Science and Technology of Catalytic Diesel Particulate Filters

CATALYSIS REVIEWS, 43(4), 489564 (2001)
SCIENCE AND TECHNOLOGY OF CATALYTIC DIESEL PARTICULATE FILTERS

Barry A. A. L. van Setten, Michiel Makkee,* and Jacob A. Moulijn Delft University of Technology, Faculty of Applied Sciences, Section for Industrial Catalysis, Julianalaan 136, 2628 BL Delft, The Netherlands
I. INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . II. THE CHARACTERISTICS OF DIESEL PARTICULATE MATTER AND EXHAUST GAS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A. Soot Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B. Diesel Particulate Matter Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . C. Exhaust Gas Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
491 492 492 493 497 500 500 501 503 503 504 508 514 514 519 526 528 537 537
III. ENVIRONMENTAL IMPACT OF DIESEL PARTICULATE MATTER AND LEGISLATION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A. Negative Aspects of Diesel Particulate Matter . . . . . . . . . . . . . . . . . . . . B. Legislation and Compliance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C. Concerns About the Effects of Legislation . . . . . . . . . . . . . . . . . . . . . . . IV. NONCATALYTIC DIESEL SOOT OXIDATION . . . . . . . . . . . . . . . . . . . . . A. Noncatalytic Oxidation Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B. Noncatalytic Filter Regeneration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . V. CATALYTIC DIESEL SOOT OXIDATION . . . . . . . . . . . . . . . . . . . . . . . . . A. Catalytic Oxidation Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B. Direct Contact Catalysts for Regeneration . . . . . . . . . . . . . . . . . . . . . . . . C. Catalyst Selectivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . D. Durability of the Catalytic Trap . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
VI. DIESEL PARTICLE TRAPS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A. Filtration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

*Address correspondence to Michiel Makkee. E-mail: m.makkee@tnw.tudelft.nl 489 Copyright q 2001 by Marcel Dekker, Inc.
www.dekker.com
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VAN SETTEN, MAKKEE, AND MOULIJN
B. VII.
Trapping by Means Other Than Filtration . . . . . . . . . . . . . . . . . . . . . . . .
545 545 545 547 548 550 550 551 553
COMMERCIAL CATALYTIC DIESEL PARTICLE FILTERS . . . . . . . . A. Flow-Through Oxidation Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B. NOx-Aided CRT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C. Integrated Catalytic Trap for Passenger Cars . . . . . . . . . . . . . . . . . . . . . EVALUATION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A. Diesel Particulate Matter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B. Diesel Particulate Matter Abatement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
VIII.
ABSTRACT
During the last few decades, concerns have grown on the negative effects that diesel particulate matter has on health. Because of this, particulate emissions were subjected to restrictions and various emission-reduction technologies were developed. It is ironic that some of these technologies led to reductions in the legislated total particulate mass while neglecting the number of particles. Focusing on the mass is not necessarily correct, because it might well be that not the mass but the number of particles and the characteristics of them (size, composition) have a higher impact on health. To eliminate the threat of diesel particulate matter, essentially absolute ltration in combination with the oxidation of all emitted hydrocarbons is what will be required. After two decades of development, the rst lters will soon be introduced on a large scale. Many different problems had to be overcome; it was especially important that the lter was robust and its regeneration was controllable. The key technology to controllable regeneration is oxidation catalysis, which is the main area of focus in this review. Catalytic lter regeneration is very complex, something which is apparent in the main aspects of catalysis (i.e., activity, stability, and selectivity). Complications are that the process conditions can be very transient and that the temperatures are usually low. It is shown that the oxidation catalyst cannot be examined isolated from the total system. Within the margins of size restrictions and an engines service life, essentially all particulate matter should be trapped, the lter should be regenerated safely, no toxic by-products should be formed, and the catalyst should not alter the ltration characteristics, and vice versa. The exhaust conditions of passenger cars are not favorable for continuous regeneration strategies, because the best strategy seems to be periodic regeneration with the aid of a catalyst. This concept is not passive, which makes it complex and expensive. The best technology for lter regeneration with trucks and buses seems to be continuous regeneration. Using the NOx present in the exhaust gas for soot oxidation amounts to a simple and robust concept. A future limitation might be the minimal required NOx:soot ratio; it is not sure if this will be met in future engines. Alternatively, a low-temperature
CATALYTIC DIESEL PARTICULATE FILTERS
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catalyst may be developed that does not require NOx. Developing such an advanced catalytic trap will be one of the major challenges of catalytic lter engineering. Key Words: Catalyst; Diesel; Exhaust purication; Filter; Oxidation; Regeneration; Soot
Combustion of fossil fuels for the purpose of transport and heating contributes signicantly to the global warming problem. In order to lower the contribution of the latter, governments should stimulate what is the most efcient internal-combustion engine: the diesel engine. However, diesel engines emit, in addition to CO and hydrocarbons, soot particles and NOx. These compounds cannot be substantially converted by using a traditional three-way catalyst, because the exhaust gas is oxygen rich, which makes straightforward NOx reduction difcult, and the residence time of the particles in the channels of monolith would be too short for complete oxidation. Developing a practical, selective DENOX catalyst for automotive applications is a big challenge. DENOX catalysis has been comprehensively reviewed in Refs. 1 4. Diesel particulate matter abatement has not been reviewed recently. Finally, after 20 years of development, devices for particulate matter control are soon to be introduced on a large scale. In the European Union (EU), particle lters have been placed in diesel passenger cars for the rst time ever, and the European Union and United States regulations for heavy-duty automotive applications will become so stringent that exhaust after treatment will be inevitable within a few years. In this review, it will be shown that oxidation catalysis is the key to nding robust ways of lowering particulate matter emissions. This review will cover the science and technology of catalytic diesel particle traps. It will mainly focus on automotive applications, but reference will also be made to megawatt (MW) engines when there are large discrepancies.
I. INTRODUCTION The air we breathe contains numerous particles, originating from natural materials, such as dust from space, skin tissue, plant materials, and wildres, and man-made materials (e.g., particles derived from construction sites, process wear, and combustion processes). The human body has protective measures against larger particles, but it cannot protect itself against particles roughly smaller than 10 mm, also known as PM-10. In the last decade, governments all over the world started to evaluate the effects on health that these particles have, especially diesel particulate matter. Diesel particulate matter is a complex multicomponent material. It consists of carbonaceous soot particles, which carry many compounds that are sometimes toxic. The formation process of diesel particulate matter will be reviewed to give a better understanding of the complexity of the material. The
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negative aspects will be briey examined to explain why governments feel that the emission of diesel particulate matter requires legislation. The way that legislation is carried out will be reviewed shortly in order to show how governments deal with this complex compound. Particles can be trapped with acceptable efciency from diesel exhaust gas by means of ltration. The lter can be regenerated by combusting the deposited soot fraction of the particulate matter. However, lter regeneration in conjunction with combustion is difcult, as it is very unpredictable. The key to control combustion is catalytic oxidation. The best way to view diesel oxidation catalysis is as a part of the integrated exhaust purication system that is intimately coupled to engine development. Catalytic diesel particulate traps will be discussed in detail: the mechanisms of catalytic and noncatalytic soot oxidation, the soot-trapping methods, soot-ignition methods, process conditions, stability requirements, the selectivity of the catalyst, and the technology of some commercially available systems.
II. THE CHARACTERISTICS OF DIESEL PARTICULATE MATTER AND EXHAUST GAS A. Soot Formation Smith (5) reviewed the different fundamental steps involved in the formation of the soot core of diesel particles. Figure 1 summarizes the main results. As a part of the fuel combustion process, diesel is sprayed into the cylinder at high pressure. The sprayed diesel fuel droplets do not mix completely with the abundant oxygen at a molecular level, which results in incomplete combustion (6). The mechanism of the reacting species is extremely complex, and many pathways lead to the polycyclic structures which are the building blocks of the soot particles. One of the main pathways is the following. Certain molecules are pyrolyzed into small unsaturated molecules where the main constituent is ethyne. The ethyne polymerizes to polyethyne and, eventually, polycyclic structures are formed by ring closure. These polycyclic structures are called platelets and are, in fact, small graphitelike sheets that could be seen as the primary building blocks of the soot particle. The platelets stack together to form crystallites, which subsequently stack together to form turbostratic particles,* as seen in Figure 1. The size of the particles increases due to particle coagulation and surface growth instigated by the addition of precursor gas-phase molecules. The surface growth lls the space between the coagulated particles, and because of this, the coagulated particles remain spherical. Ishiguro et al. (8) showed that surface growth platelets do not orient themselves in a turbostratic manner, instead they are oriented perpendicular to the radius of the particle, which gives the soot particles a rigid outer shell, which
*The denition for turbostratic is a particle where the building blocks (i.e., platelets) are concentrated in a random orientation around the center of the particle (7).
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Figure 1.
Schematic mechanism of the formation of soot particles.
is thermodynamically more stable than the turbostratic inner core. When surface growth stops, the growth of the spherical particles stops. These particles are then called primary soot particles. Those primary soot particles continue to coagulate and form chainlike aggregates. Different aggregates can even clot to form large agglomerates.
B. Diesel Particulate Matter Composition 1. Particle Size Distribution According to Kittelsons review (9) on nanoparticles, the composition of diesel particulate matter depends on where and how they are collected. In the tailpipe, where the temperatures are high, most of the volatile materials (hydrocarbons, sulfuric acid) are in the gas phase. As the exhaust gas cools down and is diluted by the ambient air, nucleation, condensation, and adsorption transform the volatile materials to solid and liquid particulate matter. During engine emission testing, this process is simulated in a dilution tunnel in order to take realistic samples for particle measurements (10). The details of the collection and cooling processes will determine the relative amounts of material that will adsorb or condense onto existing particles and nucleate to form new particles. When emitted into the environment, the particle properties continue to change due
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Figure 2. Scheme of engine exhaust particle size distribution, both mass- and number-based concentrations are shown. (From Ref. 9.)
to condensation and solar radiation (11). Figure 2 shows what a typical particle size distribution in diesel exhaust gas is like. Condensed hydrocarbon and sulfuric acid droplets can be found in the nuclei mode, chainlike aggregates of primary soot particles and associated hydrocarbons in the accumulation mode, and reentrained agglomerates of chainlike aggregates in the coarse mode (9). Figure 3 gives a schematic structure of a diesel particle. Because the measured properties of the diesel particles depend on how, when, and where they are measured, unexpected effects can be encountered. For instance, it is possible to measure a negative ltration efciency when it is dened according Filtration efficiency Particles downstream trap 100% Particles upstream trap 1
Figure 3. Schematic structure of a chainlike aggregate of primary soot particles and associated compounds. (From Ref. 185.)
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Figure 4. Illustration of the condensation mechanisms that can operate in diesel exhaust gas: (a) nucleation; (b) adsorption.
This was reported by Baumgard and Johnson (11), who found negative values for the particle number ltration efciency of 230% to 2460% when using a trap, which was caused by particle formation downstream of the trap during the dilution of the exhaust gas. This effect relates to the hydrocarbons which are present in the exhaust gas (9). As the exhaust gas cools down, hydrocarbons condense along two pathways: There is nucleation which leads to the formation of new particles and there is adsorption on existing particles. When an engine is optimized and designed to emit fewer particles in the accumulation mode, there is less surface area present in the exhaust gas for adsorption of the hydrocarbons, thus favoring the nucleation of droplets in the nuclei mode, which can result in a major increase in the total number of particles. Figure 4 shows the two pathways for condensation of hydrocarbons. A lower diesel particulate mass can thus lead to an increase in the number of nanoparticles!
2. Sulfates and Metal Ash The sulfates in diesel exhaust gas originate from organic sulfur compounds in diesel fuel. The sulfur is combusted in the engine to form SO2, approximately 2% of which is oxidized to SO3 (12). The SO3 quickly reacts with water to form sulfuric acid droplets [boiling point (bp) 3308C (13)]. A small mass fraction of diesel particulate matter consists of inorganic ash. It spans a wide range in composition, depending on factors such as engine type and age, driving conditions, type of fuel, fuel additives, motor oil additives, and
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metallurgy of the exhaust manifold and exhaust pipe. It generally consists of one or more of the following components (14): . Sulfates, phosphates, or other oxides of calcium, zinc, magnesium, and other metals that are formed in the engines combustion chamber from burning of additives in the engine lubricating oil . Oxides of metals such as iron, copper, chromium, and aluminum, resulting from wear of the diesel engine, carried into the combustion chambers by the lubricating oil . Metal oxides from catalytic fuel additives . Iron, chromium, nickel, and aluminum oxides resulting from corrosion of the engine exhaust manifold and other components of the exhaust system With small modern diesel engines, the ash contribution to the diesel particulate matter will be relatively low. In the EU and the United States, the contribution of sulfur to diesel road-transport emissions will even be lower in the near future. The permitted fuel sulfur level will be lowered from 500 ppm to 50 ppm in the EU in 2005 and to 5 30 ppm in the United States by 2007 (15). For large diesel engines used for powering ships and generating electricity (MW engines ), the contribution of sulfur and ashes to the total amount of particulate matter can be more problematic, because such engines often run on heavy fuel oil (HFO). In Table 1, the concentration of vanadium, sodium, and sulfur in HFO has been given together with the amounts that pass a typical MW engine. It is clear from Table 1 that enormous amounts of metals and sulfur are fed into a MW engine. Because these engines are designed to run continuously, one can calculate that in an extreme case, 250,000 kg sulfur, 750 kg vanadium, and 177 kg sodium will pass through such an engine on a yearly basis. If we assume that 2% of the sulfur is converted to SO3 (12) and hydrated, then approximately 15,500 kg/year sulfuric acid will pass through the exhaust pipe.
Table 1. Vanadium, Sodium, and Sulfur Concentrations in Heavy Fuel Oil (HFO), and the Fuel Consumption at the Maximum Power Output of a Typical MW Engine Compound HFO S V Na Concentration 34 g/kgfuel 102 mg/kgfuel 24 mg/kgfuel Consumption 847 kg/h 28.8 kg/h 86.4 g/h 20.3 g/h
Note: See also Table 2. Source: Ref. 191.
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3. Denition of Diesel Particulate Matter Various terms are used to describe the particles emitted by diesel engines: Diesel particles or particulates: the individual particles present in diesel exhaust gas. Diesel particulate matter: particulate means made up of particles (16). Diesel particulate matter is the generic term for the solid material that originates from diesel exhaust gas. Because the composition depends on the sampling method, the US EPA dened the term diesel particulate as the material collected from diesel exhaust gas on a polytetrauoroethylene-coated glass ber lter at 45 528C (17). Diesel soot: Diesel soot is the carbonaceous part of diesel particulate matter. It is the fraction that is oxidized during regeneration of a diesel particle lter. Often these terms lead to confusion. In order to come to unambiguous legislation, simplication was unavoidable. It is not surprising that all over the world up to now the emission has been dened as the total particulate mass (TPM) deposited on a lter under controlled conditions (see denition of diesel particulate). The denition includes both solids and condensed liquids. The EPA divided the total particulate mass in the following fractions (17): Solvent extractable fraction (SEF): the fraction that can be extracted from the TPM by various solvents and includes both organic and inorganic solvent extracts Soluble organic fraction (SOF): the fraction of the TPM that is removed by Soxhlet extraction with dichloromethane Total organic extract fraction (TOE): the fraction of the TPM that is removed by Soxhlet extraction using a binary mixture of 32:68 (w/w) of toluene:ethanol Water-soluble sulfates: the major extractable inorganic fraction in the particulate sample Combined water: water that is chemically combined with sulfuric acid and any hydrophilic metallic sulfates that may be present in the TPM Residual carbon particulate (RCP): the calculated particulate mass remaining after the removal of the total organic fraction, the sulfate fraction, and the combined water fraction.
C. Exhaust Gas Conditions Diesel exhaust gas conditions can vary from application to application, which means that in each case, a catalytic trap has to be selected and ne-tuned. In Table 2, typical data for stationary conditions of a passenger car, heavy-duty
498 Table 2. List of Exhaust Conditions in a Typical 1998 Passenger Car Diesel Engine, a Typical Heavy-Duty Truck, and a Typical MW Diesel Electricity Generator BMEPa (bar) 1 max 1 max n.q. 24.5 ( = max) 12 6 rpma (min21) 2000 2000 4000 4000 2000 599 599 599 Output (kW) n.q.a n.q. n.q. n.q. 210 3956 1935 966 qma (kg/s) 0.08 0.26 0.19 0.24 0.39 8.3 4.8 2.9 Tupa (8C) n.q. n.q. n.q. n.q. 580 530 448 392 Tdowna (8C) 190 530 250 640 530 340 322 309 TPM (g/h) 0.1 1.7 0.7 27 16.8 n.q. n.q. n.q. Boschb 0.2 0.5 0.2 1.9 0.7 0.8 1 1.3 NOx (ppm) 70 1400 250 1000 1100 n.q. 830 764 HC (ppm) 100 20 10 10 40 31 39 47 CO (ppm) 1500 150 150 150 170 40 51 75 CO2 (%) 4.5 10.8 3.3 10.2 8 3.6 4.2 4.1 O2 (%) 14.4 5.1 16.1 6.1 10 11.9 13.8 14.4 H2O (%) 4.2 10.1 3.1 9.5 n.q. n.q. n.q. n.q.
Engine Passenger car
Truck MW engine
BMEP, brake mean effective pressure; qm, exhaust gas mass ow rate; rpm, rotational speed; TPM, total particulate mass; Tup, temperature upstream turbocharger; Tdown, temperature downstream turbocharger; n.q., not quoted. b Bosch smoke number. The Bosch smoke meter is a lter-soiling spot meter: Exhaust is passed through a white lter paper, and the darkening of the paper can be taken as a gauge of the black smoke density. The Bosch number is a measure of the darkening of the lter paper; it is scaled arbitrarily from 0 to 10 (196). Source: Date from Refs. 191193.
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Figure 5. Exhaust temperature ranges and median temperatures close to the manifold for different light-duty diesel vehicles, as measured during different test procedures. DI, direct injection; IDI, indirect injection, TDI, turbo direct injection; EDC, European driving cycle; FTP, federal test procedure (US). (From Ref. 18.)
truck, and a MW engine have been listed. For the passenger car, the reported mass ow rates would result with a standard 2.5-L lter in gas hourly space velocities of 100,000 300,000 L/L/h. For trucks and MW engines, the space velocities can be lower because those engines have less stringent size restrictions for the lter. Just measuring engine characteristics under stationary conditions will not be adequate for predicting the performance of a catalytic particle trap. Diesel engines, especially those adapted for road applications, are used in a transient way, as represented by various drive cycles (Section III.B). Figure 5 shows typical exhaust temperature ranges and median temperatures close to the exhaust manifold of some light-duty vehicles during transient use (18). The median temperatures close to the exhaust manifold are in the range of 140 2508C. A particle trap will, however, not be placed directly behind the manifold, but downstream of the turbocharger, and because of this, it will experience even lower temperatures. These lower temperatures present a serious threat to lter regeneration. To avoid problems associated with low exhaust temperatures (e.g., city driving), a passenger car trap should be constantly monitored and an independent regeneration strategy should be incorporated.
1. Trade-off Effects The preferred method for diesel particulate matter abatement is that of reducing its formation. However, if engine adjustments are made to reduce the
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Figure 6. Schematic trade-off curves for NOx and particulate matter: 0, base case; 1, trade-off curve by increasing EGR and retarding injection timing; 2, shifted trade-off curve by combining higher injection pressures and cooled EGR. (From Ref. 19.)
soot formation, this will have an impact on other processes taking place in the cylinders and will thus only be acceptable if it offsets the other accompanying changes in the fuel combustion process. These considerations are referred to as trade-off effects. Figure 6 shows schematic trade-off curves for the emissions of NOx and particulate matter. Starting with an engine without exhaust gas recirculation (EGR) at standard injection timing, NOx emissions can be decreased by increasing the EGR rate or retarding the injection timing. However, these measures increase particulate mass emissions. Other measures, like reduced oil consumption, higher injection pressures, and cooled EGR, shift the curve to a lower one, but the trade-off remains present (19). III. ENVIRONMENTAL IMPACT OF DIESEL PARTICULATE MATTER AND LEGISLATION A. Negative Aspects of Diesel Particulate Matter Atmospheric particles give rise to concerns for many reasons: They diminish visibility; they change the heat balance of the atmosphere; they settle on plants and interfere with photosynthesis; and they penetrate the lungs, blocking and irritating the air passage ways (20,21). Diesel particulate matter is suspected of causing all kinds of health problems, like asthma, persistent bronchitis, and lung cancer. Several agencies have reviewed the relevant scientic aspects, including the epidemiologic, toxicologic, and experimental sides of diesel exhaust, and have classied (or proposed to classify) that diesel exhaust, or its particulate fraction, is a potential, probable, or denite human carcinogen (22). There is, however, a lack of reliable data linking lung cancer to diesel exhaust, because of which, for instance, the U.S. EPA considered characterizing diesel exhaust as being likely to cause lung cancer rather than very likely (15). For more detailed information on the physicochemical properties of airborne (nano)particles and their health effects, see Ref. 23.
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B. Legislation and Compliance A detailed description of the various diesel emission standards and vehicle certication tests is beyond the scope of the present review. Up-to-date information can be found on the Internet (24). The technology of exhaust emission tests has been comprehensively documented by Klingenberg (10).
1. Legislation In Europe, emission standards are given in g/km for light-duty vehicles (passenger cars, ,1305 kg; and vans, gross weight , 3500 kg), and in g/kW h for heavy-duty vehicles (trucks and buses, speed . 25 km/h, gross weight . 3500 kg), and off-road engines. Stepwise reduction is demanded for the total particulate mass and toxic gas components. In the EU, the steps are referred to as Euro standards. They are given in Table 3 for passenger cars and in Table 4 for heavyduty vehicles. It can be seen that in 2005 only new light-duty vehicles which produce at most 0.025 g particulate/km and new heavy-duty vehicles which produce 0.02 g particulate/kW h will be certied for driving in the EU. Engine certication for light-duty vehicles is performed on a chassis dynamometer, which is used to simulate driving behavior. Figure 7 shows
Table 3. Phase Euro Euro Euro Euro Euro I IIIDI IIDI III IV
European Emission Standards (in g/km) for New Passenger Cars Year 1992 1996 1999 2000 2005 HC+NOx 0.97 0.7 0.9 0.56 0.30 NOx 0.50 0.25 CO 2.72 1.0 1.0 0.64 0.50 TPM 0.14 0.08 0.10 0.05 0.025
Table 4. Phase Euro I Euro II Euro III Euro IV Euro V

