Heat and mass transfer kinetics

Chemical engineers have worked with polymers since the first Bakelite articles were produced early in this century. Since then, the class of polymeric materials has grown to encompass a whole range of thermoset and thermoplastic resins, as well as copolymers and polymer blends, and chemical engineers have played major roles in the rise of these materials to commercial success. From production of the resins (which involves heat and mass transfer, kinetics, fluid dynamics, process design, and control) to the fabrication of final articles (involving many of the same processes, as well as some unit operations not part of traditional chemical engineering, such as extrusion... 

Despite this last observation, for this type of simulation and modelling research, two main means of evolution remain the first consists in enlarging the library with new and newly coded models for unit operations or apparatuses (such as the unit processes mentioned above multiphase reactors, membrane processes, etc.) the second is specified by the sophistication of the models developed for the apparatus that characterizes the unit operations. With respect to this second means, we can develop a hierarchy dividing into three levels. The first level corresponds to connectionist models of equilibrium (frequently used in the past). The second level involves the models of transport phenomena with heat and mass transfer kinetics given by approximate solutions. And finally, in the third level, the real transport phenomena the flow, heat and mass transport are correctly described. In... 

An important number of factors having a key influence on this unit operation [6.19, 6.20], together vith the examples described above, show how difficult it is to formulate a complete and unitary mixing theory responding to the various technical questions such as mixing time, distribution of the residence time, power consumption, heat and mass transfer kinetics in mixed media, scaling-up of a laboratory mixing plant etc. 

The product of thermodynamic forces and fiows yields the rate of entropy production in an irreversible process. The Gouy-Stodola theorem states that the lost available energy (work) is directly proportional to the entropy production in a nonequilibrium phenomenon. Transport phenomena and chemical reactions are nonequilibrium phenomena and are irreversible processes. Thermodynamics, fiuid mechanics, heat and mass transfer, kinetics, material properties, constraints, and geometry are required to establish the relationships... 

Thermodynamics Hendrick C. Van Ness, Michael M. Abbott Heat and Mass Transfer James G. Knudsen, Hoyt C. Hottel, Adel F. Sarofim, Phillip C. Wankat, Kent S. Knaebel Fluid and Particle Dynamics Janies N. Tilton Reaction Kinetics Stanley M. Walas... 

A number of factors limit the accuracy with which parameters for the design of commercial equipment can be determined. The parameters may depend on transport properties for heat and mass transfer that have been determined under nonreacting conditions. Inevitably, subtle differences exist between large and small scale. Experimental uncertainty is also a factor, so that under good conditions with modern equipment kinetic parameters can never be determined more precisely than 5 to 10 percent (Hofmann, in de Lasa, Chemical Reactor Design and Technology, Martinus Nijhoff, 1986, p. 72). 

The ROTOBERTY internal recycle laboratory reactor was designed to produce experimental results that can be used for developing reaction kinetics and to test catalysts. These results are valid at the conditions of large-scale plant operations. Since internal flow rates contacting the catalyst are known, heat and mass transfer rates can be calculated between the catalyst and the recycling fluid. With these known, their influence on catalyst performance can be evaluated in the experiments as well as in production units. Operating conditions, some construction features, and performance characteristics are given next. 

This involves knowledge of chemistry, by the factors distinguishing the micro-kinetics of chemical reactions and macro-kinetics used to describe the physical transport phenomena. The complexity of the chemical system and insufficient knowledge of the details requires that reactions are lumped, and kinetics expressed with the aid of empirical rate constants. Physical effects in chemical reactors are difficult to eliminate from the chemical rate processes. Non-uniformities in the velocity, and temperature profiles, with interphase, intraparticle heat, and mass transfer tend to distort the kinetic data. These make the analyses and scale-up of a reactor more difficult. Reaction rate data obtained from laboratory studies without a proper account of the physical effects can produce erroneous rate expressions. Here, chemical reactor flow models using matliematical expressions show how physical... 

