Platinum Metals Review
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UK ISSN 0032-1400 PLATINUM METALS REVIEW A quarterly survey of research on the platinum metals and of developments in their application in industry VOL. 35 OCTOBER 1991 NO. 4 Contents Flow-Through Catalysts for Diesel Engine Emissions Control 178 Royal Commission Report on Diesel Emissions 187 Chemical Reaction Fronts on Platinum Surfaces 188 Platinum Catalyses the Conversion of Methane to Higher Alkanes 195 Metal-Hydrogen Systems 195 The Plastic Flow of Iridium 196 Ammonia Sensor Uses Platinum Films 200 Partners in Innovation Conference 20 1 Recovery of Platinum Group Metals from High Level Radioactive Waste 202 Platinum Silicide Temperature Detectors 208 Palladium Contact Materials 208 Second Grove Fuel Cell Symposium 209 Michael Faraday and Platinum 222 Abstracts 228 New Patents 24 1 Index to Volume 35 250 Communications should be addressed to The Editor, Platinum Metals Review Johnson Matthey Public Limited Company, Hatton Garden, London ECl N 8EE Flow-Through Catalysts for Diesel Engine Emissions Control PLATINUM COATED MONOLITHS REDUCE PARTICULATES By B. J. Cooper and S. A. Roth Johnson Matthey, Catalytic Systems Division, Wayne, Pennsylvania The treatment of vehicle emissions with an engine technology have greatly reduced the for- exhaust catalyst in order to reduce the level of mation of particulates, with the result that air three major air pollutants, namely carbon quality standards may now be met by the use of monoxide, unburnt hydrocarbons and nitrogen catalysed flow-through monoliths (9-1 1). oxides, is becoming a world-wide requirement These catalysts have the advantage of being for gasoline fuelled engines (1, 2). First stan- passive systems which do not require dards were introduced in the U.S.A. and Japan regeneration. during the early 1970s (3). Similar standards Catalysts for diesel engines must function dif- will be enforced in Europe beginning in ferently to those for gasoline engines because of 1992/93 (4, 5). Diesel engine exhaust poses an differences in the chemical composition of the additional challenge for emission control exhaust gas. Modern spark-ignition gasoline because, as compared to exhaust from gasoline powered automobiles, with emission control engines, it also contains particulate matter. Ear- devices, operate near stoichiometry (at an ly attempts at particulate control utilised airfuel ratio of - 14.7: 1) and under closed-loop catalytic trap oxidisers to filter the exhaust and electronic control. The catalyst typically oxidise the particulates (6-8). Catalytic trap ox- operates in the temperature range of 300 to idisers have the disadvantage of requiring an 9OOOC and functions by oxidising carbon active regeneration mechanism to remove monoxide and unburnt hydrocarbons to carbon particulate build-up. Recent advances in diesel dioxide and water, while oxides of nitrogen are ic HC Cal ter WET DIESEL EXHAUST DRY DIESEL EXHAUST Fig. 1 The compositions are given of typical particulates collected from the exhaust of diesel engines characterised using the European hot start Extra Urban Driving Cycle. The hydrocarbons derived from both the fuel and the lubrication oil constitute the soluble organic fraction, a high proportion of which indicates a “wet particulate”, while a high pro- portion of carbon occurs in a “dry particulate” Platinum Metals Rev., 1991, 35, (4), 178-187 178 Table I Current and Proposed World-wide Diesel Emission Laws I Market [ Test co NO, HC +NO, Particulate U.S. FTP 3.4 1.o 0.20 I 1987 I glmile _" California FTP LD 0.39" 7.0 0.4 0.08 1989 glmile U.S. HDT HD I 1.3 15.5 5.0 0.25 1991 glhph U.S. HDT HD 1.3 15.5 5.0 0.10 1994 glhph Japan 10 Mode 2.70 0.70 None 1990 glkm 2.70 0.84 None Japan 10glkm Mode 2.70 0.50 0.2 1994 g/kmglkm !:HD 0.62 2.70 1 1 f 1I::: !!!: 0.60 0.2 EC ECE+EUDC Auto 2.72 0.97 0.14 1992 glkm EC 1 proposed Stage 1 EC steady HD 1.1 4.5 8.0 0.36 1992193 state test glkWh Stage 2 EC steady HD 1.1 4.0 7.0 0.15 1995196 state test glkWh - - FTP Federal Test Procedure LD light duty * Non methane hydrocarbons HDT Heavy Duty Truck HD heavy duty EUDC Extra Urbm Driving Cyle reduced to nitrogen gas (12-16). The standard exhaust temperatures are typically cooler, 150 practice for gasoline exhaust treatment is to to 450°C, and are always oxidising. The diesel utilise a noble metal catalyst supported on a engine generates intrinsically low emission flow-through ceramic or metallic monolith, levels of gas phase hydrocarbons and carbon typically having 300 to 400 axial channels per monoxide, and when fitted with a conventional square inch of frontal area. The monolith walls oxidation catalyst there is little trouble meeting are coated with a thermally durable, high sur- regulated standards for these pollutants. The face area oxide on which are supported the ac- use of typical three-way catalysts to control tive catalyst components, generally platinum, nitrogen oxide emissions is impractical due to palladium and rhodium. the oxidising nature of the exhaust. Therefore, Combustion of diesel fuel