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To reduce NOx and Particulate Matter (PM) emissions from a heavy-duty diesel engine, the effects of urea selective catalytic reduction (SCR) systems were studied. Proto type urea SCR system was composed of NO oxidation catalyst, SCR catalyst and ammonia (NH3) reduction catalyst. The NOx reduction performance of urea SCR system was improved by a new zeolite type catalyst and mixer for urea distribution at the steady state operating conditions. NOx and PM reduction performance of the urea SCR system with DPF was evaluated over JE05 mode of Japan. The NOx reduction efficiency of the urea SCR catalyst system was 72% at JE05 mode. The PM reduction efficiency of the urea SCR catalyst system with DPF was 93% at JE05 mode. Several kinds of un-regulated matters were detected including NH3 and N2O leak from the exhaust gas. It is necessary to have further study for detailed measurements for un-regulated emissions from urea solution.

To reduce emissions from diesel engines, the effects of oxidation catalysts on the emissions reductions were studied. The effectiveness of several oxidation catalysts on both the regulated and unregulated emissions was evaluated. The oxidation activity of the catalysts was varied by changing Pt loading. The regulated emissions include particulate (PM), hydrocarbon (HC), and carbon monoxide (CO), and the unregulated emissions include benzene, formaldehyde, acetaldehyde, and benzo[a]pyrene (B[a]P). An 8 litter, turbocharged and aftercooled diesel engine was operated under the Japan Diesel 13 (D13) mode cycle for the evaluations. As the first step, evaluations were conducted with a commercially available JIS #2 diesel fuel (0.046 wt% sulfur). All the regulated and unregulated emissions except PM were reduced as the Pt loading (i.e. oxidation activity) increased. However, PM emissions were increased by the generation of sulfate when the Pt loading exceeded 0.2 g/l.

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 2-LEG NOx Storage-Reduction (NSR) catalyst system is one of potential after-treatment technology to meet stringent NOx and PM emissions standards as Post New Long Term (Japanese 2009 regulation) and US'10. Concerning NOx reduction using NSR catalyst, a secondary fuel injection is necessary to make fuel-rich exhaust condition during the NOx reduction, and causes its fuel penalty. Since fuel injected in the high-temperature (∼250 degrees Celsius) exhaust instantly reacts with oxygen in common diesel exhaust, the proportion of fuel consumption to reduce the NOx stored on NSR catalyst is relatively small. A 2-LEG NSR catalyst system has the decreasing exhaust flow mechanism during NOx reduction, and the potential to improve the NOx reduction and fuel penalty. Therefore, this paper studies the 2-LEG NSR catalyst system. The after-treatment system consists of NSR catalysts, a secondary fuel injection system, flow controlled valves and a Catalyzed Diesel Particulate Filter (CDPF).

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.

An on board burner that enables DPF regeneration even when an engine is at standstill has been researched. By employing pre evaporative combustion with a wick burner, miniaturization of the burner system was successfully accomplished as well as stable ignition and combustion. Total heat necessary for DPF regeneration was reduced in comparison to the active DPF regeneration by means of engine control and an oxidation catalyst. Uneven temperature distribution in DPF and excessive temperature rise, which had been recognized as issues in the regeneration of a DPF while engine is at standstill, were solved by increase of combustion air amount and multi-step control of regeneration temperature and reliable regeneration was accomplished.

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.

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.

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.

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.

Influence of sulfur poisoning on NOx storage - reduction catalysts (NSR catalysts) was examined using both model gas and an actual vehicle. Deterioration of NSR catalysts is explained as the balance of sulfate formation in lean operating conditions and the amount of sulfate decomposed under rich operating conditions. This study focused on sulfate decomposition characteristics of NSR catalysts. First, sulfate decomposition characteristics of an NSR catalyst were examined in a model gas test. It was found that the initial temperature of SOx release was higher than the sulfur poisoning temperature. Crystal growth of sulfate by increasing temperature was assumed, and hence suppressed SOx release. Second, various sulfur concentrations (8 - 500 ppm) in gasoline were used for vehicle durability. The duration of one durability cycle was 1,260 seconds, including a 60 second regeneration of sulfur poisoning (AFR 14.2, 700 °C).

