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Copper ion-exchanged ZSM-5 zeolite catalyst, which reduces nitrogen oxides (NOx) in the presence of oxygen and hydrocarbons, was applied to actual diesel engine exhaust. Copper ion-exchanged ZSM-5 zeolite effectively reduced NOx by 25% in normal engine operation, and by 80% when hydrocarbons in the exhaust were increased. Water in the exhaust gas decreased the NOx reduction efficiency, but oxygen and sulfur appeared to have only a small effect. Maximum NOx reduction was observed at 400°C irrespective of hydrocarbon species, and did not decrease with space velocity up to values of 20,000 1/h. THE PURPOSE of this paper is to evaluate the possibilities and problems in catalytic reduction of NOx in actual diesel engine exhaust. Here, a copper ion-exchanged ZSM-5 zeolite (Cu-Z) catalyst was applied to diesel engine exhaust to examine the dependency of the NOx reduction efficiency on temperature and space velocity. The effects of oxygen, water and hydrocarbons were also examined.

In a DI diesel engine, THC emissions increase significantly with lower compression ratios, a low coolant temperature, or during the transient state. During the transient after a load increase, THC emissions are increased significantly to very high concentrations from just after the start of the load increase until around the 10th cycle, then rapidly decreased until the 20th cycle, before gradually decreasing to a steady state value after 1000 cycles. In the fully-warmed steady state operation with a compression ratio of 16 and diesel fuel, THC is reasonably low, but THC increases with lower coolant temperatures or during the transient period just after increasing the load. This THC increase is due to the formation of over-lean mixture with the longer ignition delay and also due to the fuel adhering to the combustion chamber walls. A low distillation temperature fuel such as normal heptane can eliminate the THC increase.

Spark knock suppression with hydrogen addition was investigated at two engine speeds (2000 rpm and 4800 rpm). The experimental results showed that the spark knock is strongly suppressed with increasing hydrogen fraction at 2000 rpm while the effect is much smaller at 4800 rpm. To explain these results, chemical kinetic analyses with a two-zone combustion model were performed. The calculated results showed that the heat release in the end gas zone rises in two stages with a remarkable appearance of low temperature oxidation (LTO) at 2000 rpm, while a single stage heat release without apparent LTO process is presented at 4800 rpm due to the shorter residence time in the low temperature region.

The thermal cracking and polyaromatic hydrocarbon (PAH) formation processes of dimethyl ether (DME), ethanol, and ethane were investigated with chemical kinetics to determine the soot formation mechanism of oxygenated fuels. The modeling analyzed three processes, an isothermal constant pressure condition, a temperature rising condition under a constant pressure, and an unsteady condition approximating diesel combustion. With the same mole number of oxygen atoms, the DME rich mixtures form much carbon monoxide and methane and very little non-methane HC and PAH, in comparison with ethanol or ethane mixtures. This suggests that the existence of the C-C bond promotes the formation of PAH and soot.

Light naphtha, which exhibits two-stage ignition, was induced from the intake manifold for ignition enhancement and a low ignitability fuel or water, which does not exhibit low temperature oxidation, was directly injected early in the compression stroke for ignition suppression in an HCCI engine. Their quantitative balance was flexibly controlled to optimize ignition timing according to operating condition. Ultra-low NOx and smokeless combustion without knocking or misfiring was realized over a wide operating range. Alcohols inhibit low temperature oxidation more strongly than other oxygenated or unoxygenated hydrocarbons, water, and hydrogen. Chemical kinetic modeling for methanol showed a reduction of OH radical concentration before the onset of low temperature oxidation, and this may be the main mechanism by which alcohols inhibit low temperature oxidation.

The influence of aromatic content in fuels on the soot and NOx emissions from a diesel engine was analyzed under controlled ignition lags with spark-assisted operation. Monocyclic aromatic hydrocarbons and n-hexane mixtures were used as fuels, and the aromatic content was varied from 0 to 75 v-%. The experiments showed that, at the same equivalence ratio and regardless of the molecular structure of the fuel, the soot concentration in the exhaust gas could be described by a linear-combination function with two variables representing the ignition lag and C/H atom-ratio of the fuels. For unchanged ignition lags, the soot emissions increased linearly with increased C/H atom-ratios, which are controlled by the aromatic content. The degree of increase in soot emissions with increasing C/H atom-ratio decreased with decreasing equivalence ratios. The NOx emission increased slightly with increases in the C/H atom-ratio and ignition lag.

Unregulated emissions from a DI diesel engine with ultra-high EGR low temperature combustion were analyzed using Fourier transform infrared (FTIR) spectroscopy and the reduction characteristics of both regulated and unregulated emissions by two exhaust catalysts were investigated. With ultra-high EGR suppressing the in-cylinder soot and Nox formation as well as with the exhaust catalysts removing the engine-out THC and CO emissions, clean diesel operation in terms of ultra-low regulated emissions (Nox, PM, THC, and CO) is established in an operating range up to 50% load. To realize smokeless low temperature combustion at higher loads, EGR has to be increased to a rate with the overall (average) excess air ratio less than the stoichiometric ratio.

