Journal of Thermal Analysis and Calorimetry

, Volume 132, Issue 2, pp 1277–1289 | Cite as

Thermodynamic analysis of reduction in copper slag by biomass molding compound based on phase equilibrium calculating model

  • Zongliang Zuo
  • Qingbo Yu
  • Huaqing Xie
  • Fan Yang
  • Qin Qin
Article
  • 49 Downloads

Abstract

Copper slag is a good valuable material resource with high iron content in the form of fayalite. Biomass as reduction reducer was proposed in this paper. For the basic research of the reduction in biomass, the biomass reducer was simplified as molding compound C, CO, H2 and CH4. The reactions of 2FeO·SiO2 with C, CO, H2 and CH4 could proceed spontaneously with the addition of CaO. The Gibbs free energy is decreased significantly by addition of CaO. The equilibrium compositions of products were calculated and analyzed combing with 19 basic reactions. Beginning temperature of C, CO, H2 and CH4 is 900, 623, 567 and 511 K, respectively The reduction degree of C, CH4, H2 and CO is 1, 0.851, 0.695 and 0.452, respectively, at 1773 K when the reducer addition ratio is 1.0 calculated by phase equilibrium calculating model. Direct reduction reaction of copper slag dominates at higher temperature, and temperature region of 700–1173 K is the transformational zone. Indirect reduction index curves are in the shape of reverse ‘S,’ and the higher temperature is in favor of indirect reduction in copper slag. There is a steady increase in reduction degree with the increase in reducer. Reduction reaction path of copper slag by C, CO, H2 and CH4 is established.

Keywords

Phase equilibrium Thermodynamic analysis Reduction Copper slag Biomass molding compound 

Notes

Acknowledgements

The authors would like to acknowledge the support from the Major State Research Development Program of China (2017YFB0603603).

