Carbon monoxide oxidation— steady-state

Potentiometric techniques have been used to study autonomous reaction rate oscillations over catalysts and carbon monoxide oxidation on platinum has received a considerable amount of attention43,48,58 Possible explanations for reaction rate oscillations over platinum for carbon monoxide oxidation include, (i) strong dependence of activation energy or heat of adsorption on coverage, (ii) surface temperature oscillations, (iii) shift between multiple steady states due to adsorption or desorption of inert species, (iv) periodic oxidation or reduction of the surface. The work of Sales, Turner and Maple has indicated that the most... 

In combustion systems it is generally desirable to minimize the concentration of intermediates, since it is important to obtain complete oxidation of the fuel. Figure 13.5 shows modeling predictions for oxidation of methane in a batch reactor maintained at constant temperature and pressure. After an induction time the rate of CH4 consumption increases as a radical pool develops. The formaldehyde intermediate builds up at reaction times below 100 ms, but then reaches a pseudo-steady state, where CH2O formed is rapidly oxidized further to CO. Carbon monoxide oxidation is slow as long as CH4 is still present in the reaction system once CH4 is depleted, CO (and the remaining CH2O) is rapidly oxidized to CO2. 

Carbon Monoxide Oxidation. Analysis of the carbon monoxide oxidation in the boundary layer of a char particle shows the possibility for the existence of multiple steady states (54-58). The importance of these at AFBC conditions is uncertain. From the theory one can also calculate that CO will bum near the surface of a particle for large particles but will react outside the boundary layer for small particles, in qualitative agreement with experimental observations. Quantitative agreement with theory would not be expected, since the theoretical calculations, are based on the use of global kinetics for CO oxidation. Hydroxyl radicals are the principal oxidant for carbon monoxide and it can be shown (73) that their concentration is lowered by radical recombination on surfaces within a fluidized bed. It is therefore expected that the CO oxidation rates in the dense phase of fluidized beds will be suppressed to levels considerably below those in the bubble phase. This expectation is supported by studies of combustion of propane in fluidized beds, where it was observed that ignition and combustion took place primarily in the bubble phase (74). More attention needs to be given to the effect of bed solids on gas phase reactions occuring in fluidized reactors. 

An analysis of the stability of the steady states of the carbon monoxide oxidation system shows... 

Carbon monoxide oxidation on Pt catalysts is an example of a reaction of practical importance that can lead to multiplicity of steady states when the resistance to diffusion leads to significant concentration gradients. Typical for multiple steady states is a sudden jump from a relatively low rate of reaction or conversion to relatively high values upon an increase of the catalyst temperature. Upon decreasing the temperature, the jump back to the low reaction rate occurs... 

Hydrogenase based enzyme electrode was not inhibited, when CO content in the mixture was less than 0.1 %. In the presence of 1 % CO the rate of hydrogen oxidation was decreased by 10 % and zero-current potential was shifted positively for 30 mV. The steady-state Currents were achieved in a few minutes [10], An important advantage of the hydrogen enzyme electrode is completely reversible nature of inhibition by CO. Like the soluble hydrogenase the enzyme electrode recovered 100 % of its initial activity as soon as the atmosphere of pure carbon monoxide was changed back to hydrogen. 

For the C + C02 reaction from 500° to 900° C., Gulbransen and Andrew (3J() obtain rate data which indicate that steady-state conditions were not attained, at least at the higher temperatures. However, using a carbon-14 tracer technique, they show that between 700° and 800° C. there is a rapid reaction to give carbon monoxide and surface oxide, followed by a slow decomposition. 

Tamman (29) observed in 1920 that for electrically heated catalytic wire multiple steady states occur for a certain value of electrical current. Similar experimental observations were done by Buben (31) and Davies (30) and recently by Rader (35), Barelko (36), and Cardoso and Luss (33). The Luss results involving oxidation of butane and carbon monoxide on a platinum wire will be discussed in detail. 

If a chemical reaction is operated in a flow reactor under fixed external conditions (temperature, partial pressures, flow rate etc.), usually also a steady-state (i.e., time-independent) rate of reaction will result. Quite frequently, however, a different response may result The rate varies more or less periodically with time. Oscillatory kinetics have been reported for quite different types of reactions, such as with the famous Belousov-Zha-botinsky reaction in homogeneous solutions (/) or with a series of electrochemical reactions (2). In heterogeneous catalysis, phenomena of this type were observed for the first time about 20 years ago by Wicke and coworkers (3, 4) with the oxidation of carbon monoxide at supported platinum catalysts, and have since then been investigated quite extensively with various reactions and catalysts (5-7). Parallel to these experimental studies, a number of mathematical models were also developed these were intended to describe the kinetics of the underlying elementary processes and their solutions revealed indeed quite often oscillatory behavior. In view of the fact that these models usually consist of a set of coupled nonlinear differential equations, this result is, however, by no means surprising, as will become evident later, and in particular it cannot be considered as a proof for the assumed underlying reaction mechanism. 

