Reaction kinetics Ammonia synthesis

In the kinetic modelling of catalytic reactions, one typically takes into account the presence of many different surface species and many reaction steps. Their relative importance will depend on reaction conditions (conversion, temperature, pressure, etc.) and as a result, it is generally desirable to introduce complete kinetic fundamental descriptions using, for example, the microkinetic treatment [1]. In many cases, such models can be based on detailed molecular information about the elementary steps obtained from, for example, surface science or in situ studies. Such kinetic models may be used as an important tool in catalyst and process development. In recent years, this field has attracted much attention and, for example, we have in our laboratories found the microkinetic treatment very useful for modelling such reactions as ammonia synthesis [2-4], water gas shift and methanol synthesis [5,6,7,8], methane decomposition [9], CO methanation [10,11], and SCR deNO [12,13]. 

These pioneers understood the interplay between chemical equiUbrium and reaction kinetics indeed, Haber s research, motivated by the development of a commercial process, helped to spur the development of the principles of physical chemistry that account for the effects of temperature and pressure on chemical equiUbrium and kinetics. The ammonia synthesis reaction is strongly equiUbrium limited. The equiUbrium conversion to ammonia is favored by high pressure and low temperature. Haber therefore recognized that the key to a successful process for making ammonia from hydrogen and nitrogen was a catalyst with a high activity to allow operation at low temperatures where the equiUbrium is relatively favorable. 

Kinetics of Ammonia Synthesis on Re Crystal Surfaces. The kinetics of the ammonia synthesis reaction on Re were studied on the Re(ll50) surface which is composed of atoms having seven-fold coordination. The rate of production at 70 K and 20 atm. ... 

One or more steps may form a dead end in the form of an intermediate formed through an elementary reaction and consumed exclusively by the reverse of this step. Although the dead-end will not contribute to the overall reaction rate, the step may affect the kinetics if the intermediate is strongly adsorbed on the surface. The poisonous effect of H2O in ammonia synthesis is an example. 

Antonelli and co-workers have recently demonstrated that room temperature stoichiometric ammonia synthesis is possible with their mesoporous titanium and niobium oxide catalysts. In this study, they proposed that the ammonia species are formed via the reaction activated nitrogen with the underlying moisture of the support. Reversible, inter-conversion of and NH2 species via exposure to moist air for aluminophosphate oxynitride catalysts has been observed by FTIR and XPS by Marquez and co-workers. There has been a lot of interest in the literature in the development of novel routes for the low temperature stoichiometric conversion of nitrogen to ammonia, e.g.. However, in principle this could be realised by the nitridation of Li, followed by hydrolysis, although the kinetics would be very slow. 

From the viewpoint of the experimenter, the ammonia synthesis reaction is an advantageous subject for kinetic studies since it proceeds only in one direction without any by-products the activity of catalysts is usually sufficiently stable, it being an important condition for the success of kinetic investigations. 

The gas composition is optimized with DOFs outside the CO2 scrubbing system with regard to inert composition (methane and argon) and hydrogen to nitrogen ratio since the levels of these components affect downstream (ammonia synthesis) reaction kinetics. Improved kinetics at lower inert levels are achieved at the expense of using more fuel or feedstock, since lower inerts can be achieved by firing the primary... 

The reactor can operate with either a liquid-phase reaction or a gas-phase reaction. In both types, temperature is very important. With a gas-phase reaction, the operating pressure is also a critical design variable because the kinetic reaction rates in most gas-phase reactions depend on partial pressures of reactants and products. For example, in ammonia synthesis (N2 + 3H2 O 2NH3), the gas-phase reactor is operated at high pressure because of LeChatelier s principle, namely that reactions with a net decrease in moles should be mn at high pressure. The same principle leads to the conclusion that the steam-methane reforming reaction to form synthesis gas (CH4 + H20 O CO + 3 H2) should be conducted at low pressure. 

Unfortunately, these requirements have not yet fully been met for any catalytic reaction, although for some simple catalytic reactions reasonable approaches are known. Such reactions are the oxidation of CO over a supported Rh catalyst [46,47], ammonia synthesis over iron [48, 49], and the HCN synthesis over a Pt gauze catalyst. More recently Wolf [50] carried out a micro-kinetic analysis of the primary reaction steps in the oxidative coupling of methane and also related the rate... 

The state of iron ammonia catalysts is dealt with in the following chapters, and x-ray, magnetic, and electric data will be discussed together with adsorption measurements. Information about the catalysts combined with kinetic experiments has led to a fairly good qualitative understanding of ammonia synthesis on iron catalysts, but owing to the extremely complicated nature of the catalyst surface during reaction, a quantitative treatment based on data of catalyst and reactants will not be attained in the near future. 

The basic equation most widely accepted to express the kinetics of ammonia synthesis is that of Teml and Pyzbev (1940). It expresses the reaction rate as a function of the partial pressures of the reactants and products ... 

An analysis of this equation shows that, as in the case of ammonia synthesis, the maximum conversion rate at any point of the reactor can only be achieved by establishing a temperature gradieiiL This must be supplemented by the analyris of the kinetics relative to the reverse reaction of CO shift conversion. The models that can be constructed on the basis of published experimental results show that, wift catalysts based on cof icr... 

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