Macroscopic reactor kinetics

Microreactors are developed for a variety of different purposes, specifically for applications that require high heat- and mass-transfer coefficients and well-defined flow patterns. The spectrum of applications includes gas and liquid flow as well as gas/liquid or liquid/liquid multiphase flow. The variety and complexity of flow phenomena clearly poses major challenges to the modeling approaches, especially when additional effects such as mass transfer and chemical kinetics have to be taken into account. However, there is one aspect that makes the modeling of microreactors in some sense much simpler than that of macroscopic equipment the laminarity of the flow. Typically, in macroscopic reactors the conditions are such that a turbulent flow pattern develops, thus making the use of turbulence models [1] necessary. With turbulence models the stochastic velocity fluctuations below the scale of grid resolution are accounted for in an effective manner, without the need to explicitly model the time evolution of these fine details of the flow field. Heat- and mass-transfer processes strongly depend on the turbulent velocity fluctuations, for this reason the accuracy of the turbulence model is of paramount importance for a reliable prediction of reactor performance. However, to the... 

The role of chemical reaction engineering in catalyst development has often been minor. The primary problem [1] is that macroscopic chemical kinetic equations do not allow the d uction of a unique mechanism. In 1987, Cleaves et aL [2] introduced a reactor to acquire kinetic data at the elementary step level (in contrast to macroscopic kinetics used in conventional chemical reaction engineering). The netwoik of elementary steps and the kinetic parameters of these elementary steps most accurately represent tte chemical reaction(s), and such data can be directly used in catalyst devebpment. This reactor is now popularly known as the TAP (temporal analysis ofproducts) reactor. The type of kinetic data possible with a TAP reactor, viz. the reaction mechanism and the kinetic parameters of the elementary steps, is also useful in chemical reaction engineering where non-steady state operation is considered and where changes in reaction mechanisms can occur within the reactor. In the 1990 s, a second-generation TAP reactor [3] appeared, with inq)roved signal-to-noise ratios. 

The concept of macroscopic kinetics avoids the difficulties of microscopic kinetics [46, 47] This method allows a very compact description of different non-thennal plasma chemical reactors working with continuous gas flows or closed reactor systems. The state of the plasma chemical reaction is investigated, not in the active plasma zone, but... 

Methane can be oxidatively coupled to ethylene with very high yield using the novel gas recycle electrocatalytic or catalytic reactor separator. The ethylene yield is up to 85% for batch operation and up to 50% for continuous flow operation. These promising results, which stem from the novel reactor design and from the adsorptive properties of the molecular sieve material, can be rationalized in terms of a simple macroscopic kinetic model. Such simplified models may be useful for scale up purposes. For practical applications it would be desirable to reduce the recycle ratio p to lower values (e.g. 5-8). This requires a single-pass C2 yield of the order of 15-20%. The Sr-doped La203... 

Micro reactors permit high-throughput screening of process chemistries imder controlled conditions, unlike most conventional macroscopic systems [2], In addition, extraction of kinetic parameters from sensor data is possible, as heat and mass transfer can be fully characterized due to the laminar-flow condihons applied. More uniform thermal condihons can also be utilized. Further, reactor designs can be developed in this way that have specific research and development funchons. 

Chemical engineers have traditionally approached kinetics studies with the goal of describing the behavior of reacting systems in terms of macroscopically observable quantities such as temperature, pressure, composition, and Reynolds number. This empirical approach has been very fruitful in that it has permitted chemical reactor technology to develop to a point that far surpasses the development of theoretical work in chemical kinetics. 

The SFM requires knowledge of the reaction kinetics and the macroscopic RTD. The factor [cA(f)/cAJBR is determined by the kinetics (the designation BR indicates that the result to be inserted is that for a batch reactor, but it is the same for a PFR with a... 

Van Santen [13] identifies three levels of research in catalysis. The macroscopic level is the world of reaction engineering, test reactors and catalyst beds. Questions concerning the catalyst deal with such aspects as activity per unit volume, mechanical strength and whether it should be used in the form of extrudates, spheres or loose powders. The mesoscopic level comprises kinetic studies, activity per unit surface area, and the relationship between the composition and structure of a catalyst and its... 