a
European Emission Standards (in g/kW h) for New Heavy-Duty Vehicles Test Cycle ECE R-49a ECE R-49 ESC and ELRa ESC and ELR ESC and ELR HC 1.1 1.1 1.1 1.1 0.66 0.46 0.46 NOx 8.0 8.0 7.0 7.0 5.0 3.5 2.0 CO 4.5 4.5 4.0 4.0 2.1 1.5 1.5 TPM 0.612 0.36 0.25 0.15 0.10 0.02 0.02
Year, Category 1992, ,85 kW 1992, .85 kW 1996 1998 2000 2005 2008
ECE R-49, steady-state cycle for heavy-duty truck engines; ESC, European stationary cycle (replaces the R-49 test); ELR, European load response test.
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Figure 7. State of affairs in the EU in 1999 for diesel passenger cars. (The U.S. SULEV II standard has been given for comparison.) The sum of NOx and hydrocarbons has been plotted as a function of total particulate mass. Emission data from Ref. 186; emission data from prototypes from Ref. 187.
certication data measured during the European driving cycle for European passenger cars. The data are presented as a scattergram in which the sum of NOx and hydrocarbons has been plotted as a function of total particulate mass. In 1999, none of the licensed light-duty vehicles complied with the Euro IV total particulate mass standard, but it can be seen in Figure 7 that there are prototypes that did. It is expected that, in some cases, car producers will be able to fulll the Euro IV standards without there being a need for lters. However, because of the introduction of a lter on a serial passenger application in the EU in 2000 (Section VII.C), it is expected that other car manufacturers will follow and that soot lters will become more commonplace in the next few years. In the United States, lters might be inevitable. Figure 7 shows the Super Ultra Low Emission Vehicle II (SULEV II ) standard for NOx, hydrocarbons, and total particulate mass. The SULEV II standard is a more severe standard and it might eliminate light-duty diesel car sales in California when it is phased in between 2004 and 2007 (25). After the $1 billion settlement of the charges brought by the U.S. EPA against several heavy-duty engine producers, it became clear that the producers of heavy-duty engines have major problems when it comes to meeting emission standards and keeping fuel efciency levels high. To get trucks certied, in some cases a defeat device has been incorporated (26). The truck engine would switch to a less fuel efcient but cleaner mode during laboratory testing, whereas during real highway driving, it would switch to a fuel-efcient but more polluting mode. In the near future, emission standards for heavy-duty vehicles will become very stringent in the EU and the United States; lter technology will become inevitable.
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C. Concerns About the Effects of Legislation Whether the legislation introduced in the last few years has pushed the emission reduction technology in the right direction remains debatable. To meet the standards, cars were developed which emit less particulate mass. Unfortunately, the reduction of particulate mass may be accompanied by a dramatic increase in the number of nanoparticles (11). A possible mechanism for this was shown in Section II.B. Nanoparticles are thought to be the most dangerous diesel particulate fraction (27 29), although they only make a small contribution to the total particulate mass, as illustrated in Figure 2. Legislating particle numbers will pose many practical problems because it is difcult to carry out particle number measurements. The notion of regulating particle numbers might also be too simplistic. Bagley et al. (30) found that regardless of the engine and exhaust aftertreatment device implemented, the use of a low-sulfur fuel led to a 90% reduction of particle numbers. However, the mutagenicity of the particle phase was signicantly increased, because other fuel composition changes accompanied the change to low-sulfur fuel. The best method of legislation will be to express the toxicity of diesel particulate matter. This point was also mentioned in the VERT (Verminderung der Emissionen von Realmaschinen im Tunnelbau) program (31 33), where it was reported that gravimetric analysis is nonspecic with respect to the chemical composition and particle properties (such as size and surface) and, hence, delivers no toxically relevant information. Perhaps, the best policy is to demand essentially zero-particle emissions. Filtration is the most promising way, because for particles in the range 20 500 nm, ltration efciencies higher than 99% have already been reported (31).
IV.
NONCATALYTIC DIESEL SOOT OXIDATION
In the early 1980s, great advances were made with diesel particle-trapping techniques. The wall-ow monolith was developed and it was found that particulate emissions could be controlled without having to make engine adjustments. It was thought that a method for oxidizing the trapped soot fraction of diesel particulate matter would be discovered quickly. A catalytic device like the three-way catalyst for gasoline engines was seen as unreliable, because the onset temperature of 400 4508C of the soot combustion catalysts of those days was too high for spontaneous regeneration (34). The general regeneration strategy followed has been to substantially load the trap with soot, ignite the soot by raising the temperature, and then switch the heating off. The required high temperature for completion of the regeneration is maintained by the energy released during the exothermic soot-combustion reaction. The mechanism is known as self-supporting ame propagation (35). This type of
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regeneration can easily get out of control and damage the lter, due to chaotic thermal runaways. Higuchi et al. (36) recognized early on that it is inuenced by many variables like temperature, oxygen concentration, deposited soot amounts, and gas ow rate and that these conditions should remain within certain limits to guarantee safe regeneration. This is in conict with the demand that a trap should be able to regenerate during all driving conditions (34) without the intervention of the driver (37). Another problem that Higuchi et al. found was an inadequate regeneration efciency: Up to 35% of the soot can remain on the lter. This is undesirable because it will create a soot gradient buildup, which can lead, when nally ignited, to extremely high temperature gradients within the lter.
A. Noncatalytic Oxidation Mechanism 1. Unied Mechanism The reactivity of different carbon materials is a function of such properties as crystallite size, crystallite orientation, vacancy concentration, and impurity concentration, type, and location (38). These properties control the fraction of the carbon material that is susceptible for the carbon oxygen reaction, which is also known as the active surface area. Moulijn and co-workers (39 42) proposed a reaction mechanism for the carbon oxygen reaction. The mechanism does not account for all observations made during the combustion of carbonaceous materials, but it is considered by the authors to be a step further toward a unied carbon oxidation mechanism. The mechanism containing simplied oxygen complexes and graphite structures is shown in Figure 8. Graphite that contains a ketone surface oxygen complex reacts with oxygen to form a surface semiquinone group and a physically adsorbed oxygen atom (step a). The C}C bond strength in the semiquinone complex is only slightly weaker than the C}C bond strength in graphite. It is unlikely that the semiquinone complex will decompose, which is why this complex is called a stable surface oxygen complex. Due to the electronegativity of the oxygen atoms in the semiquinone complex, the C atom between the CO groups becomes a target for bonding with oxygen. A semiquinone complex with off-plane oxygen is formed (step b), and this results in the lowering of the C}C bond strength of the neighboring C atoms. The complex decomposes (step c) and graphite with a carbonyl group is formed. The C atom next to the carbonyl group becomes a target for bonding with oxygen due to the electronegativity of the oxygen atom in the carbonyl group. A carbonyl complex with off-plane oxygen is formed (step d), and this results in the lowering of the C}C bond strength of the neighboring C atom. CO is released (step e) and the reaction cycle can start again with step a. In steady state, the reaction rate is not inuenced by the rateconstant values of the individual steps, but by the amount of carbon complexes formed on the active surface area.
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Figure 8. Reaction mechanism of the noncatalytic oxidation of carbon. Reaction mechanism constructed based on Ref. 40.
2. Kinetics The oxidation rate of carbonaceous materials can be described using a general kinetic model equation: r N T kTf pO2 ; pH2 O ; pNO2 ; 2 in which r is the reaction rate, N T is the total number of active carbon sites, k(T ) is a temperature-dependent reaction rate constant, and f( pO2, pH2O, pNO2,) is a function which describes the dependency of the reaction rate on the partial pressures of various gas components. The temperature-dependent rate constant k(T ) can be described referring to the Arrhenius equation: kT k0 e 2Ea =RT 3
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in which T is the absolute temperature, k0 is the pre-exponential factor, R is the gas constant, and Ea is the activation energy. The inuence of the gas partial pressures is often limited to the inuence of the oxygen partial pressure, described by an nth order: f pO2 ; pH2 O ; pH2 O ; pO22 This leads to the following equation for the oxidation rate r: r N T k0 e Ea =RT pO22 The total number of active carbon sites NT can be described by NT l Sa Sa;0 6
nO nO
in which l is the surface concentration of active sites, Sa is the actual surface area, in this context known also as total surface area (TSA), and Sa,0 is the initial surface area. The dependency of N T can be described as a function of conversion. A simple approach is to use a nth-order model. The relation between the surface area and the conversion is then Sa 1 2 jnj Sa;0 7
in which j is the conversion and nj is the reaction order in carbon. For nj 2=3; the nth-order model is also known as the shrinking core model: the surface area is directly proportional to the outer surface area of the carbon particle, which is assumed to be spherical. The nth-order model does not predict the reaction of many porous solids with gases accurately. For highly porous carbons, like soot and activated carbon, Sa is created by a complex network of pores. Soot pores consist of the space between the primary soot particles: 3-nm pore openings can be found between 20-nm primary soot particles (43). Due to pore growth and opening of closed pore space, the Sa will be increased and, as a consequence, the reaction rate can increase during the reaction. Several pore models have been put forward to allow for pores in reacting solids. Pore models exist that idealize the complex internal structure by geometric assumptions of cylinders and spheres, as illustrated in Figure 9a, or by a network model of pore topology, as illustrated in Figure 9b. The random pore model of Bhatia and Perlmutter (44) describes the pores as overlapping cylindrical surfaces. Important features of the model are that Sa is described at any given conversion as a function of an initial pore structure parameter c and that reactions are represented which show a maximum in the reaction rate (i.e., c , 2) as well as ones that do not (i.e., c . 2). The conversion dependence of the surface area is described as follows: p Sa 1 2 j 1 2 c ln1 2 j Sa;0 8
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Figure 9. Illustrations of pore descriptions by different conversion models: (a) cylindrical surfaces; (b) three-coordinated Bethe network. (From Refs. 44 and 45.)
The random pore model can successfully predict experimental observations, but the effect of the pore topology is included in an average sense. Because of this, it is not possible to evaluate Sa in a fundamental fashion. Reyes and Jensen (45) used a Bethe network to describe the pore structure of a solid. With this model, the conversion dependence of the surface area is described as follows: Sa 1 2 e0 9 1 2 j 1 1 j Sa;0 e0 where e0 is the initial porosity of the material. Discrepancies between model predictions and experimental observations should not only be attributed to assumptions made in the description of the evolution of physical and transport properties with conversion, but also to catalytic effects by inorganic impurities present in the solid material (45). The surface concentration in active sites (l ) is also known to cause discrepancies, because it can change during the ongoing reaction according to Laine et al. (38) and is probably a function of the temperature according to Kapteijn et al. (41). The above-mentioned observations are mainly based on kinetic considerations. Ishiguro et al. (46) performed a microstructural analysis of diesel soot oxidation and proposed the following steps: 1. To release or oxidize occluded species 2. To allow graphitic layers to grow in primary soot particles 3. To induce ne-particle formation by aking off crystallites from the outermost shell of the primary particles It is likely that oxidation models can be further rened, but it will be very difcult to attain a unied model to account for the reaction kinetics of the complete class of carbon materials, because the class of materials is very large and there are many parameters to include.
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B. Noncatalytic Filter Regeneration 1. Induced Periodic Regeneration Basically there are two ways to ignite trapped diesel soot. The soot can be indirectly ignited by raising the temperature of the exhaust gas or lter, or directly by selectively raising the temperature of the soot itself. External Heating Placing an electrical heater or fuel burner upstream of a lter seems like an obvious method, because fuel and electricity are easily available in a vehicle. Fuel burners are favored because they are up to ve times more energy efcient than electrical heaters (47). On the other hand, a fuel burner may give rise to secondary emissions, is more complex, and is less reliable, because its ame has to be ignited. If ame ignition fails, the lter could be soaked with fuel, which can lead to a disastrous thermal runaway (48). In general, preheaters are not attractive, because they must heat up all of the exhaust gas, something which is not very energy efcient. Further, the conditions in the exhaust pipe are transient, which makes regeneration with a burner problematic (18). One way of lowering fuel usage is by using a bypass system (49), in which the full exhaust ow does not pass through the lter during regeneration. These types of systems are, however, rather difcult to apply. A niche market for such technology could be vehicles with known operation patterns, like forklifts (50). Engine Controlled Heating Modern diesel engines can have exible fuel injection and control systems that can be used to produce the required additional heat in the engine. Several options exist: . The exhaust gas can be heated by throttling the gas stream. This is not a favored method because engine power is decreased during throttling, making regeneration control difcult because of the reduced oxygen content (51). On the other hand, if the lter is highly loaded with soot, it could be a distinct advantage because the reduced oxygen content would lead to a reduced exotherm, which could provide a means of control to prevent lter damage. . By varying fuel injection timing, the combustion process can occasionally be adjusted to achieve exhaust temperatures which are high enough to induce regeneration. The four demands that have to be met when regeneration is to be induced in an acceptable manner with this approach are as follows (52): (1) maximum temperature increase at minimum fuel expense; (2) the driver should not be involved; (3) there should be no
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additional noise; and (4) no additional by-products should be formed, like CO, unburned hydrocarbons, and soot. To fulll these demands, fuel is injected during different phases of the cylinder cycle to produce the required amount of work and heat (52). Basically, it means that when regeneration is initiated, the engine is operated in the usual way, with additional fuel injection at the top end of the cylinders expansion stroke. There, no additional work can be done and the energy is released as heat. . Gantawar et al. (53) raised the temperature by temporarily ramping the engine to full load in order to initiate self-supporting regeneration and then, subsequently, reducing the engine to idle. Such a regeneration strategy is not favored in practice because it cannot be initiated independently by a management system: The driver is forced to drive at high speed once in a while. Microwave Heating Garner and Dent (51) reported regeneration efciencies of 40 80% with microwave regeneration. They attributed these low values to uneven heating of the soot: Regeneration efficiency Soot combusted during regeneration 100% Soot present at start regeneration 10
During their experiments, the soot was ignited for 7 min; the complete regeneration needed 23 min to complete. The reason why regeneration failed was probably not because the soot ignition failed, but because the regeneration reactions were not fully self-supporting. Walton et al. (54) improved the regeneration efciency by incorporating ferrite in the lter. Ferrite heats equally well in the electric and magnetic eld components of microwave radiation and it provides uniform energy input into the soot-loaded lter. Nixdorf et al. (55) solved the problem of uneven heating by developing a SiC ber material that is very efcient in converting microwave energy to heat requiring only 0.015 kW h for regeneration. The regeneration of lters based on this material was, however, only demonstrated under idle conditions, whereas it is required that particulate lters can be regenerated at all conditions. Microwave regeneration is not considered practical and it will most probably not be applied (18). Internal Filter Heating The temperature in a lter can be raised internally by incorporating electrical heating elements into the lter structure. Huthwohl et al. (35) developed a wallow monolith containing electrical heating laments. In this way, the soot could be ignited directly, without the need to heat all exhaust gas. The system was further optimized with catalysts to achieve a maximum regeneration efciency
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Figure 10.
Schematic illustration of monolith channels with internal electrical heating wires.
during self-supporting regeneration. Figure 10 shows a monolith with internal electrical heating wires. Sekhar et al. (56) developed a foam lter based on a metal ceramic composite. When an electric current is applied to the composite lter, it will heat up like a heating element. No results relating to improved regeneration were reported for this composite trap. Simon et al. (34) developed a rotating miniburner which could heat a wall-ow monolith locally to achieve a regeneration efciency of 100% with a fuel efciency loss of only 1%, without the need for all exhaust gas to be heated. Aerodynamical Regeneration Since the early 1990s, Levendis and co-workers (57,58) have been developing an aerodynamical regeneration system. A more recent prototype consists of a normally operated wall-ow monolith where the exhaust ow is switched off every 13 min and a 7.3-bar backpulse is given for 3 s. During these 3 s, the exhaust gas and the ltered particulate matter is made to ow into a nylon lter bag or in an electrical incinerator. For practical applications, the system is rather complex and impractical (18). 2. Induced Continuous Regeneration Certain induced regeneration methods do not rely on high temperatures. They might be applied in a continuous manner at an acceptable energy expense. Nonthermal Plasma Reactors A plasma is a highly reactive gas that consists of ions and radicals. In the plasma, electrons are usually accelerated by voltages of 20 30 kV. The high-
