Adiabatic commercial applications

This paper surveys the field of methanation from fundamentals through commercial application. Thermodynamic data are used to predict the effects of temperature, pressure, number of equilibrium reaction stages, and feed composition on methane yield. Mechanisms and proposed kinetic equations are reviewed. These equations cannot prove any one mechanism however, they give insight on relative catalyst activity and rate-controlling steps. Derivation of kinetic equations from the temperature profile in an adiabatic flow system is illustrated. Various catalysts and their preparation are discussed. Nickel seems best nickel catalysts apparently have active sites with AF 3 kcal which accounts for observed poisoning by sulfur and steam. Carbon laydown is thermodynamically possible in a methanator, but it can be avoided kinetically by proper catalyst selection. Proposed commercial methanation systems are reviewed. 

The adiabatic fixed-bed reactor with periodic flow reversal has three commercial applications, oxidation of SO2 for sulfuric acid production, oxidation of volatile organic compounds (VOCs) for purification of industrial exhaust gases, and NO, reduction by ammonia in industrial exhaust gases. Other possible future applications are steam reforming and partial oxidation of methane for syngas production, synthesis of methanol and ammonia, and catalytic dehydrogenations (Matros and Bunimovich, 1996). 

Peclet number independent of Reynolds number also means that turbulent diffusion or dispersion is directly proportional to the fluid velocity. In general, reactors that are simple in construction, (tubular reactors and adiabatic reactors) approach their ideal condition much better in commercial size then on laboratory scale. On small scale and corresponding low flows, they are handicapped by significant temperature and concentration gradients that are not even well defined. In contrast, recycle reactors and CSTRs come much closer to their ideal state in laboratory sizes than in large equipment. The energy requirement for recycle reaci ors grows with the square of the volume. This limits increases in size or applicable recycle ratios. 

Catalytic combustion is an environmentally-driven, materials-limited technology with the potential to lower nitrogen oxide emissions from natural gas fired turbines consistently to levels well below 10 ppm. Catalytic combustion also has the potential to lower flammability at the lean limit and achieve stable combustion under conditions where lean premixed homogeneous combustion is not possible. Materials limitations [1,2] have impeded the development of commercially successful combustion catalysts, because no catalytic materials can tolerate for long the nearly adiabatic temperatures needed for gas turbine engines and most industrial heating applications. 

A common application of flash devolatilization is the removal of 10-15% styrene-ethylbenzene from polystyrene. One commercial process uses Tin = 240°C and Tout = 1.3 kPa (10 torr). Equilibrium calculations for an adiabatic flash predict Tout = 220°C and Wout = 500 ppm actual operation gives about 1200 ppm. 

The most accurate results are obtained with adiabatic calorimeters, which are useful over a temperature range from fractions of a Kelvin to about 1000 K. These instruments permit specific heat capacities to be determined with very small uncertainties (< 1 %). Nevertheless, such measurements are so complex that they are rarely applicable to normal laboratory practice in industry, especially given the lack of commercial instruments. 

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