High-efficient adsorption and removal of elemental mercury from smelting flue gas by cobalt sulfide

  • Hui Liu
  • Zhiwen You
  • Shu Yang
  • Cao Liu
  • Xiaofeng Xie
  • Kaisong Xiang
  • Xiaoyang Wang
  • Xu Yan
Research Article


Nonferrous metal smelting produces a large amount of Hg0 in flue gas, which has caused serious damage to the environment and human health. In this work, amorphous cobalt sulfide was synthesized by a liquid-phase precipitation method and was used for capturing gaseous Hg0 from simulated smelting flue gas at low temperatures (50~150 °C). In the adsorption process, Hg0 can be transformed into the stable mercury compound, which is confirmed to be HgS by X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption of Hg (Hg-TPD) analysis. Meanwhile, XPS results also demonstrate that S22− species on the surface of cobalt sulfide play an important role in Hg0 transformation. At the temperature of 50 °C (inlet Hg0 concentration of 214 μg·m−3), the Hg0 adsorption capacity of cobalt sulfide (penetration rate of 25%) is as high as 2.07 mg·g−1, which is much higher than that of popular adsorbents such as activated carbons and metal oxides. In addition, it was found that the Hg0 removal efficiency by cobalt sulfide in the flue gas with high concentration of SO2 (5%) remained more than 94%. The good adsorption and Hg0 removal performance guarantee cobalt sulfide the great superiority and application potential in the treatment of Hg0 in smelting flue gas with high concentration of SO2.


Hg0 Adsorption Cobalt sulfide SO2 resistance Smelting flue gas 


Funding information

This study is financially supported by the National Key R&D Program of China (2017YFC0210405), National Natural Science Foundation of China (51722407), Science and Technology Project of Hunan Province (2017RS3011), and the Project of Innovation-driven Plan in Central South University (2019CX009).


