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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.

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 a Diesel Oxidation Catalyst (DOC) and Catalyzed Soot Filter (CSF) system, the DOC is used to oxidize additional fuel injected into the cylinder and/or exhaust pipe in order to increase the CSF's inlet temperature during soot regeneration. The catalyst's hydrocarbon (HC) oxidation performance is known to be strongly affected by the HC species present and the catalyst design. However, the engine operating conditions and additive fuel supply parameters also affect the oxidation performance of DOCs, but the effects of these variables have been insufficiently examined. Therefore, in this study, the oxidation performance of a DOC was examined in experiments in which both exhaust gas recirculation (EGR) levels and exhaust pipe injection parameters were varied. The results were then analyzed and optimal conditions were identified using modeFRONTIER.

Heavy soot deposition in wall-flow type diesel particulate filters reduces engine output and fuel efficiency. This necessitates forced regeneration to oxidize soot via exothermic reactions in a diesel oxidation catalyst upstream of the Diesel Particulate Filter (DPF). Soot loading in the wall of the DPF during forced regeneration causes much greater pressure drops than cake deposition, which is undesirable because high pressure drops reduce engine performance. We show that the description of soot deposition using a DPF model is improved by using a shrinking sphere soot oxidation sub-model. We then use this revised model to analyze cake deposition during forced regeneration, and to study the effects of varying the forced regeneration temperature and duration on the local soot reaction rate and soot mass distribution in the radial and longitudinal directions of the DPF channels during forced regeneration.

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.

For diesel emission control systems containing a Diesel Oxidation Catalyst (DOC) and a Catalyzed Soot Filter (CSF) the DOC is used to oxidize the additional fuel injected into the cylinder and/or the exhaust pipe for the purpose of increasing the CSF inlet temperature during the soot regeneration. Hydrocarbon (HC) oxidation performance of the DOC is affected by HC species as well as a catalyst design, i.e., precious metal species, support materials and additives. How engine-out HC species vary as a function of fuel supply conditions is not well understood. In addition, the relationship between catalyst design and oxidation activity of different hydrocarbon species requires further study. In this study, diesel fuel was supplied by in-cylinder, post injection and exhaust HC species were measured by a gas chromatograph-mass spectrometry (GC-MS) and a gas analyzer. The post injection timing was set to either 73°, 88° or 98° ATDC(after top dead center).

A urea SCR system was combined with a DPF system to reduce NOx and PM in a four liters turbocharged with intercooler diesel engine. Significant reduction in NOx was observed at low exhaust gas temperatures by increasing NH3 adsorption quantity in the SCR catalyst. Control logic of the NH3 adsorption quantity for transient operation was developed based on the NH3 adsorption characteristics on the SCR catalyst. It has been shown that NOx can be reduced by 75% at the average SCR inlet gas temperature of 158 deg.C by adopting the NH3 adsorption quantity control in the JE05 Mode.

Three types of combustion chamber configurations (Types A, B, and C) with compression ratio lower than that of the baseline were tested for improved performance and exhaust gas emissions from an inline-four-cylinder 1.7-liter common-rail diesel engine manufactured for use with passenger cars. First, three combustion chambers were examined numerically using CFD code. Second, engine tests were conducted by using Type B combustion chamber, which is expected to have the best performance and exhaust gas emissions of all. As a result, 80% of NOx emissions at both low and medium loads at 1500 rpm, the engine speed used frequently in the actual city driving, improved with nearly no degradation in smoke emissions and brake thermal efficiency. It was shown that a large amount of cooled EGR enables NOx-free combustion with long ignition delay.

Homogeneous Charge Compression Ignition (HCCI) is effective for the simultaneous reduction of soot and NOx emissions in diesel engine. In general, high octane number fuels (gasoline components or gaseous fuels) are used for HCCI operation, because these fuels briefly form lean homogeneous mixture because of long ignition delay and high volatility. However, it is necessary to improve injection systems, when these high octane number fuels are used in diesel engine. In addition, the difficulty of controlling auto-ignition timing must be resolved. On the other hand, HCCI using diesel fuel (diesel HCCI) also needs ignition control, because diesel fuel which has a low octane number causes the early ignition before TDC. The purpose of this study is the ignition and combustion control of diesel HCCI. The effects of parameters (injection timing, injection pressure, internal/external EGR, boost pressure, and variable valve timing (VVT)) on the ignition timing of diesel HCCI were investigated.

Synthetic fuels can significantly improve the combustion and emission characteristics of heavy-duty diesel engines toward decarbonizing heavy-duty propulsion systems. This work analyzes the effects of engine operating conditions and synthetic fuel properties on spray, combustion, and emissions (soot, NOx) using a supercharging single-cylinder engine experiment and KIVA-4 code combined with CHEMKIN-II and in-house phenomenological soot model. The blended fuel ratio is fixed at 80% diesel and 20% n-paraffin by volume (hereafter DP). Diesel, DP1 (diesel with n-pentane C5H12), DP2 (diesel with n-hexane C6H14), and DP3 (diesel with n-heptane C7H16) are used in engine-like-condition constant volume chamber (CVC) and engine experiments. Boosted engine experiments (1080 rpm, common-rail injection pressure 160 MPa, multi-pulse injection) are performed using the same DP fuel groups under various main injection timings, pulse-injection intervals, and EGR = 0-40%.

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.

A mixed time-scale subgrid large eddy simulation was used to simulate mixture formation, combustion and soot formation under the influence of turbulence during diesel engine combustion. To account for the effects of engine wall heat transfer on combustion, the KIVA code's standard wall model was replaced to accommodate more realistic boundary conditions. This were carried out by implementing the non-isothermal wall model of Angelberger et al. with modifications and incorporating the log law from Pope's method to account for the wall surface roughness. Soot and NOx emissions predicted with the new model are compared to experimental data acquired under various EGR conditions.

