Pyrolysis rate limiting step

A limitation of vacuum pyrolysis technology is heat transfer. Previous studies have shown that the rate of heat transfer is essentially the rate limiting step for pyrolysis reactions [2]. Conventional pyrolysis reactors such as multiple hearth furnaces, rotary kilns and screw type reactors exhibit overall heat transfer coefficients ranging from 10 to 60 [3], depending on the type of feedstock handled. The low thermal... 

Since the conversion of C2H5 into C2H4 + H is indeed the slow step in the ethane pyrolysis, the occurrence of this reaction does explain the non-zero rates at maximal inhibition and the increase in rate at high NO concentrations. On the other hand, for reactions like the acetaldehyde pyrolysis the g - P transition is not rate limiting, and the Norrish-Pratt mechanism then gives no explanation for the behavior. Also, the Norrish-Pratt mechanisms as originally written down do not explain the large amounts of products such as H2O, N2 and N2O that are found in the ethane pyrolysis. 

Benson has interpreted the general features of the kinetic behaviour for the gas phase pyrolysis af organic iodides by proposing two steps which can be rate-limiting in these systems... 

This first limiting case implies that the radical process 3 is definitely more difficult than radical process 2, It follows that, in the pyrolysis of pure yH, process 3 is the rate determining step of chain propagation one has ( y. ) ( 3. ) and the chain termination chiefly involves process 33,... 

However, many reactions, although their mechanism may be quite complex, do conform to simple first or second-order rate equations. This is because the rate of the overall reaction is limited by just one of the elementary reactions which is then said to be rate-determining. The kinetics of the overall reaction thus reflect the kinetics of this particular step. An example is the pyrolysis of ethane(4> which is important industrially as a source of ethylene01 (see also Section 1.7.1 Example 1.4). The main overall reaction is ... 

As for the pressure levels in the reaction operations, 1.5 atm is selected for the chlorination reaction to prevent the leakage of air into the reactor to be installed in the task integration step. At atmospheric pressure, air might leak into the reactor and build up in sufficiently large concentrations to exceed the flammability limit. For the pyrolysis operation, 26 atm is recommended by the B.F. Goodrich patent (1963) without any justification. Since the reaction is irreversible, the elevated pressure does not adversely affect the conversion. Most likely, the patent recommends this pressure to increase the rate of reaction and, thus, reduce the size of the pyrolysis furnace, although the tube walls must be thick and many precautions are necessary for operation at elevated pressures. The pressure level is also an important consideration in selecting the separation operations, as will be discussed in the next synthesis step. 

The values of the real systems, obtained from experiments at pressures up to 50 bar, may be extrapolated to still higher pressures since E = f(P) and log A = f(F) are continuous functions. The supply of oxygen in the oxidation experiments at 50 bar pressure is sufficient to ensure attainment of the asymptotic limits at least in the first reaction step (LTO). Evaluation of the second reaction step of the oxidation (fuel deposition) is more difficult because an increase of the heating rate provokes the occurrence of additional peaks, which will be flattened as a consequence of a rise of the pressure. For the consecutive and parallel oxidation and pyrolysis reactions in this step, overall values of E and log A have been found, which only give steady functions for the vacuum residue. The data of the last reaction step (fuel combustion) may be evaluated very easily. They also give steady functions for E = f(P) and log A = f(P). All substances tested behave similarly to activated carbon (charcoal). Only the coke residue of -hexylpyrene reacts completely differently and demonstrates different curves in the plots of the reaction rate constant and the half life time versus the pressure. In this reaction step the curves did not reach the asymptote even at pressures of 50 bar, but they may be extrapolated to higher pressures. 

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