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In this study, reaction path analysis and modeling of NOx reduction phenomena by fast SCR reaction on a Cu-chabazite catalyst were conducted, considering the formation and decomposition of ammonium nitrate (NH4NO3). White crystals of NH4NO3 decompose at temperatures < 200 °C. Thus, the reaction behavior changes at 200 °C under fast SCR reaction conditions. NH4NO3 formation can occur on both Cu sites and Brønsted acid sites, which are active sites for NOx reduction in the Cu-chabazite catalyst, but it is unclear where NH4NO3 accumulates on the catalyst. Analyses using catalyst test pieces with different active sites were performed to estimate this accumulation. The results suggested that NH4NO3 accumulation does not depend on the presence of either Cu sites or Brønsted acid sites. Therefore, it is assumed that NH4NO3 can be accumulated everywhere on the catalyst, including on the zeolite framework. This phenomenon was included in the model as formation/accumulation sites S'.

In this study, reaction path analysis and modeling of NOx reduction phenomena by selective catalytic reduction (SCR) with NH3 over a Cu-chabazite catalyst were conducted considering changes in the valence state of Cu sites and local structure due to differences in ligands to the Cu sites. The analysis showed that in the Cu-chabazite catalyst, NOx was mainly reduced by adsorbed NH3 on divalent Cu sites accompanied by a change in valence state of Cu from divalent to monovalent. It is known that the activation energy of NOx reduction on a Cu-chabazite catalyst changes between low temperatures ≤ 200 °C and mid to high temperatures ≥ 300 °C. To express this phenomenon, a reversible hydrolysis reaction based on the difference in coordination state of hydroxyl groups (OH−) to Cu sites at low and high temperatures was introduced into the model.

This paper describes a method for estimating constants related to NH3 gas diffusion phenomena to the active sites in a selective catalytic reduction diesel particulate filter (SCR/DPF) catalyst. A simple one-dimensional NH3 gas diffusion model based on the pore structure inside the catalyst was developed and used to estimate the intracrystalline diffusion coefficient. It was shown that the estimated value agreed well with experimental data.

The NOx-reducing activity of a Cu-chabazite selective catalytic reduction (SCR) catalyst was analyzed over a wide temperature range. The analysis was based on the ammonia SCR (NH3-SCR) mechanism and accounted for Cu redox chemistry and reactions at Brønsted acid sites. The reduction of NOx to N2 (De-NOx) at Cu sites was found to proceed via different paths at low and high temperatures. Consequently, the rate-limiting step of the SCR reaction at Cu sites varied with the temperature. The rate of NOx reduction at Cu sites below 200°C was determined by the rate of Cu oxidation. Conversely, the rate of NOx reduction above 300°C was determined by the rate of NH3 adsorption on Cu sites. Moreover, the redox state of the active Cu sites differed at low and high temperatures. To clarify the role of the chabazite Brønsted acid sites, experiments were also performed using a H-chabazite catalyst that lacks Cu sites.

Ammonia-selective catalytic reduction (SCR) systems have been introduced commercially in diesel vehicles, however catalyst systems with higher conversion efficiency and better control characteristics are required to know the actual emissions during operation and the emissions in random test cycles. Computational fluid dynamics (CFD) is an effective approach when applied to SCR catalyst development, and many models have been proposed, but these models need experimental verification and are limited in the situations they apply to. Further, taking account of redox cycle is important to have better accuracy in transient operation, however there are few models considering the cycle. Model development considering the redox reactions in a zeolite catalyst, Cu-ZSM-5, is the object of the research here, and the effects of exhaust gas composition on the SCR reaction and NH3 oxidation at high temperatures are investigated.

Experimental studies were carried out to investigate the effect of soot deposition on NOx purification phenomena in an ammonia selective catalytic reduction coated diesel particulate filter (SCR/DPF) catalyst. To study soot deposition effects on the chemical reactions and mass transfer, two types of testing device were used. A synthetic gas bench enabling tests to be conducted with temperature and flow rate ranges relevant to real driving conditions was used to investigate the soot influence on reduction of NOx to N2 (DeNOx). A micro-reactor that removed the effect of soot deposition on mass transfer in the catalyst layer was used to analyze chemical reactions on a soot surface and their interaction with the SCR catalyst. A filter test brick of a Cu-zeolite SCR/DPF catalyst and a powder catalyst were used for the synthetic gas bench and micro-reactor tests, respectively. Engine soot was sampled in all the tests.