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energy electrons collide with gas molecules and transfer their energy by two pathways: dissociation of molecules or by raising the vibrational energy of molecules, thereby raising the temperature. A plasma which is very efcient in the rst pathway but not in the second one is called a nonthermal plasma. Its energy might be applied to convert low-concentration pollutants rather than to raise the temperature of the total exhaust gas volume. However, due to the low contamination concentrations in exhaust gas, it is unlikely that the contaminants will be directly dissociated. In exhaust gas, the electrons deposit their kinetic energy primarily into the major exhaust gas components, N2 and O2 (59): e 1 N2 !e 1 N 1 N e 1 O2 !e 1 O 1 O 11 12
The N and O radicals can cause various reactions, the reduction of NO being the desired one (59): N 1 NO !N2 1 O 13
There are two reasons why plasma reactors were not instantaneously a success. First, the highest electric eld that can be applied while maintaining a nonthermal plasma (the electric breakdown threshold) coincides with the optimal electron mean energy for dissociation of high amounts of oxygen molecules, and not for dissociation of nitrogen molecules (59). Figure 11 illustrates this. Mainly oxygen radicals are produced, and the number of nitrogen radicals needed for reaction (13) are quite low. The production of each nitrogen radical costs 310 eV at the electric breakdown threshold. If we assume that only nitrogen molecules are dissociated and that all of the produced nitrogen atoms are used for reaction (13) in
Figure 11. Number of ground-state and metastable excited-state N and O radicals produced per 100 eV electrical input as a function of the average kinetic energy of the electrons in the plasma for a typical exhaust gas containing 10% O2, 10% CO2, 5% H2O, and N2. (From Ref. 59.)
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order to convert the 1100 ppm NOx present in the exhaust gas of the truck given in Table 2, then 460 kW(!) would be required to achieve 100% NOx reduction (the truck engine produces 210 kW at the given conditions). Even if the electric breakdown threshold could be raised to a higher value, the energy requirement would still be very high. For an electron mean energy of 20 eV, a power of 74 kW would be required. Practically, this means that plasmas cannot reduce NOx to N2, which was conrmed by Hoard (60). Second, the combination of highly reactive radicals and a wide range of diesel exhaust components makes for a wide range of products which can be formed, such as a net NOx production (61,62), organic nitrates (63), NO2 (61 64), acetaldehydes and alcohols (63 65), CO from CO2 (66), particulate matter (66), and unknown by-products (66,67). This gives rise to two additional problems. First, it complicates the analysis of the part played by the plasma in reducing NOx; second, whether the formation of these by-products is desirable remains doubtful. Hoard and Balmer (63) showed clearly that it is easy to misinterpret NO conversion with a plasma for reduction to N2. They measured, with a dielectric barrier discharge noncatalytic plasma reactor, a NOx conversion of 26% by using a chemiluminescence analyzer (CLA) for measuring NOx and Fourier-transform infrared (FTIR) analysis for measuring NO, NO2, HONO, and NH3. It is tempting to conclude, based on the analysis of these nitrogen-containing species, that the plasma was capable of reducing NO to N2. This happened not to be the case, because the NO reappeared when a Cu ZSM catalyst was placed downstream of the plasma, which led to the conclusion that the NO conversion was due to the formation of an undetected product, which was later identied as HNO3 (60). The best way to determine the amount of NOx converted to N2 would be by detecting the amount of N2 that is formed. However, N2 is the main constituent of exhaust gas, which makes changes in the ppm level hard to detect without isotopic labeling or by replacing with another balance gas. Hoard and Balmer (63) performed such experiments with helium as the balance gas, in which they used CLA, mass spectrometry, and gas chromatography for analyzing the product gases. On one hand, they found, for a conguration where a proprietary catalyst was placed downstream of the plasma reactor, an apparent NOx reduction of 60%. On the other hand, they found that only 41% of the NOx converted was reduced to N2.
Possible Applications Because O2 is easily dissociated at the electric breakdown threshold, it will be mainly O radicals that are produced in exhaust gas. Most research currently focuses on the utilization of these O radicals for, for instance, NO2 production. NO2 is more reactive than NO, because, depending on which plasma is generated, NO2 enhances catalytic reduction with NOx (66,68 70) and, as with a NOx-aided continuously regenerated trap (CRT), oxidation of soot (65). Figure 12 is a diagram of a plasma CRT.
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Figure 12.
Simplied diagram of a continuously regenerated plasma trap.
Winterbottom and co-workers (71) developed a more practical design for a nonthermal plasma reactor (Fig. 13) and claimed that it is the holy grail of diesel emission purication. They claimed a promising performance both for removing NOx and particles at an acceptable energy consumption. In a more recent publication (72), the system is no longer the holy grail, because the claim of NOx reduction is not mentioned anymore and only the soot-removal claim remains. The ndings are based on short-term experiments because of which it is difcult, at present, to determine what the real potential of the system is. Thermal Plasma Levendis and Larsen (73) investigated soot oxidation in air that had been ionized with a thermal plasma. They conducted experiments in the range 200 4508C and occasionally found that the oxidation rate increased more than 100%. They attributed this to the generation of O radicals and NO2. The applicability of the system is questionable because it generates NOx.
Figure 13.
Illustration of the Electrocat system. (Courtesy of AEA Technology.)
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Figure 14.
Illustration of the electrochemical diesel particle lter. (Courtesy of DINEX.)
Electrochemical Regeneration Christensen et al. (74,75) reported having developed an electrochemical reactor (Fig. 14) which can remove 90% particulate mass, 50% CO, 50% hydrocarbons, and 10% NOx at temperatures above 2508C with a fuel penalty of only 1%. The system consists of porous ceramic lter tubes, covered with a catalytic electrode, to which a voltage of 20 60 V dc is applied. Particulate matter that has been deposited on the lter tubes is oxidized electrochemically. This system looks interesting, but, until now, only very short time-scale experiments have been reported.
V. CATALYTIC DIESEL SOOT OXIDATION In general, the catalytic oxidation of soot is slow, because the solid particles are large and, when deposited, immobile. Because of this, they do not penetrate into the catalysts micropores or mesopores where catalytic processes usually take place. Soot oxidation takes place on the lter walls of the particle lter where the catalyst has been deposited. Table 5 gives some of the characteristic physical properties of a monolith, ceramic foam, and a typical g-alumina catalyst pellet bed; for reference, the size of a typical soot particle and a benzene molecule are indicated. It is clear that there are enormous size differences when there is a sootto-benzene diameter ratio of 1000:1 and a monolith-to-pellet bed surface-area ratio of 1:340.
A. Catalytic Oxidation Mechanism The mechanism underlying catalytic oxidation of carbonaceous materials is difcult to study because of the complexity of the processes taking place at different size scales.
CATALYTIC DIESEL PARTICULATE FILTERS Table 5. Property Channel opening (mm) Size of pellet (mm) Bulk density (g/mL) Void (vol%) Pore volume (vol%) Solid part (vol%) Surface area (m2/g) Outer surface area (cm2/g) (cm2/mL) Diameter reactant (nm) Physical Properties of a Monolith, Ceramic Foam, and g-Alumina Pellet Monolith 1.5 0.68 63 18.6 18.4 0.53 25c 17c Foam 0.25 0.36 79.3 3.0 17.7 0.10 31 11 Pellet 1.425 0.60b 42.1b 15.1b 42.8b 180 76 46 Soot 500d
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Benzenea 0.5
Note: By way of comparison, the diameter of an average soot particle and a benzene molecule are given. a Benzene was chosen to represent a typical hydrocarbon. b Values on a basis of dense packing in a reactor of 8.5-mm inner diameter. c It was only inner wall surfaces of straight channels that were considered. d Average particle on mass basis, as seen in Figure 2. Source: Ref. 89.
1. Atomic Processes Two general ways have been proposed for the catalytic action on an atomic scale; they can be classied as either electron-transfer mechanisms or oxygentransfer mechanisms: Electron transfer: The electron-transfer mechanism was originally proposed by Long and Sykes (76). The mechanism (for which no rm proof exists) is thought to act by altering the distribution of p electrons in the graphite sheets, thereby making the carbon substrate more susceptible to oxidation. Oxygen transfer: The oxygen-transfer mechanism, originally proposed in general outline by Neumann et al. (77), is thought to be the general mechanism for the catalytic oxidation reaction (78). Amariglio and Duval (79) suggested that only metals which can oscillate between two oxidation states can catalyze the oxidation of graphite sheets. An illustration of such oscillation or redox cycle is given in Figure 15. 2. Processes on a Mesoscopic and Macroscopic Level Pioneering Analysis Techniques The surface of cleaved graphite crystals is ideal for the analysis of carbon oxidation by means of microscopy. Microscopy made it possible to see the effect of crystallographic orientation and introduced irregularities on oxidation. The
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Figure 15. Illustration of the behavior of a V2O5 particle during the oxidation of a graphite sheet. (From Ref. 188.)
pioneering work of Hennig (80) in the 1960s with transmission electron microscopy (TEM) made clear that the catalyzed reaction of graphite is dominated by catalyst droplets that physically come into contact with edges, steps, or vacancies in the graphite sheets. Irregularities were introduced by etching, for instance, with an oxygen chlorine mixture and they were made visible (even in the case of monolayer graphite sheets) to ex situ TEM analysis by decorating them with gold nuclei (i.e., etch-decoration, ex situ TEM ). It was recognized early on that catalysts that have an improved physical contact with the graphite will show high reaction rates. For instance, V2O5 was found to be abnormally active due to the molten state of the catalyst during the reaction. The development of the controlled-atmosphere electron microscope by Baker and Harris (81) made it possible to directly observe the catalytic action in situ on a scale of more than 30 graphite sheets (82). This method, in combination with etch-decoration TEM, provided a reasonably good understanding of the catalytic processes taking place on graphite surface layers.
Direct Contact Catalysts Most catalysts require direct physical contact with carbonaceous materials if oxidation is to be accelerated. The catalyst may activate the carbon atoms or it may act itself as a renewable, activated oxygen donor. The physical contact requirement places restrictions on the development of such catalysts, because the catalyst should not only be intrinsically active but should also be able to establish intimate
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physical contact with the carbon by means of a mesoscopic or macroscopic mechanism: Channeling: Channeling has been observed during the catalytic oxidation of graphite. The process commences on the edge or in a step of a graphite sheet. Catalysts operating according to this mechanism are, therefore, known as edge-specic. The catalyst particles catalyze the oxidation of high-coordination edge carbon atom sites, thereby creating new highcoordination sites and so on and leaving a channel behind them that is of the same width as the diameter of the catalyst particle (83). The process is called deep channeling when it involves multiple graphite layers, and monolayer channeling when it involves single graphite sheets. The channeling mode that occurs depends on the rate-limiting step evident during oxidation and it can differ from one catalyst to another (82). Figure 16a gives a schematic representation of catalytic channeling. Edge recession: Edge recession starts on the edge of a graphite ake, at a step between different graphite layers, or in a vacancy on a graphite layer. The catalyst catalyzes the oxidation of the high-coordination edge carbon atom sites, thereby creating new high-coordination carbon sites and so forth. The catalyst moves like a front, as shown in Figure 16b. The catalyst gradually penetrates each graphite layer at vacancies released by removal of the layers on top (80). The way in which the catalyst operates is governed, to a large degree, by the strength of the interaction between the metal and the graphite edge atoms (84). Figure 17 shows the extremes of catalyst graphite interaction. In a nonwetting situation, no reaction occurs. In the intermediate wetting state, the catalyst is present as a cap-shaped particle and the mode of attack is channeling. In a complete wetting situation, edge recession occurs, which leads to the most efcient catalyst use (84). The actual mechanism depends on the chosen reaction conditions and catalyst (80,82,85). Table 6 shows how different metals can operate according to different mechanisms. Baker (84) found, for ruthenium, rhodium, and
Figure 16. Illustration of different macroscopic oxidation mechanisms on graphite sheets: (a) deep channeling; (b) edge recession. (From Ref. 189.)
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Figure 17. Illustration of the inuence of the metal graphite interaction on the mode of catalytic attack. (From Ref. 84.)
iridium, that they can operate according to both mechanisms, depending on the reaction temperature. Indirect Contact Catalysts Some catalysts can oxidize soot without having intimate physical contact. They catalyze the formation of a mobile compound (NO2, Oads, etc.) that is more reactive than O2. In the absence of physical contact, the formation of those mobile species is the main advantageous property of this type of catalyst. For indirect contact catalysts, two main reaction mechanisms are known: NOx-aided gas-phase mechanism: Cooper and Thoss (12) discovered a way of using gas-phase NO2 as an activated mobile species for soot oxidation. They proposed that the NO:NO2 combustion cycle
Table 6. Classication of the Modes of Catalyzed Oxidation of Graphite by Various Metals
Note: Compilation of experimental data obtained with controlled atmosphere electron microscopy. Source: Ref. 84.
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accelerates soot combustion: 2NO 1 O2 !2NO2 NO2 1 C !NO 1 CO NO2 1 CO !NO 1 CO2 14 15 16
Spillover mechanism: Some catalysts can dissociate oxygen and transfer it to the soot particle, where it reacts as it was in a noncatalytic reaction. This mechanism is known as the spillover mechanism (Fig. 18). Some examples exist that show that contact is not prerequisite in this reaction type. For instance, Baumgarten and Schuck (86) showed that the rate of catalytic coke oxidation can be accelerated while there is no direct contact between the catalyst and the coke, which they explained by oxygen spillover. Baker and Chludzinksi (87) showed that Cr2O3 can accelerate edge recession of graphite while being motionless. Mul et al. (88) showed with a labeled oxygen study that spillover and redox oxidation can occur simultaneously. They discussed that the dominating mechanism will depend on the degree of physical contact between the catalyst and the soot. B. Direct Contact Catalysts for Regeneration The development of a direct contact soot-oxidation catalyst is problematic, because it is difcult to realize a direct contact with the solid soot. An option may be the utilization of, for instance, a channeling mechanism for creating the contact. For a catalyst supported on a lter, such a mechanism is hard to imagine, because
Figure 18.
Illustration of spillover soot-oxidation mechanism on a catalyst surface.
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the catalyst should (1) leap over from the lter to the soot, (2) oxidize the soot, and (3) after oxidation, return to its default position, without compromising on stability. This is hard to imagine in a practical application. Fuel additives seem to be better direct contact catalysts, because they are built into the soot and continuously replenished. 1. Supported Catalysts Simple metal oxides can be supported on a trap for soot oxidation, but they only operate satisfactorily at high temperatures (. 4508C). During the last decade, several research groups have tried to develop catalysts that can oxidize diesel soot at lower temperatures, preferably below 3008C. In all of the studies, the catalysts were tested under simulated model conditions. The powder catalysts (, 250 mm) were mixed with synthetic soot and tested with temperature programmed oxidation (TPO) experiments [except for Inui and Otowa (89,90), who used isothermal conditions]. The reaction carried out is a batch reaction, because no additional soot is fed to the reactor. Type of Contact Inui and Otowa (89) and Lowe and Mendoza-Frohn (91) were among the rst to realize that the contact of deposited soot on a catalytic lter is poor. Neeft et al. (92,93) systematically investigated the effect that the degree of physical contact has on catalytic soot combustion: They mixed soot and catalyst powders with a spatula and dened that as loose contact; they did the same with a mechanical mill and dened that as tight contact; they ltered diesel soot from an exhaust stream on a bed of catalyst particles and dened that as in situ contact. Figure 19 shows the results of the investigation. Tmax. rate is the temperature at which the maximum oxidation rate is observed. Combustion temperature differences as large as 2008C can be found between loose and tight contact samples of one catalyst. It is clear that Neeft et al. measured apparent activities which were a function of the intrinsic activity and the degree of physical interaction. They found that with the in situ samples, the combustion temperatures were similar to the combustion temperatures of the loose contact samples and concluded that the contact that arises during practical conditions is similar to loose contact. This is, of course, unfortunate. Various reasons exist why tight contact mixtures are more reactive: (1) the catalyst will have more contact points with the soot; (2) the catalyst particles will be smaller and better dispersed; and (3) Mul et al. (88) found that the type of contact controls the mechanism that is occurring. They found that for V2O5 and MoO3, a redox and spillover mechanism occurs simultaneously in tight contact and discussed that in loose contact, only the spillover mechanism occurs. They expected that for soot oxidation in a catalytic lter, oxygen spillover would be the predominant mechanism.