occurs by high nitrogen oxide emissions must be controlled by pressure ignition, raker than by spark ignition, engine design and calibration, often at the ex- and at air:fuel ratios greater than 20:l. The pense of increased particulate emissions. As a Platinum Metals Rev., 1991, 35, (4) 179 Fig. 2 In the absence of platinum, the pressure drop across a catalyst monolith varies with time, due to pro- gressive obstruction of the axial passages by the build- up of carbon particulates TEST TIME ON ENGINE, hours result, the major challenge to diesel exhaust soluble organic fraction consists of hydrocar- emission control by catalytic means remains bons derived from both fuel and lubricating oil one of particulate removal. Additionally, in which condense as the exhaust cools, or adsorb Europe, where there is a combined hydrocar- during collection. The sulphuric acid/water bon + nitrogen oxide standard, removal of low fraction arises from oxidation of sulphur diox- temperature gas phase hydrocarbons is ide to sulphur trioxide and condensation with beneficial to meeting the overall design re- water vapour. quirements. There are a variety of diesel engine designs Importance of Sulphur in Diesel and these may be classified according to the Particulate Control method of fuel and air injection, as well as by Sulphur is present to some extent in all diesel the end-use application. Engines with indirect fuel and, as a result of the combustion process, injection of fuel are typically utilised for is emitted in the exhaust as sulphur dioxide. A passenger cars and light-duty trucks, while small fraction, typically about 2 per cent, is fur- direct injection engines have inherently better ther olddised to sulphur trioxide which con- fuel economy and are utilised in heavy duty denses with water in the exhaust as sulphuric vehicles. Many manufacturers are developing acid, and is then absorbed on carbonaceous soot high speed direct injection engines for use in particles, thus contributing to the total light-duty applications. Air is added to the measured mass of particulate emissions. The combustion chamber by natural aspiration or use of a catalyst can increase the fraction of fuel under pressure by turbocharging, and tur- sulphur converted to sulphate, and even a bocharging is often accompanied by intercool- modest increase in this fraction will result in the ing. World-wide emissions standards for diesel “manufacture” of significant particulate. For fuelled engines will finally require the use of example for a 0.05 weight per cent sulphur fuel, catalytic converters in the 1992-94 time frame, 100 per cent conversion of the sulphur in the see Table I. fuel to sulphuric acid would by itself result in a particulate emission five times higher than the Diesel Particulate Catalysis 1994 U.S. heavy duty truck standard. Particulate Composition Diesel particulate standards are measured via Particulate Control Strategy the weight increase of a fibre fiter placed in the A “flow-through’’ monolithic reactor, as op- diesel exhaust. The material collected consists posed to a particulate trap, achieves particulate of graphitic “hard” carbon or “soot”, a solu- reduction by catalytic oxidation of the soluble ble organic fraction (SOF), water, sulphuric organic fraction. However, this will result in acid and an inorganic ash residue. Typical par- minimal conversion of the hard carbon, and ticulate compositions are given in Figure 1. The therefore, the catalyst must be able to keep Platinum Metals Rev., 1991, 35, (4) 180 itself free from particulate fouling. During low Sulphur dioxide adsorbs strongly on platinum temperature operation particulate increase via at room temperature and inhibits carbon sulphuric acid formation is not significant, but monoxide, nitrogen monoxide and alkene ox- under these low temperature conditions it is idation. Sulphur dioxide oxidation is kinetically necessary for the catalyst to remove the soluble limited at low temperature and ther- organic fraction and the gas phase hydrocar- modynamically limited at high temperature, bons. During high temperature operation the but near 500 to 6OOOC can reach 80 to 90 per oxidation of hydrocarbon is facile, but the in- cent conversion. Factors which can limit crease of particulates due to sulphate formation sulphur dioxide oxidation activity in this must be minimised or eliminated. temperature range include oxygen concentra- tion, space velocity (Figure 3), and intrinsic Catalytic Carbon Oxidation catalytic activity. It has been reported previously that the removal of carbon requires reaction with Removal of the Soluble Organic nitrogen dioxide, which is formed by the oxida- Fraction tion of nitrogen monoxide over a platinum Hydrocarbon species in diesel exhaust consist catalyst (17). Palladium and rhodium are much of gaseous compounds as well as heavy, con- less effective for the oxidation of nitrogen densable hydrocarbons (soluble organic frac- monoxide at low temperatures, and their inclu- tion) which can be solubilised from the diesel sion with platinum in a catalyst formulation particulate.