pyrolysis was performed to study the process of soot formation without oxidation. The effects of temperature, residence time, and lubricating oil presence on soot formation were investigated through measurement of particle size distribution, morphology, and C/H ratio as well as through thermal analysis. The results show that the formation of soot during diesel pyrolysis depended strongly on both temperature and residence time. The critical temperature for the creation of soot with a primary particle diameter of 20 nm was about 1100 °C. Greater temperatures and residence times resulted in diesel soot particles that were more mature, i.e., with a higher C/H ratio, larger particle size, and higher ignition temperature. The carbonization of diesel soot through pyrolysis was also weakly affected by the addition of 5% lubricating oil to the diesel fuel. The results of this experiment provide information for modeling the formation of diesel soot without oxidation as well as for developing soot generators for after-treatment systems.     

Quantitation method of N,N ′‐disalicylidene‐1,2‐propanediamine by comprehensive two‐dimensional gas chromatography coupled to a nitrogen chemiluminescence detector

Metal deactivator additives (MDAs) have been used for over 60 years to prevent metal catalyzed reactions in petroleum products; a commonly used metal deactivator is N,N′‐disalicylidene‐1,2‐propanediamine. The quantitation of low MDA concentrations in fuels is challenging due to the complexity of the sample matrix. In this work, this difficulty was overcome using GC × GC hyphenated with a nitrogen chemiluminescence detector. The high resolution power of GC × GC avoided co‐elution between the MDA and other sample matrix compounds; while the enhanced sensitivity of GC × GC and the use of a nitrogen chemiluminescence detector supplied a high sensitivity and specificity for nitrogen compounds. For the analysis, the MDA additive was derivatized with the silylation agent N,O‐bis (trimethylsilyl)trifluoroacetamide at room temperature and its quantitation was based on an external calibration curve; good linear response was obtained in the 1.4–8.6 ppm range.     

Experimental and Numerical Investigation on Cavitating Flows in Diesel Injection Systems

The present study is concerned with the phase change during rapid depressurization of fluids: the role of vapor bubbles nucleation and growth and the effect on the system fluid dynamics were modeled and experimental measurements were made. Following a control-volume approach, averaged equations governing the motion of a one-dimensional, homogeneous, no-slip two-phase flow were used considering both thermal equilibrium (equal temperature) and non-equilibrium (non-equal temperature) between the liquid and vapor phases. In the non-equilibrium model, the heat transfer from the liquid to the vapor and the corresponding mass transfer velocity were modeled. Model results were compared with experimental data for a loss-of-coolant accident in nuclear power plants: the comparison of numerical vs. experimental data showed the role of nucleation velocity during the earliest phase of rapid depressurization. The experimental study of two-phase flow in a diesel engine injection system has been carried out using a rotative pump which is operated by using a purpose-developed test-bench; pressure measurements inside the system pipes were performed using pressure transducers; moreover, an ultrasonic technique was employed to study phase change phenomena. Several measurements were performed comparing the results obtained by different experimental techniques with the model outputs.Sommario.presente studio riguarda il fenomeno della cavitazione durante la depressurizzazione di fluidi. E'stata considerata la velocità di formazione e nucleazione delle bolle di vapore e le equazioni di conservazione sono state integrate con solutori al 1°e 2°ordine di tipo ENO. Sono stati utilizzati dati sperimentali ottenuti durante incidenti per perdita di refrigerante in centrali nucleari; per quanto riguarda gli apparati di iniezione, gli autori hanno sviluppato due differenti tecniche sperimentali, basate rispettivamente sulla pressione e sulla riflessione degli ultrasuoni. Il confronto dei risultati numerici con quelli sperimentali è stato soddisfacente.     

Shock tube studies of thermal radiation of diesel-spray combustion under a range of spray conditions

A tailored interface shock tube and an over-tailored interface shock tube were used to measure the thermal energy radiated during diesel-spray combustion of light oil, α-methylnaphthalene and cetane by changing the injection pressure. The ignition delay of methanol and the thermal radiation were also measured. Experiments were performed in a steel shock tube with a 7 m low-pressure section filled with air and a 6 m high-pressure section. Pre-compressed fuel was injected through a throttle nozzle into air behind a reflected shock wave. Monochromatic emissive power and the power emitted across all infrared wavelengths were measured with IR-detectors set along the central axis of the tube. Time-dependent radii where soot particles radiated were also determined, and the results were as follows. For diesel spray combustion with high injection pressures (from 10 to 80 MPa), the thermal radiation energy of light oil per injection increased with injection pressure from 10 to 30 MPa. The energy was about 2% of the heat of combustion of light oil at P _inj = about 30 MPa. At injection pressure above 30 MPa the thermal radiation decreased with increasing injection pressure. This profile agreed well with the combustion duration, the flame length, the maximum amount of soot in the flame, the time-integrated soot volume and the time-integrated flame volume. The ignition delay of light oil was observed to decrease monotonically with increasing fuel injection pressure. For diesel spray combustion of methanol, the thermal radiation including that due to the gas phase was 1% of the combustion heat at maximum, and usually lower than 1%. The thermal radiation due to soot was lower than 0.05% of the combustion heat. The ignition delays were larger (about 50%) than those of light oil. However, these differences were within experimental error.

