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A practical ZrO2 NOx sensor using dual oxygen pumping cells has been introduced for the control of NOx emitted from a lean-burn gasoline engine and diesel engine.(1),(2). However, the measuring accuracy was not high enough to be useful for controlling or monitoring a low level of NOx concentration such as several tens ppm behind a three way catalyst or lean NOx catalyst which is NOx adsorption or De-NOx catalyst. This paper describes improvement of the interference effect of oxygen in the exhaust gas from the lean-burn gasoline engine and diesel engine. The cause of oxygen dependency is analyzed/revealed and a method of improvement is introduced. The improved NOx sensor has an approximately · · 2% measuring error in the wide range of oxygen concentration on a model gas system, compared to the · ·10% of the previous one.

The in-line hydrocarbon (HC) adsorber is a passive after-treatment technology to address cold-start hydrocarbons in automotive engine exhaust gas. A major technical challenge of the in-line HC adsorber is the difference between the HC release temperature of the adsorber and the light-off temperature of the burn-off (BO) Catalyst. We call this phenomenon the “reversed-temperature difference”. To reduce the reversed temperature difference, NGK has proposed a new “In-line HC Adsorber System” which consists of light-off (LO) Catalyst + Barrel Zeolite Adsorber (BZA), with a hole through the center, BO Catalyst and secondary air injection management (SAE 970266). This, our latest paper, describes the evaluation of various adsorbents and the effect of the center hole on the Adsorber BZA. The adsorber system, which had the Adsorber BZA with a 25mm ϕ center hole and adsorbent coated, confirmed 30% lower FTP NMHC emission versus a system with no center hole or adsorbent coating.

Ceramic honeycombs have been used as automotive catalyst supports in US, Japan, Europe and other highly urbanized countries. Now, engine output is a great concern for automanufacturers, and reduction of the wall thickness of honeycomb substrates became indespensable for maintenance of gas flow restriction to a certain low level. To reduce wall thickness, material should be strong to maintain canning strength of substrates. Mechanical strength was improved with high density cordierite. However, isostatic strength of whole substrates was still insufficient with reduced thin walls for canning in spite of the material's high mecanical strength. Discussion is carried out on further possibility of improving canning performance of thin wall substrates as well as flow restriction, and warm up characteristics.

Further stringent emission legislation requires advanced technologies, such as sophisticated engine management and advanced catalyst and substrate to achieve high catalytic performance, especially during the light-off phase. This paper presents the results of calculations and measurements of hydrocarbon and carbon monoxide light-off performance for substrates of different wall thickness, cell density and cell shapes. The experimental data from catalyst light-off testing on an engine dynamometer are compared with theoretical results of computer modeling under different temperature ramps and flow rates. The reaction kinetics in the computer modeling are derived from the best fit for the performance of conventional ceramic substrate (6mil/400cpsi), by comparing the theoretical and experimental results on both HC and CO emissions. The calibrated computer model predicts the effects of different wall thickness, cell density and cell shape.

The future emission limits for gasoline fuelled passenger cars require more and more efficient exhaust gas aftertreatment devices - the catalytic converter being one essential part of the complex system design. The present paper summarizes the results of several basic research programs putting major emphasis on the application of highly sophisticated three-way catalyst technologies being taylored for the utilization on ultra thin-wall ceramic substrates. In the first part of the investigation the following effects were examined in detail: Different washcoat loadings at constant PGM-loadings Different volumes of catalysts for constant amounts of PGM and washcoat Similar washcoat technologies at different ratios of WC-loading to precious metal concentration in the washcoat.

NOx adsorber has already been used for the after-treatment system of series production vehicle installed with a lean burn or direct injection engine [1,2,3]. In order to improve NOx adsorbability at high temperatures, many researchers have recently been trying an addition of potassium (K) as well as other conventional NOx adsorbents. Potassium, however, reacts easily with the cordierite honeycomb substrate at high temperatures, and not only causes a loss in NOx adsorbability but also damages the substrate. Three new technologies have been proposed in consideration of the above circumstances. First, a new concept of K-capture is applied in washcoat design, mixed with zeolite, to improve thermal stability of K and to keep high NOx conversion efficiency, under high temperatures, of NOx adsorber catalyst. Second, another new technology, pre-coating silica over the boundary of a substrate and washcoat, is proposed to prevent the reaction between potassium and cordierite.

