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In recent years, emission regulations have become more stringent as a result of increased environmental awareness in each region of the world. For lean-burn diesel engines, since it is not possible to use three-way catalytic converters, reducing NOX emissions is a difficult technical challenge. To respond to these strict regulations, an exhaust gas aftertreatment system was developed, featuring a lean NOX catalyst (LNC) that uses a new chemical reaction mechanism to reduce NOX. The feature of the new LNC is the way it reduces NOX through an NH3-selective catalytic reduction (SCR), in which NOX adsorbed in the lean mixture condition is converted to NH3 in the rich mixture condition and reduced in the following lean mixture condition. Thus, the new system allows more efficient reduction of NOX than its conventional counterparts. However, an appropriate switching control between lean and rich mixture conditions along with compensation for catalyst deterioration was necessary.

In recent years, emission regulations have become more stringent as a result of increased environmental awareness in each region of the world. For diesel engines, reducing NOX emissions is a difficult technical challenge.[1],[2],[3],[4]. To respond to these strict regulations, an exhaust gas aftertreatment system was developed, featuring a lean NOX catalyst (LNC) that uses a new chemical reaction mechanism to reduce NOX. The feature of the new LNC is the way it reduces NOX through an NH3-selective catalytic reduction (SCR), in which NOX adsorbed in the lean mixture condition is converted to NH3 in the rich mixture condition and reduced in the following lean mixture condition. Thus, the new system allows the effective reduction of NOX. However, in order to realize cleaner emission gases, precise engine control in response to the state of the exhaust aftertreatment system is essential.

Lean-burn is an effective means of reducing CO2 emissions. To date, Homogenous Lean Charge Spark Ignition (HLSI) combustion, which lowers emissions of both CO2 and NOx, has been studied. Although HLSI realizes lower emission, it is a major challenge for lean-burn engines to meet SULEV regulations, so we have developed a new aftertreatment system for HLSI engines. It consists of three types of catalysts that have different functions, as well as special engine control methods. As the first stage in achieving SULEV emissions, this study focused on enhancing performance under lean conditions. HLSI engine exhaust gases contain high concentrations of hydrocarbons, including a large amount of paraffin, which are difficult to purify, rather than low concentrations of NOx. Therefore, the key point in low emissions is to purify not only NOx, but also high concentrations of paraffin at the same time.

Polymer electrolyte membrane fuel cell (PEFC) systems for fuel cell vehicles (FCVs) require both performance and durability. Carbon is the typical support material used for PEFC catalysts. However, hydrogen starvation at the anode causes high electrode potential states (e.g., 1.3 V with respect to the reversible hydrogen electrode) that result in severe carbon support corrosion. Serious damage to the carbon support due to hydrogen starvation can lead to irreversible performance loss in PEFC systems. To avoid such high electrode potentials, FCV PEFC systems often utilize cell voltage monitor systems (CVMs) that are expensive to use and install. Simplifying PEFC systems by removing these CVMs would help reduce costs, which is a vital part of popularizing FCVs. However, one precondition for removing CVMs is the adoption of a durable support material to replace carbon.

Three-way catalyst shows high performance under stoichiometric atmosphere. The CeO2-ZrO2 based materials (CZ) are added as a buffer of O2 concentration. To improve the catalyst performance the larger O2 storage capacity (OSC) are needed. Theoretically, the sulfur oxidation-reduction reaction moves oxygen 8 times larger than cerium. We focused on this phenomenon and synthesized Ln2O2SO4 as a new OSC material. The experimental result under model gas shows that the OSC of Ln2O2SO4 is 5 times lager than CZ.

Performance improvements were studied for the diesel particulate and NOx reduction system (DPNR), a system that simultaneously reduces NOx and Particulate Matter (PM) from diesel engine exhaust gas. The experimental system (hereinafter called the “dual DPNR”) consists of two DPNR catalysts arranged in parallel, each provided with an exhaust throttle valve downstream to control the exhaust gas flow to the catalyst, plus a fuel injector that precisely controls the air-fuel ratio and the catalyst bed temperature. The fuel injector is used to supply a rich mixture to the DPNR catalyst, and the flow of exhaust gas is switched between the two catalysts by operating the exhaust throttle valves alternately. Tests were conducted with the engine running at steady state. The results indicated that the NOx reduction performance dramatically improved and the loss of fuel economy from the NOx reduction reduced.

The development of an alternative oxygen reduction electrocatalyst to platinum based electrocatalysts is critical for practical use of the polymer electrolyte membrane fuel cell (PEMFC). Transition metal sulfide chalcogenides have recently been reported as a possible candidate for Pt replacement. Our work focused on chalcogenides composed of ruthenium, molybdenum, and sulfur (RuMoS). We elucidate the factors affecting electrocatalytic activity of carbon supported RuXMoY SZ catalyst. This was demonstrated through a correlation of oxygen reduction reaction (ORR) activity of the catalysts with structural changes resulting from designed changes in sulfur composition in the catalysts.