In the previous section, the molecular basis for the processes of momentum transfer, heat transfer and mass transfer has been discussed. It has been shown that, in a fluid in which there is a momentum gradient, a temperature gradient or a concentration gradient, the consequential momentum, heat and mass transfer processes arise as a result of the random motion of the molecules. For an ideal gas, the kinetic theory of gases is applicable and the physical properties p,/p, k/Cpp and D, which determine the transfer rates, are all seen to be proportional to the product of a molecular velocity and the mean free path of the molecules. 

Mala GM, Li D, Werner C (1997b) Flow characteristics of water through a micro-channel between two parallel plates with electro kinetic effects. Int J Heat Fluid Flow 18 491 96 Male van P, Croon de MHJM, Tiggelaar RM, Derg van den A, Schouten JC (2004) Heat and mass transfer in a square micro-channel with asymmetric heating. Int J Heat Mass Transfer 47 87-99 Maranzana G, Perry I, Maillet D (2004) Mini- and micro-channels influence of axial conduction in the walls. Int J Heat Mass Transfer 47 3993 004 Maynes D, Webb BW (2003) Full developed electro-osmotic heat transfer in microchannels. Int J Heat Mass Transfer 46 1359-1369... 

The selection of reactor type in the traditionally continuous bulk chemicals industry has always been dominated by considering the number and type of phases present, the relative importance of transport processes (both heat and mass transfer) and reaction kinetics plus the reaction network relating to required and undesired reactions and any aspects of catalyst deactivation. The opportunity for economic... 

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. 

Estimation of parameters. Model parameters in the selected model are then estimated. If available, some model parameters (e.g. thermodynamic properties, heat- and mass-transfer coefficient, etc.) are taken from literature. This is usually not possible for kinetic parameters. These should be estimated based on data obtained from laboratory expieriments, if possible carried out isothermal ly and not falsified by heat- and mass-transport phenomena. The methods for parameter estimation, also the kinetic parameters in complex organic systems, and for discrimination between models are discussed in more detail in Section 5.4.4. More information on parameter estimation the reader will find in review papers by Kittrell (1970), or Froment and Hosten (1981) or in the book by Froment and Bischoff (1990). 

In the design of an industrial scale reactor for a new process, or an old one that employs a new catalyst, it is common practice to carry out both bench and pilot plant studies before finalizing the design of the commercial scale reactor. The bench scale studies yield the best information about the intrinsic chemical kinetics and the associated rate expression. However, when taken alone, they force the chemical engineer to rely on standard empirical correlations and prediction methods in order to determine the possible influence of heat and mass transfer processes on the rates that will be observed in industrial scale equipment. The pilot scale studies can provide a test of the applicability of the correlations and an indication of potential limitations that physical processes may place on conversion rates. These pilot plant studies can provide extremely useful information on the temperature distribution in the reactor and on contacting patterns when... 

The performance of adsorption processes results in general from the combined effects of thermodynamic and rate factors. It is convenient to consider first thermodynamic factors. These determine the process performance in a limit where the system behaves ideally i.e. without mass transfer and kinetic limitations and with the fluid phase in perfect piston flow. Rate factors determine the efficiency of the real process in relation to the ideal process performance. Rate factors include heat-and mass-transfer limitations, reaction kinetic limitations, and hydro-dynamic dispersion resulting from the velocity distribution across the bed and from mixing and diffusion in the interparticle void space. 

Modem catalysts have to be very active and very (100%) selective, that is, they have to catalyze the desired reaction in the temperature window, where the equilibrium conversion is the highest possible and the reaction rate is high enough to permit suitable process economics. To engineer the reaction, one has to obtain first the intrinsic reaction rate, free of heat- and mass-transfer limitations. In many cases this is very difficult, because in the core of the catalytic process there are several physical and chemical steps that must occur and which may preclude the reaction running in the kinetic regime. These steps are as follows ... 

In many operations, for instance in a distillation column, it is necessary to understand the fluid dynamics of the unit, as well as the heat and mass transfer relationships. These factors are frequently interdependent in a complex manner, and it is essential to consider the individual contributions of each of the mechanisms. Again, in a chemical reaction the final rate of the process may be governed either by a heat transfer process or by the chemical kinetics, and it is essential to decide which is the controlling factor this problem is discussed in Volume 3, which deals with both chemical and biochemical reactions and their control. 

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