Dynamic reactor studies are not new, but they have not been widely used in spite of the fact that they can provide a wealth of information regarding reaction mechanisms. In this research, oxidation of carbon monoxide over supported cobalt oxide (C03O4) was studied by both dynamic and conventional steady state methods. Among metal oxides, cobalt oxide is known to be one of the most active catalysts for CO and hydrocarbon oxidation, its activity being comparable to that of noble metals such as palladium or platinum. 

The oxidation of carbon monoxide has been studied by both the usual step-response and isotopic experiments and by the TAP system (2/7). The general conclusion is that the fast response of the TAP system did not produce any additional mechanistic information to that obtained from step-response experiments. A number of the points discussed in previous paragraphs are mentioned, and it is suggested that the final pattern of multipulse response experiments be termed a pseudo-steady state. A factor not mentioned is that transient IR experiments are valuable with the step-response method but not compatible with the TAP system. 

Methane is oxidized primarily in the troposphere by reactions involving the hydroxyl radical (OH). Methane is the most abundant hydrocarbon species in the atmosphere, and its oxidation affects atmospheric levels of other important reactive species, including formaldehyde (CH2O), carbon monoxide (CO), and ozone (O3) (Wuebbles and Hayhoe, 2002). The chemistry of these reactions is well known, and the rate of atmospheric CH4 oxidation can be calculated from the temperature and concentrations of the reactants, primarily CH4 and OH (Prinn et al., 1987). Tropospheric OH concentrations are difficult to measure directly, but they are reasonably well constrained by observations of other reactive trace gases (Thompson, 1992 Martinerie et al., 1995 Prinn et al., 1995 Prinn et al., 2001). Thus, rates of tropospheric CH4 oxidation can be estimated from knowledge of atmospheric CH4 concentrations. And because tropospheric oxidation is the primary process by which CH4 is removed from the atmosphere, the estimated rate of CH4 oxidation provides a basis for approximating the total rate of supply of CH4 to the atmosphere from aU sources at steady state (see Section 8.09.2.2) (Cicerone and Oremland, 1988). 

As mentioned in the introduction, the following discussion on modeling results takes as a lead that distinction should be made between steady-state models, unsteady-state models, and dynamic models. The results mentioned focus mainly on automotive exhaust gas treatment, which application has been widely studied, with major emphasis on the oxidation of carbon monoxide. 

The steady-state surface coverage by the carbon monoxide residue can be studied by anodic stripping voltammetry. By this technique, it is possible to separate the adsorption residue contribution from the bulk electrooxidation process. The micro-flux cell is adapted with a big flask containing the supporting electrolyte, which is used to wash the cell until there is no trace of methanol in solution. The current vs. potential profile mn from the adsorption potential upward is the tripping profile for the oxidation of the adsorbed residue. An example is presented in Figure 2.4. 

A fairly general treatment of trace gases in the troposphere is based on the concept of the tropospheric reservoir introduced in Section 1.6. The abundance of most trace gases in the troposphere is determined by a balance between the supply of material to the atmosphere (sources) and its removal via chemical and biochemical transformation processes (sinks). The concept of a tropospheric reservoir with well-delineated boundaries then defines the mass content of any specific substance in, its mass flux through, and its residence time in the reservoir. For quantitative considerations it is necessary to identify the most important production and removal processes, to determine the associated yields, and to set up a detailed account of sources versus sinks. In the present chapter, these concepts are applied to the trace gases methane, carbon monoxide, and hydrogen. Initially, it will be useful to discuss a steady-state reservoir model and the importance of tropospheric OH radicals in the oxidation of methane and many other trace gases. 

The proper design of fuel reformer systems must pay careful attention to the minimization of carbon monoxide before the processed fuel stream enters the fuel cell stack. Many reformer systems use a secondary preferential oxidation reactor that selectively oxidizes the carbon monoxide present in reformate streams. In most transportation applications the steam reformer and the selective oxidation reactors do not operate under steady state conditions large transients may occur which produce relatively large amounts of carbon monoxide. It is highly desirable to have a low-cost real-time carbon monoxide measurement system that provides feedback control to the fuel processing system in order to protect the PEM fuel cells from performance degrading concentrations of carbon monoxide. 

---