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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.

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.

This research aimed to identify how combustion characteristics are affected by the addition of hydrogen to methane, which is the main components of natural gas, and to study a combustion method that takes advantage of the properties of the blended fuel. It was found that adding hydrogen did not achieve a thermal efficiency improvement effect under stoichiometric conditions because cooling loss increased. The same result was obtained under EGR stoichiometric conditions. In contrast, under lean burn conditions, higher thermal efficiency and lower NOx than with methane combustion was achieved by utilizing the wide flammability range of hydrogen to expand the lean limit. Although NOx can be decreased easily by the addition of large quantities of hydrogen, the substantially lower energy density of the fuel causes a substantial reduction in cruising range. Consequently, this research improved the combustion of a CNG engine by increasing the tumble ratio to 1.8.

Among the challenges for the future facing the development of gasoline engines, one of the most important is the reduction of particles emissions. This study proposes a critical and objective evaluation of the influence of fuel characteristics on gasoline particles emission through the use of Fuel Particle Indices. For this, a selected fuel matrix composed of 22 fuels was built presenting different volatility and chemical composition (content in total aromatics, heavy cuts and ethanol). To represent the fuel sooting tendency, seven Fuel Particle Indices were selected based on a literature review, namely, Particulate Matter Index (PMI), Particulate Number index (PNI), Threshold Sooting index (TSI), Smoke point (SP), Oxygen Extended Sooting Index (OESI), Simplified index 1 and 2 (sPMI 1, sPMI 2). These indices were computed on the fuel matrix and compared on the basis of three main axes. First, the sensitivity to fuel variation.

Countries and regions around the world are tightening emissions regulations in reaction to the increasing awareness of environmental conservation. At the same time, growing concerns about the depletion of raw materials as vehicle ownership continues to increase is prompting automakers to look for ways of decreasing the use of platinum-group metals (PGMs) in the exhaust systems. This research has developed a new catalyst with strong robustness against fluctuations in the exhaust gas and excellent nitrogen oxide (NOx) conversion performance. This catalyst incorporates rhodium (Rh) clusters with a particle size of several nanometers, and stabilized CeO2-ZrO2 solid-solution (CZ) with a pyrochlore crystal structure as a high-volume oxygen storage capacity (OSC) material with a slow O2 storage rate.

The new generation engines currently being developed tend to require cold type spark plugs, which are prone to fouling. This paper describes the development of a new Coil on Plug ignition system that resolves this problem by using the high energy and the fast secondary voltage rise time of a capacitive ignition while maintaining inductive ignition characteristics for good ignitability. To evaluate the effectiveness of the system, spark plug insulation resistance was monitored and cold tests were conducted. The results demonstrated that the new ignition system is remarkably effective: insulation resistance remains high and startability and driveability are unaffected under conditions normally leading to excessive misfires and failure to start with a conventional inductive system. To satisfy environmental concerns, automobile manufactures are increasingly turning to high compression ratio engines in view of their improved performance.

Diesel engines with relatively good fuel economy are known as an effective means of reducing CO₂ emissions. It is expected that diesel engines will continue to expand as efforts to slow global warming are intensified. Diesel particulate and NOx reduction system (DPNR), which was first developed in 2003 for introduction in the Japanese and European markets, shows high purification performance which can meet more stringent regulations in the future. However, it is poisoned by sulfur components in exhaust gas derived from fuel and lubricant. We then developed the sulfur trap DPNR with a sulfur trap catalyst that traps sulfur components in the exhaust gas. High purification performance could be achieved with a small amount of platinum group metal (PGM) due to prevention of sulfur poisoning and thermal deterioration.

The outline of the TOYOTA FCHV-adv is described in this paper. The TOYOTA FCHVadv achieved an approximately 25 percent improvement in vehicle fuel efficiency and about 1.9 times the amount of usable hydrogen in comparison with the previous model. These improvements have enabled almost 2.5 times longer practical cruising range, more than 500 km. The freeze start capabilities of the FCHV-adv were improved by modifying the FC stack and control system. As a result, the FCHV-adv has been capable of starting at a temperature of -30°C. In the future, TOYOTA intends to improve durability and reduce costs.

