Mechanisms of CO and COS formation in the Claus furnace

Citation
Pd. Clark et al., Mechanisms of CO and COS formation in the Claus furnace, IND ENG RES, 40(2), 2001, pp. 497-508
Citations number
35
Categorie Soggetti
Chemical Engineering
Journal title
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
ISSN journal
08885885 → ACNP
Volume
40
Issue
2
Year of publication
2001
Pages
497 - 508
Database
ISI
SICI code
0888-5885(20010124)40:2<497:MOCACF>2.0.ZU;2-N
Abstract
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.