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By G.R. Gavalas

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Additional resources for Coal Pyrolysis (Coal Science & Technology)

Example text

In this subsection we discuss the elemental composition and certain other properties of char and tar with an eye towards their mechanistic significance. We also summarize data about the partition of sulfur and nitrogen among tar, char and gases, which is important to the utilization of these pyrolysis products as fuels. 11 display the elemental composition of char and tar as functions of pyrolysis temperature for a high volatile bituminous coal studied by Solomon (ref. 70). The effect of temperature on hydrogen, oxygen and carbon is quite predictable.

1 units. 8. 3 RECOMBINATION OF ALPHA RADICALS This is the reverse of reaction (D5), Ph-CH Z' + Ph'-CH Z· -+ Ph-CHZCHZPh' (R1) As mentioned earlier,reactions (D5) and (R1) are diffusion limited when they take place in the condensed coal phase. The A-factor estimated below assumes diffusion free recombination, therefore is strictly limited to gas phase recombination. Under gas phase conditions the activation energy of (R1) is zero. The activation entropy is related to the activation entropy of the reverse reaction as follows 6so t (R1) = 6so t (D5) + 6S0(R1) where 6S0(R1) is the entropy of the reaction.

Since the content of hydroxyl and carboxyl groups is higher in coals of low rank, the above condensation reactions offer an explanation for the low amount of tar produced in the pyrolysis of subbituminous coals and lignites. The kinetics of the condensation reactions (i)-(iii) have not been studied at the temperatures of interest to pyrolysis (above 400°C). Moreover, the experimental evidence has not as yet been sufficient to distinguish which of these three reactions is more important. At temperatures above 600°C the reactions of hydroxyl groups become more complex leading to a variety of products including carbon monoxide.

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