In conventional gasoline engine vehicles, three-way catalysts are used to simultaneously remove HC, CO and NOx from the exhaust gas. The effectiveness of the catalyst to remove these harmful species depends strongly on the oxygen concentration in the exhaust gas. Deterioration of three-way catalyst results in a reduction in its purification activity and OSC (oxygen storage capacity). In this investigation, additive elements were used to enhance the durability and OSC of the catalyst support material. An optimized formulation of a CeO2-ZrO2 and a ZrO2 material was developed to have excellent durability, improved OSC, enhanced interaction between precious metals and support materials, and increase thermal stability. Using these newly developed support materials, catalysts with increased performance was designed.

The new Toyota FCV “Mirai” has reduced the weight, size, and cost of the high-pressure hydrogen storage system while improving fueling performance. The four 70 MPa tanks used on the 2008 Toyota FCHV-adv were reduced to two new larger diameter tanks. The laminated structure of the tanks was optimized to reduce weight, and a high-strength low-cost carbon fiber material was newly developed and adopted. The size of the high-pressure valve was reduced by improving its structure and a high-pressure sensor from a conventional vehicle was modified for use in a high-pressure hydrogen atmosphere. These innovations helped to improve the weight of the whole storage system by approximately 15% in comparison with Toyota FCHV-adv, while reducing the number of component parts by half and substantially reducing cost. The time required to fuel the FCV was greatly reduced by chilling the filling gas temperature at the hydrogen filling station to −40°C (as per SAE J2601).

A methanol fueled, lean burn system has been developed to improve both specific fuel consumption and NOx emissions. A 1.6L four-cylinder engine with increased compression ratio has been used to develop this system. Three major components of the Toyota Lean Combustion System (T-LCS) have been applied: (1) A helical port with a swirl control valve (2) A lean mixture sensor (3) Timed, multi-point fuel injection. A 2250 lb. Inertia Weight test vehicle has been fitted with this engine, and fuel system materials have been modified. This methanol, lean burn system has improved the fuel economy by about 12% still satisfying the 1986 emission standards of the U.S.A. and Japan. Aldehyde emissions have also been evaluated.

In preparation for compliance with California's SULEV standard and Euro STAGE 4 standard, which will take effect in 2002 and 2005, respectively, we have developed a laminated planar oxygen sensor. The developed sensor has the following characteristics: high thermal conductivity and superior dielectric characteristic, due to direct joining of the heater element alumina substrate and the sensor element zirconia electrolyte; low heat stress at temperature rise, due to optimized heater design; superior sensor protection from water droplets, and improved sensor response, due to optimized arrangement of intake holes in the sensor cover. With these characteristics, the developed oxygen sensor can be activated in 10 seconds after cold start. This report describes the technologies we used to develop the early-activation oxygen sensor.

Automotive catalysts with a good thermal durability have been developed by modifying the composition of additives. The stability of alumina supports against the loss of the surface area depends on the ionic radius and amount of additives. Some lanthanides and alkaline earthes with large ionic radii of 0.11-0. 15nm are most effective. Among these elements, lanthanum improves not only the alumina stability but the catalytic activities of rhodium and cerium oxide. Infrared spectroscopic studies show that lanthanum oxide affects NO adsorbed on Rh to improve the activity for NO reduction. Moreover, lanthanum forms the complex oxide with cerium to improve the activity of cerium oxide. CO pulse reactions on the complex oxide (Ce, La)O2 -x have proved that the oxygen defect in the lattice promotes the diffusion of oxygen atoms to improve the oxide activity.

An on-board particulate matter (PM) sensor, consisting of a gas-permeable electrochemical cell with a porous yttria-stabilized zirconia solid oxide electrolyte, was developed to assist the on-board diagnostics (OBD) system of a vehicle. Exhaust is pumped from the anode side to the cathode side and PM deposited on the anode is instantly oxidized by the catalytic effects of the metal component of the electrode at temperatures higher than 350°C. The PM oxidation reaction occurs at the three-phase boundary between the anode, electrolyte and gas phase, and causes a slight change in the bulk average oxygen concentration, which produces electrochemical polarization by the difference in oxygen partial pressures between the anode and cathode. The developed PM sensor has a detection limit of 2 mg/m₃, at which level will enable PM detection in the OBD system according to the EURO VI regulation.