Three-way catalyst (TWC) converters can purify harmful substances, such as carbon monoxide, nitrogen oxides, and hydrocarbons, from the exhaust gases of gasoline engines. However, large amounts of these substances may be emitted before the TWC reaches its light-off temperature during cold starts, and its performance may be impaired by thermal deterioration during high-load driving. In this work, a simulation model was developed using axisuite commercial software by Exothermia S.A to predict the light-off conversion performance of Pd/CeO2-ZrO2-Al2O3 catalysts with different degrees of thermal deterioration. The model considered detailed surface reactions and the main factor of the deterioration mechanism. In the detailed reaction mechanism, adsorption, desorption, and surface reactions of each gas species at active sites of the platinum group metal (PGM) particles were considered based on the Langmuir-Hinshelwood mechanism.

Urea-SCR system has a high NOx reduction potential in the steady-state diesel engine operation. In complicated transient operations, however, there are certain problems with the urea-SCR system in that NOx reduction performance degrades and adsorbed NH3 would be emitted. Here, optimum urea injection methods and exhaust bypass control to overcome these problems are studied. This exhaust bypass control enables NO/NOx ratio at the inlet of SCR catalyst to be decreased widely, which prevents over production of NO2 at the pre-oxidation catalyst. Steady-state and simple transient engine tests were conducted to clarify NOx reduction characteristics when optimum urea injection pattern and exhaust bypass control were applied. In simple transient test, only the engine load was rapidly changed for obtaining the fundamental knowledge concerning the effect of those techniques.

In our previous reports, we proposed a new focusing engine with high thermal efficiency based on relatively-silent high compression and nearly-complete air-insulation effect, which employs pulsed multi-jets of gas collided around chamber center. Local compression level due to the gas jets colliding around chamber center before reaction can be varied from zero to 100MPa and 3000K, by changing the number of jets and intake pressure. Relatively-silent high compression is possible, because region around chamber wall is at pressure level of traditional engines. This is suitable for various usages of automobiles, aerocrafts, and rockets, and also for various fuels including hydrogen, because high compression around chamber center leads to stable auto-ignition and potential of low NOx at very lean burning operation. We developed two types of focusing compression engines, without and with piston. For the new engine without piston, we obtained nearly-complete air-insulation and high thrust.

The authors have previously proposed a plume ignition and combustion concept (i.e., PCC combustion), in which a hydrogen fuel is directly injected to the combustion chamber in the latter half of compression stroke and forms a richer mixture plume. By combusting the plume, both cooling losses and NOx formation are reduced. In this study, thermal efficiency was substantially improved and NOx formation was reduced with PCC combustion by optimizing such characteristics as direction and diameter of the jets in combination with combustion of lean mixture. Output power declined due to the lean mixture, however, was recovered by supercharging while keeping NOx emissions at the same level. Thermal efficiency was further improved by slightly re-optimizing the jet conditions.

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 recent and future trends of energy for heavy-duty vehicles are considered e-fuel, H2, and electricity, and the Selective Catalytic Reduction (SCR) system is necessary for achieving the goals of zero-emission internal combustion engines that use e-fuel and H2 as a fuel. The Japanese automotive industry uses a Cu-zeolite based SCR catalyst since Vanadium is designated as a specific chemical substance, which the Ministry of Environment prohibits its release into the atmosphere. This study attempted purification rate improvement by controlling the NH3 supply with a mini-reactor and by simulated exhaust gas. Specifically, the experiment was done by examining the effect of the pulse amplitude, frequency, and duty ratio on the purification rate by supplying the NH3 pulse injection to the test piece Cu-chabazite catalyst. Additionally, the results of the reactor experiment were validated by numerical simulation considering the detailed surface reaction processes on the catalyst.

Urea SCR (Selective Catalytic Reduction) exhaust after-treatment systems are one of the most promising measures to reduce NOx emissions from diesel engines. Both Cu-zeolite (Cu-SCR) and Fe-zeolite (Fe-SCR) urea SCR systems have been studied extensively but not many detailed studies have been conducted on the combination of both systems. Thus, we carried out studies on such Combined-SCR systems and their capability to reduce NOx under various engine operating conditions. We also conducted transient engine tests using different catalyst systems to compare their performance. The results show that combined-SCR systems can reduce NOx more effectively than Fe-SCR or Cu-SCR alone. The best NOx reduction performance was achieved at a Cu ratio of 0.667 (i.e. Fe: Cu =1: 2). Combined-SCR thus apparently benefits from the characteristics of both Cu-SCR and Fe-SCR, allowing it to reduce NOx over a wide range of operating conditions.

N₂O is known to have a significantly high global warming potential. We measured N₂O emissions in engine-bench tests by changing the NO/NH₃ ratio and exhaust gas temperature at the oxidation catalyst inlet in a heavy-duty diesel engine equipped with a urea SCR (selective catalytic reduction) system. The results showed that the peak N₂O production ratio occurred at an exhaust gas temperature of around 200°C and the maximum value was 84%. Moreover, the N₂O production ratio increased with increasing NO/NH₃. Thus, we concluded that N₂O is produced via the NO branching reaction. Based on our results, two methods were proposed to decrease N₂O formation. At low temperatures ~200°C, NO should be reduced by controlling diesel combustion to lower the contribution of NO to N₂O production. This is essential because the SCR system cannot reduce NOx at low temperatures.