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In order to clarify future automobile technologies and fuel qualities to improve air quality, second phase of Japan Clean Air Program (JCAPII) had been conducted from 2002 to 2007. Predicting improvement in air quality that might be attained by introducing new emission control technologies and determining fuel qualities required for the technologies is one of the main issues of this program. Unregulated material WG of JCAPII had studied unregulated emissions from gasoline and diesel engines. Eight gaseous hydrocarbons (HC), four Aldehydes and three polycyclic aromatic hydrocarbons (PAHs) were evaluated as unregulated emissions. Specifically, emissions of the following components were measured: 1,3-Butadiene, Benzene, Toluene, Xylene, Ethylbenzene, 1,3,5-Trimethyl-benzene, n-Hexane, Styrene as gaseous HCs, Formaldehyde, Acetaldehyde, Acrolein, Benzaldehyde as Aldehydes, and Benzo(a)pyrene, Benzo(b)fluoranthene, Benzo(k)fluoranthene as PAHs.

We have developed a revolutionary automotive catalyst that maintains high activity by the suppression of grain growth of precious metals. This catalyst contains Pd-perovskite crystal which has shown a capacity for self-regeneration of Pd in a cycle of solid solution and segregation in perovskite crystals [1, 2, 3, 4, 5 and 6]. We named this catalyst the “Intelligent Catalyst” and first commercialized it in the Japanese market in October 2002 [7, 8]. In this study, we investigated the activity of Pd at various temperatures to confirm that the self-regenerative mechanism worked well at low temperatures like those right after engine starting. We also examined the durability of perovskite structure at high temperatures and tested its catalytic activity after engine aging at high temperatures above 1000 °C up to 1100 °C. It is proved that the intelligent catalyst has both excellent activity and durability under practical conditions.

The engine in the research is a single cylinder DI diesel using the emission reduction techniques such as high boost, high injection pressure and broad range and high quantity of exhaust gas recirculation (EGR). The study especially focuses on the reduction of particulate matter (PM) under the engine operating conditions. In the experiment the authors measured engine performance, exhaust gases and mass of PM by low sulfur fuel such as 3 ppm and low sulfur lubricant oil such as 0.26%. Then the PM components were divided into soluble organic fraction (SOF) and insoluble organic fraction (ISOF) and they were measured at each engine condition. The mass of SOF was measured from the fuel fraction and lubricant oil fraction by gas chromatography. Also each mass of soot fraction and sulfate fraction was measured as components of ISOF. The experiment was conducted at BMEP = 2.0 MPa as full load condition of the engine and changing EGR rate from 0% to 40 %.

Intermittent Dual-fluid Exhaust Burner (IDEB) has been developed to reduce emissions from methanol fueled vehicles during the warm-up period after a cold start. The IDEB does not need any special fuel injector or blower, and has been built mainly through software modification of an ECU. An FTP mode test while operating an IDEB confirmed that the catalyst temperature was rapidly increased to significantly reduce the emissions to meet a level of ULEV standards.

In the urea SCR system, urea solution is injected by injector installed in the front stage of the SCR catalyst, and NOx can be purified on the SCR catalyst by using NH3 generated by the chemical reaction of urea. NH3 is produced by thermolysis of urea and hydrolysis of isocyanic acid after evaporation of water in the urea solution. But, biuret and cyanuric acid which may cause deposit are sometimes generated by the chemical reactions without generating NH3. Spray behavior and chemical reaction of urea solution injected into the tail-pipe are complicated. The purpose of this study is to reveal the spray behavior and NH3 generation process in the tail-pipe, and to construct the model capable of predicting those accurately. In this report, the impingement spray behavior is clarified by scattered light method in high temperature flow field. Liquid film adhering to the wall and deposit generated after evaporation of water from the liquid film are photographed by the digital camera.

Single cylinder engine testing was carried out to clearly understand the test results of multi-cylinder engines reported by the Diesel WG in JCAP (Japan Clean Air Program) (1), (2), (3) and (4). In this tests, engine specifications such as fuel injection pressure, nozzle hole diameter, turbo-charging pressure, EGR rate, and fuel properties such as 1-, 2-, 3-ring aromatics content, n-,i-paraffins content, and T90 were parametrically changed and their influence on the emissions were studied. PM emission generally increased in each engine condition with increased aromatic contents and T90. In particular, multi ring aromatics brought about large increases in PM regardless of the engine conditions. The influence of fuel properties on NOx emission is smaller than the influence on PM emission. Some other fuels that have various side chain structures of 1-ring aromatics, normal paraffins only and various naphthene contents were also investigated.

