The Additive Effect of K2CO3-NiSO4 on the Carbothermal Reduction Process of Phosphate Rock and SiO2

Abstract

In this study, K2CO3 and NiSO4 were used for doping the carbothermal reduction system of phosphate rock, and the effect of a K-Ni composite catalyst on the carbothermal reduction of phosphate rock was studied. The effects of the SiO2-CaO mass ratio, carbon excess coefficient, and the mass ratio of K2CO3-NiSO4 loading on the carbothermal reduction of phosphate rock were investigated. At the temperature of 1300 °C and the reducing time of 90 min, the optimal reaction conditions were as follows: SiO2-CaO mass ratio, 1.1; coke excess factor, 1.1; mass of the supporting K2CO3-NiSO4, 10% of coke mass, and the mass ratio of K2CO3-NiSO4 loading of 6/4. The maximum values of phosphorus conversion were 66.45% and 65.34%, when single components K2CO3 and NiSO4 were added, respectively, and the composite dopants increased phosphorus conversion by 4.5% and 5.61%, respectively, indicating that composite dopants compared with single dopants have certain advantages. Kinetic analysis indicated that the reaction order was not changed by the coke-supported K2CO3-NiSO4 and remained in accordance with the first-order reaction law, and the activation energy decreased by 39.49 kJ/mol from 253.58 kJ/mol to 214.09 kJ/mol, compared with the unsupported system. In order to ensure that the conversion of phosphorus meets the requirements, the residence time of reactants in yellow phosphorus production by an electric furnace method is generally 4 h, and the residence time of general materials is more than 4 h in the existing industrial production of the kiln phosphoric acid process. Therefore, the reaction time was increased to 4 h, and the actual kiln process for phosphate production was simulated. Finally, at 1300 °C for 4 h, SEM analysis were used to determine whether the slag phase was discharged in the form of solid sintering and whether it met the slag discharge requirements for the kiln method.

This is a preview of subscription content, access via your institution.

References

  1. 1.

    Rashid MM, Jahan M, Islam KS (2016) Impact of nitrogen, phosphorus and potassium on Brown Plant hopper and tolerance of its host Rice plants. Rice Sci 23:119–131

    Article  Google Scholar 

  2. 2.

    Cao RF, Xia JP, Li WL, Han YW (2018) Effects of alkali metal carbonates on Carbothermal reduction of phosphate rock. J Chem Eng Chin Univ 32:568–576

    CAS  Google Scholar 

  3. 3.

    Geng RX, Xia JP, Chen ZJ, Yang J, Zheng S, Liu HL (2016) Effects of potassium feldspar on slagging and fluxing in phosphorus produced via electric furnace. Phosphorus Sulfur Silicon Relat Elem 192:475–480

    Article  Google Scholar 

  4. 4.

    Regina K, Zygmunt K, Danuta PK, Zbigniew W, Katarzyna G (2008) Tripolyphosphate made from wet-process phosphoric acid with the use of a rotary kiln. Ind Eng Chem Res 47:6821–6827

    Article  Google Scholar 

  5. 5.

    Wang XJ, Tang L, Jiang Z (2014) Numerical simulation of venturi ejector reactor in yellow phosphorus purification system. Nucl Eng Des 268:18–23

    CAS  Article  Google Scholar 

  6. 6.

    Chen SJ (2004) Summary of comprehensive utilization of by-products from phosphorus by electric furnace in China. S P Bmh Rel Eng 15:7–12

    Google Scholar 

  7. 7.

    Liu ML (2009) Study of producing industrial phosphoric acid with middle-low grade phosphate rock by vertical kiln method. Chem Res App 21:131–134

    CAS  Google Scholar 

  8. 8.

    Deng SY, Liang B, Li C, Wu P, Qiu LY, Wang LM (2012) Research progress of kiln phosphoric acid process. Chem Ind Eng Prog 31:402–406

    Google Scholar 

  9. 9.

    Lu L, Liang B, Liu Q, Liu WZ, Yang HH, Wu P, Li C (2016) Reactions between P2O5 and calcium phosphate in kiln phosphoric acid. J Chem Ind Eng 67:4399–4405

    CAS  Google Scholar 

  10. 10.

    Ren ZD, Chen L, Ning P (2006) Progress in purification of PH3, H2S in yellow phosphorus tail gas with activated carbon. Mod Chem Ind 11:0253–4320

    Google Scholar 

  11. 11.

    Zhang Y, Ning P, Xu HD, Hu CS, Wang XQ, Deng CL (2007) Adsorptive removal of PH3 in off-gas of yellow phosphorus by modified activated carbon. Chin J of Environ Eng:74–78

  12. 12.

    Megy JA (2005) Rotary kiln process for phosphoric acid manufacture: US2005019598

  13. 13.

    Jacob KD, Reynolds DS, Hill WL (2002) Reduction of tricalcium phosphate by carbon. Ind Eng Chem 20:1204–1210

    Article  Google Scholar 

  14. 14.

    Cao RF, Li Y, Xia JP, Li WL, Han YW (2019) Study on carbothermal reduction process and kinetics of fluoroapatite. J Chem Eng Chin Univ 33:372–379

    CAS  Google Scholar 

  15. 15.