The second generation methanol lean burn system has been developed. The power unit is a new, 4 valve 1.6L in-line four with compact combustion chambers. Lean misfire limit was extended by using a swirl control valve in the intake port which improves combustion under partial load. Lean mixture control is made by using a signal from lean mixture sensor provided in the exhaust manifold. An EGR system has been newly adopted to reduce NOx emissions and a under-floor type catalyst is also used to reduce formaldehyde emission in the cold transient mode in addition to the manifold type catalyst. Permissible excess air ratio range (PEXARR) was defined and used to indicate the potential for reducing vehicle NOx emissions in engine dynamometer tests to optimize compression ratio, valve timing and swirl ratio and to evaluate the effect of the EGR.

The effects of methanol/cosolvent/gasoline blends on hot weather driveability are surveyed. Results show that startability after engine-off soak drastically deteriorates in an EFI vehicle. By observing the behavior of the fuel in the delivery pipe during hot-start testing and the injected fuel spray shape at high fuel temperature, the authors confirmed that the main cause of this malfunction was the vapor lock in the injector nozzle. The relationship between hot weather driveability and fuel properties is discussed. The gasoline volatility expression commonly used to indicate deterioration in hot weather driveability was found to underestimate the increase in volatility of blended fuels at higher temperatures. A suggestion is made for a modification to the expression to include the effects of methanol blending on volatility characteristics at high temperatures so that EFI vehicle hot-startability may be predicted.

The stability of Diesel/Biodiesel blends can play an important role in deposits formation inside the fuel injection system (FIS). The impact of the stability of FAME/Diesel fuel blends on lacquer deposits formation and on the behavior and reliability of the FIS was investigated using blends of Rapeseed and Soybean methyl esters (RME, SME) and conventional Diesel fuel (volume fractions of RME and SME range from 0 to 20%v/v). Fuels were aged under accelerated conditions and tested on an injection test rig according to an operating cycle developed to provoke injector needle blocking. The soaking duration was found to affect injector fouling. A relationship between the injector fouling tendency and the fuel stability was established. Under current test condition, injectors fouling increased with fuel oxidation measured with Total-Acid-Number.

From the energy security and CO2 reduction point of view, much attention has been paid to the usage of bio-fuel. Recently, highly concentrated ethanol is used in some areas (“E85”; 85% ethanol and 15% gasoline in North America and Sweden, and “ethanol”; 93% ethanol and 7% water in Brazil). In these regions, Flexible Fuel Vehicles FFVs are being introduced that are capable of using fuels with a wide range of ethanol concentrations. Advantages of highly concentrated ethanol in internal combustion engine applications are higher thermal efficiency obtained due to higher octane number, and a reduction of nitrogen oxides due to lower combustion temperatures On the other hand, the latent heat of vaporization for ethanol is greater than gasoline, causing poor cold startability and high NMOG emissions. This paper examines the effect of highly concentrated ethanol on exhaust emissions at cold start in a SI- engine.

In Biodiesel Fuel Research Working Group(WG) of Japan Auto-Oil Program(JATOP), some impacts of high biodiesel blends have been investigated from the viewpoints of fuel properties, stability, emissions, exhaust aftertreatment systems, cold driveability, mixing in engine oils, durability/reliability and so on. In the impact on exhaust emissions, the impact of high biodiesel blends into diesel fuel on diesel emissions was evaluated. The wide variety of biodiesel blendstock, which included not only some kinds of fatty acid methyl esters(FAME) but also hydrofined biodiesel(HBD) and Fischer-Tropsch diesel fuel(FTD), were selected to evaluate. The main blend level evaluated was 5, 10 and 20% and the higher blend level over 20% was also evaluated in some tests. The main advanced technologies for exhaust aftertreatment systems were diesel particulate filter(DPF), Urea selective catalytic reduction (Urea-SCR) and the combination of DPF and NOx storage reduction catalyst(NSR).

Premixed diesel combustion modes including low temperature combustion and MK combustion are expected to realize smokeless and low NOx emissions. As ignition must be delayed until after the end of fuel injection to establish these combustion modes, methods for active ignition control are being actively pursued. It is reported that alcohols including methanol and ethanol strongly inhibit low temperature oxidation in HCCI combustion offering the possibility to control ignition with alcohol induction. In this research improvement of diesel combustion and emissions by ethanol intake port injection for the promotion of premixing of the in-cylinder injected diesel fuel, and by increased EGR for the reduction of combustion temperature.