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Journal Article

Analysis of Oxidative Deterioration of Biodiesel Fuel

Methyl esters of saturated/unsaturated higher aliphatic acids (FAMEs) and a FAME of waste cooking oil (WCOME) were heated at 120°C in an air gas flow. The samples were analyzed before and after heating, using six different methods including electrospray ionization mass spectrometry. As a result, the samples after heating were found to contain low molecular weight aliphatic compounds and oligomers of the FAME. Based on the chemical structure of these oxidation products, reaction schemes were proposed for the deterioration of FAMEs. In addition, two unsaturated FAMEs containing 2,6-di-t-butyl-p-cresol (BHT) were similarly heated and analyzed to examine the effect of BHT on the oxidation of these FAME.
Technical Paper

Analysis of the Deterioration of Nylon-66 Immersed in GTL Diesel Fuel Part 1. Analysis and Test of Nylon and GTL Diesel Fuel Before and After Immersion

The effect of GTL diesel fuel on organic materials used in fuel delivery systems of vehicles was investigated. Specimens made from 16 kinds of organic materials were immersed in GTL diesel fuels synthesized at Refinery-A and Refinery-B (referred to as GTL-A and GTL-B, respectively) and then subjected to tensile testing. The tensile test results revealed that elongation of the nylon sample immersed in GTL-A was extremely small, about 4% of that of untreated nylon. In the light of this finding, the GTL diesel fuels and nylons before and after immersion test were analyzed in detail using about 20 analysis methods to determine the cause for poor elongation. The following points were found. (1) GTL-A consisted of low molecular-weight paraffins. (2) GTL-A had low molecular-weight i-paraffins. (3) The nylon immersed in GTL-A contained low molecular-weight paraffins. (4) The paraffins in the nylon immersed in GTL-A were richer in i-paraffins than the original GTL-A.
Technical Paper

Analysis of the Deterioration of Nylon-66 Immersed in GTL Diesel Fuel Part 2. Analysis of Model Fuel and Nylon Before and After Immersion

In a previous paper (Part 1 of this series), nylon-66 specimens were immersed in two GTL diesel fuels (GTL-A and GTL-B) and then subjected to tensile testing. The tensile test results revealed that the elongation of the specimen immersed in GTL-A was dramatically reduced. The GTL diesel fuels and nylon specimens before and after immersion were analyzed to determine the cause of the decline in elongation. It was found that the poor elongation was caused by penetration and oxidation of low molecular-weight paraffins and that the ease of penetration and oxidation of paraffin depended on the structure of paraffin. In this paper, the low molecular-weight paraffins detected in GTL-A were mixed to produce model fuels. Then, pieces of nylon cut from the tensile test specimen, were immersed in the model fuels. In addition, partial oxidation products of the paraffin (alcohol, aldehyde or ketone and acid) were used in immersion tests of the nylon pieces.
Technical Paper

Fuel Effects on Particulate Emissions from D.I. Engines - Precise Analyses and Evaluation of Diesel Fuel

Precise analytical methods for characterizing diesel fuel yielding the lowest particulate emissions were developed. The methods consist of preparative-scale high pressure liquid chromatography (HPLC), field ionization mass spectrometry (FIMS), analytical-scale HPLC, and carbon-13 nuclear magnetic resonance spectrometry (13C-NMR). A diesel fuel was first separated into an aliphatic fraction and an aromatic fraction by semipreparative-scale HPLC. Then, the aliphatic fraction was analyzed by FIMS and the spectrum was compared with that of the whole fuel. The aromatic fraction was analyzed by analytical-scale HPLC to obtain the chromatogram of the aromatic hydrocarbons with a high S/N. In addition to these analyses, the fuel was analyzed by 13C-NMR to obtain the concentration of the carbon atoms of the straight chain, branched chain and aromatic-ring in hydrocarbons.
Technical Paper

Effect of Hydrocarbon Molecular Structure on Diesel Exhaust Emissions Part 1: Comparison of Combustion and Exhaust Emission Characteristics among Representative Diesel Fuels

Combustion and exhaust emission characteristics were compared among three representative diesel fuels called “Base (corresponding to a Japanese market fuel)”, “Improved” and Swedish “Class-1” using both a modern small and an optically accessible single-cylinder DI diesel engines. In these tests, the relative amount of PM collected in the exhaust was “Base” >“Class-1” >“Improved” at almost all of the operating conditions. This means that “Class-1” generated more PM than “Improved”, even though “Class-1” has significantly lower distillation temperatures, aromatic content, sulfur, and density compared with “Improved”. There was little difference in combustion characteristics such as heat release rate pattern, mixture formation and flame development processes between these two fuels. However, it was found that “Class-1” contained more branches in the paraffin fraction and more naphthenes.
Technical Paper

Fuel Effects on Particulate Emissions from D.I. Engine - Relationship among Diesel Fuel, Exhaust Gas and Particulates

The compositions of hydrocarbons in diesel fuel, exhaust gas and particulates were analyzed and the relationships among them were determined. It was found that the compositions of the hydrocarbons in the exhaust gas were almost the same as that of the fuel, and that the hydrocarbons in the particulates corresponded to their heavy fractions. When the engine condition was fixed, both the soluble organic fraction (SOF) and insoluble fraction ( ISF) showed positive correlation coefficients versus HC×R310, where HC denotes the hydrocarbon emission and R310 denotes the backend fraction, as measured by the fraction of fuel boiling above 310°C. On the other hand, when the engine condition was varied, ISF had negative correlation coefficients versus HC×R310, while SOF showed positive correlation coefficients.
Technical Paper