A new after-treatment system called DPNR (Diesel Particulate-NOx Reduction System) has been developed for simultaneous and continuous reduction of particulate matter (PM) and nitrogen oxides (NOx) in diesel exhaust gas. This system consists of both a new catalytic technology and a new diesel combustion technology which enables rich operating conditions in diesel engines. The catalytic converter for the DPNR has a newly developed porous ceramic structure coated with a NOx storage reduction catalyst. A fresh DPNR catalyst reduced more than 80 % of both PM and NOx. This paper describes the concept and performance of the system in detail. Especially, the details of the PM oxidation mechanism in DPNR are described.

Recently, much research has been carried out on secondary O2 feedback which performs control based on the output from a secondary O2 sensor (HEGO sensor). In this research it has been found that, regardless of catalyst aging conditions, the HEGO sensor output indicates 0.6 V when the catalyst reduction rate is maintained at the optimum level. Therefore, based on this relationship, we designed an accurate secondary O2 feedback with the aim of reducing emissions by stabilizing the HEGO sensor output to 0.6 V. In order to realize this control, it was necessary to solve the three problems of nonlinear catalyst characteristics, dead time characteristics, and changes in dynamic characteristics due to catalyst aging conditions. Therefore, these problems were solved using the modeling approach of robust control and a new robust adaptive control named Prediction and Identification Type Sliding Mode Control.

This emission reduction technique has been researched on motorcycles equipped with a four-cylinder, liquid-cooled engine of 1100cm3 displacement in order to comply with the EURO-3 emission regulation. The EURO-3 emission regulation will be enforced in Europe beginning in year 2006. Compared to the EURO-2 regulation, reduction of cold-start HC and reduction of NOx from the extra-urban driving cycle are the main issues for EURO-3 compliance. The hydrocarbon reduction during cold-starting was achieved by the method of early catalyst activation using a combination of an Idle Air Control Valve system (IACV), ignition-retard, and atomization of fuel spray. In the extra-urban driving cycle, the fine controlled air-fuel ratio reduced. In addition, optimization of the number of three-way catalyst cells and their capacity also reduced NOx. Moreover, power loss decline caused by increased exhaust resistance due to increasing the catalyst size was avoided by optimizing the catalyst location.

The details of Di-Air, a new NOx reduction system using continuous short pulse injections of hydrocarbons (HC) in front of a NOx storage and reduction (NSR) catalyst, have already been reported. This paper describes further studies into the deNOx mechanism, mainly from the standpoint of the contribution of HC and intermediates. In the process of a preliminary survey regarding HC oxidation behavior at the moment of injection, it was found that HC have unique advantages as a reductant. The addition of HC lead to the reduction or metallization of platinum group metals (PGM) while keeping the overall gas atmosphere in a lean state due to adsorbed HC. This causes local O₂ inhibition and generates reductive intermediate species such as R-NCO. Therefore, the specific benefits of HC were analyzed from the viewpoints of 1) the impact on the PGM state, 2) the characterization of intermediate species, and 3) Di-Air performance compared to other reductants.

Just as CO2 reduction is required of four wheeled vehicles for environmental protection, similar environmental concerns drive the development of motorcycle oil technology. Zinc dialkyldithiophosphate (Zn-DTP) type additives are widely used for engine oil formulations. However, phosphorus compounds are environmental load materials. The reduction of the quantity of phosphorus compounds in engine oils is required to reduce poisoning of three-way catalysts used to purify exhaust gases from internal combustion engines. Mr. Ito and his co-authors1) reported that they developed a sulfur-based additive as a substitute for Zn-DTP. Their non-phosphorus engine oil formulation for four-wheeled vehicles with a sulfur-based additive was examined to evaluate its anti-wear performance using the following test methods:JASO M328 for gasoline engines (KA24E) and JASO M354 for Diesel engine (4D34T4).

The knock-suppression effectiveness of exhaust-gas recirculation (EGR) can vary between implementations that take EGR gases after the three-way catalyst and those that use pre-catalyst EGR gases. A main difference between pre-and post-catalyst EGR gases is the level of trace species like NO, UHC, CO and H2. To quantify the role of NO, this experiment-based study employs NO-seeding in the intake tract for select combinations of fuel types and compression ratios, using simulated post-catalyst EGR gases as the diluent. The four investigated gasoline fuels share a common RON of 98, but vary in octane sensitivity and composition. To enable probing effects of near-zero NO levels, a skip-firing operating strategy is developed whereby the residual gases, which contain trace species like NO, are purged from the combustion chamber. Overall, the effects of NO-seeding on knock are consistent with the differences in knock limits for preand post-catalyst EGR gases.