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Figure 19. Comparison between Tmax. rate of the oxidation of soot deposited on different catalyst powders. The samples were prepared according to different methods: loose, tight, and in situ in exhaust gas. (From Ref. 93.)
Reported Catalysts Watabe et al. (94) was the rst to report a catalyst based on a formulation of Cu/K/M/(Cl), where M is V, Mo, or Nb. For years, catalysts based on this formulation were investigated extensively (92,93,95 105) because they exhibited high soot-oxidation rates at low temperatures. The high activity was related to the mobility and volatility of the active copper chloride component of the catalyst (106). Unfortunately, catalyst compounds evaporated during soot oxidation (95,102), because of which the catalyst should be kept below 3508C at all times (102), which makes the feasibility of the catalyst questionable (95). Various alternatives for the Cu/K/M/(Cl) catalyst have been investigated. What they have in common is that the mobility of the catalytic phase played a major part in the oxidation mechanism. This mobility probably explains why the stability of some of the reported catalysts was low. Querini et al. (107) stated that the high activity of Co/MgO and Co/K/MgO could be caused by enhanced catalyst mobility caused by potassium. Badini et al. (103,108) reported that KCl:KVO3 and KI:KVO3 are active catalysts, but they also reported the emission of volatile components of the catalyst. Ahlstrom and Odenbrand (109) and Moulijn and coworkers (110 114) reported mobile catalysts that did not evaporate during soot oxidation. They used liquid catalysts for soot oxidation.
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Simultaneous NOx and Soot Reduction Teraoka et al. (115,116) investigated several mixed metal oxides consisting of mixtures of La, Sr, K, Co, Li, Cs, Fe, Mn, Cu, and V for the simultaneous reduction of soot and NOx (NOx conversions into N2 as high as 60%). It is, however, questioned if the test conditions used and, therefore, the results used are realistic (i.e., the tight contact mixtures of soot and catalyst were heated in helium for 3 h at 4008C in order to remove contaminations such as water). This pretreatment could well have led to early interactions between the catalyst and soot (e.g., catalyst reduction). It might well be possible that such interactions instigated the simultaneous and NOx soot reduction. It would have been better if the high-temperature treatment was given to the soot before it was mixed with the catalyst.
Benchmarking Table 7 ranks the performance of several catalysts by their Tmax. rate. The order of Tmax. rate in Table 7 is no true benchmark for the performance of the catalysts, because of the different experimental procedures applied. In general, for the loose contact samples prepared with a spatula, a high Tmax. rate was found, whereas for tight contact samples prepared with ball mills and mortars, a low Tmax. rate was found. It is clear that tight contact has a serious advantage over loose contact because it makes catalytic oxidation at low temperatures possible. However, it has
Table 7. List of Experimental Conditions and Results for Different Soot-Oxidation Catalysts Reported by Different Authors Tmax. rate (8C) 295 300 330 340 350 360 369 385 390 428 440 440 464 585 Heating Rate (8C/min) 0.2 5 1 50 12 10 5 10 10 1 10 0.2 0.2 10 10
Catalytic Phase Cs2SO4:V2O5 Cu/Nb/K(Cl) Cu/K/V(Cl) Co/K/MgO Cu/K/V(Cl) Na/CuO Cu/K/Mo(Cl) KI:KVO3 CuFe2O4 Cu/K/Mo(Cl) Cs2SO4:V2O5 Cs2SO4:V2O5 Cu/K/Mo(Cl) KI:KVO3
TPO Method Fow analysis TGA/DSC TGA/DSC Flow reactor Flow reactor TGA/DSC TGA/DSC Flow reactor Flow reactor TGA/DSC Flow analysis Flow analysis TGA/DSC Flow reactor
Sample Mixing Ball mill Ball mill Mortar Mech. mixed Mortar Ball mill Ball mill Mortar Mortar In situ Spatula In situ Spatula Shaking
Ref. 114 197 98, 99 107 103 198 93, 97 108 115 93, 97 114 114 93, 97 108
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not been reported how such a contact can be created in a practical catalytic lter. Therefore, the tight contact activities often reported for powder mixtures can be regarded as an overestimation, because of which, they give an unrealistic prediction of the potential of such catalysts.
2. Catalytic Fuel Additives for Induced Regeneration A good way of improving the quality of induced self-supporting regeneration of a particle lter is by increasing the reactivity of the soot with a built-in metal catalyst. The catalyst can be incorporated during the soot-formation process. Blending a stable organometallic additive into the fuel (typically 10 100 ppm) is the most convenient method. These catalytic fuel additives are also known as fuel-borne catalysts, and the type of regeneration as quasicontinuous regeneration (117) or passive active regeneration (118).
Types of Fuel Additives Huthwohl et al. (35) were among the rst to investigate the mechanism of induced regeneration with fuel additives. They investigated the role of manganese (240 ppm) and iron (60 ppm) additives. In the case of manganese, they witnessed that owing, glowing catalyst particles were igniting local combustion reactions in the monolith channels, after which a self-supporting ame propagated through the channels. Gantawar et al. (53) investigated the effect of copper (60 ppm) on induced regeneration and found that there was up to a sevenfold increase in regeneration efciency due to the fuel additive. Bloom et al. (37) compared copper (30 ppm), iron (30 ppm), and cerium (50 ppm) additives with each other during consecutive induced regenerations and found that only copper could regenerate a lter efciently, whereas the regeneration remained partial with cerium and iron additives, which caused the pressure drop in the lter to constantly increase, as shown in Figure 20. The activity order was copper @ cerium . iron. Some fuel additives are so active that they spontaneously initiate selfsupporting regeneration reactions at low temperatures. Richards et al. (119) tested mixed fuel additives based on strontium and iron for passive periodic regeneration without additional heating. They reported successful road tests of 5000 km for certain passenger cars with mixed driving patterns. Spontaneous self-supporting regeneration was found every 100 600 km at exhaust temperatures higher than 225 4008C. Lepperhoff et al. (117) found that copper and iron can spontaneously initiate complete regeneration at temperatures even below 2008C! They considered such a high activity not a blessing. It could lead to extremely high local temperatures and to lter damage. With cerium, this behavior was not found: The regeneration reactions it initiated spontaneously at low temperatures remained
524
Figure 20. Comparison of cerium (50 ppm), copper (30 ppm), and iron (30 ppm) fuel additives by multiple, consecutive particulate matter loading and regeneration cycles. Negative slopes indicate regeneration; positive slopes indicate particulate matter loading of the lter. (From Ref. 37.)
local. This means that cerium-activated soot can be reliably ignited by employing on-board diagnostics, and undesired spontaneous regeneration does not occur. Hardenberg et al. (120,121) tested a dissolved copper catalyst that was injected upstream of the lter into the exhaust prior to regeneration. They used 0.07 g/km, which is a high amount. Even if this amount was to be cut down to more acceptable levels, other limitations remain: The spray nozzle can be plugged with deposits, the catalyst should be distributed evenly over the soot surface, and the amount of catalyst used should be proportional to the amount of soot. In this respect, fuel additives are superior.
3. Catalytic Fuel Additives for Passive Regeneration Catalytic fuel additives have often been investigated for passive regeneration. During passive regeneration, a trap regenerates itself, without the intervention of on-board diagnostic and control systems. Passive regeneration is often a continuous process, because of which, it is sometimes referred to as continuous regeneration. During continuous passive regeneration, catalytic fuel additives bring the rate of soot oxidation in equilibrium with the rate of soot deposition, which causes a constant pressure drop over the lter. Oser and Thoms (122) dened the temperature at which equilibrium occurs as the balance temperature. Figure 21 shows the results of a typical balance temperature determination experiment with a Corning EX80 wall-ow monolith, where the lowest balance temperature for 100 ppm cerium additive was found to be between 4308C and 4408C (123).
525
Figure 21. Typical result of a balance temperature experiment: positive slopes, normal operation with soot deposition; negative slopes, regeneration; horizontal line, equilibrium. (From Ref. 123.)
Types of Fuel Additive Lepperhoff et al. (117) compared cerium, iron, and copper additives. They found the lowest balance temperatures for iron and copper, which were 3508C. Jelles et al. (123) measured balance temperatures for different mixed additives to discover whether synergetic effects play a role, as was tried earlier with little success for a copper manganese combination by Daly et al. (124). Jelles et al. found that after some time of running on low-concentration fuel additive combinations, there was a dramatic balance temperature reduction to 3258C. The reduced balance temperature was explained as follows. Platinum, which was deposited on the monolith, started to catalyze the oxidation of NO to NO2. NO2 subsequently reacted with the fuel-additive-catalyzed soot. The enhanced activity was explained by assuming that each NOx molecule is used many times, as is illustrated in Figure 38. Figure 22 shows a reaction scheme of the proposed mechanism of the oxidation of soot by using platinum:cerium fuel additive. Road
Figure 22. Mechanism of the oxidation of soot with NOx and O2 catalyzed by platinum and cerium fuel additives. (From Ref. 123.)
526 Table 8.
VAN SETTEN, MAKKEE, AND MOULIJN List of Measured Balance Temperatures for Different Catalytic Fuel Additives
Wall-Flow Monolith Producer: Corning EX47 EX47 EX47 EX80 EX80/Pt EX80/Pt EX80/Pt EX80/Pt EX80
a
Additive Ce Fe Cu None None Pt/Ce Pt/Cu Pt/Fe Ce
ca (ppm) 100 100 100 0.5/5 0.5/5 0.5/22 100
Tbal.a (8C) 400 350 350 537 557 417 427 327 347 357 432
Ref. 117 117 117 123 123 123 123 123 123
c, additive concentration; Tbal., balance temperature. Source: Data from Refs. 117 and 123.
trials of the mixed catalysts showed that not only is the regeneration of the lter altered but also the fuel combustion: The fuel efciency increased by 5 7% with, at the same time, a decrease by the engine produced particulate mass of 10 25% (125). The results of the studies of Lepperhoff et al. and Jelles et al. have been summarized in Table 8. It should be noted that the listed balance temperatures are only valid for the conditions under which they were measured. As Daly et al. (124) indicated, they depend on several factors: particulate matter loading, trap volume, trap materials, trap pore size, additive concentration, oxygen concentration, engine type, and engine load. C. Catalyst Selectivity The selectivity of oxidation catalysts applied in diesel exhaust gas is a critical parameter. The preferred reaction products are N2, CO2, and H2O. 1. Reactant Selectivity Diesel oxidation catalysts should oxidize soot, hydrocarbons, and CO, but not SO2. When the latter is converted, reaction with water occurs and sulfuric acid is formed, which adds up to the total particulate mass. For the NOx-aided CRT, sulfuric acid formation is so critical that it, until now, slowed down the market introduction of the system (Section VII.B). Figure 23 shows the emitted total particulate mass as a function of the fuel sulfur level of an engine running with and without NOx-aided CRT. The increase in total particulate mass at higher sulfur levels can be attributed to an increase of the sulfate fraction (126).
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Figure 23. Emitted total particulate mass as a function of the fuel sulfur level of an engine running with and without NOx-aided CRT. (From Ref. 126.)
2. Product Selectivity N2O: Shangguan et al. (115) reported that CuFe2O4 could be a promising catalyst for the simultaneous removal of soot and NOx. They found a reduction in NOx; however, in addition to N2, also a conceivable amount of the greenhouse gas N2O was formed, which is undesirable. N2O formation has also been reported for plasma reactors (Section IV.B.2). NOx: The NOx-aided CRT uses NO2 for soot oxidation, without producing additional NOx. Thermal and nonthermal plasma reactors can also produce NO2 for soot combustion. In some cases, however, they cause a net NOx production (Section IV.B.2), which is, of course, highly undesirable. Dioxins and dibenzofurans: Municipal incinerators and trafc are the main sources of the highly toxic dibenzodioxins and dibenzofurans. In trafc, heavy-duty diesel engines have a high share; they contribute 20 times more than passenger cars (127). The formation of dibenzodioxins is a three-step process (128). First, Cl2 is formed from HCl and O2, second, chlorinated aromatics are formed as a result of substitution reactions with Cl2, and, third, dioxins are formed due to the condensation of chlorophenols, as shown in Figure 24. The presence
Figure 24. Diagram showing the formation of a dibenzodioxin molecule by copper(II) catalyzed condensation.
528
of Cu(II) is highly undesirable because it enhances the condensation reaction (128,129). Neeb (130,131) and Clunies-Ross et al. (132) investigated the effect of copper fuel additives on the composition of diesel exhaust gases. Both discovered a signicant increase in the dioxin levels when the copper additive was applied. Neeb compared copper with iron and cerium fuel additives. He found concentration increased by four orders of magnitude in dibenzodioxins and dibenzofurans when the copper additive was applied, wheares iron and cerium additives had no effect. Hydrocarbons: Flow-through diesel oxidation catalysts (Section VII.A) have been reported to increase the mutagenic activity of a fraction of the hydrocarbons that are only partially oxidized (133). Fortunately, the relative increase reported was offset by the absolute reduction in the hydrocarbon concentration.
D. Durability of the Catalytic Trap Legislation demands a minimal distance in which a vehicle should fulll the emission standards. For instance, the EPA Tier 2 standard demands that passenger cars and light-duty trucks meet the emission standards for 193,000 km (24). Such a lifetime will not be adequate for a passenger cars lter trap system because an overaged lter system might inuence the safety and overall performance of the car. Depending on the anticipated vehicle life, 300,000 400,000 km seems more adequate. In a few years time, heavy-duty diesel vehicles emission control devices in the EU and the United States should have durabilities of 500,000 and 700,000 km, respectively (134). Durability is so important that one failure can deter all producers from pursuing a certain route to a solution, as occurred after the introduction of a lter system in 1985 to the Californian market that led to failure. To enhance the temperature for soot oxidation, the lter was placed in front of the turbocharger, but the system failed because ceramic lter akes destroyed the turbochargers radial turbine (135). This failure is one of the main reasons why the placement of a lter upstream of the turbocharger is not favored nowadays. There are basically two types of failure in relation to the durability of the catalytic trap: fouling due to solid deposits, and lter breakage.
1. Mechanical Damage In time, a lter can deteriorate, which may result in emission of particulate matter. Vehicle vibrations in combination with poorly canned lters, mounting pressures that are too high, and temperature inuences can all lead to deterioration. The rst two processes relate to mechanical stress, and the third to thermal stress.
529
Mechanical Stress Vibrations are caused by road shocks and the internal frequency of the engine. Problems deriving from vibrations were overcome by canning with intumescent ber mats. The mat is stuffed between the ceramic lter and the can, where it compensates for the thermal expansion coefcient differences, which can be as high as 10. A popular mat is based on vermiculite [Mg3(Al,Si)4O10(OH)2: (H2O)4] mixed with alumina silicate bers: Vermiculite has a thermal expansion coefcient higher than that of metal and ceramics and the alumina silicate bers provide high-temperature resistance and they contain the vermiculite (136,137). The canning process of ceramic lters should be well controlled, because the canning mat can exert high forces on the lter (138). Canning failures that occur are normally due to improper alignment of the lter prior to can closure, nonuniform mat, inadequate dimensional tolerances, unoptimized mat properties, and high closure rates (136), and result in localized damage, such as shear failure, as shown in Figure 25.
Determining Mechanical Strength A simple test for the determination of the mechanical strength of a lter is the crush test performed with a compression bench, which measures the uniaxial compressive strength. The test is well suited for testing relative differences, but in the case of a cylindrical lter, it does not simulate the radial force exerted by the intumescent mat. To measure the radial compressive strength, Gulati and Reddy developed the single- (139) and double-band (140) xture test. These tests use a draw bench and a special tourniquet in which the cylindrical lter is wrapped, as shown in Figure 26 for the double-band xture test. A more realistic but rather arbitrary test is the hot vibration test (141,142) which exposes the lter in its actual can to high temperatures and vibrations (Fig. 27).
Figure 25. stress.
Scheme of different types of crack in a cylindrical lter due to mechanical or thermal
530
Figure 26. Scheme of double-band xture test. (From Ref. 140.)
Thermal Stress High temperatures can cause melting of a lter; thermal stress can break lters instantly or decrease their strength by introducing microcracks. In particular, high-temperature gradients are damaging. The most severe temperature gradients are encountered during uncontrolled regeneration. The worst type of uncontrolled regeneration occurs when a car with a highly loaded lter goes up a slope under a high engine load and then goes into idle (143). When idling, the high oxygen concentration level promotes the reaction of the hot particulate matter, and the lack of adequate ow prevents the combustion heat from being removed from the lter by convective processes (144). Essentially, optimal conditions are created for a serious thermal runaway. Material Properties The thermal properties of a lter should be optimal if high temperatures are to be attenuated. The key thermal properties are the thermal expansion coefcient (a ), the specic heat (Cp), the thermal conductivity (k ), and the melting point (Tmp). Table 9 shows the thermal properties of cordierite, silicon carbide, stainless
Figure 27. Scheme of hot vibration test equipment. (From Ref. 142.)
Table 9. Material
Structural Formulas and Properties of Cordierite, Silicon Carbide, Stainless Steel AISI 409, and 3M Interam 100 Vermiculite Canning Mat Chemical Formula 2MgO:2Al2O3:5SiO2 SiC 86%Fe 11%Cr (+additives) Mg3(Al,Si)4O10(OH)2:(H2O)4 Al2O3:SiO2 Tmpa (8C) 1200 1650 (dec) 1468 950 (erosion) Cpa (J/g/8C) 0.6 0.75 0.46 1.02
aa (mm/m/8C)
1.0 4.6 11.7 450
ka (W/m/8C)
,0.5 11 25 0.1
Cordierite Silicon carbide Stainless steel Canning mat

