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This paper, written in collaboration with Ford, evaluates the effectiveness of higher cell density combined with higher porosity, lower thermal mass substrates for emission control capability on a customized, RDE (Real Driving Emissions)-type of test cycle run on a chassis dynamometer using a gasoline passenger car fitted with a three-way catalyst (TWC) system. Cold-start emissions contribute most of the emissions control challenge, especially in the case of a very rigorous cold-start. The majority of tailpipe emissions occur during the first 30 seconds of the drive cycle. For the early engine startup phase, higher porosity substrates are developed as one part of the solution. In addition, further emission improvement is expected by increasing the specific surface area (GSA) of the substrate. This test was designed specifically to stress the cold start performance of the catalyst by using a short, 5 second idle time preceding an aggressive, high exhaust mass flowrate drive cycle.

Selective catalyst reduction (SCR) using cordierite honeycomb substrate is generally used as a DeNOx catalyst for diesel engines exhaust in both on-road and commercial off-highway vehicles to meet today’s worldwide emission regulations. Worldwide NOx emission regulations will become stricter, as represented by CARB2027 and EuroVII. Technologies which can achieve further lower NOx emissions are required. Recently, several technologies, like increased SCR catalyst loading amount on honeycomb substrates, and additional SCR catalyst volume in positions closer to the engine are being considered to achieve ultra-low NOx emissions. However, undesirable pressure drop increase and enlarging after treatment systems will be caused by adopting these technologies. Therefore, optimization of the material and honeycomb cell structure for SCR is inevitable to achieve ultra-low NOx emissions, while minimizing any system drawbacks.

In order to meet the challenging CO2 targets beyond 2020 without sacrificing performance, Gasoline Direct Injection (GDI) technology, in combination with turbo charging technology, is expanding in the automotive industry. However, while this technology does provide a significant CO2 reduction, one side effect is increased Particle Number (PN) emission. As a result, from September 2017, GDI vehicles in Europe are required to meet the stringent PN emission limits of 6x1011 #/km under the Worldwide harmonized Light vehicles Test Procedure (WLTP). In addition, it is required to meet PN emission of 9x1011 #/km under Real Driving Emission (RDE) testing, which includes a Conformity Factor (CF) of 1.5 to account for current measurement inaccuracies on the road. This introduction of RDE testing in Europe and China will especially provide a unique challenge for the design of exhaust after-treatment systems due to its wide boundary conditions.

In order to meet the challenging CO2 targets beyond 2020 despite keeping high performance engines, Gasoline Direct Injection (GDI) technology usually combined with charged aspiration is expanding in the automotive industry. While providing more efficient powertrains to reduce fuel consumption one side effect of GDI is the increased particle formation during the combustion process. For the first time for GDI from September 2014 there is a Particle Number (PN) limit in EU of 6x10 sup 12 #/km, which will be further reduced by one order of magnitude to 6x10 sup 11 #/km effective from September 2017 to be the same level as applied to Diesel engines. In addition to the PN limit of the certification cycle NEDC further certification of Real Driving Emissions (RDE) including portable PN measurements are under discussion by the European Commission. RDE test procedure requires stable and low emissions in a wide range of engine operations and durable over a distance of 160 000 km.

All vehicles sold today are required to meet emissions standards based on specific driving cycles. Emissions standards are getting tighter and the introduction of real driving tests is imminent, potentially calling for improved aftertreatment systems. A dual stage catalyst system, with exhaust temperature control, can provide a robust solution to meet challenging modes of operation such as rapid acceleration and other heavy-duty transients. The Ultera® technology, developed and successfully implemented on stationary natural gas CHP (Combined Heat and Power) engines, introduces a second stage catalyst downstream of a three-way catalyst. Air is injected between the two stages to provide oxygen required for the second stage reaction that removes additional CO and NMOG. Critical to the process is to avoid the reformation of NOx.

Diesel engines are widely used to reduce CO2 emission due to its higher thermal efficiency over gasoline engines. Considering long term CO2 targets, as well as tighter gas emission, especially NOx, diesel engines must become cleaner and more efficient. However, there is a tradeoff between CO2 and NOx and, naturally, engine developers choose lower CO2 because NOx can be reduced by a catalytic converter, such as a SCR catalyst. Lower CO2 engine calibration, unfortunately, leads to lower exhaust gas temperatures, which delays the activation of the catalytic converter. In order to overcome both problems, higher engine out NOx emission and lower exhaust gas temperatures, close-coupled a diesel particulate filter (DPF) system with integration of SCR catalyst technology is preferred. For SCR catalyst activity, it is known that the catalyst loading amount has an influence on NOx performance, so a high SCR catalyst loading will be required.