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An abridged version of this paper was presented at the 18th Int. Symposium on Shock Waves at Sendai, Japan during July 21 to 26, 1991 and at the 19th Int. Symposium on Shock Waves at Marseille, France during July 26 to 30, 1993.     

Thermal regeneration of diesel particulate in metallic fibrous filter

Experiments were performed to study the aerodynamic thermal regeneration of a metallic fibrous particulate filter, which was used to reduce particulate emissions from diesel vehicles. Heated air diluted with nitrogen was used to initiate the regeneration process. Temperatures at 11 locations inside the filter were measured with embedded thermocouples which were equally spaced in the axial direction. Based on the temperature data, the instantaneous heat release of the filter was derived and analyzed. The peak regeneration temperature was found to occur at the region near the filter exit, and fibers in this region could melt when the temperature was sufficiently high. The normal regeneration temperature was around 800°C to 1000°C but local temperature could be as high as 1300°C. Thermal regeneration of the filter was found to depend on several factors, including, oxygen concentration in the heated air, initial particulate loading, packing density, thickness of the filtering element, and flow rate of the heated air. It was found that for regeneration to occur, the temperature of the heated air should exceed 500°C, the filtering element should have a minimum thickness of 50mm and a minimum initial particulate loading of 2 gram. Regeneration, and hence, heat release, was found to start earlier at higher oxygen concentration in the heated air, higher heated air flow rate, lower packing density and higher initial particulate loading. Regeneration temperature was higher at higher oxygen concentration in the heated air, lower heated air flow-rate, higher packing density and higher initial particulate loading. The results had also been compared with those of Kim et al. [12] and Park et al. [13] obtained on ceramic filter and those simulated by Garner and Dent [7].     

Quantification of nitrogen compounds in diesel fuel samples by comprehensive two‐dimensional gas chromatography coupled with quadrupole mass spectrometry

Although several methods for the analysis of nitrogen compounds in diesel fuel have been described in the literature, the demand for rapid, sensitive, and robust analyses has increased in recent years. In this study, a comprehensive two‐dimensional gas chromatographic method was developed for the identification and quantification of nitrogen compounds in diesel fuel samples. The quantification was performed using the standard addition method and the analysis was conducted using comprehensive two‐dimensional gas chromatography coupled with fast quadrupole mass spectrometry. This study is the first to report quantification of nitrogen compounds in diesel fuel samples using the standard addition method without fractionation. This type of analysis was previously performed using many laborious separation steps, which can lead to errors and losses. The proposed method shows good linearity for target nitrogen compounds evaluated (m‐toluidine, 4‐ethylaniline, indole, 7‐methylindole, 7‐ethylindole, carbazole, isoquinoline, 4‐methylquinoline, benzo[h]quinolone, and acridine) over a range from 0.05 to 2.0 mg/L, and limits of detection and quantification of <0.06 and 0.16 mg/L, respectively, for all nitrogen compounds studied.     

Chemie im Motor: Verbrennungsmotoren versus Brennstoffzelle und Elektromotor

This article draws a bow from the fundamentals of the flame chemistry to combustion in engines. Aspects of radical chemistry, pollutant formation and combustion are highlighted. Concepts of current and future internal combustion engines are presented. A main focus lies on pollutant formation and reduction (CO₂, CO, NO_x, HC and soot). Finally, a vision of the future role of the internal combustion engine with respect to fuel cell and electrical engine is outlined.     

Angled jet flow model for a diesel engine intake process—random vortex method

A numerical model is developed to study the interactions of multiple angled jet flows in the inlet port plane of the Detroit Diesel 6V-92 two-stroke engine cylinder. The random vortex method is used in two dimensions. Results show axisymmetric swirl initially. As flow develops, the centre of the swirl moves to the mid-radius region and begins to precess about the cylinder centre. The flow becomes progressively more chaotic as time progresses.     

氧弹燃烧-ICP-OES用于柴油标准物质中硫含量的定值

本文是柴油系列标准物质研究课题中的子课题,研究了用氧弹燃烧-电感耦合等离子发射光谱法对柴油中硫系列标准物质的定值。通过实验条件的最佳化,包括氧弹燃烧消解样品的影响因素、仪器分析的最佳条件等,利用新型的电感耦合等离子发射光谱仪器(SPECTRO CIROS)真空紫外谱线灵敏高,重现性好的优点,测量两个水平的硫标准物质,使用内标元素Y和进行基体匹配达到消除基体影响而提高测量准确度的目的。该方法展伸不确定度优于2％,测定的结果与其它的不同方法测定的结果一致。