A thermodynamic study of the removal of HCl and H<sub>2</sub>S from syngas

doi:10.1007/s11705-011-1162-4

Front Chem Sci Eng

2012, Vol. 6

Issue (1) : 67-83 https://doi.org/10.1007/s11705-011-1162-4

RESEARCH ARTICLE

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

Joseph LEE, Bo FENG(

)

School of Mechanical and Mining Engineering, the University of Queensland, St Lucia Qld4072, Australia

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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

Corresponding Author(s): FENG Bo,Email:b.feng@uq.edu.au

Issue Date: 05 March 2012

Cite this article:

Joseph LEE,Bo FENG. A thermodynamic study of the removal of HCl and H₂S from syngas[J]. Front Chem Sci Eng, 2012, 6(1): 67-83.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-011-1162-4
https://academic.hep.com.cn/fcse/EN/Y2012/V6/I1/67

Fig.1 Optimum dechlorination conditions for (a) CaO, (b) KCO, (c) NaCO, (d) NaHCO. Initial conditions: temperature 300 K-1500 K, pressure 0.1-11 MPa, initial concentrations 0.5 mol sorbent + 1 mol HCl + 999999 mol N (or 9999 mol N or 99 mol N)

Fig.2 Optimum dechlorination conditions for (a) CaO, (b) KCO, (c) NaCO, (d) NaHCO with the presence of steam. Initial conditions: temperature 300 K–1500 K, pressure 0.1–11 MPa, initial concentrations 0.5 mol sorbent + 1 mol HCl + 1 mol HO + 999998 mol N (or 9998mol N or 98 mol N)

Fig.3 Optimum desulphurisation conditions for (a) CuO, (b) NaCO, (c) NaHCO, (d) KCO, (e) CaO, (f) ZnO, (g) MnO, (h) FeO, (i) PbO. Initial conditions: temperature 300 K–1500 K, pressure 0.1–11 MPa, initial concentrations 1 mol sorbent + 1 mol HS + 999999 mol N (or 9999 mol N or 99 mol N)

Fig.4 Optimum desulphurisation conditions for (a) CuO, (b) NaCO, (c) NaHCO, (d) KCO, (e) CaO, (f) ZnO, (g) MnO, (h) FeO, (i) PbO with the presence of steam. Initial conditions: temperature 300 K–1500 K, pressure 0.1–11 MPa, initial concentrations 1 mol sorbent + 1 mol HS + 1 mol HO + 999998 mol N (or 9998 mol N or 98 mol N)

Fig.5 Optimum dechlorination conditions for (a) CaO, (b) KCO, (c) NaCO, (d) NaHCO when HS is present. Initial conditions: temperature 300–1500K, pressure 0.1–11 MPa, initial concentrations 1.5 mol sorbent + 1 mol HCl + 1 mol HS + 999998 mol N (or 9998 mol N or 98 mol N). Optimum dechlorination conditions for (e) CaO, (f) KCO, (g) NaCO, (h) NaHCO when HS and HO are both present. Initial conditions: temperature 300 K–1500 K, pressure 0.1–11 Mpa, initial concentrations 1.5 mol sorbent+1 mol HCl + 1mol HS + 1 mol HO + 999997 mol N (or 9997 mol N or 97 mol N).

Fig.6 Optimum desulphurisation conditions for (a) CuO, (b) NaCO, (c) NaHCO, (d) KCO, (e) CaO, (f)ZnO, (g) MnO, (h) FeO, (i) PbO when HCl is present. Initial conditions: temperature 300 K–1500 K, pressure 0.1–11 MPa, initial concentrations 1.5 mol sorbent + 1 mol HS + 1 mol HCl + 999998 mol N (or 9998 mol N or 98 mol N)

Fig.7 Optimum desulphurisation conditions for (a) CuO, (b) NaCO, (c) NaHCO, (d) KCO, (e) CaO, (f) ZnO, (g) MnO, (h) FeO, (i) PbO when HCl and HO are both present. Initial conditions: temperature 300 K–1500 K, pressure 0.1–11 MPa, initial concentrations 1.5 mol sorbent + 1 mol HS + 1 mol HCl + 1 mol HO + 999997 mol N (or 9997 mol N or 97 mol N)

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