For the purpose of developing onboard gasoline reforming technology for higher octane number fuel on demand, octane number enhancement of gasoline surrogate by aerobic oxidation using N-hydroxyphthalimide catalyst was investigated. At first, octane numbers of the oxygen-containing products from alkane and aromatic compound were estimated using a fuel ignition analyzer. As a result, not only alcohol but also ketones and aldehydes have higher octane numbers than the original alkanes and aromatic compound. Next, gasoline surrogate was oxidized aerobically with N-hydroxyphthalimide derivative catalyst and cobalt catalyst at conditions below 100 °C. As a result, fuel molecules were oxidized to produce alcohols, ketones, aldehydes, and carboxylic acids. N-hydroxyphthalimide derivative catalyst with higher solubility in gasoline surrogate has higher oxidation ability. Furthermore, the estimated octane number of the oxidized gasoline surrogate improves 17 RON.

To evaluate the relationship between the exhaust gas purification performance and the catalyst pore properties related to gas diffusion, an elementary reaction model was combined with gas diffusion into catalyst pores, referred to as the pseudo-2D gas diffusion/reaction model. It was constructed for Pt/Al2O3 + CeO2 catalyst as lean NOx catalyst. The gas diffusion was described as macro pore diffusion between the catalyst particles and meso pore diffusion within the particle. The kinetic model was composed of 26 reactions of NO/CO/O2 chemistry including 17 Pt/Al2O3 catalyst reactions and 9 CeO2 reactions. Arrhenius parameters were optimized using activity measurement results from various catalysts with various pore properties, meso pore volume and diameter, macro pore volume and diameter, particle size, and washcoat thickness. Good agreement was achieved between the measured and calculated values.

Catalyst simulation, which can analyze the complicated reaction pathway of exhaust gas purifications and identify the rate-determining step, is an essential tool in the development of catalyst materials. This requires an elementary reaction model which describes the detailed processes, i.e. adsorption, decomposition, and others. In our previous work, the elementary reaction model on Pt/CeO2 catalyst was constructed. In this study, we focused on extending the Zeolite catalyst and including the gas diffusivity through the catalyst layer. The reaction rate of a Zeolite catalyst was expressed by an Arrhenius equation, and the elementary reaction model was composed of 17 reactions. Each Arrhenius parameter was optimized by the catalytic activity measurements. The constructed model was validated with NOx conversion in cyclic experiments which were repeated with Lean phase (NOx adsorption) and Rich phase (NOx reduction).

HEV and PHEV require an improved aftertreatment system to clean the exhaust gas in various driving situations. The efficiency of aftertreatment system is significantly influenced by the residence time of the gas in a catalyst which gas flow has generally strong pulsation. Simulation showed up to 70% reduction of exhaust gas emission if the pulsation could be completely attenuated. A new concept exhaust manifold was designed to minimize pulsation flow by wall impingement, with slight increase of pressure loss. Experimental results with new concept exhaust manifold showed exhaust gas emission were reduced 16% at cold condition and 40% at high-load condition.

A new concept for trapping NOx and HC during cold start, the NOx Trap Three-Way Catalyst (N-TWC), is proposed. N-TWC adsorbs NOx at room temperature, and upon reaching activation temperature under suitable air-fuel ratio conditions, it reduces the adsorbed NOx. This allows a reduction in NOx emissions during cold start. N-TWC's reduction mechanism relies on NOx adsorption sites which are shown to be highly dispersed palladium on acid sites in the zeolite. Testing on an actual vehicle equipped with N-TWC confirmed that N-TWC is able to reduce emissions of NOx and HC during cold start, which is a challenge for conventional TWCs.

Development is proceeding on catalysts which separate the NOx in lean exhaust gas by adsorption and then reduce the adsorbed NOx in combustion exhaust gas with the stoichiometric or a slightly richer air fuel ratio, as well as exhaust conversion technology that uses these catalysts. Amidst this research it has been found that catalysts containing mixed metal oxides exhibit superior NOx adsorption performance, so the authors prepared a mixed metal oxide catalyst by adding precious metals and promoters, etc. The resulting catalyst has high heat resistance and also offers excellent SOx durability. These properties were presumed to be due to an adsorbent including the mixed metal oxide, and the relation between the physical properties and NOx conversion properties of the catalyst was investigated.

Urea selective catalytic reduction (SCR) systems are a promising technology for helping to lower NOx emissions from diesel engines. These systems also require on-board diagnostic (OBD) systems to detect malfunctioning catalysts. Conventional OBD methodology for a SCR catalyst involves the measurement of NOx concentration downstream of the catalyst. However, considering future OBD regulations, erroneous diagnostics may occur due to variations in the actual environment. Therefore, to enhance OBD accuracy, a new methodology was examined that utilizes NH3 slip as a new diagnostic parameter in addition to NOx. NH3 slip increases as the NOx reduction performance degrades, because both phenomena are based on deterioration in the capability of the SCR catalyst to adsorb NH3. Furthermore, NH3 can be measured by existing NOx sensors because NH3 is oxidized to NO internally. To make use of NH3 slip, an estimation model was developed.