Noble metal automotive catalyst

CO oxidation, an important step in automotive exhaust catalysis, is relatively simple and has been the subject of numerous fundamental studies. The reaction is catalyzed by noble metals such as platinum, palladium, rhodium, iridium, and even by gold, provided the gold particles are very small. We will assume that the oxidation on such catalysts proceeds through a mechanism in which adsorbed CO, O and CO2 are equilibrated with the gas phase, i.e. that we can use the quasi-equilibrium approximation. 

Figure 10.5. Monolith, washcoat and noble metal particles in an automotive exhaust catalyst.

Examination of automotive catalysts by various chemisorption techniques has shown that a loss in noble metal surface area caused by higher temperatures correlates monotonically with various activity indices (62, 63). Moreover, Dalla Betta and co-workers (64) were able to separate the additional effect of poisons on the surface of the precious metal by painstaking attention to detail. They developed techniques for accurately measuring the crystallite-size distribution in used automotive catalysts by... 

All the surface processes on automotive catalysts which have been tested for the effects of lead poisoning are affected by the access of lead to the catalyst surface. The effect will differ, though, for different surface processes. Oxidation of hydrocarbons has been found repeatedly to be more vulnerable than oxidation of carbon monoxide to lead poisoning (10, 19, 25). The initial oxidation activity of noble metal catalysts, never exposed to poisons, is higher for CO than for hydrocarbons (54). Therefore, it is best to use the effect of lead on hydrocarbon oxidation for assessing the susceptibility of a given oxidation catalyst to this type of poisoning. 

In contrast to lead, the possible poisoning by metallic elements, derived from the vehicle system, is not easily documented. Many formulations of automotive catalysts contain both base and noble metals, but the detailed effect of such combinations on the particular reactions is rarely known with precision. One study was concerned with the effect of Cu on noble metal oxidation catalysts, since these, placed downstream from Monel NOx catalysts, could accumulate up to 0.15% Cu (100). The introduction of this amount of Cu into a practical catalyst containing 0.35% Pt and Pd in an equiatomic ratio has, after calcination in air, depressed the CO oxidation activity, but enhanced the ethylene oxidation. Formation of a mixed Pt-Cu-oxide phase is thought to underlie this behavior. This particular instance shows an example, when an element introduced into a given catalyst serves as a poison for one reaction, and as a promoter for... 

Shelef, M., Dalla Betta, R. A., Larson, J. A., Otto, K., and Yao, H. C., Poisoning of Monolithic Noble Metal Oxidation Catalysts in Automotive Exhaust Environment, Am. Inst. Chem. Eng., New Orleans Meet. (1973). 

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. 

A few classicaV studies on the reactivity of HCs to reduce NOx with catalysts indicated that the use of such reductants for controlling mobile NOx emissions was quite attractive to the automotive industry, thereby the advent of a new type of HC-SCR technology in the mid-1980s. An example may be the treatment process of the tail gas from nitric acid production plant via ammonia oxida-tion. The process includes the usual injection of excessive amounts of HCs over supported noble metals such as Pt, Pd and Rh to eliminate the yellowish stack plume due to 0.1 - 0.5% NOx, mainly NO2, from the nitric acid plant. 

Cerium-based catalysts have been successfully used in several processes. For example, ceria (Ce02) is used as an additive [ 1,2] in modem automotive exhaust catalysts. Ceria acts as an excellent oxygen store [3-5] in the catalyst, which is thus rendered a very effective catalyst for combustion [6]. Moreover, addition of ceria to the automotive exhaust catalysts minimises the thermally induced sintering of the alumina support and stabilises the noble metal dispersion [7]. Ceria also enhances nitric oxide dissociation when added to various supported metal catalysts [8], which is another important function of the automotive exhaust catalyst. Recent investigations by Harrison et al have shown that ceria doped with certain lanthanides and promoted with copper and chromium have catalytic activities comparable to that of the noble metal catalysts [9]... 

A nice example of cooperation between metal particles and a support with redox properties concerns the three-way catalysts for automotive exhaust gases treatment composed of a noble metal (Pt, Pd, Rh) on a support with ceria additive. The cooperation was put in evidence in the CO/NO/O2 reactions [135-137] and... 

In this section we will discuss an example of recent laboratory work on the impact of sulfur on palladium catalysts formulations compared to other noble metal formulations. The laboratory studies discussed here have been performed using an apparatus which simulates the exhaust gas generated from a vehicle under several operating modes. The simulated exhaust gas is then heated to a controlled level and directed to a sample core taken from a commercial automotive converter. Quantitative analysis of pollutant and other gas species (CO, HC, NOx, COj and Oj) is performed using gas bench analyzers prior to and following the catalyst sample to determine the conversion efficiency for HC, CO and NOx. 

Zalc, J.M. Sokolovskii, V. Loffler, D.G. Are noble metal based water-gas shift catalysts practical for automotive fuel processing J. Catal. 2002, 206, 169-171. 

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