Electrode catalyst (platinum) degradation represents a major challenge to the performance and durability of polymer electrolyte membrane fuel cells (PEMFCs) in Fuel Cell Vehicles (FCVs). While various mechanisms have been proposed and investigated previously, there is still a need to develop in situ imaging techniques that can characterize and provide direct evidence to confirm the degradation process. In the present study, we report an in situ transmission electron microscopy (TEM) method that enables real time, high-resolution observation of carbon-supported platinum nanoparticles in liquid electrolyte under working conditions. By improving the design of the Micro Electro Mechanical Systems (MEMS) sample holder, the migration and aggregation of neighboring platinum nanoparticles could be visualized consistently and correlated to applied electrode potentials during aging process (i.e., cyclic voltammetry cycles).

Transmission electron microscope (TEM) is a powerful tool for studying catalyst materials at nano-size and/or atomic level. Conventional TEM usually needs to be observed at room temperature in high vacuum conditions. A gaseous atmosphere and high temperature condition may change the properties of catalyst materials. Recently we developed an in situ observation system in TEM for observing the oxidation and reduction under a gas atmosphere at high temperature. Using the new in situ observation system in TEM, the morphological changes of the nano particle and support were observed in the heated gaseous atmosphere at atomic level in real time.

In order to enhance the catalytic performance of the NOx Storage-Reduction Catalyst (NSR Catalyst), the sulfur tolerance of the NSR catalyst was improved by developing new support and NOx storage materials. The support material was developed by nano-particle mixing of ZrO2-TiO2 and Al2O3 in order to increase the Al2O3-TiO2 interface and to prevent the ZrO2-TiO2 phase from sintering. A Ba-Ti oxide composite material was also developed as a new NOx storage material containing highly dispersed Ba. It was confirmed that the sulfur tolerance and activity of the developed NSR catalyst are superior to that of the conventional one.

In order to further improve the performance of NOx storage-reduction catalysts (NSR catalysts), focus was placed on their high temperature performance deterioration via sulfur poisoning and heat deterioration. The reactions between the basicity or acidity of supports and the storage element, potassium, were analyzed. It was determined that the high temperature performance of NSR catalysts is enhanced by the interaction between potassium and zirconia, which is a basic metal oxide. Also, a new zirconia-titania complex metal oxides was developed to improve high temperature performance and to promote the desorption of sulfur from the supports after aging.

Diesel engine has a good fuel economy and high durability and used widely for power source such as heavy duty in the world. On the other hand, it is required to reduce NOx (Nitrogen Oxides) and PM (Particulate Matter) emissions further from diesel exhaust gases to preserve atmosphere. The urea-SCR (Selective Catalytic Reduction) system is the most promising measures to reduce NOx emissions. DPF (Diesel Particulate Filter) system is commercialized for PM reduction. However, in case that a vehicle has a slow speed as an urban area driving, a diesel exhaust temperature is too low to activate SCR catalyst for NOx reduction in diesel emissions. Moreover, the diesel exhaust temperature becomes lower as a future engine has less fuel consumption. The purpose of this study is reduction of NOx emission from a heavy-duty diesel engine using the Urea SCR system at the low temperature.

Emission regulations for diesel-powered vehicles have been gradually tightening. Installation of after-treatment devices such as diesel particulate filters (DPF), NOx storage reduction (NSR) catalysts, and so on is indispensable to satisfy rigorous limits of particulate matter (PM) and nitrogen oxides (NOx). Japan Clean Air Program II Oil Working Group (JCAPII Oil WG) has been investigating the effect of engine oil on advanced diesel after-treatment devices. First of all, we researched the impact of oil-derived ash on continuous regeneration-type diesel particulate filter (CR-DPF), and already reported that the less sulfated ash in oil gave rise to lower pressure drop across CR-DPF [1]. In this paper, impact of oil-derived sulfur and phosphorus on NSR catalyst was investigated using a 4L direct injection common-rail diesel engine with turbo-intercooler. This engine equipped with NSR catalyst meets the Japanese new short-term emission regulations.