The Three Way Catalyst

The three-way catalyst, consisting of Pt and Rh particles supported on a ceramic monolith, represents a remarkably successful piece of catalytic technology. It enables the removal of the three pollutants CO, NO and hydrocarbons by the following overall reactions (Tab. 10.3)  

Additionally, NO is reduced by H2 and by hydrocarbons. To enable the three reactions to proceed simultaneously - notice that the two first are oxidation reactions while the last is a reduction - the composition of the exhaust gas needs to be properly adjusted to an air-to-fuel ratio of 14.7 (Fig. 10.1). At higher oxygen content, the CO oxidation reaction consumes too much CO and hence NO conversion fails. If however, the oxygen content is too low, all of the NO is converted, but hydrocarbons and CO are not completely oxidized. An oxygen sensor (l-probe) is mounted in front of the catalyst to ensure the proper balance of fuel and air via a microprocessor-controlled injection system. 

Catalytic treatment of motor vehicle exhaust has been applied in all passenger cars in the USA since the 1975 models. The first cars with electronic feedback systems and three-way catalysts were 1979 Volvos, sold in California. Today all new gasoline cars sold in the Western world are equipped with catalytic converters. It 

The principle of the A-probe is shown in Fig. 10.2. It is a simple oxygen sensor made in a similar manner to the solid oxide fuel cell discussed in Chapter 8. An oxide that allows oxygen ions to be transported is resistively heated to ensure sufficiently high mobility and a short response time ( 1 s.). 

The oxygen content in the exhaust is measured against a suitable reference, in this case atmospheric air. The response is given by the Nernst equation  

Modern three way catalysts are nanocomposite materials containing catalytic and non-catalytic components which allow the materials to efficiently carry out a range of functions (CO oxidation, CxHy oxidation and NOx reduction) imder a wide range of temperature conditions (250-800°C) in a process stream of variable composition (varying continuously between net oxidising and net reducing character). 

Legislation has driven the development of these systems in order to decrease the emission of pollutants such as CO (a poisonous gas), volatile organic compounds (VOC) and NOx (implicated in smog formation) from vehicle exhausts [3]. 

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Numerous permutations in composition exist, but usually the precise composition, particularly that of the washcoat, is a commercial secret. Detailed accounts of the three-way catalyst have been given by Heck and Farrauto [R.M. Heck and R.J. Farrauto, Catalytic Air Pollution Control, (2002, 2" Edition), WUey, New York.]. Here we briefly describe the functions of the catalyst ingredients. 

The ideal operating temperatures for the three-way catalyst lie between 350 and 650 °C. After a cold start it takes at least a minute to reach this temperature, implying that most CO and hydrocarbons emission takes place directly after the start. Temperatures above 800 °C should be avoided to prevent sintering of the noble metals and dissolution of rhodium in the support. 

Catalytic Reactions in the Three-way Catalyst Mechanism and Kinetics... 

One of the most straightforward methods to reduce carbon dioxide emissions is to enhance the fuel efficiency of engines. The three-way catalyst, although very successful at cleaning up automotive exhaust, dictates that engines operate at air-to-fuel ratios of around 14.7 1. Unfortunately, this is not the optimum ratio with respect to fuel efficiency, which is substantially higher under lean-burn conditions at A/F ratios of about 20 1, where the exhaust becomes rich in oxygen and NOx reduction is extremely difficult (Fig. 10.1). 

The three-way catalyst and the NOx storage-reduction catalyst represent remarkably successful catalytic technology. The catalysts are unique in that they have to operate under a wide range of conditions, depending on type of use, personal driving style, local climate, etc. This in contrast to the usual situation in industry, where conditions are optimized and kept constant. 

Why is lead a more severe poison for (parts of) the three-way catalyst than sulfur ... 

Cerium oxides are outstanding oxide materials for catalytic purposes, and they are used in many catalytic applications, for example, for the oxidation of CO, the removal of SOx from fluid catalytic cracking flue gases, the water gas shift reaction, or in the oxidative coupling reaction of methane [155, 156]. Ceria is also widely used as an active component in the three-way catalyst for automotive exhaust pollution control,... 

Figure 1. Schematic diagram of an engine and emission control system The microcomputer also reads signals from sensors measuring other engine operating parameters. In some emission control systems, the three-way catalyst is followed by supplementary air injection and an oxidizing catalyst to provide additional control of CO and hydrocarbon emissions.

Catalysis plays a prominent role in our society. The majority of all chemicals and fuels produced in the chemical industry have been in contact with one or more catalysts. Catalysis has become indispensable in environmental pollution control selective catalytic routes are replacing stoichiometric processes that generate waste problems. The three-way catalyst effectively reduces pollution from car engines. Catalytic processes to clean industrial exhaust gases have been developed and installed. In short, catalysis is vitally important for our economy now, and it will be even more important in the future. 

