Catalytic converter studies

The effect of alkali presence on the adsorption of oxygen on metal surfaces has been extensively studied in the literature, as alkali promoters are used in catalytic reactions of technological interest where oxygen participates either directly as a reactant (e.g. ethylene epoxidation on silver) or as an intermediate (e.g. NO+CO reaction in automotive exhaust catalytic converters). A large number of model studies has addressed the oxygen interaction with alkali modified single crystal surfaces of Ag, Cu, Pt, Pd, Ni, Ru, Fe, Mo, W and Au.6... 

Recently, it is reported that Xi02 particles with metal deposition on the surface is more active than pure Ti02 for photocatalytic reactions in aqueous solution because the deposited metal provides reduction sites which in turn increase the efficiency of the transport of photogenerated electrons (e ) in the conduction band to the external sjistem, and decrease the recombination with positive hole (h ) in the balance band of Xi02, i.e., less defects acting as the recombination center[l,2,3]. Xhe catalytic converter contains precious metals, mainly platinum less than 1 wt%, partially, Pd, Re, Rh, etc. on cordierite supporter. Xhus, in this study, solutions leached out from wasted catalytic converter of automobile were used for precious metallization source of the catalyst. Xhe XiOa were prepared with two different methods i.e., hydrothermal method and a sol-gel method. Xhe prepared titanium oxide and commercial P-25 catalyst (Deagussa) were metallized with leached solution from wasted catalytic converter or pure H2PtCl6 solution for modification of photocatalysts. Xhey were characterized by UV-DRS, BEX surface area analyzer, and XRD[4]. 

This review has highlighted the key contributions of modern surface science to the understanding of the kinetics and mechanism of nitrogen oxide reduction catalysis. As discussed above, the conversion of NO has been taken as the standard to represent other NOx, and CO has typically been used as the reducing agent in these studies. The bulk of the work has been carried out on rhodium and palladium surfaces, the most common transition metals used in three-way catalytic converters. 

NASA conducted studies on the development of the catalysts for methane decomposition process for space life-support systems [94], A special catalytic reactor with a rotating magnetic field to support Co catalyst at 850°C was designed. In the 1970s, a U.S. Army researcher M. Callahan [95] developed a fuel processor to catalytically convert different hydrocarbon fuels to hydrogen, which was used to feed a 1.5 kW FC. He screened a number of metals for the catalytic activity in the methane decomposition reaction including Ni, Co, Fe, Pt, and Cr. Alumina-supported Ni catalyst was selected as the most suitable for the process. The following rate equation for methane decomposition was reported ... 

Recently there has been a growing emphasis on the use of transient methods to study the mechanism and kinetics of catalytic reactions (16, 17, 18). These transient studies gained new impetus with the introduction of computer-controlled catalytic converters for automobile emission control (19) in this large-scale catalytic process the composition of the feedstream is oscillated as a result of a feedback control scheme, and the frequency response characteristics of the catalyst appear to play an important role (20). Preliminary studies (e.g., 15) indicate that the transient response of these catalysts is dominated by the relaxation of surface events, and thus it is necessary to use fast-response, surface-sensitive techniques in order to understand the catalyst s behavior under transient conditions. 

A recent study shows that the (RAP)IrH2 complex can catalytically convert alkane to alkene at temperatures ranging from 150 to 250 °C through an acceptorless, thermal reaction. Three suggested reaction mechanisms, associative (A), dissociative (D) and interchange (I) will... 

The hugely complicated chemistry of the catalytic converter is described in some depth in the Open University s excellent book Physical Chemistry Principles of Chemical Change, Topic study 2 . Its part 1 is entitled the three-way catalytic converter , Open University, Milton Keynes, 1996. It covers the composition of the catalytic surface and the role of each dopant, the actual chemical reactions occurring, and details of the current legal situation regarding atmospheric pollution. 

K-absorption edges in study of, 12 149 structure of, and magnetism, 3 27 Catalytic behaviors, metallic oxides, 29 240 Catalytic converter automotive, 24 71, 72 single-bed, 24 72, 74 design of, 24 75-77, 83-86 dual-bed, 24 73... 

The oxidation of CO by Oj over group VIII metal catalysts has been the subject of a large body of ultrahigh vacuum surface science and high pressure catalysis work due to its importance in pollution control. Currently, the removal of CO as CO2 from automobile exhaust is accomplished by catalytic converters which employ a supported Pt, Pd, and Rh catalyst. The importance of CO oxidation has led to numerous recent studies of the kinetics of this reaction on supported metal catalysts and transient kinetic studies on polycrystalline foils , which have sought to identify and quantify the parameters of the elementary mechanistic steps in CO oxidation. 

Case study Man-made mineral fibres in automotive catalytic converters ... 

Innovation drivers An important impulse was the classification of ceramic fibres as carcinogenic category K2 (Directive 97/69/EC), which has been applicable since January 1998. Since July 2001 there has been a ban on the marketing of ceramic fibres for the general public . An impending ban also for the industrial sector caused alarm in the automotive industry. A scientific study by Wuppertal University" also directed attention on the subject of ceramic fibres in catalytic converter recycling . 

In an automobile s catalytic converter, CO and hydrocarbons present in the exhaust gases are oxidized. Unfortunately the effectiveness of these units decreases with use. The phenomenon was studied by Summers and Hegedus in /. Catalysis, 51, 185 (1978) by means of an accelerated aging test on a palladium impregnated porous pellet packed bed converter. From the reported data on hydrocarbon conversion shown below, develop an expression to represent the deactivation rate of this catalyst. 

The cordierite extruded monoliths, having 400 square cellsAn, were similar to those used in automobile catalytic converters. However, instead of using an alumina washcoat as in the catalytic converter, these catalyst supports were loaded directly with 12 to 14 wt.% Pt in the same manner as the foam monoliths. Because these extruded monoliths consist of several straight, parallel channels, the flow in these monoliths is laminar (with entrance effects) at the flow rates studied. 

An important requirement of kinetic studies for automotive aftertreatment devices is the capability of performing dynamic reactive experiments. Steady-state tests provide useful information for identification of reaction pathway and stoichiometry, but cannot capture the real operating behavior of catalytic converters for vehicles, which is transient in nature. Indeed, this is so not only because of the continuously changing conditions (temperature, composition, flow rate) of the engine exhausts as extensively addressed in the following sections, the principles of NSRC and SCR applications largely rely on the storage/reaction/release dynamics of NOx and of NH3, respectively. 

There are many chemically reacting flow situations in which a reactive stream flows interior to a channel or duct. Two such examples are illustrated in Figs. 1.4 and 1.6, which consider flow in a catalytic-combustion monolith [28,156,168,259,322] and in the channels of a solid-oxide fuel cell. Other examples include the catalytic converters in automobiles. Certainly there are many industrial chemical processes that involve reactive flow tubular reactors. Innovative new short-contact-time processes use flow in catalytic monoliths to convert raw hydrocarbons to higher-value chemical feedstocks [37,99,100,173,184,436, 447]. Certain types of chemical-vapor-deposition reactors use a channel to direct flow over a wafer where a thin film is grown or deposited [219]. Flow reactors used in the laboratory to study gas-phase chemical kinetics usually strive to achieve plug-flow conditions and to minimize wall-chemistry effects. Nevertheless, boundary-layer simulations can be used to verify the flow condition or to account for non-ideal behavior [147]. 

Particularly, the formation of C02 by the oxidation of CO over platinum metal catalysts is the reaction that has been studied most extensively in the past years and whose elementary steps appear to be best understood. This reaction is an important process in automobile catalytic converters [92] and its mechanism proceeds as follows [129] ... 

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