In Fig. 1, various elements involved with the development of detailed chemical kinetic mechanisms are illustrated. Generally, the objective of this effort is to predict macroscopic phenomena, e.g., species concentration profiles and heat release in a chemical reactor, from the knowledge of fundamental chemical and physical parameters, together with a mathematical model of the process. Some of the fundamental chemical parameters of interest are the thermochemistry of species, i.e., standard state heats of formation (A//f(To)), and absolute entropies (S(Tq)), and temperature-dependent specific heats (Cp(7)), and the rate parameter constants A, n, and E, for the associated elementary reactions (see Eq. (1)). As noted above, evaluated compilations exist for the determination of these parameters. Fundamental physical parameters of interest may be the Lennard-Jones parameters (e/ic, c), dipole moments (fi), polarizabilities (a), and rotational relaxation numbers (z ,) that are necessary for the calculation of transport parameters such as the viscosity (fx) and the thermal conductivity (k) of the mixture and species diffusion coefficients (Dij). These data, together with their associated uncertainties, are then used in modeling the macroscopic behavior of the chemically reacting system. The model is then subjected to sensitivity analysis to identify its elements that are most important in influencing predictions. 

Using these methods, the elementary reaction steps that define a fuel s overall combustion can be compiled, generating an overall combustion mechanism. Combustion simulation software, like CHEMKIN, takes as input a fuel s combustion mechanism and other system parameters, along with a reactor model, and simulates a complex combustion environment (Fig. 4). For instance, one of CHEMKIN s applications can simulate the behavior of a flame in a given fuel, providing a wealth of information about flame speed, key intermediates, and dominant reactions. Computational fluid dynamics can be combined with detailed chemical kinetic models to also be able to simulate turbulent flames and macroscopic combustion environments. 

Another reason for describing surface reaction kinetics in more detail is that we need to examine the processes on a microscopic scale. While we are interested primarily in the macroscopic description of catalytic reactor behavior, we cannot do this intelligently until we understand these processes at a molecular level. 

The link between the microscopic description of the reaction dynamics and the macroscopic kinetics that can be measured in a catalytic reactor is a micro-kinetic model. Such a model will start from binding energies and reaction rate constants deduced from surface science experiments on well defined single crystal surfaces and relate this to the macroscopic kinetics of the reaction. 

The kinetics of a catalytic reaction is usually measured in a reactor under conditions relevant to the industrial process. The measured overall rates can then be fitted to a mathematical model, the macroscopic kinetics. This is extremely convenient for process design purposes. 

In addition to the patent literature available on the production of BR in the gas-phase there is some scientific literature which mainly refers to the modeling of reaction kinetics. Details on the experimental procedure for the determination of the macroscopic kinetics of the Nd-mediated gas-phase polymerization of BD in a stirred-tank reactor are reported [568,569]. Special emphasis is given to video microscopy of individual supported catalyst particles, individual particle growth and particle size distribution (PSD). These studies reveal that individual particles differ in polymerization activity [536,537,570,571]. Reactor performance and PSD are modeled on the... 

Many constraints on the industrial use of a catalyst have a macroscopic origin. In applied catalysis (Chapter 7) we show how catalytic reaction engineering deals with such macroscopic considerations. The transport and kinetic phenomena in both model reactors and industrial reactors are outlined. 

Salt nucleation and growth studies have also been performed to better understand kinetics and mechanisms associated with these phenomena. Most of these types of studies involve sudden contact of a dissolved salt stream with another fluid or solid body whose temperature is sufficient to cause precipitation of the salt. This approach allows one to observe the morphology of salt particles as they form and grow. The particle morphology can have a signilicanl impact on the particular macroscopic transport characteristics exhibited by the salt as it moves or accumulates within a SCWO reactor. Notable salt nucleation and growth studies in supercritical water have been performed within an optically accessible cell, within a heated tubular reactor, and on a heated solid cylinder. ... 

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