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Our two types of NOx storage-reduction (NSR) catalyst have been tested under various conditions of thermal endurance; the performance of these catalysts have been regressed to give the formulas that enable to estimate the performance after thermal endurance; and we have found the method to simplify (shorten the duration of) the thermal endurance tests and that the thermal deterioration of NSR catalysts is controlled by the worst condition of endurance (at least approximately). The regression formula for the amount of potassium that contributes to the catalyst performance (active K) after the endurance has also been obtained. These formulas predict that the amount of active K is the least for the worst condition of endurance and suggest a difference in deterioration mechanism that reflects the performance between low and high temperatures and the portion of worse deterioration (front or rear).

By using analytical techniques (FT-IR, TG-MS, ICP) and DFT calculations, the potassium (K) used as a storage component in NOx Catalysts can be analyzed. The results from this study show that the, K exists as K2CO3, and that the amount, molecular structure, and thermal stability of K2CO3 are different, depending on the support material (ZrO2, Al2O3, or TiO2). If the amount of K that interacts with the support to form an inactive complex oxide is decreased, the amount of K2CO3 and NOx storage is increased. The amount of the inactive K varies with the basicity of the supports. K2CO3 that exists in unstable structures on the supports can be easy to react with NOx to form the nitrate. So, the higher the quantity of unstable K2CO3, the higher the NOx storage capacity. Based on these results, a development guideline was proposed to improve the NOx storage performance.

Diesel particulate and NOx reduction system (DPNR) is an effective technology for the diesel after-treatment system, which can reduce particulate matter (PM) and nitrogen oxides (NOx) simultaneously. Further improvement of the DPNR is expected for cleaner air in the future. The catalyst for the DPNR (called DPNR catalyst) consists of a NOx Storage Reduction (NSR) catalyst coated onto a Diesel Particulate Filter (DPF). The development of the DPNR catalyst for the decrease of exhaust weight has been considered before now with respect to the PM combustion. But it will be necessary to focus on PM particle number emissions in the future. In this study, the relationship between the pore structure of the DPNR catalyst and the trapping of PM to lower particle number was clarified by evaluating a high-porosity, large-pore cordierite DPF with an average pore size of 20 μm or greater. Furthermore, the optimal pore structure to trap PM particles in a highly effective manner was discussed.

In a Diesel engine with a Diesel particulate filter (DPF) system, high-sulfur fuel causes white smoke containing odorous and harmful pollutants during DPF regeneration. This study investigates the conditions and mechanisms of sulfur-related white smoke generation. Engine and vehicle tests found that sulfur compounds emitted from the engine accumulated on the catalysts in the DPF system and were emitted as white smoke during DPF regeneration. The white smoke was observed when the catalyst temperature was more than 450°C, under conditions such as the early stage of DPF regeneration. Model gas tests were conducted to clarify the mechanism of the white smoke. It was found that SO2 emitted from the engine was oxidized to SO3 on the catalyst, which was then mainly absorbed on the oxidation catalyst support (Al2O3). Then, the absorbed SO3 was desorbed and converted into white smoke.

This paper considers an application of reference governor (RG) to automotive diesel aftertreatment temperature control. Recently, regulations on vehicle emissions have become more stringent, and engine hardware and software are expected to be more complicated. It is getting more difficult to guarantee constraints in control systems as well as good control performance. Among model-based control methods that can directly treat constraints, this paper focuses on the RG, which has recently attracted a lot of attention as one method of model prediction-based control. In the RG, references in tracking control are modified based on future prediction so that the predicted outputs in a closed-loop system satisfy the constraints. This paper proposes an online RG algorithm, taking account of the real-time implementation on engine embedded controllers.

To meet future stringent emission regulations such as Euro6, the design and control of diesel exhaust after-treatment systems will become more complex in order to ensure their optimum operation over time. Moreover, because of the strong pressure for CO₂ emissions reduction, the average exhaust temperature is expected to decrease, posing significant challenges on exhaust after-treatment. Diesel Oxidation Catalysts (DOCs) are already widely used to reduce CO and hydrocarbons (HC) from diesel engine emissions. In addition, DOC is also used to control the NO₂/NOx ratio and to generate the exothermic reactions necessary for the thermal regeneration of Diesel Particulate Filter (DPF) and NOx Storage and Reduction catalysts (NSR). The expected temperature decrease of diesel exhaust will adversely affect the CO and unburned hydrocarbons (UHC) conversion efficiency of the catalysts. Therefore, the development cost for the design and control of new DOCs is increasing.

To prevent global warming, many countries are making efforts to reduce CO2 emissions toward achieving 2050 carbon neutrality. In order to reduce CO2 concentration quickly, in addition to spread of renewable energy and expansion of BEV, it is also important to reduce CO2 emissions by improving thermal efficiency of ICE (internal combustion engine) and utilizing carbon neutral fuels such as synthetic fuels and biofuels. It is well known that lean burn is an effective technology to increase thermal efficiency of engine highly. However, since NOx emission from lean burn engine cannot be reduced with three-way catalyst, there have been issues such as complicated system configuration due to the addition of NOx reduction catalyst or limiting lean operation to narrow engine speed and load in order to meet emission regulation of each country.

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.