a
a, thermal expansions coefcient; C, heat capacity; k, thermal conductivity; Tmp, melting point; dec, decomposition. Source: Data from Refs. 53, 137, 194, and 195.
531
532
Figure 28. (a) Diagram of a cordierite crystal with average thermal expansion coefcients (25 8008C) along the three axes. (From Ref. 145.) (b) Typical result deriving from measurement of the expansion behavior of a cordierite wall-ow monolith; expansion relative to room temperature. (From Ref. 190.)
steel AISI 409, which is commonly used for producing cans (137), and 3M Interam 100, a popular canning mat. Ceramic particle lters are mainly fabricated from cordierite and silicon carbide. Their physical characteristics are very different, which makes them behave differently under demanding conditions. The cordierite crystal has anisotropic expansion behavior* (145), as shown in Figure 28a. Microcracks caused by local expansion mismatches are avoided by aligning the cordierite crystals during the extrusion of the monolith (145). Although local stress is avoided, the crystal alignment makes the complete monolith itself expand anisotropically, as shown in Figure 28b, which can lead to high thermal stress (54). In addition to the anisotropic expansion behavior, cordierite cannot attenuate high local temperatures quickly, as it has a low thermal conductivity. It is not surprising that cordierite lters can break easily under certain regeneration conditions (36). Stroom et al. (136) showed that for homogeneous cordierite lters, axial and radial temperature gradients lead to axial and tangential stress, which respectively cause ring-off and facial cracks, as seen in Figure 25. The melting point of 12008C is on the low side, because such temperatures can be encountered during regeneration (36). It has been reported that silicon carbide has better thermal properties for regeneration: It has (1) an acceptable thermal expansion coefcient, (2) a high decomposition temperature, giving it a large operating window, (3) a high specic heat, allowing storage of released heat, and (4) a high thermal conductivity, leading to efcient heat distribution. Gantawar et al. (53) and Hy et al. (146) conrmed that during extreme regenerations, silicon carbide has better thermal
*Anisotropic is dened as having properties which vary according to the direction in which they are measured (16).
533
Figure 29. Tolerance of cordierite and SiC lters expressed in soot loading as a function of gas velocity. Regeneration conditions: no catalyst, 21 vol% O2, start regeneration at 7208C. (From Ref. 143.)
properties. Under similar regeneration conditions, maximum temperature of 11008C occurred in cordierite wall-ow monoliths, whereas for silicon carbide, the temperatures did not exceed 7008C. However, the regeneration efciency of the silicon carbide lter was lower due to the lower maximum temperatures. Ohno et al. (143) measured the tolerance of cordierite and SiC wall-ow monoliths as a function of soot load and gas velocity during uncontrolled regeneration. Figure 29 shows their results. For the cordierite wall-ow monolith, the soot loading should not exceed 3 5 g/Llter; SiC can tolerate soot loadings that are three times higher. Homogeneity Table 10 shows the results of various studies of the effects of inhomogeneities in lters on thermal mechanical properties. Scardi et al. (147) reported that the strength of cordierite monoliths with inhomogeneous composition decreased even after homogeneous heating. The inhomogeneous composition led to a mismatch of the thermal expansion coefcients of the present phases, which gave rise to local mechanical stress. Lucchini and Maschio (148) investigated the effect of repeated heating and quenching on cordierite and found that a glass phase was formed which caused cracks. The other authors mentioned in Table 10 investigated the effects of ash contaminants on the thermal mechanical properties. For instance, Dario and Bachiorrini (149) investigated the effect of V2O5 and Na2O on silicon carbide and found that sodium silicates were formed at temperatures as low as 5508C and that SiO2 was formed above 7508C. They concluded that silicon carbide had insufcient thermal and chemical resistance for diesel applications. This conclusion may be true in the case of MW engines running on heavy fuel oil, which contains high vanadium and sodium
534
Table 10. Geometry Monolith
List of Diesel-Exhaust-Filter-Related Studies on the Effect of Contamination on Thermal Mechanical Properties Treatment Isothermal high temperature Heating and quenching Isothermal high temperature Heating and quenching Contamination Fe2O3 ZnO V2O5 None CaO ZnO Na2O PbO V2O5 Na2O Phase Formed (Mg,Fe)2Al4Si5O18 ZnAl2O4, Zn2SiO4, glass, MgV2O6, Al2V2O4, SiO2 Glass Ca2(Al,Mg)[(Al,Si)SiO7] ZnAl2O4 Na2Si2O5, Na2SiO3 Pb2SiO4 SiO2 Amorphous phase Effect Cracks Ref. 147
Ceramic Cordierite
Monolith Monolith Powder
Cordierite Cordierite SiC
Cracks Cracks
148 199 149
Powder
Cordierite
Cyclic heating
200
Note: In the studies, contaminations were deliberately introduced, temperature treatment was given, and the effects were studied.
535
concentrations (Table 1), but silicon carbide lters implemented in light-duty applications will probably have no problems with lter deterioration caused by ash because these engines use relatively clean fuel. 2. Fouling Filter surfaces might be plugged by particulate matter, because of which, the pressure drop over the lter will increase, the fuel efciency will decrease, and, ultimately, the engine will stop. Inorganic Ash Ash accumulation may slowly plug the lter surface, and unless the lter has enough storage capacity, it should be cleaned periodically. Current state-of-the-art catalytic fuel-additive-based systems for passenger cars have to free their lter from cerium deposits every 80,000 km. This can be done by ushing them out with highpressure water and air jets (52). Flushing out ash may be more difcult when the lter experienced temperatures over 11008C, at which temperature, ashes may start to adhere to the lter surface or show chemical interaction with the lter by sintering or eutectic melting reactions (14). The severity of such an interaction have the following order in magnitude: bulk melting, leading to lter destruction . pin holes, leading to lowered ltration efciency . surface glazing, leading to increased back pressure and staining. It can be anticipated that the ash effects in the case of passenger cars and trucks may be well controlled, which might not be the case for MW engines. From Table 1, it can be calculated that in the case of a MW engine running on heavyfuel oil, roughly 3.5 kg/day of sodium and vanadium oxides can pass through the exhaust pipe, which amounts to a volume of roughly 20 L/day, if we assume the porosity of the ash to be 83%, as Merkel et al. found for inorganic diesel ash (14). Catalyst Deactivation Several mechanisms can lead to catalyst deactivation in catalytic particle traps. There are three variations: a chemical change, which leads to a less active phase, a physical change, which leads to a less active phase, and catalyst loss. Poisoning. A poison may adsorb on the catalytic sites, thereby inhibiting the reaction. An example of precious metal inhibition in diesel oxidation catalysis is the platinum catalyst in the NOx-aided CRT system (Section VII.B), where the catalytic NO oxidation is inhibited by SO2 (12). Figure 30 gives the balance temperature of NOx-aided CRT as a function of the fuel sulfur level (126). It is clear that SO3 is inhibiting the system. The effect was reversible: The catalyst recovered when the fuel was switched to low sulfur fuel again.
536
Figure 30. Balance temperature of NOx-aided CRT as a function of the fuel sulfur level. (From Ref. 126.)
With metal oxides, the sulfur may be incorporated in the catalyst, which, in general, is irreversible (150). Van Doorn et al. (151) reported an example of deactivation of a metal oxide soot-oxidation catalyst; vanadium oxide reacted with SO2 to the less active vanadium sulfate. However, the opposite can occur when vanadium oxide is converted to vanadium pyrosulfate, which is a more active sootoxidation catalyst due to its high mobility (152). Catalyst Support Interaction. The catalyst might react with the support material, which will lead to a change in the composition of the catalyst. If this change leads to reduced combustion activity, one could view the support as a poison to the catalyst. McKee (153) reported that by forming an alloy, alumina can inhibit the catalytic action of copper during graphite oxidation. When a catalytic lter is designed, negative catalyst support interactions can be predicted by examining phase diagrams. Catalyst Loss. There are three causes of catalyst loss. It can disappear along with the support when support pieces break off from the lter. Water may be introduced into the catalyst by rain, auto washes, or water condensation from exhaust gas (138), and if the catalyst can dissolve, then it might leave the exhaust pipe with water droplets. If high temperatures are attained, the catalyst might evaporate and leave the catalytic trap. In studies of the very active Cu/K/Mo/(Cl) (95), Cu/K/V/(Cl) (102), and KI:KVO3 (108) soot-oxidation catalysts, progressive loss of catalyst components was found due to evaporation, which made the applicability questionable. Catalyst Sintering. Catalyst sintering is not detrimental for catalytic fuel additives because the catalyst is constantly replenished. NOx-aided CRT is a continuous process in which extremely high temperatures do not occur, and ashes, some components of which might be good sintering aids, mainly deposit in the lter downstream of the catalyst.
537
Stability Testing Long-term on-road tests are the most realistic way of testing the stability of a lter system, but such tests are expensive, hard to interpret, and cost much time. In the early developmental stages, accelerated tests under simulated conditions are often used. Such tests could help to avoid failure in later stages. Table 11 summarizes some aging tests in which model conditions were used to simulate aging in diesel exhaust. Overview Durability studies are complex because of the many processes that can lead to failures. To complicate matters, the different processes can interconnect. For instance, ashes can simultaneously plug a lter, react with the catalyst to form a new phase, react with the support to form a new phase, catalyze phase transitions, and even catalyze soot oxidation. Figure 31 is an overview of the different processes than can affect the durability of a catalytic lter. VI. DIESEL PARTICLE TRAPS There are many possible ways of removing particles from a gas stream. Regarding the diesel particle trap application, certain minimum conditions need to be fullled. With current passenger cars, the trapping efciency for the total particulate mass should be at least 90% in order to meet the Euro IV standards (see Fig. 7). Particle number ltration efciencies should be 99% for a lter in order to compete with state-of-the-art wall-ow monoliths. The average pressure drop should be low to attain a high fuel efciency. For MW engines, a maximum average pressure drop of 50 mbar is permitted (154). With passenger cars, a higher average pressure drop might be allowed because customers often consider speed, size, gadgets, and price to be more important. The lter capacity should be sufcient. In a recent application, 500 km was stipulated for passenger cars (155). The lter should be durable and suitable for reliable regeneration. The lter volume should be low. One to two times the engine displacement is usually considered acceptable (156). The production costs should be reasonable. The lter should require no special attention from the driver of the vehicle (37) and should need no maintenance (18).
A. Filtration 1. Surface Filtration The most popular way to trap diesel particles is by means of surface ltration, sometimes known as cake ltration or sieving. In this process, the
538
Table 11. Test SO2 SO2 SO2 TS TS TS TS TSR TSR Sample Catalyst Catalyst Catalyst Catalyst Monolith Monolith Catalyst Monolith Monolith Gas 100 ppm SO2 200 ppm SO2, or steam 1000 ppm SO2
Laboratory-Scale Aging Tests t 6 20 h 24 96 h 8h 3 h 15 d 3h 3h 3 h 1 y 60 sh 100 sh T (8C) 350 650 380 600 300 400 1000 800 1200 800 1200 500 1000 600 900 DT 600 DT Analysis TPO TPO, XRD TPO TPO, XRD SEM, XRD SEM, XRD, DRM, DM, FT FTIR XRD, DM, FT, SEM, MP RST Ref. 151 103 152 102 147 199 200 148 201
Note: TS, thermal stability test; TSR, thermal shock-resistance test; DRM, digital resonance method; RST, rupture strength test; FT, exure test; DM, dilatometry; MP, mercury porosimetry; sh, thermal shock.
539
Figure 31.
Overview of the processes that can affect the durability of a catalytic trap.
particles ow through a porous support and are captured to form a layer: the lter cake, which is itself an efcient lter medium, especially for the particles of which it is composed. During the process, the thickness of the cake increases continuously, which results in ow restrictions and increasing pressure drop. In practice, the ow usually abides by Darcys law: 1 vs 2 kdp h 17
where vs is the supercial velocity, dp is the pressure drop over the cake, h is the viscosity of the gas, and k is the permeability of the cake. Figure 32 gives a schematic representation of cake ltration.
Figure 32. Illustration of the ow pattern in a surface lter. The arrows indicate the stream direction of the exhaust gas. The circles represent soot particles which form a cake on the lter surface.
540
Figure 33. Illustration of ow pattern in a wall-ow monolith. The black arrows indicate exhaust gas with particles; the gray arrows indicate ltered exhaust gas. (Courtesy of Corning.)
In commercial applications, surface lters of the wall-ow monolith type, originally introduced by Howitt and Montierth (157), are commonly found. They are extruded, ceramic, porous honeycomb structures which have alternately blocked channel openings, as shown in Figure 33. The obvious advantage of this structure is the large lter surface-to-volume ratio. According to Opris and Johnson (158) the wall-ow monolith lter only acts as a cake lter after some initial particle deposition in the pores of the monolith walls. When a steady-state particle loading in the walls has been established, a cake layer is formed which becomes the dominant ltration medium. The mechanism gives rise to a high ltration efciency, which has been reported to be . 90% for total particulate mass, . 97% for elementary carbon, and . 99% for 20 500-nm particles (31).