Fuel Effects on Particulate Emissions from D. I. Engine - Chemical Analysis and Characterization of Diesel Fuel

The properties of diesel fuels were investigated in terms of particulate emissions to clarify the specification of such a diesel fuel for minimizing particulate emissions. Diesel fuels were analyzed using thin layer chromatography (TLC), and gas chromatography/mass spectrometry (GC/MS). These analysis revealed the entire composition of hydrocarbons in diesel fuels according to molecular formula. The entire composition of hydrocarbons in diesel fuels could be expressd on a three-dimensional graph: the X-axis as carbon number, the Y-axis as H/C ratio and the Z-axis as the amount of hydrocarbons of identical molecular formula. By using the graph, the properties reported so far were investigated. Also, simplified images of the fuel sprayed into a cylinder and its flame were derived from the observational results previously reported.
Technical Paper

Effects of California Phase 2 Reformulated Gasoline Specifications on Exhaust Emission Reduction

In response to various reformulated gasoline regulations, several studies have been conducted to evaluate the relationship between fuel properties and vehicle exhaust emissions. These studies, however, have focused on the fuel effect and have not examined the most promising advanced technology emission control systems on low emission vehicles. Toyota's reformulated gasoline research first set out to study the effect fuel compositions has on 2 different emission control systems. On both systems, non-methane hydrocarbon (NMHC) emissions were significantly affected by the 50% and 90% distillation temperature (T50 and T90). A correlation was also found exhaust olefine content and the amount of MTBE contained in the fuel. Research was also conducted on the specific ozone reactivity (SOR) of exhaust hydrocarbons. Various fuels with similar specifications but blended from different feedstocks were evaluated.
Technical Paper

Mechanism of Intake Valve Deposit Formation Part III: Effects of Gasoline Quality

Quality control of gasoline constituents and its effect on the Intake Valve Deposits (IVD) has become a recent issue. In this paper, the effects of gasoline and oil quality on intake valve deposits were investigated using an Intake Valve Deposit Test Bench and a Sludge Simulator. The deposit formation from the gasoline maximized at an intake valve temperature of approximately 160 °C, and the deposits formed from the engine oil were maximum at approximately 250 °C. Therefore, the contribution of the gasoline or the engine oil appears to depend on the engine conditions. The gasoline which contains MTBE or ethanol with no detergent additive slightly increases the deposition amount. The gasoline with a superior detergent significantly decreases the deposition amount even when MTBE or ethanol is blended in the gasoline. Appropriate detergent fuel additive retards the oil deterioration.
Technical Paper

Analysis of Poor Engine Response Caused by MTBE-Blended Gasoline from the Standpoint of Fuel Evaporation

Fifty percent distillation temperature (T50) can be used as a warm-up driveability indicator for a hydrocarbon-type gasoline. MTBE-blended gasoline, however, provides poorer driveability than a hydrocarbon-type gasoline with the same T50. The purposes of this paper are to examine the reason for poor engine driveability caused by MTBE-blended gasolines, and to propose a new driveability indicator for gasolines including MTBE-blended gasolines. The static and dynamic evaporation characteristics of MTBE-blended gasolines such as the evaporation rate and the behavior of each component during evaporation were analyzed mainly by using Gas Chromatography/Mass Spectrometry. The results of the analysis show that the MTBE concentration in the vapor, evaporated at ambient temperature (e.g. 24°C), is higher than that in the original gasoline. Accordingly, the fuel vapor with enriched MTBE flows into the combustion chamber of an engine just after the throttle valve is opened.
Technical Paper

Analyzing the Influence of Gasoline Characteristics on Transient Engine Performance

It has been reported that the middle range of gasoline distillation temperatures strongly affects vehicle driveability and exhaust hydrocarbon (HC) emissions, and that MTBE(CH3-O-C4H9)- blended gasoline causes poor driveability during warm-up. The present paper is concerned with the results of subsequent detailed research on gasoline characteristics, exhaust emissions and driveability. In this paper, first it is demonstrated by using four models of passenger cars having different types of exhaust gas treatment system that decreased 50% distillation temperature (T50) reduces exhaust HC emission. This result indicates lowering T50 in the market will contribute to improving air quality. Secondly gasoline behavior in the intake manifold is investigated by using an engine on the dynamometer in order to clarify the mechanisms of HC emission increase and poor engine response which are caused by high T50.
Technical Paper

The Influence of Fuel Qualities on White Smoke Emissions from Light-Duty Diesel Engine

In many countries, cetane number and distillation properties of diesel fuel have been changing, thus affecting the performance of diesel engines. This paper describes investigations made on the effect of diesel fuel quality on white smoke (one of the important emissions of diesel engines). The result of simple laboratory tests simulating high altitude conditions plus field tests using three types of disel engines supplied with various types of diesel fuels is given. It was found that white smoke appearing tendency correlated best with cetane number and the 90 percent distillation point of the fuel. The field tests performed at high altitude correlated well with the simple laboratory tests.