Fuel kinetics

In spite of their relevance to air pollution and to the combustion of sulphur-contaminated fuels, kinetic data for the homogeneous decomposition of S03 are practically non-existent. The thermal decomposition is dominated by a heterogeneous component, even in clean silica vessels390 reactions of S03 at a glass surface are evident even at room temperature380. The kinetics of approach to the equilibrium... 

Thybaut, J., Production of low aromate fuels Kinetics and industrial application of Hydrocracking , PhD Thesis, Ghent University (2002). 

Alkaline Fuel Cell. The electrolyte ia the alkaline fuel cell is concentrated (85 wt %) KOH ia fuel cells that operate at high (- 250° C) temperature, or less concentrated (35—50 wt %) KOH for lower (<120° C) temperature operation. The electrolyte is retained ia a matrix of asbestos (qv) or other metal oxide, and a wide range of electrocatalysts can be used, eg, Ni, Ag, metal oxides, spiaels, and noble metals. Oxygen reduction kinetics are more rapid ia alkaline electrolytes than ia acid electrolytes, and the use of non-noble metal electrocatalysts ia AFCs is feasible. However, a significant disadvantage of AFCs is that alkaline electrolytes, ie, NaOH, KOH, do not reject CO2. Consequentiy, as of this writing, AFCs are restricted to specialized apphcations where C02-free H2 and O2 are utilized. 

The analytical mechanisms for predicting the corresponding pollutant formation associated with fossil-fuel-fired furnaces lag the thermal performance prediction capabiUty by a fair margin. The most firmly estabUshed mechanism at this time is the prediction of thermal NO formation (24). The chemical kinetics of pollutant formation is, in fact, a subject of research. 

Fuel. Natural gas is used as a primary fuel and source of heat energy throughout the iadustrialized countries for a broad range of residential, commercial, and iadustrial appHcations. The methane and other hydrocarbons react readily with oxygen to release heat by forming carbon dioxide and water through a series of kinetic steps that results ia the overall reaction,... 

Flame or Partial Combustion Processes. In the combustion or flame processes, the necessary energy is imparted to the feedstock by the partial combustion of the hydrocarbon feed (one-stage process), or by the combustion of residual gas, or any other suitable fuel, and subsequent injection of the cracking stock into the hot combustion gases (two-stage process). A detailed discussion of the kinetics for the pyrolysis of methane for the production of acetylene by partial oxidation, and some conclusions as to reaction mechanism have been given (12). 

At the high temperatures found in MHD combustors, nitrogen oxides, NO, are formed primarily by gas-phase reactions, rather than from fuel-bound nitrogen. The principal constituent is nitric oxide [10102-43-9] NO, and the amount formed is generally limited by kinetics. Equilibrium values are reached only at very high temperatures. NO decomposes as the gas cools, at a rate which decreases with temperature. If the combustion gas cools too rapidly after the MHD channel the NO has insufficient time to decompose and excessive amounts can be released to the atmosphere. Below about 1800 K there is essentially no thermal decomposition of NO. 

Third, design constraints are imposed by the requirement for controlled cooling rates for NO reduction. The 1.5—2 s residence time required increases furnace volume and surface area. The physical processes involved in NO control, including the kinetics of NO chemistry, radiative heat transfer and gas cooling rates, fluid dynamics and boundary layer effects in the boiler, and final combustion of fuel-rich MHD generator exhaust gases, must be considered. 

The rate (kinetics) and the completeness (fraction dissolved) of oxide fuel dissolution is an inverse function of fuel bum-up (16—18). This phenomenon becomes a significant concern in the dissolution of high bum-up MO fuels (19). The insoluble soHds are removed from the dissolver solution by either filtration or centrifugation prior to solvent extraction. Both financial considerations and the need for safeguards make accounting for the fissile content of the insoluble soHds an important challenge for the commercial reprocessor. If hydrofluoric acid is required to assist in the dissolution, the excess fluoride ion must be complexed with aluminum nitrate to minimize corrosion to the stainless steel used throughout the facility. Also, uranium fluoride complexes are inextractable and formation of them needs to be prevented. 

In the United States, Hquid HLW from the reprocessing of defense program fuels was concentrated, neutralized with NaOH, and stored in underground, mild steel tanks pending soHdification and geologic disposal (see Tanks AND PRESSURE VESSELS). These wastes are a complex and chemically active slurry. Suspended in the supernatant Hquid are dissolver soHds which never went into solution, insoluble reaction products which formed in the tank, and salts which have exceeded their solubiHty limit. The kinetics of many of the reactions taking place are slow (years) so that the results of characterization... 

The development of combustion theory has led to the appearance of several specialized asymptotic concepts and mathematical methods. An extremely strong temperature dependence for the reaction rate is typical of the theory. This makes direct numerical solution of the equations difficult but at the same time accurate. The basic concept of combustion theory, the idea of a flame moving at a constant velocity independent of the ignition conditions and determined solely by the properties and state of the fuel mixture, is the product of the asymptotic approach (18,19). Theoretical understanding of turbulent combustion involves combining the theory of turbulence and the kinetics of chemical reactions (19—23). 

The industrial economy depends heavily on electrochemical processes. Electrochemical systems have inherent advantages such as ambient temperature operation, easily controlled reaction rates, and minimal environmental impact (qv). Electrosynthesis is used in a number of commercial processes. Batteries and fuel cells, used for the interconversion and storage of energy, are not limited by the Carnot efficiency of thermal devices. Corrosion, another electrochemical process, is estimated to cost hundreds of millions of dollars aimuaUy in the United States alone (see Corrosion and CORROSION control). Electrochemical systems can be described using the fundamental principles of thermodynamics, kinetics, and transport phenomena. 

Moehida, I., Kuroda, K., Kawano, S., Matsumura, Y. and Yoshikawa, M., Kinetic study of the continuous removal of SO, on polyacrylonitrilc-bascd activated carbon fibres. 1. Catalytic activity of PAN ACF heat treated at 800 °C,Fuel, 1997, 76(6), 533 536. 

Although desulfurization is a process, which has been in use in the oil industry for many years, renewed research has recently been started, aimed at improving the efficiency of the process. Envii onmental pressure and legislation to further reduce Sulfur levels in the various fuels has forced process development to place an increased emphasis on hydrodesulfurization (HDS). For a clear comprehension of the process kinetics involved in HDS, a detailed analyses of all the organosulfur compounds clarifying the desulfurization chemistry is a prerequisite. The reactivities of the Sulfur-containing structures present in middle distillates decrease sharply in the sequence thiols sulfides thiophenes benzothiophenes dibenzothio-phenes (32). However, in addition, within the various families the reactivities of the Substituted species are different. 

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