Oxidation platinum monolithic

S.E. Voltz and D. Liederman, "Thermal Deactivation of a Platinum Monolithic Carbon Monoxide/Hydrocarbon Oxidation Catalyst", Ind. Eng. Chem. Prod. Res. Dev.. 1974,1314). 243-250. 

T he successful use of platinum monolithic oxidation catalysts to control automobile emissions over many thousands of miles requires an intimate understanding of the many factors which contribute to catalyst degradation. Contamination of the active catalyst by lead and phosphorus compounds present in fuel and lubricating oil is a major factor in catalyst deterioration. 

Salomons S, Votsmeier M, Hayes R, Drochner A, Vogel H, GieshofJ CO andH2 oxidation on a platinum monolith diesel oxidation catalyst, Catal Today 117 491—497, 2006. 

Starting with a ceramic and depositing an aluminum oxide coating. The aluminum oxide makes the ceramic, which is fairly smooth, have a number of bumps. On those bumps a noble metal catalyst, such as platinum, palladium, or rubidium, is deposited. The active site, wherever the noble metal is deposited, is where the conversion will actually take place. An alternate to the ceramic substrate is a metallic substrate. In this process, the aluminum oxide is deposited on the metallic substrate to give the wavy contour. The precious metal is then deposited onto the aluminum oxide. Both forms of catalyst are called monoliths. 

A sophisticated quantitative analysis of experimental data was performed by Voltz et al. (96). Their experiment was performed over commercially available platinum catalysts on pellets and monoliths, with temperatures and gaseous compositions simulating exhaust gases. They found that carbon monoxide, propylene, and nitric oxide all exhibit strong poisoning effects on all kinetic rates. Their data can be fitted by equations of the form ... 

The fit of these equations to the data is very good, as seen in Fig. 18. These equations are valid to very small values of CO concentrations, where the reaction becomes first order with respect to CO. In a mixture of CO with oxygen, there should be a maximum in reaction rate when the CO concentration is at 0.2%, as shown in Fig. 19. When the oxidation of olefins and aromatics over a platinum loaded monolith is over 99% complete, the conversion of higher paraffins may be around 90% and the conversion of the intractable methane is only 10%. 

Many elements of a mathematical model of the catalytic converter are available in the classical chemical reactor engineering literature. There are also many novel features in the automotive catalytic converter that need further analysis or even new formulations the transient analysis of catalytic beds, the shallow pellet bed, the monolith and the stacked and rolled screens, the negative order kinetics of CO oxidation over platinum,... 

Since 1981, three-way catalytic systems have been standard in new cars sold in North America.6,280 These systems consist of platinum, palladium, and rhodium catalysts dispersed on an activated alumina layer ( wash-coat ) on a ceramic honeycomb monolith the Pt and Pd serve primarily to catalyze oxidation of the CO and hydrocarbons, and the Rh to catalyze reduction of the NO. These converters operate with a near-stoichiometric air-fuel mix at 400-600 °C higher temperatures may cause the Rh to react with the washcoat. In some designs, the catalyst bed is electrically heated at start-up to avoid the problem of temporarily excessive CO emissions from a cold catalyst. Zeolite-type catalysts containing bound metal atoms or ions (e.g., Cu/ZSM-5) have been proposed as alternatives to systems based on precious metals. 

The upstream monolith (containing platinum) catalyzes oxidation of hydrocarbons and CO to CO2 and NO to NO2, which is highly reactive... 

The use of supported platinum-based catalysts in hydrogen cyanide synthesis has been described, and some are in use in certain plants. For instance, Merrill and Perry recommended natural beryl coated with platinum or a platinum alloy [12], and a range of alternative supports were considered by Schmidt and his co-workers [13], including coated foamed ceramic and monolithic substrates. They are claimed to have some advantages in ammonia oxidation [14,15]. 

Not all catalysts need the extended smface provided by a porous structure, however. Some are sufficiently active so that the effort required to create a porous catalyst would be wasted. For such situations one type of catalyst is the monolithic catalyst. Monolithic catalysts are normally encountered in processes where pressure drop and heat removal are major considerations. Typical examples include the platinum gauze reactor used in the ammonia oxidation portion of nitric acid manufacture and catalytic converters used to oxidize pollutants in automobile exhaust. They can be porous (honeycomb) or non-porous (wire gauze). A photograph of a automotive catalytic converter is shown in Figure CD 11-2. Platinum is a primary catalytic material in the monolith. 

Fig. 5.7. The three-way catalyst consists of platinum and rhodium (or palladium) metal particles on a porous oxidic washcoat, applied on a ceramic monolith.

A development in catalyst support systems in which half of the 5-10% rhodium-platinum alloy gauzes were replaced by nonnoble metal supports or by ordinary metal catalysts gave cost economies without adversely affecting operating efficiency [47]. More recently, ammonia oxidation in a two-bed system (Pt gauzes followed by monolithic oxide layers) gave nearly the same ammonia conversion while reducing platinum losses by 50% [48]. 

Figure 102. Emission of particulates (part) and gaseous hydrocarbons (HC) from a heavy duty diesel engine in the US transient engine test cycle, as a function of the catalyst volume (monolith catalyst with 46 cells cm" diesel oxidation catalyst formulation with platinum at a loading of 1.76 g 1 , fresh).

Figure 103. The amount of soluble organic fraction (SOF) adsorbed on an aged diesel oxidation catalyst, as a function of the washcoat formulation (monolith catalyst with 62cellscm", dedicated diesel washcoat formulations with platinum at a loading of l.76gl diesel engine bench aging for 50 h diesel fuel containing 0.15 wt. % sulfur). Reprinted with permission from ref. (68], C 1991 Society of Automotive Engineers, Inc.

Figure 109. Conversion of carbon monoxide and gaseous hydrocarbons reached over a diesel oxidation catalyst at various settings of the exhaust gas temperature, for a model gas composition with and without SO2 (monolith catalyst with 62cells cm dedicated diesel washcoat formulations with platinum loading of 1.76gl" in the fresh state model gas light-off test at a space velocity of 50000Nir h model gas simulates the exhaust gas composition of an IDI passenger car diesel engine at medium load and speed).

Figure 111. Emission of aldehydes, acrolein and various polynuclear aromatic hydrocarbons of two passenger cars equipped with an IDI/NA and with a DI/NA diesel engine, once without and once with a diesel oxidation catalyst, in the US-FTP 75 vehicle test cycle (monolith catalyst with 62 cells cm dedicated diesel washcoat formulation with a platinum loading of 1.76 g 1 in the fresh state vehicle dynamometer tests according to the US-FTP 75 vehicle test procedure, with passenger cars equipped with a DI/NA and with an IDI/NA diesel engine of displacement 2.0 1). Reprinted with permission from ref [70], 1990 Society of Automotive Engineers, Inc.

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