A thermodynamic study of the removal of HCl and H₂S from syngas

Abstract

Advanced integrated-gasification combined-cycle (IGCC) and integrated-gasification fuel cell (IFGC) systems require high-temperature sorbents that are capable of removing hydrogen chloride and hydrogen sulfide from coal derived gases to very low levels. HCl and H₂S are highly reactive, corrosive, and toxic gases that must be removed to meet stringent environmental regulations, to protect power generation equipment and to control the emissions of contaminants. The thermodynamic behavior of 13 sorbents for the removal of HCl and H₂S under various conditions including: initial toxic gas concentration (1–10000 ppm), operating pressure (0.1–11 Mpa), temperature (300 K–1500 K), and the presence of H₂O were investigated. The correlation between HCl and H₂S was also examined. Thermodynamic calculations were carried out for the reactions of the 13 sorbents using a FactSage 5.2 software package based on free energy minimization. The sorbents, Na₂CO₃, NaHCO₃, K₂CO₃, and CaO are capable of completely removing chlorine at high temperatures (up to ~1240 K) and at high pressures. Water vapor did not have any significant effects on the dechlorination capability of the sorbents. Nine of the sorbents namely; Cu₂O, Na₂CO₃, NaHCO₃, K₂CO₃, CaO, ZnO, MnO, FeO, and PbO, were determined to have great potential as desulfurization sorbents. Cu₂O and ZnO had the best performance in terms of the optimum operating temperature. The addition of water vapor to the reactant gas produces a slightly detrimental effect on most of the sorbents, but FeO exhibited the worst performance with a reduction in the maximum operating temperature of about 428 K. The dechlorination performance of the alkali sorbents was not affected by the presence of H₂S in the reactions. However, the desulfurization capability of some sorbents was greatly affected by the presence of HCl. Particularly, the performance of Cu₂O was significantly reduced when HCl was present, but the performance of FeO improved remarkably. The thermodynamic results gathered are valuable for the developments of better sorbents.

Keywords

syngas cleaning / sorbent / desulfurization / dechlorination

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Acknowledgements

The financial support of the Australian Research Council is gratefully acknowledged.

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2014 Higher Education Press and Springer-Verlag Berlin Heidelberg