Highly exothermic reactions

The highly exothermic reaction is catalyzed by strong acids sulfuric, hydrofluoric. 

Polyester resins can also be rapidly formed by the reaction of propylene oxide (5) with phthaUc and maleic anhydride. The reaction is initiated with a small fraction of glycol initiator containing a basic catalyst such as lithium carbonate. Molecular weight development is controlled by the concentration of initiator, and the highly exothermic reaction proceeds without the evolution of any condensate water. Although this technique provides many process benefits, the low extent of maleate isomerization achieved during the rapid formation of the polymer limits the reactivity and ultimate performance of these resins. 

In cases where a large reactor operates similarly to a CSTR, fluid dynamics sometimes can be estabflshed in a smaller reactor by external recycle of product. For example, the extent of soflds back-mixing and Hquid recirculation increases with reactor diameter in a gas—Hquid—soflds reactor. Consequently, if gas and Hquid velocities are maintained constant when scaling and the same space velocities are used, then the smaller pilot unit should be of the same overall height. The net result is that the large-diameter reactor is well mixed and no temperature gradients occur even with a highly exothermic reaction. 

Heat Release and Reactor Stability. Highly exothermic reactions, such as with phthaHc anhydride manufacture or Fischer-Tropsch synthesis, compounded with the low thermal conductivity of catalyst peUets, make fixed-bed reactors vulnerable to temperature excursions and mnaways. The larger fixed-bed reactors are more difficult to control and thus may limit the reactions to jacketed bundles of tubes with diameters under - 5 cm. The concerns may even be sufficiently large to favor the more complex but back-mixed slurry reactors. 

When catalysts are used in a highly exothermic reaction, an active phase may be diluted with an inert material to help dissipate heat and moderate the reaction. This technique is practiced in the commercial oxychlorination of ethylene to dichloroethane, where an alumina-supported copper haUde catalyst is mixed with a low surface area inert diluent. 

Although in principle the high-pressure polymerisation of ethylene follows the free-radical-type mechanism discussed in Chapter 2 the reaction has two particular characteristics, the high exothermic reaction and a critical dependence on the monomer concentration. 

The highly exothermic reaction has already been mentioned. It is particularly important to realise that at the elevated temperatures employed other reactions can occur leading to the formation of hydrogen, methane and graphite. These reactions are also exothermic and it is not at all difficult for the reaction to get out of hand. It is necessary to select conditions favourable to polymer formation and which allow a controlled reaction. 

Hydrochloric acid may conveniently be prepared by combustion of hydrogen with chlorine. In a typical process dry hydrogen chloride is passed into a vapour blender to be mixed with an equimolar proportion of dry acetylene. The presence of chlorine may cause an explosion and thus a device is used to detect any sudden rise in temperature. In such circumstances the hydrogen chloride is automatically diverted to the atmosphere. The mixture of gases is then led to a multi-tubular reactor, each tube of which is packed with a mercuric chloride catalyst on an activated carbon support. The reaction is initiated by heat but once it has started cooling has to be applied to control the highly exothermic reaction at about 90-100°C. In addition to the main reaction the side reactions shown in Figure 12.6 may occur. 

A substance which gives rise to highly exothermic reaction when in contact with other substances, particularly flammable substances. 

H2 Oxidizing substances and preparations which exhibit highly exothermic reactions when in contact with... 

An important effect in the design of a tubular flow reactor is the development of a radial temperature gradient in a highly exothermic reaction with wall cooling. The temperatures near the tube axis are... 

Adiabatic Reaction Temperature (T ). The concept of adiabatic or theoretical reaction temperature (T j) plays an important role in the design of chemical reactors, gas furnaces, and other process equipment to handle highly exothermic reactions such as combustion. T is defined as the final temperature attained by the reaction mixture at the completion of a chemical reaction carried out under adiabatic conditions in a closed system at constant pressure. Theoretically, this is the maximum temperature achieved by the products when stoichiometric quantities of reactants are completely converted into products in an adiabatic reactor. In general, T is a function of the initial temperature (T) of the reactants and their relative amounts as well as the presence of any nonreactive (inert) materials. T is also dependent on the extent of completion of the reaction. In actual experiments, it is very unlikely that the theoretical maximum values of T can be realized, but the calculated results do provide an idealized basis for comparison of the thermal effects resulting from exothermic reactions. Lower feed temperatures (T), presence of inerts and excess reactants, and incomplete conversion tend to reduce the value of T. The term theoretical or adiabatic flame temperature (T,, ) is preferred over T in dealing exclusively with the combustion of fuels. 

Older methods use a liquid phase process (Figure 10-11). ° New gas-phase processes operate at higher temperatures with noble metal catalysts. Using high temperatures accelerates the reaction (faster rate). The hydrogenation of benzene to cyclohexane is characterized by a highly exothermic reaction and a significant decrease in the product volume... 

Polymerizing ethylene is a highly exothermic reaction. Eor each gram of ethylene consumed, approximately 3.5 KJ (850 cal) are released ... 

Sometimes, particularly in biochemistry, reactive substances that undergo highly exothermic reactions, such as ATP adenosine triphosphate), are referred... 

The combination of highly exothermic reactions with a sharp increase in viscosity as conversion proceeds controls reactor design and operational conditions in full-scale operations. The art of sulfonation is to maintain the optimal reaction temperature and reaction time, resulting in products with small amounts of byproducts and good color. 

A promising novel structure for highly exothermic reactions is shown in Figure 9.8. The void fraction of this structure exceeds 90% and the geometric... 

The feasibility of operating highly exothermic reactions in a HEX reactor has been demonstrated, some considerations can also be given concerning the inherently safer characteristics of an intensified continuous HEX reactor. This type of evaluation has been conducted on the OPR, using the esterification of propionic anhydride by 2-butanol as test reaction [36, 37]. 

In highly exothermic reactions such as this, that proceed over deep wells on the potential energy surface, sorting pathways by product state distributions is unlikely to be successful because there are too many opportunities for intramolecular vibrational redistribution to reshuffle energy among the fragments. A similar conclusion is likely as the total number of atoms increases. Therefore, isotopic substitution is a well-suited method for exploration of different pathways in such systems. 

Rebrov, E. V., de Croon, M. H. J. M., ScHOUTEN, J. C., Design of a micro-structured reactor with integrated heat-exchanger for optimum performance of highly exothermic reaction, Catal. Today 69 (2001) 183-192. 

The oxidative propane dehydrogenation is well investigated and also a highly exothermic reaction. In a fixed-bed reactor, steep temperature gradients are ob-servableandtheconversionofpropaneandselectivityofthereactionarestrongly determinedbytemperatureandtotalflowrate[133]. 

The motivation for an industrial investigation was to gather kinetic and mechanistic information for a very fast and highly exothermic reaction [127]. In particular, by-product formation was analyzed. 

Semibatch reactors are often used to mn highly exothermic reactions isothermally, to run gas-liquid(-solid) processes isobarically, and to prevent dangerous accumulation of some reactants in the reaction mixture. Contrary to batch of)eration, temperature and pressure in semibatch reactors can be varied independently. The liquid reaction mixture can be considered as ideally mixed, while it is assumed that the introduced gas flows up like a piston (certainly this is not entirely true). Kinetic modelling of semibatch experiments is as difficult as that of batch, non-isotherma experiments. 

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