Developing ultra thin wall ceramic substrates is necessary to meet stricter emissions regulations, in part because substrate cell walls need to be thinner in order to improve warm-up and light-off characteristics and lower exhaust system backpressure. However, the thinner the cell wall becomes, the poorer the mechanical and thermal characteristics of the substrate. Furthermore, the conditions under which the ultra thin wall substrates are used are becoming more severe. Therefore both the mechanical and thermal characteristics are becoming important parameters in the design of advanced converter systems. Whereas square cells are used world-wide in conjunction with oxidation and/or three-way catalysts, hexagonal cells, with features promoting a homogeneous catalyst coating layer, have found limited use as a NOx absorber due to its enhanced sulfur desorption capability.

To meet stringent emissions regulations, high conversion efficiency is required. This calls for advanced catalyst substrates with thinner walls and higher cell density. Higher cell density is needed because it brings higher mass transfer from the gas to the substrate wall. Basically, the increase in total surface area (TSA) causes higher mass transfer. However, not only the TSA, but the cell shape also has a great effect on mass transfer. There are two main kinds of substrates. One is the extruded ceramic substrate and the other is the metal foil type substrate. These have different cell shapes due to different manufacturing processes. For the extruded ceramic substrate, it is possible to fabricate various cell shapes such as triangle, hexagon, etc. as well as the square shape. The difference in the cell shape changes not only the mass transfer rate, but also causes pressure loss change. This is an important item to be considered in the substrate design.

Diesel engines are more fuel efficient due to their high thermal efficiency, compared to gasoline engines and therefore, have a higher potential to reduce CO2 emissions. Since diesel engines emit higher amounts of Particulate Matter (PM), DPF systems have been introduced. Today, DPF systems have become a standard technology. Nevertheless, with more stringent NOx emission limits and CO2 targets, additional NOx emission control is needed. For high NOx conversion efficiency, SCR catalysts technology shows high potential. Due to higher temperature at the close coupled position and space restrictions, an integrated SCR concept on the DPFs is preferred. A high SCR catalyst loading will be required to have high conversion efficiency over a wide range of engine operations which causes high pressure for conventional DPF materials.

Ammonia Selective Catalytic Reduction (SCR) and Lean NOx Trap (LNT) systems are key technologies to reduce NOx emission for diesel on-highway vehicles to meet worldwide tighter emission regulations. In addition DeNOx catalysts have already been applied to several commercial off-road applications. Adding the DeNOx catalyst to existing Diesel Oxidation Catalyst (DOC) and Diesel Particulate Filter (DPF) emission control system requires additional space and will result in an increase of emission system back pressure. Therefore it is necessary to address optimizing the DeNOx catalyst in regards to back pressure and downsizing. Recently, extruded zeolite for DeNOx application has been considered. This technology improves NOx conversion at low temperature due to the high catalyst amount. However, this technology has concerned about strength and robustness, because the honeycomb body is composed of catalyst.

HC emission standards will be tightened during the 1990's in the US. A key issue in reducing HC emission is improving the warm-up characteristics of catalysts during the cold start of engines. For this purpose, studies are under way on reduction of heat mass of ceramic substrates. Reduction of cell walls in substrates to thickness smaller than the current thickness of 12mil or 6mil has resulted in reduced heat mass, and also reduced flow restriction of substrates. The warm-up characteristics of low bulk density catalysts are better than those of high bulk density, i.e., the warm-up characteristics of thinner wall or lower cell density catalysts are better than those of thicker wall or higher cell density catalysts. A relationship between geometric surface area and warm-up characteristics is observed.

It is well known that an EHC (Electrically Heated Catalyst) is very effective in reducing cold start HC emissions. However, the large electric power consumption of the EHC is a major technical issue. When installed in the exhaust manifold, the EHC can take advantage of exhaust heat to warm up faster, resulting in a reduced electric power demand. Therefore, a structurally durable EHC which can withstand the severe manifold conditions is desirable. Through the use of a extruded monolithic metal substrate, with a flexible hexagonal cell structure and a special canning method, we have succeeded in developing a structurally durable EHC. This new EHC installed in the exhaust manifold with a light-off catalyst directly behind it demonstrated a drastic reduction in FTP (Federal Test Procedure) Total HC emissions.

In this study, to satisfy increasingly strict emission regulations, the conversion efficiency of a 0.11 mm (4 mil) thin-wall catalyst is discussed. The effects of catalyst bulk density on reducing heat mass to improve catalyst emission conversion in the early cold transient mode (Bag 1 in the FTP-75 mode) is quantitatively discussed. To analyze the effects of low heat mass, catalyst's bed temperatures were measured. Effects of the geometric surface area (GSA) and volume of the catalyst were also analyzed. An early feedback control system with an HEGO oxygen sensor and a secondary air injection control system with an original oxygen sensor were compared with an original control system on THC, CO, and NOx emission amounts.