References

  1. 1.
    Alp I, Deveci H, Sungun H. Utilization of flotation wastes of copper slag as raw material in cement production. J Hazard Mater. 2008;159(2–3):390–5.CrossRefGoogle Scholar
  2. 2.
    Gorai B, Jana R, K Premchand. Characteristics and utilisation of copper slag—a review. Resour Conserv Recycl. 2003;39(4):299–313.CrossRefGoogle Scholar
  3. 3.
    Palacios J, Sánchez M. Wastes as resources: update on recovery of valuable metals from copper slags. Min Proc Ext Met Rev. 2011;120(4):218–23.CrossRefGoogle Scholar
  4. 4.
    Yang Z, Lin Q, Xia J, He Y, Liao G, Ke Y. Preparation and crystallization of glass–ceramics derived from iron-rich copper slag. J Alloys Compd. 2013;574:354–60.CrossRefGoogle Scholar
  5. 5.
    Liu H, Lu H, Chen D, Wang H, Xu H, Zhang R. Preparation and properties of glass–ceramics derived from blast-furnace slag by a ceramic-sintering process. Ceram Int. 2009;35(8):3181–4.CrossRefGoogle Scholar
  6. 6.
    Zhao D, Zhang Z, Tang X, Liu L, Wang X. Preparation of slag wool by integrated waste-heat recovery and resource recycling of molten blast furnace slags: from fundamental to industrial application. Energies. 2014;7(5):3121–35.CrossRefGoogle Scholar
  7. 7.
    de Rojas MIS, Rivera J, Frias M, Marin F. Use of recycled copper slag for blended cements. J Chem Technol Biotechnol. 2008;83(3):209–17.CrossRefGoogle Scholar
  8. 8.
    Shi C, Meyer C, Behnood A. Utilization of copper slag in cement and concrete. Resour Conserv Recycl. 2008;52(10):1115–20.CrossRefGoogle Scholar
  9. 9.
    Heo JH, Kim BS, Park JH. Effect of CaO addition on iron recovery from copper smelting slags by solid carbon. Metall Mater Trans B. 2013;44(6):1352–63.CrossRefGoogle Scholar
  10. 10.
    Zhang H, Shi X, Zhang B, Hong X. Reduction of molten copper slags with mixed CO–CH4–Ar gas. Metall Mater Trans B. 2013;45(2):582–9.Google Scholar
  11. 11.
    Siwiec G, Oleksiak B, Matula T. Reduction of copper slag with the use of carbon granulates. Metalurgija. 2014;53(4):585–7.Google Scholar
  12. 12.
    Zhang J, Qi Y, Yan D. A new technology for copper slag reduction to get molten iron and copper matte. J Iron Steel Res Int. 2015;22(5):396–401.CrossRefGoogle Scholar
  13. 13.
    Hu JH, Wang H, Li L. Recovery of iron from copper slag by melting reduction. Kunming: Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology; 2011. p. 541–4.Google Scholar
  14. 14.
    Heo JH, Chung Y, Park JH. Recovery of iron and removal of hazardous elements from waste copper slag via a novel aluminothermic smelting reduction (ASR) process. J Clean Prod. 2016;137:777–87.CrossRefGoogle Scholar
  15. 15.
    Zhang L, Zhang L, Wang M. Oxidization mechanism in CaO–FeOx–SiO2 slag with high iron content. Trans Nonferr Met Soc. 2006;20(1):79–82.Google Scholar
  16. 16.
    Gyurov S, Rabadjieva D, Kovacheva D, Kostova Y. Kinetics of copper slag oxidation under nonisothermal conditions. J Therm Anal Calorim. 2014;116(2):945–53.CrossRefGoogle Scholar
  17. 17.
    Bruckard WJ, Somerville M, Hao F. The recovery of copper, by flotation, from calcium-ferrite-based slags made in continuous pilot plant smelting trials. Miner Eng. 2004;17(4):495–504.CrossRefGoogle Scholar
  18. 18.
    Warczok A, Riveros G. Slag cleaning in crossed electric and magnetic fields. Miner Eng. 2007;20(1):34–43.CrossRefGoogle Scholar
  19. 19.
    Seo K, Fruehan R. Reduction of FeO in slag with coal char. ISIJ Int. 2000;40(1):7–15.CrossRefGoogle Scholar
  20. 20.
    Utigard T, Sanchez G, Manriquez J. Reduction kinetics of liquid iron oxide-containing slags by carbon monoxide. Metall Mater Trans B. 1997;28(5):821–6.CrossRefGoogle Scholar
  21. 21.
    Nagasaka T, Hino M, Ban-Ya S. Interfacial kinetics of hydrogen with liquid slag containing iron oxide. Metall Mater Transa B. 2000;31(5):945–55.CrossRefGoogle Scholar
  22. 22.
    Strezov V. Iron ore reduction using sawdust: experimental analysis and kinetic modelling. Renew Energy. 2006;31(12):1892–905.CrossRefGoogle Scholar
  23. 23.
    Luo S, Yi C, Zhou Y. Direct reduction of mixed biomass-Fe2O3 briquettes using biomass-generated syngas. Renew Energy. 2011;36(12):3332–6.CrossRefGoogle Scholar
  24. 24.
    de Lima LC. A proposal of an alternative route for the reduction of iron ore in the eastern Amazonia. Int J Hydrogen Energy. 2004;29(6):659–61.CrossRefGoogle Scholar
  25. 25.
    Abd Rashid RZ, Mohd SH, Ani MH, Yunus NA, Akiyama T, Purwanto H. Reduction of low grade iron ore pellet using palm kernel shell. Renew Energy. 2014;63:617–23.CrossRefGoogle Scholar
  26. 26.
    Guo D, Zhu L, Guo S, Cui B, Luo S, Laghari M, Chen Z, Ma C, Zhou Y, Chen J, Xiao B, Hu M, Luo S. Direct reduction of oxidized iron ore pellets using biomass syngas as the reducer. Fuel Process Technol. 2016;148:276–81.CrossRefGoogle Scholar
  27. 27.
    Norgate T, Haque N, Somerville M, Jahanshahi S. Biomass as a source of renewable carbon for iron and steelmaking. ISIJ Int. 2012;52(8):1472–81.CrossRefGoogle Scholar
  28. 28.
    Xie H, Yu Q, Zhang Y, Zhang J, Liu J, Qin Q, Zuo Z. New process for hydrogen production from raw coke oven gas via sorption-enhanced steam reforming: thermodynamic analysis. Int J Hydrogen Energy. 2017;42(5):2914–23.CrossRefGoogle Scholar
  29. 29.
    Li P. Thermodynamic analysis of waste heat recovery of molten blast furnace slag. Int J Hydrogen Energy. 2017;42(15):9688–95.CrossRefGoogle Scholar
  30. 30.
    Zuo Z, Yu Q, Wei M, Xie H, Duan W, Wang K, Qin Q. Thermogravimetric study of the reduction of copper slag by biomass. J Therm Anal Calorim. 2016;126(2):481–91.CrossRefGoogle Scholar
  31. 31.
    Li H, Chen Y, Cao Y, Liu G, Li B. Comparative study on the characteristics of ball-milled coal fly ash. J Therm Anal Calorim. 2016;124(2):839–46.CrossRefGoogle Scholar
  32. 32.
    Sun Y, Han Y, Wei X, Gao P. Non-isothermal reduction kinetics of oolitic iron ore in ore/coal mixture. J Therm Anal Calorim. 2016;123(1):703–15.CrossRefGoogle Scholar
  33. 33.
    Yu W, Tang Q, Chen J, Sun T. Thermodynamic analysis of the carbothermic reduction of a high-phosphorus oolitic iron ore by FactSage. Int J Miner Metall Mater. 2016;23(10):1126–32.CrossRefGoogle Scholar
  34. 34.
    Zuo Z, Yu Q, Liu J, Qin Q, Xie H, Yang F, Duan W. Effects of CaO on reduction of copper slag by biomass based on ion and molecule coexistence theory and thermogravimetric experiments. ISIJ Int. 2017;57(2):220–7.CrossRefGoogle Scholar
  35. 35.
    Zhao Z, Tang H, Guo Z. Effects of carbon precipitation on reduction of iron oxides under CO atmosphere. J Chin Rare Earth Soc. 2012;30:544–8.Google Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2018

Authors and Affiliations

  1. 1.School of MetallurgyNortheastern UniversityShenyangPeople’s Republic of China

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