  1. Behra P, Bonnisselgissinger P, Alnot M, Revel R, Ehrhardt JJ (2001) XPS and XAS study of the sorption of Hg(II) onto pyrite. Surf Interface Anal 30:269–272Google Scholar
  2. Dang H, Liao Y, Ng TW, Huang G, Xiong S, Xiao X, Yang S, Wong PK (2016) The simultaneous centralized control of elemental mercury emission and deep desulfurization from the flue gas using magnetic Mn–Fe spinel as a co-benefit of the wet electrostatic precipitator. Fuel Process Technol 142:345–351CrossRefGoogle Scholar
  3. Dong C, Guo L, He Y, Shang L, Qian Y, Xu L (2018) Ultrafine Co1-xS nanoparticles embedded in a nitrogen-doped porous carbon hollow nanosphere composite as an anode for superb sodium-ion batteries and lithium-ion batteries. Nanoscale 10:2804–2811CrossRefGoogle Scholar
  4. Driscoll CT, Mason RP, Chan HM, Jacob DJ, Pirrone N (2013) Mercury as a global pollutant: sources, pathways, and effects. Environ Sci Technol 47:4967–4983CrossRefGoogle Scholar
  5. Dyvik F, Borve K (1987): Method for the purification of gases containing mercury and simultaneous recovery of the mercury in metallic form. US Patent 4640751Google Scholar
  6. Ehrhardt JJ, Behra P, Bonnissel-Gissinger P, Alnot M (2015) XPS study of the sorption of Hg(II) onto pyrite FeS2. Surf Interface Anal 30:269–272CrossRefGoogle Scholar
  7. Gao Y, Zhang Z, Wu J, Duan L, Umar A, Sun L, Guo Z, Wang Q (2013) A critical review on the heterogeneous catalytic oxidation of elemental mercury in flue gases. Environ Sci Technol 47:10813–10823CrossRefGoogle Scholar
  8. Hsi HC, Rood MJ, Asce M, Rostam-Abadi M, Chen S, Chang R (2015) Mercury adsorption properties of sulfur-impregnated adsorbents. J Environ Eng 128:1080–1089CrossRefGoogle Scholar
  9. Huang ZJ, Duan YF, Wang YJ, Meng SL, Jiao YG (2009) Experimental investigation on absorption of Hg in simulated fuel gas by modified Ca(OH)2. Proc CSEE 29:56–62Google Scholar
  10. Jean G, Remi L, Denys P (1998) Process for the removal of mercury from smelter gases. WO Patent 1998006478 A1Google Scholar
  11. Jiang T, Yang S, Dai P, Yu X, Bai Z, Wu M, Li G, Tu C (2018) Economic synthesis of Co3S4 ultrathin nanosheet/reduced graphene oxide composites and their application as an efficient counter electrode for dye-sensitized solar cells. Electrochim Acta 261:143–150CrossRefGoogle Scholar
  12. Krishnan SV, Gullett BK, Jozewicz W (1994) Sorption of elemental mercury by activated carbons. Environ Sci Technol 28:1506–1512CrossRefGoogle Scholar
  13. Lee J-Y, Kim YJ (2013) Hg(0) removal using Se(0)-doped montmorillonite from selenite (IV). B Korean Chem Soc 34:3767–3770CrossRefGoogle Scholar
  14. Li P, Feng XB, Qiu GL, Shang LH, Li ZG (2009a) Mercury pollution in Asia: a review of the contaminated sites. J Hazard Mater 168:591–601CrossRefGoogle Scholar
  15. Li Y, Daukoru M, Suriyawong A, Biswas P (2009b) Mercury emissions control in coal combustion systems using potassium iodide: bench-scale and pilot-scale studies. Energy Fuel 23:236–243CrossRefGoogle Scholar
  16. Li H, Zhu L, Wang J, Li L, Shih K (2016) Development of nano-sulfide sorbent for efficient removal of elemental mercury from coal combustion fuel gas. Environ Sci Technol 50:9551–9557CrossRefGoogle Scholar
  17. Liao Y, Xiong S, Dang H, Xiao X, Yang S, Wong PK (2015) The centralized control of elemental mercury emission from the flue gas by a magnetic rengenerable Fe-Ti-Mn spinel. J Hazard Mater 299:740–746CrossRefGoogle Scholar
  18. Liao Y, Chen D, Zou S, Xiong S, Xiao X, Dang H, Chen T, Yang S (2016) Recyclable naturally derived magnetic pyrrhotite for elemental mercury recovery from flue gas. Environ Sci Technol 50:10562–10569CrossRefGoogle Scholar
  19. Liu Z, Peng B, Chai L, Liu H, Yang S, Yang B, Xiang K, Liu C, Wang D (2017a) Selective removal of elemental mercury from high-concentration SO2 flue gas by thiourea solution and investigation of mechanism. Ind Eng Chem Res 56:4281–4287CrossRefGoogle Scholar
  20. Liu Z, Wang D, Peng B, Chai L, Liu H, Yang S, Yang B, Xiang K, Liu C (2017b) Transport and transformation of mercury during wet flue gas cleaning process of nonferrous metal smelting. Environ Sci Pollut Res 24:22494–22502CrossRefGoogle Scholar
  21. Liu Z, Wang D, Peng B, Chai L, Yang S, Liu C, Zhang C, Xie X, Liu H (2017c) Mercury re-emission in the smelting flue gas cleaning process: the influence of arsenite. Energy Fuel 31:11053–11059CrossRefGoogle Scholar
  22. Pan Y, Liu Y, Liu C (2015) Phase- and morphology-controlled synthesis of cobalt sulfide nanocrystals and comparison of their catalytic activities for hydrogen evolution. Appl Surf Sci 357:1133–1140CrossRefGoogle Scholar