2. Deep-Bed Filtration It is possible to design lters that have a relatively open structure compared to surface lters. In such lters, particulate matter is found throughout the lter structure and not just on one side of the lter surface, as with surface lters. This technology is called deep-bed ltration. Particles may deposit in one of three ways (159) (see Fig. 34): Inertial interception: On approaching a collecting body, a particle carried along a gas stream tends to follow the streamline, but it may well strike an obstruction because of its inertia.
541
Figure 34. Ref. 159.)
Schematic overview of particle deposition mechanisms on collecting bodies. (From
Brownian diffusion: Smaller particles, particularly those typically below 300 nm, exhibit considerable Brownian movement and do not move uniformly along the gas streamline. These particles diffuse from the gas to the surface of the collecting body and may be collected. Flow-line interception: If a uid streamline passes within one particle radius of the collecting body, a particle traveling along a gas streamline will touch the body and may be collected without being inuenced by inertia or Brownian diffusion. Ceramic foams and woven ceramic bers are often mentioned as diesel particle deep-bed lters. Ceramic foams are positive images of sponges (160) that operate according to the deep-bed ltration mechanism (91,161,162). Ceramic foams do not qualify as absolute lters because their ltration efciency depends on the exhaust gas velocity (163), lter length (164), pore size (163 165), and lter surface roughness (166). In contrast, when selecting a wall-ow monolith, only its dimensions need to be considered in design studies. Table 12 lists the performance of deep-bed lters revealed in different studies. The reported efciencies of the foam lters are reasonable, especially when one considers that more or less standard foam materials were used, made by producers for quite a different application (i.e., molten-metal ltration). Higher ltration efciencies might be expected for tailor-made foams with optimized geometry. The ceramic ber lter consists of a number of perforated cylindrical metal tubes with ceramic ber threads (SiO2 or SiO2:Al2O3) woven in a diamond pattern, as shown in Figure 35. The tubes are placed in a container and exhaust gas ows to
542 Table 12. Filter Foam Foam Foam Foam Foam Foam Fiber Fiber
VAN SETTEN, MAKKEE, AND MOULIJN List of Diesel Engine Tests Conducted on Ceramic Foam and Fiber Filters
Pore Size (Pores/cm) 26 25 32 28 24 39 16 31 8 9
hf (%)
71 74 40 78 43 82 48 78 70 75 35 60 95 99 75 99
dp (mbar) 140 40 110 0 250 90 390 50 450 25 40 0 100 0 100
Vlter (L) n.r. 7 2.5 0.5 1.5 n.r. 3.4 20 n.r.
Engine (L) 2.3 n.r. 1.6 4.3 14.6 2.2 n.r. 12
Ref. 54 162 163 164 165 202 37 120
Note: hf, ltration efciency; dp, pressure drop over lter; Vlter, lter volume; engine, engine displacement; n.r., not reported.
the outside of the lter tubes and passes through the bers to the inside. Because of its shape, the lter is also known as a candle lter. The main advantage of ber lters is that they have good ltration efciencies at low-pressure drops, as is shown in Table 12. The range of 75 99% efciency is caused by the ltration mechanism. Initially, the efciency is relatively low, but during particle deposition, it increases to 99% (120).
3. High-Temperature Resistance of Different Filter Geometries During operation the particles are deposited in a tubular formation in the inlet channels of the wall-ow monolith. The tubular deposits are isolated from each other by the lter walls and the air space in the surrounding outlet channels. During self-supporting regeneration, the deposits burn like an array of parallel, independent wicks going from the inlet to the outlet (54), as shown in Figure 36, which can lead to locally high temperatures and thermal stress.
Figure 35. 3M.)
Illustration of the construction and ow pattern of a ceramic ber lter. (Courtesy of
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Figure 36. Illustration of the combustion of tubular, separated particulate matter deposits in a wallow monolith.
Foams and other deep-bed lters have three-dimensional connected structures, resulting in better transport of heat and particles through the lter than through the wall-ow monolith. During regeneration this leads to nearly isotropic* propagation of the combustion front (54), which, in turn, results in lower temperatures and less thermal stress. Table 13 shows the ignition temperatures and the maximum temperatures found during soot combustion in a wall-ow monolith and a foam lter. Maximum temperature differences of 3008C were observed between the two lter types. The structure of ceramic ber lters is optimal for high temperatures (50). Fiber lters consist of many independent bers that are not cross-linked, which makes the total structure less stiff than the monolith and ceramic foam. If the bers are bonded to each other, the structure becomes more brittle and can be damaged by thermal and mechanical stress (37).
4. Compatibility Between Filters and Regeneration Strategies An important difference between deep-bed lters and the wall-ow monolith surface lter is that the latter has closed ends which requires that the exhaust gas must pass via the soot cake through the lter surface, whereas the former is open
Table 13. The Ignition Temperatures and Maximum Temperatures Which Were Found During Soot Combustion in a Cordierite Wall-Flow Monolith and a Foam Filter Filter Monolith Foam Tign. (8C) 495 440 Tmax. (8C) 900 1000 640 740
Note: Tign., ignition temperature; Tmax., maximum temperature during regeneration. Source: Data from Refs. 54 and 163.
*The denition of isotropic is having the same properties along all axes (16).
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which gives the exhaust gas a free pathway. These differences may give rise to different problems if certain regeneration strategies are applied on the two lter types. For instance, the wall-ow monolith is less suited as a catalyst support; the catalytic washcoat lls up the pores in the lter walls, which leads to an increased pressure drop over the lter (167), and in the case of NOx-aided regeneration strategies, the Pt catalyst should be located upstream of the lter and not in the lter, as illustrated in Figure 37. The U.S. Diesel Emission Control Sulfur Effects Program (DECSE) (126) compared NOx-aided CRT (catalyst upstream of lter) with a precious-metalcoated wall-ow monolith (catalyst within lter). Pressure drops, balance temperatures, and CO and hydrocarbon emissions were examined. The clean pressure drops (i.e., no particulate matter present) of the lters were similar; apparently, the precious-metal-coated wall-ow monolith was not obstructed by the catalyst (the catalyst layer was probably very thin). The balance temperature of the precious-metal-coated lter was 50 708C higher, which was probably caused by the unoptimized location of the catalyst, as illustrated in Figure 37a, or by the thin catalyst layer (i.e., low catalyst loading). An oxidation catalyst deposited on a ceramic foam lter would probably hardly affect the pressure drop for such a lter. It is even conceivable that NOx-aided CRT would utilize the precious metal catalyst more efciently when deposited in the foam, because each NO molecule could then undergo multiple NO:NO2 combustion cycles, as illustrated in Figure 38, and, therefore, less precious metal would be needed, or the catalytic lter could be used for engines with less favorable NOx:soot ratios. The very open structure of the ceramic foam lter may make it less suitable for periodic regeneration strategies, because trapped particulate matter (with fuel additive ash) may reentrain into the exhaust gas. For instance, it has been reported that particulate matter can easily be blown off from foam lters by sudden exhaustgas speed changes (163).
Figure 37. Formation of NO2 in a catalytic particle trap: (a) formation in a lter surface; (b) NO2 formation upstream of lter surface.
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Figure 38. Illustration of a soot-oxidation mechanism in which one NOx molecule subsequently reacts with three consecutive soot particles.
The ber lter might not be suited for every continuous regeneration strategy because it only lters efciently after some initial particle deposition (37). If continuous regeneration causes a deposition oxidation equilibrium at a low particle equilibrium loading in the lter, then a low ltration efciency might be the result. B. Trapping by Means Other Than Filtration Although most research and applications for particle trapping have concentrated on ltration, there are other ways of separating particles from exhaust gas. In general, the advantage of these methods is that they not only separate the particles from the gas stream but also transport them away from the gas stream, which blocks pressure buildup problem from developing. Figure 39 shows schematic structures of different traps. Ludecke and Dimick (168) evaluated some of them for automobile applications. In all cases, they seemed not applicable for diesel particulate abatement. They found that the gas cyclone required too high gas velocities or volume, the electrostatic precipitator was unreliable and inefcient, and water scrubbers and oil baths were impractical and inefcient. Despite the problems, alternative methods are still being developed. For instance, Moulijn and co-workers (169) patented a turbulent ow precipitator with an oxidation catalyst for soot oxidation that is based on the turbulent ow precipitator developed by Dullien (170). The precipitator creates stagnant, turbulence-free regions where the particles enter and settle. Maganas and Harrington (171) reported a uidized-bed trap of silica or alumina particles for diesel particulate abatement. At temperatures of 300 3758C, they removed 98% of the particles from a heavy-duty truck engine with a reactor that contained 775 kg (!) silica particles. It remains to be seen if this type of device is viable for automotive applications, but they may show some promise for applications which have less stringent size restrictions, as in ships and stationary engines. VII. COMMERCIAL CATALYTIC DIESEL PARTICLE FILTERS A. Flow-Through Oxidation Catalysts When diesel particulate matter became part of environmental awareness, engines were not optimized for clean combustion and, at that time, traps started to
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Figure 39. Different particle traps based on trapping mechanisms other than ltration. (From Refs. 159, 168, 170, and 171.)
be studied extensively. Advances in diesel fuel combustion technology have, however, greatly reduced the total particulate mass, with the result that, initially, air standards could be satised by using an oxidation catalyst deposited on a owthrough monolith (172). Of course, soot particles are not trapped, but the oxidation catalyst converts CO and hydrocarbons (including the ones that form the soluble organic fraction of the total particulate mass) from temperatures of 2008C (172), with less than 5% oxidation of the soot fraction of the particulate matter (173) at gas hourly space velocities of 50,000 300,000 L/L/h (174). 1. Sulfuric Acid Formation The ow-through diesel oxidation catalyst is based on platinum, which happens to also be an excellent SO2 oxidation catalyst (172). At temperatures above 300 3508C, the catalyst oxidizes to SO2 to SO3, which quickly combines with water to form sulfuric acid and contributes signicantly to the total particulate mass (175). A good knowledge of the exhaust gas temperatures and particulate matter composition is required if the catalyst is to be tailored to meet specic requirements (172,176). In practice, this means that if average temperatures are below 2508C, a very active catalyst will not be a problem because the SO2 oxidation rate is low, but if temperatures are often above 3008C,
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a less active catalyst will be required to minimize SO2 oxidation. Rhodium and palladium are less active oxidation catalysts, and by alloying them with platinum, a tailored catalyst with compromise activity can be made (172). Base metals were also found to tailor the activity of platinum (173). In a special case where only the soluble organic fraction of the total particulate matter needed to be lowered to meet the total particulate mass standard, a base-metal-only catalyst sufced (175). B. NOx-Aided CRT The NOx-aided continuously regenerated trap (NOx-aided CRT ) for trucks and buses was invented by Cooper and Thoss (12). It consists of a wall-ow monolith with an upstream ow-through diesel oxidation catalyst, which is called, in this context, the preoxidizer. Figure 40 provides a schematic representation of the system. The oxidation catalyst converts 90% of the CO and hydrocarbons present to CO2 and 20 50% of the NO to NO2 (177). Downstream, the particles are trapped on a cordierite wall-ow monolith and subsequently oxidized by the NO2. 1. Modular Design The modular design of the separated and detachable preoxidizer and lter facilitates a high exibility of the system, which is a great advantage for retrotting of different buses and trucks. In each case, the optimal trap and preoxidizer can be chosen, which can, in many cases, save space, heat loss, backpressure, and system costs. Another advantage of the modular design with clamshells is that the canning can be easily opened in order to remove deposits of inorganic ash.
Figure 40.
Illustration of NOx-aided CRT. (Courtesy of Johnson Matthey.)
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The lter should produce a surplus of NO2 in order to compensate for time periods in which the temperature is too low for regeneration. The surplus NO2 should not be too high because NO2 is foul smelling in the vicinity of the vehicle, where it has not yet been diluted sufciently with ambient air. For the environment, the NO2 gives no additional problems, because NO reacts to NO2 anyway in short time scales (177).
2. Advantages The NOx-aided CRT system is an effective catalytic lter that oxidizes all carbon components in diesel exhaust gas, including small particles, and unregulated compounds (178), and it reduces the NOx concentration by 3 8% (177). It is a simple concept that allows for t-and-forget usage. The temperature window of 2004508C (177) is very reasonable; 2008C is needed for CO and hydrocarbon oxidation (134), whereas 4508C relates to the chemical equilibrium between NO and NO2, which is not favorable above 4508C (12). The balance temperature is actually higher than 2008C and depends on the fuel sulfur level, as was shown in Figure 30. In the case of a 30-ppm sulfur fuel, the temperature in the lter should be higher than 2758C for at least 40% of the time for effective lter regeneration (179). Because of continuous regeneration, extreme temperatures are avoided, which enhances stability; a satisfactory performance during 600,000 km (134) has been reported.