The structure of supported rhodium catalysts has been the subject of intensive research during the last decade. Rhodium is the component of the automotive exhaust catalyst (the three-way catalyst) responsible for the reduction of NO by CO [1], In addition, it exhibits a number of fundamentally interesting phenomena, such as strong metal-support interaction after high temperature treatment in hydrogen [21, and particle disintegration under carbon monoxide [3]. In this section we illustrate how techniques such as XPS, STMS, EXAFS, TEM and infrared spectroscopy have led to a fairly detailed understanding of supported rhodium catalysts. 

The studies discussed above deal with highly dispersed and therefore well-defined rhodium particles with which fundamental questions on particle shape, chemisorption and metal-support interactions can be addressed. Practical rhodium catalysts, for example those used in the three-way catalyst for reduction of NO by CO, have significantly larger particle sizes, however. In fact, large rhodium particles with diameters above 10 nm are much more active for the NO+CO reaction than the particles we discussed here, because of the large ensembles of Rh surface atoms needed for this reaction [28]. Such particles have also been extensively characterized with spectroscopic techniques and electron microscopy we mention in particular the work of Wong and McCabe [29] and Burkhardt and Schmidt [30], These studies deal with the materials science of rhodium catalysts that are closer to the ones used in practice, which is of great interest from an industrial point of view. 

It is fair to state that by and large the most important application of structured reactors is in environmental catalysis. The major applications are in automotive emission reduction. For diesel exhaust gases a complication is that it is overall oxidizing and contains soot. The three-way catalyst does not work under the conditions of the diesel exhaust gas. The cleaning of exhaust gas from stationary sources is also done in structured catalytic reactors. Important areas are reduction of NOv from power plants and the oxidation of volatile organic compounds (VOCs). Structured reactors also suggest themselves in synthesis gas production, for instance, in catalytic partial oxidation (CPO) of methane. 

Many different filter designs have been the subject of experimental studies on diesel soot combustion. In the early investigations, structured honeycomb filters made from cordierite, such as those applied for the three-way catalyst for the reduction of spark ignition engine gas emissions, were the focus of the experimental studies [29-39]. The experimental results with these filters were not promising, because the cordierite honeycomb filter did not withstand the thermal stress. Temperature peaks of almost 1200 °C were measured, after which the ceramic structure was partly melted or totally destroyed [29, 40],... 

In 1980 additional regulations imposed by the U.S. Environmental Protection Agency (EPA) required control of NOx (NO, N02, N20) emissions. Its removal coupled with the continuing need to remove CO and CyHn proved to be quite challenging because the latter had to be oxidized and the former reduced. Thus it appeared two separate environments were needed. This problem was solved by the development of the three-way catalyst or TWC capable of catalyzing the conversion of all three pollutants simultaneously provided the exhaust environment could be held within a narrow air-to-fuel range. This is shown in Fig. 7.10. 

Cerium is an important component of the three-way catalyst (TWC) technology used to control atmospheric pollution from internal combustion engines. Addition of ceria helps... 

Complex oxides of the perovskite structure containing rare earths like lanthanum have proved effective for oxidation of CO and hydrocarbons and for the decomposition of nitrogen oxides. These catalysts are cheaper alternatives than noble metals like platinum and rhodium which are used in automotive catalytic converters. The most effective catalysts are systems of the type Lai vSrvM03, where M = cobalt, manganese, iron, chromium, copper. Further, perovskites used as active phases in catalytic converters have to be stabilized on the rare earth containing washcoat layers. This then leads to an increase in rare earth content of a catalytic converter unit by factors up to ten compared to the three way catalyst. 

The name refers to the three reactions that are catalyzed, oxidation of CO, oxidation of hydrocarbons, and reduction of NO. The three-way catalyst for gasoline engines is an enormous success. 

Ceria affords a number of important applications, such as catalysts in redox reactions (Kaspar et al., 1999, 2000 Trovarelli, 2002), electrode and electrolyte materials in fuel cells, optical films, polishing materials, and gas sensors. In order to improve the performance and/or stability of ceria materials, the doped materials, solid solutions and composites based on ceria are fabricated. For example, the ceria-zirconia solid solution is used in the three way catalyst, rare earth (such as Sm, Gd, or Y) doped ceria is used in solid state fuel cells, and ceria-noble metal or ceria-metal oxide composite catalysts are used for water-gas-shift (WGS) reaction and selective CO oxidation. 

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