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.

Water and diesel fuel emulsions containing 13% and 26% water by volume were investigated in a modern diesel engine with relatively early pilot injection, supercharging, and cooled EGR. The heat release from the pilot injection with water emulsions is retarded toward the top dead center due to the poor ignitability, which enables larger pilot and smaller main injection quantities. This characteristic results in improvements in the thermal efficiency due to the larger heat release near the top dead center and the smaller afterburning. With the 26% water emulsion, mild, smokeless, and very low NOx operation is possible at an optimum pilot injection quantity and 15% intake oxygen with EGR at or below 0.9 MPa IMEP, a condition where large smoke emissions are unavoidable with regular unblended diesel fuel. Heat transfer analysis with Woschni's equation did not show the decrease in cooling loss with the water emulsion fuels.

To determine the engine noise reduction methods, an engine noise research was conducted experimentally with a PCCI diesel engine. The engine employed in the experiments was a supercharged, single-cylinder DI diesel engine with a high pressure common rail fuel injection system. The engine noise was sampled by two microphones and the sampled engine noise was averaged and analyzed by an FFT sound analyzer. The engine was equipped with a pressure transducer and the combustion noise was calculated from the power spectrum of the FFT analysis of the in-cylinder pressure wave form and the cross power spectrum of the sound pressure of the engine noise. It is well known that the maximum pressure rise rate is the main parameter related to the engine noise. The PCCI engine was operated at a 1.0 MPa/°CA maximum pressure rise rate to eliminate the effects of the maximum pressure rise rate, and parameters which had the dominant effect on engine noise and combustion noise were determined.

Combustion and exhaust gas emissions of alcohol and vegetable oil blends including a 20% ethanol + 40% 1-butanol + 40% vegetable oil blend and a 50% 1-butanol + 50% vegetable oil blend were examined in a single cylinder, four-stroke cycle, 0.83L direct injection diesel engine, with a supercharger and a common rail fuel injection system. A 50% diesel oil + 50% vegetable oil blend and regular unblended diesel fuel were used as reference fuels. The boost pressure was kept constant at 160 kPa (absolute pressure), and the cooled low pressure loop EGR was realized by mixing with a part of the exhaust gas. Pilot injection is effective to suppress rapid combustion due to the lower ignitability of the alcohol and vegetable oil blends. The effects of reductions in the intake oxygen concentration with cooled EGR and changes in the fuel injection pressure were investigated for the blended fuels.

The HCCI engine offers the potential of low NOx emissions combined with diesel engine like high efficiency, however HCCI operation is restricted to low engine speeds and torques constrained by narrow noise (HCCI knocking) and misfiring limits. Gasoline like fuel vaporizes and mixes with air, but the mixture may auto-ignite at the same time, leading to heavy HCCI knocking. Retarding the CA50 (the crank angle of the 50% burn) is well known as a method to slow the maximum pressure rise rate and reduce HCCI knocking. The CA50 can be controlled by the fuel composition, for example, di-methyl ether (DME), which is easily synthesized from natural gas, has strong low temperature heat release (LTHR) characteristics and ethanol generates strong LTHR inhibitor effects. The utilization of DME-ethanol binary blended fuels has the potential to broaden the HCCI engine load-speed range.

To allow the HCCI vehicles to enter the market in the future, it is important to investigate the combustion deviations and operational range differences between the same research octane number fuels. In this paper, eighteen kinds of two hydrocarbon blended fuels, which were composed of n-heptane and another hydrocarbon, such as iso-octane, diisobutylene, 4-methyl-1-pentene, toluene or cyclopentane, were evaluated. Those fuels were blended to have the same research octane numbers of 75, 80, 85 and 90 by changing the blending volume ratio of n-heptane and counterpart hydrocarbon. Intake air was supercharged to 155 kPa abs and its temperature was kept at 58 °C. The HCCI engine was operated at 1000 rpm. Neither hot EGR, nor any other combustion stratification system was utilized in order to investigate the purely hydrocarbon effects on HCCI combustion.