This paper is a systematic investigation of the effects of combustion and injection systems on hydrocarbon(HC) and particulate emissions from a DI diesel engine. Piston cavity diameter, swirl ratio, number of injection nozzle openings, and injection direction are varied as the experimental parameters, and the constituents in the soluble organic fraction (SOF) of the particulate were analyzed. The results show that the emission characteristics of deep dish chambers greatly differ from those of shallow dish chambers varying with the number of nozzle openings, the injection direction, and swirl intensity. The HC analysis shows mainly low carbon number gaseous HC constituents, and there is a tendency towards increasing polynucleation of polynuclear aromatic hydrocarbon(PAH) in SOF with increasing soot formation.

In a natural gas fueled engine ignited by diesel fuel, the addition of hydrogen to the engine could be a possible way to improve thermal efficiency and reduce unburned methane which has a warming potential many times that of carbon dioxide as it promotes a more rapid and complete combustion. This study carried out engine experiments using a single cylinder engine with natural gas and hydrogen delivered separately into the intake pipe, and with pilot-injection of diesel fuel. The percentages of hydrogen in the natural gas-hydrogen mixtures were varied from 0% to 50% of the heat value. The results showed that the hydrogen addition has an insignificant effect on the ignition delay of the diesel fuel and that it shortens the combustion duration. The increase in the hydrogen ratio decreased the unburned hydrocarbon emissions more than the reduction of the amount of natural gas that was replaced by the hydrogen.

The influence of the molecular structure of hydrocarbon fuels on soot, SOF, and NOx emissions from a diesel engine was analyzed while ignition delay and other physical fuel properties were kept constant. Mixtures of normal paraffin (n-tetradecane) and iso-paraffin (heptamethylnonane) were used as a base fuel and one of 5 kinds of hydrocarbons including mono-aromatic, di-aromatic, and non-aromatic was added. The aromatic content varied in the range of 0-60 vol % for the mono-aromatic fuels and 0-40 vol % for the di-aromatic fuels. The experimental results showed that regardless of the molecular structure of the fuel, both particulate and NOx emissions increased linearly with the C/H atomic ratio of the fuels under constant ignition lag. The increase in particulate emissions with C/H atomic ratio was caused by increases in dry soot. The SOF, THC, and BSEC were little affected by the C/H atomic ratio and molecular structure of the fuels.

Smokeless and ultra low NOx combustion without knocking in a dual-fuel diesel engine with induced LPG as the main fuel was established with a uniquely developed piston cavity divided by a lip in the sidewall. A small quantity of diesel fuel was directly injected at early compression stroke into the lower part of the cavity as an ignition source for this confined area, and this suppressed explosively rapid combustion just after ignition and spark-knock like combustion at later stage. A combination of the divided cavity, EGR, and intake air throttling was effective to simultaneously eliminate knocking, and reduce THC and NOx significantly.

This paper provides information on measurements and measurement techniques for particulate and unburnt hydrocarbon emissions from diesel engines. A dilution mini-tunnel was used to characterize the effects of the dilution ratio and sample temperature on the total particulate mass and soluble organic fraction(SOF) constituents. Increasing the sample temperature resulted in changes in the polynuclear aromatic hydrocarbon(PAH) constituents in SOF. The SOF was isolated by column chromatography, and the PAH fraction was determined by high performance liquid chromatography(HPLC). Column chromatography with silicagel, an octadecylsilan-bonded column, and keeping at high temperatures improved the analytical efficiency of HPLC. The gaseous hydrocarbon in raw exhaust was analysed by GC with FID. The temperature of the sample glass syringe affected measurements of high boiling point hydrocarbon constituents.

The chemical composition of marketed gasoline varies depending on the crude oil, refinery processes of oil refineries, and season. The combustion characteristics of HCCI engines are very sensitive to the fuel composition, and a fuel standard for HCCI is needed for HCCI vehicles to be commercially viable. In this paper, the effects of the structure of the fuel components on auto-ignition characteristics and HCCI engine performance were investigated. The engine employed in the experiments is a research, single cylinder HCCI engine with a compression ratio of 14.7. The intake manifold was equipped with a heater attachment allowing control of the intake air temperature up to 150 °C at 2000 rpm. Thirteen kinds of hydrocarbons, 4 kinds of paraffins, 3kinds of naphthenes, and 6 kinds of aromatics, were chosen for the investigation, and 20vol% of each of the pure hydrocarbons was blended with the 80 vol% of PFR50 fuel.

Time resolved changes in unburned hydrocarbon emissions and their components were investigated in a DI diesel engine with a specially developed gas sampling system and gas chromatography. The tested transient operations include starting and increasing loads. At start-up with high equivalence ratios the total hydrocarbon (THC) at first increased, and after a maximum gradually decreased to reach a steady state value. Reducing the equivalence ratio of the high fueling at start-up and shortening the high fueling duration are effective to reduce THC emissions as long as sufficient startability is maintained. Lower hydrocarbons, mainly C1-C8, were the dominant components of the THC and mainly determined the THC behavior in the transient operations while the proportion of hydrocarbon (HC) components did not significantly change. The unregulated toxic substances, 1,3 butadiene and benzene were detected in small quantities.