The electrically-heated catalyst ( EHC ) has been established as an effective technology for lower-emission regulations. High electrical power consumption was a major concern for the EHC system in the past. This issue was addressed through the development of the EHC design and the alternator-powered EHC system combined with a light-off ( L/O ) catalyst. The subsequent challenges have been to prove the EHC's reliability and durability. NGK has developed a durable, extruded EHC for very severe exhaust system installations. In addition, the EHC's electrical connector system is required to meet high performance and reliability objectives under extreme environmental conditions unique to this application. This report describes the design concept of NGK's EHC including our new electrical connector system and durability results. In summary, the NGK EHC design concept has been confirmed to have excellent durability performance.

This paper describes a newly-developed, high-performance RTD,(Resistive Temperature detector), which meets OBD-II monitoring requirements. The OBD-II catalyst monitoring requirements are high temperature durability, high accuracy, and narrow piece-to-piece variation. Catalyst monitoring methods have been reviewed and studied by checking the catalyst exotherm(1)(2). The preliminary test results of catalyst monitoring are also described herein.

Since the monolithic ceramic substrate was introduced for automotive catalytic converters, the reduction of the substrate wall thickness has been a continuing requirement to reduce pressure drop and improve catalytic performance. The thin wall substrate of 0.10 mm (4 mil) thick wall/400 cpsi cell density has been introduced to production by achieving mechanical strength equivalent to a conventional 0.15 mm (6 mil)/400 cpsi substrate. Although a round cross-section substrate can have a reduced catalyst volume compared to an oval cross-section substrate because of uniform gas flow distribution, the smaller cross-section of the round substrate increases pressure drop. The thin wall technology was applied to the round substrate to offset the pressure drop increase and to further improve catalytic performance.

Catalytic performance can be improved by increasing geometric surface area (GSA) and reducing bulk density (BD), namely heat capacity, using high cell-density / thinwall advanced ceramic substrates. The advanced substrates, such as 3 mil/600 cpsi and 2 mil/900 cpsi have improved the catalytic performance over the conventional substrates, and are expected to help in complying with future emission regulations, as well as catalyst downsizing. This paper describes the effects of GSA and BD using Pd-based catalysts. The reduction of hydrocarbons emissions was demonstrated significantly at close-coupled location, and dual bed design was proven effective. The effectiveness at under-floor location was not as significant as the close-coupled location.

This paper proposes a high temperature manifold converter with a thin wall ceramic substrate, such as; 4mil/400cpsi and 4mil/600cpsi. Double-wall cone insulation design was proposed for close-coupled converters to protect the conventional intumescent mat from high temperature. However, the double wall cone insulation is not applicable when the converter is directly mounted to the exhaust manifold without an inlet cone. The prototype manifold converter was tested under hot vibration test with a non-intumescent ceramic fiber mat and retainer rings as a supplemental support. The converter demonstrated durability for 10 hours under 80G acceleration and 100 hours under 60G acceleration with 1,050 °C catalyst bed temperature. The skin temperature of the heat shield was kept below 400 °C.

In order to meet the strict automobile emission regulations in the U.S.A. and Europe, new aftertreatment technologies such as the EHC and HC Adsorber have been developed to reduce the cold start emissions. The EHC is obviously effective in reducing emissions, but has the demerits of a large electric power demand and a complicated power control system to support it (13). A by-pass type HC adsorber system has the concerns of unreliable by-pass valves and complicated plumbing (10). A major technical challenge of the in-line type HC adsorber was the difference between the HC desorption temperature and the light-off temperature of the burn-off catalyst. This paper describes the evaluation results of a completely passive “In-line HC Adsorber System” which can reduce the cold start emissions without the application of any type of mechanical or pneumatic control valve in the exhaust system.

Although air pollution has mitigated since the introduction of exhaust emission regulations, further reduction of it especially in the metropolitan areas is anticipated. An effective way to resolve this issue is to improve the catalyst performance. Of many approaches, improving substrate is one promising way to achieve this goal. Results of applying high cell density and light- weight substrates, coupled with high precious metal content, are discussed theoretically and verified experimentally here. The significant improvements made in the low temperature activity and warmed-up conversions by increasing geometrical surface areas and lowering thermal mass of high cell density substrates are described.