Due to regulations for even lower levels of pollutants in exhaust gas, development of advanced combustion techniques and increasingly efficient catalysts has become more crucial than ever. One of the essential technologies to achieve this goal is an advanced measurement method, which can detect the characteristics of exhaust gas, such as temperature and chemical compositions, in real-time to clarify their reaction mechanisms. A direct and fast response (1ms) measurement technique was developed based on diode laser absorption spectroscopy and applied to practical engine exhaust measurement to prove the validity of this technology for various applications such as clarification of engine start phenomena and improvement of EGR controls.

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%.

One primary result of the reduction of platinum group metals (PGM) within a catalytic converter is the decline in NOx conversion efficiency. This paper hypothesizes that the primary factor of this decline to be hydrocarbon (HC) poisoning. To maintain high NOx conversion efficiency as the PGM reduces, Rh activation improvement becomes significant to overcome the HC poisoning. Analysis of the Rh deterioration mechanism found that it is effective to separately arrange Rh and CeO2 on the converter, avoiding the Rh deactivation. By this improvement, we improved the catalyst activity at less than 25% of the original Rh loading.

The first MIRAI was launched in 2014 as the world’s first commercial fuel cell vehicle (FCV) [1]. Compared to the FC stack used in the first MIRAI, the FC stack in the new MIRAI achieved one of the highest volumetric power densities in the world (5.4 kW/L, excluding end plates, 1.5 times higher than the FC stack in the first MIRAI) by adopting a new flow channel for the bipolar plate and an improved electrode [2]. Enhancing the current density is an important means of increasing power performance and reducing size. The bipolar plate functions to distribute gas and drain water inside the cells to stabilize current generation. However, a conventional straight flow channel tends to cause flooding, which makes it difficult to maintain stable current generation. A partially narrow flow channel was developed to enhance oxygen diffusion without the 3D fine-mesh flow field that was adopted in the previous FC stack.

The Diesel Particulate and NOx Reduction System (DPNR) is an effective technology as a diesel after-treatment system, which can reduce particulate matter (PM) and nitrogen oxides (NOx) simultaneously. However, it requires desulfurization control since the DPNR catalyst is poisoned by sulfur components in the exhaust gas from the fuel and lubricant. Desulfurization control causes some degree of fuel penalty and thermal deterioration of the DPNR catalyst because it requires control of rich air fuel ratio and high temperature simultaneously. In this paper, we investigated a new system with a sulfur trap catalyst which can trap sulfur components included in the exhaust gas as sulfates (Sulfur trap DPNR). In this system, desulfurization control is not performed because the sulfur poisoning of the DPNR catalyst is drastically suppressed by the sulfur trap catalyst. In the present DPNR, periodic desulfurization control is required.

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.

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).

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.

In recent years, electrically heated catalysts (EHCs) have been developed to achieve lower emissions. In several EHC heating methods, the direct heating method, which an electric current is applied directly to the catalyst substrate, can easily activate the catalyst before engine start-up. The research results reported on the use of the direct heating EHC to achieve significant exhaust gas purification during cold start-up [1]. From the perspective of catalyst loading, ceramics is considered to be a better material for the substrate than metal due to the difference in coefficient of thermal expansion between the catalyst and the substrate, but the EHC made of ceramics has difficulties such as controllability of the current distribution, durability and reliability of the connection between the substrate and the electrodes.

Emission regulations in many countries and regions around the world are becoming stricter in reaction to the increasing awareness of environment protections, and it has now become necessary to improve the performance of catalytic converters to achieve these goals. A catalytic converter is composed of a catalytically active material coated onto a ceramic honeycomb-structured substrate. Honeycomb substrates play the role of ensuring intimate contact between the exhaust gas and the catalyst within the substrate’s flow channels. In recent years, high-load test cycles have been introduced which require increased robustness to maintain low emissions during the wide range of load changes. Therefore, it is extremely important to increase the probability of contact between the exhaust gas and catalyst. To achieve this contact, several measures were considered such as increasing active sites or geometrical surface areas by utilizing substrates with higher cell densities or larger volumes.

We, at Toyota, have been working to develop a new DPNR (Diesel Particulate-NOx Reduction) system to decrease both PM and NOx emissions by combining the NOx storage-reduction catalyst for direct injection gasoline engines with the most advanced engine control technologies. The purpose of the DPNR catalyst is to decrease PM and NOx in order to purify automotive exhaust gas. To reduce PM emissions, the PM trapping rate and PM oxidizing performance must be improved. Since the deposition of PM increases the pressure drop across the catalytic converter, it should also be suppressed. To attain these objectives, we have developed a new DPNR catalyst by the adoption of a new porous substrate structure and the improvement of the catalyst coating technique. The new DPNR catalyst will be mounted on the Avensis for commercial use in the European market.

The second-generation air-fuel ratio control method has been developed to reduce exhaust gas emissions in accordance with the improvements in catalysts. The control system consists of a feedforward control using a fuel behavior model, a feedback control using an universal exhaust gas oxygen (UEGO) sensor and a feedback control utilizing the heated exhaust gas oxygen (HEGO) sensor. This significantly improves air-fuel ratio tracking performance by feedforward control derived from the models that express the dynamic phenomena and the disturbance attenuation by UEGO feedback controller which compensates for the long dead-time characteristics by the state predictive control. The tracking performance and the disturbance attenuation can be achieved independently by a two-degree-of-freedom structure presented in this paper. The exhaust air-fuel ratio downstream of the catalyst precisely converges to stoichiometry, which maximizes the conversion efficiency of the catalyst.