A one-dimensional (1-D) micro-kinetic reaction model with considering mass transport inside porous washcoat was developed to promote an effective development of multi-functional catalysts. The validation of this model has been done successfully through the comparison with a set of basic experiments. A numerical simulation study was conducted for the various catalyst configurations of three-way catalysts under Federal Test Procedure (FTP75) condition. It was found that a double layer type had a significant advantage in the total mass emissions, especially in NOx emissions. The reaction mechanisms in these catalysts were numerically clarified from the view point of detailed reaction dynamics. We concluded that the utilization of the numerical simulation with the detailed chemistry was effective for the optimization of catalyst design.

To meet the strict emission regulations for diesel engines, an advanced processing device such as a Urea-SCR (selective catalytic reduction) system is used to reduce NOx emissions. The Real Driving Emissions (RDE) test, which is implemented in the European Union, will expand the range of conditions under which the engine has to operate [1], which will lead to the construction of a Urea-SCR system capable of reducing NOx emissions at lower and higher temperature conditions, and at higher space velocity conditions than existing systems. Simulations are useful in improving the performance of the urea-SCR system. However, it is necessary to construct a reliable NOx reduction model to use for system design, which covers the expanded engine operation conditions. In the urea-SCR system, the mechanism of ammonia (NH3) formation from injected aqueous urea solution is not clear. Thus, it is important to clarify this mechanism to improve the NOx reduction model.

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.

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.

Four urea SCR systems were developed and evaluated on a C/D and on the road to investigate their potential for Japanese emission regulations in 2005 and beyond. Test results showed that NOx conversion ratios were 50 to 70% during the Japanese D13 mode cycle, and the ratios under the transient driving cycle were lower than those tested during a steady state. Unregulated emissions, such as benzene, aldehyde and benzo[a]pyrene, existed either at a trace level using the oxidation catalyst, or lower than a base diesel engine, when no oxidation catalyst was used. The health effects of particulate matter emitted from the SCR system were almost the same as those from conventional diesel engines, as evaluated by the Ames test and in vitro micronucleus test. Thermal degradation products, such as cyanuric acid and melamine, were two to four figures lower compared with the toxicological information of Safety Information Resources Inc. (SIRI).

In the Japan Clean Air Program II (JCAP II) Diesel WG, effects of fuel properties on the performance of two types of diesel NOx emission aftertreatment devices, a Urea-SCR system and a NOx storage reduction (NSR) catalyst system, were examined. For a Urea-SCR system, the NOx emission reduction performance with and without an oxidation catalyst installed in front of the SCR catalyst at low exhaust gas temperature operation was compared. For an NSR catalyst system, the effect of fuel sulfur on both emissions and fuel economy during 50,000 km driving was examined. Furthermore, effects of other fuel properties such as distillation on exhaust emissions were investigated. The results show that sulfur is the influential factor for both devices. Namely, high NOx emission reduction performance of the Urea-SCR system with the oxidation catalyst at low exhaust gas temperature operation is influenced by sulfur.

We have developed a Pd-intelligent catalyst with a self-regenerative function that is realized by the passage of Pd through consecutive solid solution and segregation states in and out of a perovskite crystal, and commercialized it for the first time in the world [1, 2, 3, 4, 5, 6, 7, 8 and 9]. In this study, we investigated the self-regenerative function of Rh as an alternative for Pd, in two types of Rh-perovskite (LaFeRhO3 and CaTiRhO3), and found that a CaTiRhO3 perovskite has an excellent capacity for the self-regenerative function of Rh. In a LaFeRhO3 perovskite with a composition similar to the Pd-perovskite (LaFePdO3), Rh was fixed so stably in the perovskite structure that it hardly segregated from the perovskite even in high temperature reduction atmospheres. However, in the CaTiRhO3 perovskite, with its A2+B4+O3 formula, the amount of Rh that actually segregated increased greatly in reduction atmospheres.