3. Limitations The system has not yet been introduced on a wide scale because it requires the use of low-sulfur fuel [,50 ppm (134)], because SO2 restricts the performance (Section V.D.2), and when oxidized by the platinum catalyst, it adds up signicantly to the total particulate mass (Section V.C). Low-sulfur fuel can easily be made available to public transport companies, which often have their own diesel depots, but for many other heavy-duty applications, that is not practical yet. In a few years time, this will, however, change, when low-sulfur fuel becomes widespread in Europe and the United States (Section III.B). Problems may arise for international transport companies that operate in countries that will not introduce low-sulfur fuels on the short term. Another problem of the system is its dependency on NOx, because it is uncertain if the required NOx-to-soot ratio for successful regeneration will be met in future engines.
C. Integrated Catalytic Trap for Passenger Cars The issue of regeneration of lters for light-duty vehicles has provided a major challenge. It took two decades to identify the salient problems and to
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develop the key components that would lead to satisfactory performance. The key components are as follows: Silicon carbide wall-ow monolith: The obvious reason for choosing a wallow monolith lter is its high ltration efciency (Section VI.A.1). Silicon carbide is the preferred construction material for a periodically regenerated lter because of its superior physical properties (Section V.D.1). Engine-controlled heating: Engine-controlled heating is the most practical way of temporarily raising exhaust temperatures (Section IV.B.1). The preferred method is fuel-injection-timing control because it does not affect drivability. Cerium fuel additive: Fuel additives are a good choice for ensuring a high regeneration efciency (Section V.B.2). Cerium is the preferred fuel additive, because it is sufciently active for helping self-supporting regeneration reactions sustaining themselves, and its activity is too low for spontaneously igniting self-supporting regeneration reactions (Section V.B.2). It is environment-friendly, because it does not catalyze the formation of unwanted toxic by-products (Section V.C). Preoxidizer: At low engine loads and speeds, additional heat to initiate regeneration cannot be produced in the engine without producing extra engine power (52). In such cases, rst some additional engine heat is produced to light-off a preoxidizer, then the hydrocarbon concentration in the exhaust gas is raised to produce heat by oxidation in the preoxidizer catalyst (52). Figure 41 shows the two critical temperature regions for this method. Peugeot-Citroen was the rst car manufacturer to commercialize the above components for serial production. Figure 42 gives a schematic representation of their system. The system is a good example of clever component selection and technology integration. The strongest point of the system is the way in which it integrates two catalyst technologies, because of which, several oxidation mechanisms might become available: . Cerium-aided, periodically induced self-supporting regeneration. . Cerium-catalyzed spontaneous, local regeneration reactions at low temperatures, as was reported by Lepperhoff et al. (117). . Cerium-catalyzed continuous soot oxidation at high temperatures, as was reported by Lepperhoff et al. (117) and Jelles et al. (123). . Cerium-catalyzed reduction of black smoke, after some initial cerium deposition in the combustion chamber and exhaust system (180). Cerium fuel additive reduces the raw particulate emissions by 20% (117). . Platinum-catalyzed oxidation of volatile hydrocarbons and CO. . Platinum-catalyzed production of NO2 at favorable temperatures.
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Figure 41. Plot of critical preoxidizer temperatures of engine-controlled exhaust heating in combination with catalytic combusion. (From Ref. 52.)
. Platinum- and cerium-catalyzed synergetic oxidation of soot. The combination of platinum and cerium might lead to a reaction that is analogous to the one reported by Jelles et al. (123) (Fig. 22). The system has some shortcomings. The trap should be cleaned periodically in connection with cerium deposits (52). Many components are present: Additives, additive storage, additive precision dosing pump, preoxidizer, pressure sensors, temperature sensors, common-rail fuel-injection system, and management system make the system complex and expensive. To give a price indication, a traditional uncanned three-way catalyst, the construction of which is similar to the preoxidizer, C C may cost to = 40 to = 150 (181). An integrated catalytic trap for passenger cars with catalytic fuel-additive dosing system will cost much more than that.
VIII.
EVALUATION
A. Diesel Particulate Matter In view of its complex formation process, it is not surprising that many types of diesel particulate matter exist. What all types have in common is that they are suspected of causing respiratory diseases from bronchitis to lung cancer. In many countries, legislation has been issued. In the coming years, the emission standards for diesel-powered vehicles will become so stringent that exhaust aftertreatment will become inevitable, especially for heavy-duty trucks and buses.
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Figure 42. Schematic overview of the catalytic lter system introduced in European passenger cars in 2000. (Courtesy of PSA Peugeot-Citroen.)
Whether the legislation of the last few years pushed emission reduction technology in the right direction is doubtful, because, for the sake of simplicity, a decrease in total particulate mass is demanded. Recently, it became clear that decreasing the total particulate mass does not guarantee that toxicity will decrease; the opposite might, in fact, be true. For new legislation purposes, the total particle number is currently often mentioned rather than the total particulate mass, but the particle number may also be erroneous. The best way to guarantee that diesel exhaust is safe will be to demand essentially zero-particulate emission by using sulfur-free fuel and absolute ltration in combination with essentially complete catalytic oxidation of the hydrocarbons in the exhaust gas.
B. Diesel Particulate Matter Abatement For several reasons, diesel particulate matter abatement poses a real challenge. There are numerous different engines for various applications (kW to MW applications, steady state to transient operations, clean to dirty fuels), which makes it very difcult to develop one device that solves all problems. The device adopted should be able to operate under a wide range of conditions during the service life of the vehicle and it should not produce toxic by-products. In a sense, removing the particulate matter from diesel exhaust is the easy part.
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Commercially available lters exist which are capable of ltering out more than 99% of the number of particles and 90% of the total particulate mass. Used in combination with a ow-through diesel oxidation catalyst and low-sulfur fuel, the total particulate mass could even be further reduced. However, the necessary regeneration of the lter complicates lter technology. Especially light-duty diesel engines present a challenge, because their exhaust temperature is too low for even catalytic soot oxidation. Additional energy has to be put into the exhaust gas to enhance the oxidation rate. Two energy-efcient strategies for regenerating the trap can be envisaged. First, the lter can be substantially loaded with particulate matter and then regeneration can be induced by temporarily raising the temperature to ignite an exothermic regeneration reaction that sustains itself. Engine-controlled heating is the most promising method for igniting regeneration. By varying the timing of fuel injection, the temperature can be raised without inuencing drivability. When ignited, the regeneration reaction might smother. To ascertain complete regeneration, a catalyst can be applied. Catalytic fuel additives are very suitable aids, because the rate of exothermic regeneration is high and intimate catalytic contact could be essential for the reaction to sustain itself. Second, additional energy can be introduced in a selective manner by using, for instance, a plasma or electrochemical reactor. Such reactors should be evaluated with great care, in view of the fact that some of the initial euphoria was based on the misinterpretation of experimental data. Plasmas have been reported to produce all kinds of compounds in addition to H2O, CO2, and N2. The possible production of toxic organic molecules should be checked. Signicant increases in, for instance, nitro- and oxy-polycyclic aromatic hydrocarbons would be most undesirable. Clean diesel vehicles can become a reality. By integrating existing reduction, oxidation, and ltration techniques, a total solution may be provided (182 184). Figure 43 shows a simplied design of an integrated system for heavy-duty vehicles based on NOx-aided CRT and a DENOX catalyst (183). Other options for NOx abatement might be reduction with hydrocarbons or, in the future, direct dissociation of NOx. One of the advantages of the diesel engine is its robustness. The application of advanced integrated catalyst technology will signicantly increase the
Figure 43. Illustration of a combined HC, CO, NOx, and particulate matter abatement system. (From Ref. 183.)
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complexity of diesel-powered vehicles, which might lead to decreased robustness. An alternative and more convenient way to total emission reduction might be the application of a simple aftertreatment device in combination with engine optimization. Optimizing the engine to produce less particulate matter will probably lead to more NOx because of trade-off effects. It might, however, not solve the particle number problem. Optimizing the engine to produce less NOx in combination with a catalytic lter might be more logical: The exhaust gas is oxygen rich, which means that no additional chemical reactant is required and ltration will not only solve the total particulate mass but it will also solve the particle number problem. Less NOx will, however, make lter regeneration more difcult, because NOx is an essential component for continuous, low-temperature regeneration. Also, other trade-off effects, like reduced fuel efciency, might surface. The problem of the low NOx concentration might be solved by introducing advanced catalytic traps that use NOx more efciently. Alternatively, a low-temperature catalyst may be developed that does not require NOx. Developing such an advanced catalytic trap will be one of the major challenges of catalytic lter engineering.
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Typical prices of a three-way catalyst. Quoted by Johnson Matthey, Royston (UK), 2000. Khair, M.; Lemaire, J.; Fischer, S. Integration of Exhaust Gas Recirculation, Selective Catalytic Reduction, Diesel Particulate Filters, and Fuel-Borne Catalyst for NOx/PM Reduction. SAE paper 2000-01-1933, 2000. Chandler, G.R.; Cooper, B.J.; Harris, J.P.; Thoss, J.E.; Uusimaki, A.; Walker, A.P.; Warren, J.P. An Integrated SCR and Continuously Regenerating Trap System to Meet Future NOx and PM Legislation. SAE paper 2000-01-0188, 2000. Krijnsen, H.C.; Bertin, S.S.; Makkee, M.; van den Bleek, C.M.; Moulijn, J.A.; Calis, H.P.A. Bench-Scale Demonstration of an Integrated deSoot deNOx System. SAE paper 2001-01-0515, 2001. Johnson, J.H.; Bagley, S.T.; Gratz, L.D.; Leddy, D.G. A Review of Diesel Particulate Control Technology and Emissions Effects. 1992 Horning Memorial Award Lecture. SAE paper 940233, 1994. Kraftstoffverbrauchs- und Emissions Typprufwerte von Kraftfahrzeugen mit allgemeiner Betriebserlaubnis EGW-Typgenehmigung. Kraftfahrt-Bundesamt: Flensburg (Germany), 1999. Luders, H.; Stommel, P.; Geckler, S.; Diesel Exhaust Treatment. New Approaches to Ultra Low Emission Diesel Vehicles. SAE paper 1999-01-0108, 1999. McKee, D.W. Mechanisms of the Alkali Metal Catalysed Gasication of Carbon. Fuel 1983, 62, 170 175. Mims, C.A Catalytic Gasication of Carbon: Fundamentals and Mechanism. In Fundamental Issues in Control of Carbon Gasication Reactivity; Series NATO ASI. Series E. Applied Sciences, Lahaye, J., Ehrburger, P. Eds.; Kluwer Academic: Dordrecht, 1991; 383 407. Kitagawa, J.; Hijikata, T.; Makino, M. Effects of DPF Volume on Thermal Shock Failures During Regeneration. SAE paper 890173, 1989. Engine Characteristics and Fuel Specications of the Wartsila 6L38 Electricity Generator. Quoted by Stork-Wartsila, Zwolle (The Netherlands), 1997. Characteristics of a Typical Heavy-Duty Truck Engine. Quoted by Johnson Matthey, Royston (UK), January 2000. Characteristics of a 1998 DI Light-Duty Passenger Car Diesel Engine. Quoted by Centro Ricerche FIAT, Torino (Italy), 1999. Matweb The Online Materials Information Resource. http://www.matweb.com (accessed April 2001). Heat Capacity of 3M Interam 100. Quoted by 3M, Neuss (Germany), January 2000. Challen, B.; Baranescu, R., Eds. Diesel Engine Reference Book. Society of Automotive Engineers: Warrendale, PA, 1999. Bellaloui, A.; Varloud, J.; Meriaudeau, P.; Perrichon, V.; Lox, E.; Chevrier, M.; Gauthier, C.; Mathis, F. Low Temperature Diesel Soots Combustion Using Copper Based Catalysts Modied by Niobium and Potassium Promoters. Catal. Today 1996, 29, 421 425. Yuan, S.; Meriaudeau, P.; Perrichon, V. Catalytic Combustion of Diesel Soot Particles on Copper Catalysts Supported on TiO2. Effect of Potassium Promoter on the Activity. Appl. Catal. B 1994, 3, 319 333. Agostini, L.; de Portu, G.; Guicciardi, S.; Borello, C.; Demaestri, P.P.; Giachello, A. Characteristics of Porous Cordierite Traps Intentionally Contaminated with
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Calcium and Zinc. Proceedings of the 4th International Symposium on Ceramic Materials and Components for Engines 1991, 1154 1161. Bachiorrini, A. New Hypotheses on the Mechanism of the Deterioration of Cordierite Diesel Filters in the Presence of Metal Oxides. Ceram. Int. 1996, 22, 73 77. Helferich, R.L.; Schenck, R.C. Evaluation of a Stacked Element Diesel Particulate Trap using a Newly Developed Membrane Covered Ceramic Foam Filtering Media. SAE paper 890787, 1989. Shinozaki, O.; Shinoyama, E.; Saito, K. Trapping Performance of Diesel Particulate Filters. SAE paper 900107, 1990.

