The aim of this study was to determine the major pathways leading to COS an
d CO formation and consumption during the processing of H2S and CO2 in the
partially oxidizing conditions of the Claus furnace. Both species were foun
d to be produced by a multitude of pathways, which include the direct react
ion of H2S with CO2 to form COS and H2O and the reaction of CO2 with SS, on
e of the major primary products in a Claus furnace. This last reaction prod
uced SO2 and CO as the major products, with COS being formed in lesser quan
tities. The dissociation of H2S to H-2 and S-2 at high temperatures (> 1000
degreesC) was shown to promote a further cascade of reactions stemming fro
m the reduction of COS and CO2, both of which lead to CO. Because of the kn
own formation of CS2 from hydrocarbon carry-over into the furnace, the reac
tions of CS2 with CO2, H2O, and SO2 were also studied as potential CO- and
COS-forming reactions. Reaction with CO2 was slow at < 1200 <degrees>C, but
reaction with either H2O or SO2 was fast above 900 degreesC. Conversion of
CS2 by H2O led to CO, H-2, H2S, S-2, and CO2, whereas reaction with SO2 re
sulted in CO2 and St as the major products. Similar observations were made
for the reactions of COS with HzO and SO2. The summary of pathways presente
d in Scheme 5 shows a complex interlinkage among many reactions involving H
2S, CO2, CO, COS, SO2, and S-2, leading to the conclusion that previous exp
lanations of the production of COS from CO f Sg and CO from incomplete comb
ustion dramatically oversimplifies the formation/consumption for these comp
ounds. It also shows that modeling of individual kinetic rate expressions i
s somewhat impractical.