Global focus on CO2 reduction and environmental protection is increasing. To comply with stricter exhaust gas regulations and reduce real world emissions, it is becoming increasingly important to improve the performance of three-way catalysts. Therefore, highly efficient conversion of hydrocarbons (HC), carbon monoxide (CO), and nitrogen oxides (NOx) is required. In general, the more active the precious metals used, the better the conversion performance. However, precious metals have supply risks, such as price fluctuation and the uneven distribution of production areas. Therefore, it is necessary to lower emissions while also lowering the amount of precious metals used. This paper focuses on how catalysts are used and describes the development of a new three-way catalyst for the purpose of strengthening cold conversion and decreasing the usage of precious metals.

Growing concerns about the depletion of raw materials as vehicle ownership continues to increase is prompting automakers to look for ways of decreasing the use of platinum-group metals (PGMs) in the exhaust systems. This research has developed a new catalyst with strong robustness against fluctuations in the exhaust gas and excellent nitrogen oxide (NOx) conversion performance. One of the key technologies is a new OSC material that has low surface area (SA) and high OSC performance. We enhanced the pyrochlore- ceria/zirconia (CZ) which has a very small SA. In order to enhance the heat resistance and promote the OSC reaction, we selected and optimized the additive element. This material showed high OSC performance especially in the temperature range of 400 degrees or less. Another key technology is washcoat structure that has high gas diffusivity by making connected pore in the washcoat (New pore forming technology).

Further improvements in catalyst performance are required to help protect the atmospheric environment. However, from the viewpoint of resource availability, it is also necessary to decrease the amount of precious metals used at the active sites of the catalyst. Therefore, a high-performance three-way catalyst with an advanced coating layer has been developed to lower the amount of precious metal usage. Fuel efficiency improvement technologies such as high compression ratios and a large-volume exhaust gas recirculation (EGR) generally tend to increase the ratio of hydrocarbons (HC) to nitrogen oxides (NOx) in exhaust gas. This research focused on the palladium (Pd) loading depth in the coating layer with the aim of improving the hydrocarbon (HC) conversion activity of the catalyst.

It is critical to develop high performance three-way catalysts to meet increasing regulations around the world. It was found that a double-layered catalyst loaded with Pt and Rh suppresses Pt-Rh alloying, thereby improving catalytic performance. A double-layered catalyst has the effect of decreasing OSC performance, but this has been overcome by a newly developed Rh support and suppressed Pt grain growth. The developed catalyst is capable of lowering the amount of PGM required by approximately 40%.

In recent years the regulations governing emissions from automobiles have been strengthened as awareness of global environmental problems has increased. Furthermore, the amount of precious metals being used has continued to decrease due to concerns over the exhaustion of natural resources and worries about the risk of fluctuations in the price of these precious metals. As a result, a high performance three-way catalyst that can satisfy the emissions regulations is now required. By applying zone-coating and carrier degradation control technology, a high performance three-way catalyst has been developed. The zone-coating technology improves the conversion performance of the catalyst through improvement of HC and NOx conversion reactions and oxygen storage capacity (OSC) reactions. The addition of an Nd surface-enriched layer strengthened the mutual interactions between the carrier and Rh.

We have reported the innovation of “An Intelligent Catalyst” which has the function for self-regeneration of Pd realized through the solid solution and segregation of Pd in a perovskite crystal [1, 2, 3, 4 and 5]. We have looked for a design configuration for LaFePdO3 perovskite in the washcoat by comparing single and double layer washcaots as well as different loading locations for precious metals in order to maximize the Intelligent Catalyst's function in the practical conditions. The catalysts were attached to an engine exhaust system and subjected to an accelerated aging. The bed temperature of the catalysts reached to 1050 °C. The performance of the catalysts was evaluated on the engine dynamometer. Catalytic activity and long durability were improved by development of the washcoat configuration. The optimum design of the washcoat was double-layer with a tri-metal (Pt, Rh and Pd) system. The perovskite was located in the lower layer.

With emission regulations getting tighter and tighter, catalysts will need to be active at ever lower temperatures in order to meet future standards. To meet this need, automotive catalysts are being installed closer to the engine so as to be active immediately after start-up. In this location, catalysts must have high temperature durability. In this paper, we examined a heat-resistant support material, “hexa-aluminate”, for possible use in future automotive catalysts. Catalytic activity of hexa-aluminate was more better than La added γ - alumina after redox treatment in model gas and after engine aging. Since hexa-aluminate had the excellent thermal durability, and Pd, which are supported on it, maintains finer particles than those on La added γ-alumina. We suggest that hexa-aluminate is a effective support material for automotive catalysts. More specifically, hexa-aluminate is expected to be a key technology for meeting the stringent emission standards of the future.