Since the implementation of Euro 6 in September 2014, diesel engines are facing another drastic reduction of NOx emission limits from 180 to only 80 mg/km during NEDC and real driving emissions (RDE) are going to be monitored until limit values are enforced from September 2017. Considering also long term CO2 targets of 95 g/km beyond 2020, diesel engines must become cleaner and more efficient. However, there is a tradeoff between NOx and CO2 and, naturally, engine developers choose lower CO2 because NOx can be reduced by additional devices such as EGR or a catalytic converter. Lower CO2 engine calibration, unfortunately, leads to lower exhaust gas temperatures, which delays the activation of the catalytic converter. In order to overcome both problems, higher NOx engine out emission and lower exhaust gas temperatures, new aftertreatment systems will incorporate close-coupled DeNOx systems.

Platinum Group Metal (PGM) use is dominated by the automotive industry. The PGM market is sensitive to shifts in the drivers for emission control and the delicate supply-demand balance. Technology shifts in the emission control industry are particularly impactful because of the automotive market's dominance and the consequent ability to significantly affect metal prices. On the supply side, evolving ore ratios of platinum, palladium and rhodium, production ramp-up times, geopolitical factors, and labor relations contribute to a challenging production environment. This is mitigated by a growing above-ground supply from spent autocatalysts. The availability of spent autocatalyst is critical to alleviate the pressure on primary supply and is especially important in light of the hurdles primary PGM producers face. This paper reviews technology developments, legislative drivers, and consumer trends in the automotive industry and their impact on PGM demand.

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.

This session focuses on particle emissions from combustion engines, including measurement methods and fuel effects. Presenter Leonidas D. Ntziachristos, Aristotle University Thessaloniki

The presentation describes technology developments and the integration of these technologies into new emission control systems. As in other years, the reader will find a wide range of topics from various parts of the world. This is reflective of the worldwide scope and effort to reduce diesel exhaust emissions. Topics include the integration of various diesel particulate matter (PM) and Nitrogen Oxide (NOx) technologies as well as sensors and other emissions related developments. Presenter Atsuo Kondo, NGK Insulators, Ltd.

Modern filter systems allow a significant reduction of diesel particulate emissions. The new silicon bonded silicon carbide particulate filters (Si-SiC filters) play an important role in this application, because they provide flexibility in terms of mean pore size and porosity and also have a high thermal shock capability to meet both engineering targets and emission limits for 2005 and beyond. Particulate filters are exposed to high temperatures and a harsh chemical environment in the exhaust gas of diesel vehicles. This paper will present further durability evaluation results of the new Si bonded SiC particulate filters which have been collected in engine bench tests and vehicle durability runs. The Si-SiC filters passed both 100 and 200 regeneration cycles under severe ageing conditions and without any problems. The used filters were subjected to a variety of analytical tests. The back pressure and ash distribution were determined. The filter material was also analysed.

As emissions regulations are becoming more stringent, various efforts to improve emission performance have been carried out in different areas including the honeycomb structure of catalytic converters. This report describes the development of a simulation tool to predict emission performance and simulation results for different cell structures. The simulation model was developed based on global kinetic chemical reaction model [1]. Having tuned the reaction parameters through a light-off test and estimated oxygen storage capacity through an oxygen storage test, we ultimately tuned the model in a vehicle test (with Bags 1 and 2, FTP 75). As a result, the simulated cumulative tailpipe emissions are within ±25 percent of the test results. Parameter analyses indicate that the amount of emissions decreased as the density of cells increased and that the amount of emissions also decreased the thinner the wall thicknesses were.

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.

DPF substrate is exposed to high temperature during regeneration and to acid components in exhaust gas. Therefore, DPF material needs to have an excellent thermal shock resistance, thermal and chemical stability to the sulfuric acid. This paper presents the durability test results of the Si-SiC DPF material. In particular, thermal shock resistance, oxidation resistance and acid resistance parameters have been evaluated by comparison with recrystallized-SiC and cordierite materials. As the results, the strength of Si-SiC decreased between ΔT=500 and 600deg.C, while that of recrystallized-SiC decreased between ΔT=300 and 400deg.C. The result is attributed to the difference in the elastic modulus. About oxidation resistance, material properties of Si-SiC, compared between pre- and post- oxidation, have greater stability than those of recrystallized SiC. And naturally, both SiC materials have superior acid resistance to cordierite.

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.