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CATALYSIS REVIEWS, 43(4), 489564 (2001)

SCIENCE AND TECHNOLOGY OF CATALYTIC DIESEL PARTICULATE FILTERS

VI. DIESEL PARTICLE TRAPS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A. Filtration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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Trapping by Means Other Than Filtration . . . . . . . . . . . . . . . . . . . . . . . .

545 545 545 547 548 550 550 551 553

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Schematic mechanism of the formation of soot particles.

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CATALYTIC DIESEL PARTICULATE FILTERS

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Note: See also Table 2. Source: Ref. 191.

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Engine Passenger car

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CATALYTIC DIESEL PARTICULATE FILTERS

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Table 4. Phase Euro I Euro II Euro III Euro IV Euro V

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CATALYTIC DIESEL PARTICULATE FILTERS

NONCATALYTIC DIESEL SOOT OXIDATION

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CATALYTIC DIESEL PARTICULATE FILTERS

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CATALYTIC DIESEL PARTICULATE FILTERS

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Schematic illustration of monolith channels with internal electrical heating wires.

CATALYTIC DIESEL PARTICULATE FILTERS

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CATALYTIC DIESEL PARTICULATE FILTERS

Simplied diagram of a continuously regenerated plasma trap.

Illustration of the Electrocat system. (Courtesy of AEA Technology.)

VAN SETTEN, MAKKEE, AND MOULIJN

Illustration of the electrochemical diesel particle lter. (Courtesy of DINEX.)

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CATALYTIC DIESEL PARTICULATE FILTERS

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Table 6. Classication of the Modes of Catalyzed Oxidation of Graphite by Various Metals

CATALYTIC DIESEL PARTICULATE FILTERS

Illustration of spillover soot-oxidation mechanism on a catalyst surface.

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CATALYTIC DIESEL PARTICULATE FILTERS

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CATALYTIC DIESEL PARTICULATE FILTERS

Additive Ce Fe Cu None None Pt/Ce Pt/Cu Pt/Fe Ce

ca (ppm) 100 100 100 0.5/5 0.5/5 0.5/22 100

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Figure 25. stress.

Scheme of different types of crack in a cylindrical lter due to mechanical or thermal

VAN SETTEN, MAKKEE, AND MOULIJN

Figure 26. Scheme of double-band xture test. (From Ref. 140.)

CATALYTIC DIESEL PARTICULATE FILTERS

Cordierite Silicon carbide Stainless steel Canning mat