  23. Peng B, Liu Z, Chai L, Liu H, Yang S, Yang B, Xiang K, Liu C (2016) The effect of selenite on mercury re-emission in smelting flue gas scrubbing system. Fuel 168:7–13CrossRefGoogle Scholar
  24. Peng B, Liu Z, Chai L, Liu H, Yang S, Yang B, Xiang K, Liu C (2017) Effect of copper ions on the mercury re-emission in a simulated wet scrubber. Fuel 190:379–385CrossRefGoogle Scholar
  25. Qu Z, Xie J, Xu H, Chen W, Yan N (2015) Regenerable sorbent with a high capacity for elemental mercury removal and recycling from the simulated flue gas at a low temperature. Energy Fuel 29:6187–6196CrossRefGoogle Scholar
  26. Rumayor M, Díaz-Somoano M, López-Antón MA, Ochoa-González R, Martínez-Tarazona MR (2015a) Temperature programmed desorption as a tool for the identification of mercury fate in wet-desulphurization systems. Fuel 148:98–103CrossRefGoogle Scholar
  27. Rumayor M, Fernandez-Miranda N, Lopez-Anton MA, Diaz-Somoano M, Martinez-Tarazona MR (2015b) Application of mercury temperature programmed desorption (Hg-TPD) to ascertain mercury/char interactions. Fuel Process Technol 132:9–14CrossRefGoogle Scholar
  28. Rupp EC, Granite EJ, Stanko DC (2013) Laboratory scale studies of Pd/γ-Al2O3 sorbents for the removal of trace contaminants from coal-derived fuel gas at elevated temperatures. Fuel 108:131–136CrossRefGoogle Scholar
  29. Schroeder WH, Yarwood G, Niki H (1991) Transformation processes involving mercury species in the atmosphere— results of a literature survey. Water Air Soil Pollut 56:653–666CrossRefGoogle Scholar
  30. Senior C, Bustard CJ, Durham M, Baldrey K, Michaud D (2004) Characterization of fly ash from full-scale demonstration of sorbent injection for mercury control on coal-fired power plants. Fuel Process Technol 85:601–612CrossRefGoogle Scholar
  31. Takaoka M, Takeda N, Shimaoka Y, Fujiwara T (1999) Removal of mercury in flue gas by the reaction with sulfide compounds. Toxicol Environ Chem 73:1–16CrossRefGoogle Scholar
  32. Uddin MA, Ozaki M, Sasaoka E, Wu S (2009) Temperature-programmed decomposition desorption of mercury species over activated carbon sorbents for mercury removal from coal-derived fuel gas †. Fuel 23:3610–3615Google Scholar
  33. Vidic RD, Chang MT, Thurnau RC (1998) Kinetics of vapor-phase mercury uptake by virgin and sulfur-impregnated activated carbons. J Air Waste Manage Assoc 48:247–255CrossRefGoogle Scholar
  34. Xie J, Qu Z, Yan N, Yang S, Chen W, Hu L, Huang W, Liu P (2013) Novel regenerable sorbent based on Zr-Mn binary metal oxides for flue gas mercury retention and recovery. J Hazard Mater 261:206–213CrossRefGoogle Scholar
  35. Xie J, Xu H, Qu Z, Huang W, Chen W, Ma Y, Zhao S, Liu P, Yan N (2014) Sn-Mn binary metal oxides as non-carbon sorbent for mercury removal in a wide-temperature window. J Colloid Interface Sci 428:121–127CrossRefGoogle Scholar
  36. Yang J, Zhao Y, Zhang J, Zheng C (2014) Regenerable cobalt oxide loaded magnetosphere catalyst from fly ash for mercury removal in coal combustion flue gas. Environ Sci Technol 48:14837–14843CrossRefGoogle Scholar
  37. Yang S, Liu C, Liu Z, Yang B, Xiang K, Zhang C, Liu H, Chai L (2018) High catalytic activity and SO2-poisoning resistance of Pd/CuCl2/γ-Al2O3 catalyst for elemental mercury oxidation. Catal Commun 105:1–5CrossRefGoogle Scholar
  38. Ye H, Wang L, Deng S, Zeng X, Nie K, Duchesne PN, Wang B, Liu S, Zhou J, Zhao F (2016) Amorphous MoS3 infiltrated with carbon nanotubes as an advanced anode material of sodium-ion batteries with large gravimetric, areal, and volumetric capacities. Adv Energy Mater 7(5):1601602CrossRefGoogle Scholar
  39. Zhao H, Yang G, Gao X, Pang C, Kingman S, Lester E, Wu T (2016a) Hg0-temperature-programmed surface reaction and its application on the investigation of metal oxides for Hg0 capture. Fuel 181:1089–1094CrossRefGoogle Scholar
  40. Zhao H, Yang G, Gao X, Pang CH, Kingman SW, Wu T (2016b) Hg(0) capture over CoMoS/γ-Al2O3 with MoS2 nanosheets at low temperatures. Environ Sci Technol 50:1056–1064CrossRefGoogle Scholar
  41. Zheng Y, Jensen AD, Windelin C, Jensen F (2012) Review of technologies for mercury removal from flue gas from cement production processes. Prog Energy Combust 38:599–629CrossRefGoogle Scholar
  42. Zhu Y (1999) Boliden-Norzink mercury removal technology. Nonferrous Metals 51:93–95Google Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.School of Metallurgy and EnvironmentCentral South UniversityChangshaChina
  2. 2.Chinese National Engineering Research Center for Control & Treatment of Heavy Metal PollutionCentral South University ChangshaChina

Personalised recommendations