    Liu Q, Liu WZ, Lv L, Li RH, Liang B, Yue HR, Tang SW, Li C (2018) Article study on reactions of gaseous P2O5 with Ca3(PO4)2 and SiO2 during a rotary kiln process for phosphoric acid production. Chin J Chem Eng 26:1007–6220

    Article  Google Scholar 

  16. 16.

    Belyaev AA (2016) Effect of alkali metal carbonate additives on the rate of oxidation of the organic matter of anthracite. Solid Fuel Chem 47:226–230

    Article  Google Scholar 

  17. 17.

    Ma YJ, Liu B, Jing MM, Zhang RY, Chen JY, Zhang YH, Li JL (2016) Promoted potassium salts based Ru/AC catalysts for water gas shift reaction. Chem Eng J 287:155–161

    CAS  Article  Google Scholar 

  18. 18.

    Kopyscinski J, Habibi R, Mims CA, Hill JA (2013) K2CO3-catalyzed CO2 gasification of ash-free coal: kinetic study. Energy Fuel 27:4875–4883

    CAS  Article  Google Scholar 

  19. 19.

    Bai S, Wen S, Liu D, Zhang W, Cao Q (2013) Effects of sodium carbonate on the carbothermic reduction of siderite ore with high phosphorus content. Miner Metall Process 30:100–107

    CAS  Google Scholar 

  20. 20.

    Lin ZF, Hu RM, Zhou XL (2017) Research Progress of Ni- based catalysts. Chem Ind Eng 68:26–36

    CAS  Google Scholar 

  21. 21.

    Cao RF, Li Y, Xia JP, Chen ZJ, Yang J (2019) NiSO4 as additive effect on the Carbothermal reduction process of phosphate rock and SiO2. Silicon: 1:1–8

  22. 22.

    Othman NF, Bosrooh MH (2016) Catalytic Adaro coal gasification using dolomite and nickel as catalyst. Procedia Eng 148:308–313

    CAS  Article  Google Scholar 

  23. 23.

    Huang GB, Wang ZQ, Li QF, Huang JJ (2014) Syngas methanation over nickel catalyst in liquid-phase. Fuel Chem Tech 42:952–957

    CAS  Google Scholar 

  24. 24.

    Li WB, Lin R, Yang Y (2019) Investigation on the reaction area of PEMFC at different position in multiple catalyst layer. Electrochim Acta 302:241–248

    CAS  Article  Google Scholar 

  25. 25.

    Yang JB, Wang JX, Zhu L, Zeng W, Wang JF (2019) Multiple hollow CeO2 spheres decorated MnO2 microflower as an efficient catalyst for oxygen reduction reaction. Mater Lett 234:331–334

    CAS  Article  Google Scholar 

  26. 26.

    Fang MX, WB LI, Cen JM, Wang QH, Luo ZY (2015) Progress and prospect of research on catalytic gasification of coal. Chem Ind Eng Prog 34:3656–3664

    CAS  Google Scholar 

  27. 27.

    Yeboah YD, Xu Y, Sheth A, Godavarty A, Agrawal PK (2003) Catalytic gasification of coal using eutectic salts: identification of eutectics. Carbon 41:203–214

    CAS  Article  Google Scholar 

  28. 28.

    Jing N, Wang Q, Cheng L, Luo Z, Cen K, Zhang D (2013) Effect of temperature and pressure on the mineralogical and fusion characteristics of Jincheng coal ash in simulated combustion and gasification environment. Fuel 104:647–655

    CAS  Article  Google Scholar 

  29. 29.

    Jiang MQ, Zhou R, Hu J, Wang FC, Wang J (2012) Calcium-promoted catalytic activity of potassium carbonate for steam gasification of coal char: influences of calcium species. Fuel 99:64–71

    CAS  Article  Google Scholar 

  30. 30.

    Li Q, Hu B, Wu YX (2014) Process parameters and kinetics of smelting reduction technology for low-phosphate ore reduction. J Chem Eng Chin Univ 28:905–910

    CAS  Google Scholar 

  31. 31.

    Yang J, Chen JJ, Liu HY (2015) Enhanced effect of aluminum impurity on solid state carbothermal reduction of fluorapatite. J Sichuan Univ Eng Sci Ed 47:186–191

    Google Scholar 

  32. 32.

    Li Q, Hu B, Wu YX (2013) Reaction kinetics of phosphate ore with carbon by smelting reduction technology. Chem Eng Chin 41:53–56

    Google Scholar 

  33. 33.

    Liu J, Xia JP, Chen ZJ, Luo ZQ, Geng RX (2017) Yellow phosphorus production in electric furnace using potassium feldspar to replace silica as flux. J Chem Eng Chin Univ 31:1419–1425

    CAS  Google Scholar 

  34. 34.

    Qiu LY, Liang B, Jiang LK (1996) Investigation on the solid state reduction of fluorapatite. J Chem Ind Eng 47:65–71

    CAS  Google Scholar 

Download references

Acknowledgments

The authors thank the National Natural Science Foundation of China (No. 21566018).

Author information

Affiliations

Authors

Corresponding authors

Correspondence to Jupei Xia or Zhengjie Chen.

Additional information

Publisher’s Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Zheng, G., Cao, R., Li, Y. et al. The Additive Effect of K2CO3-NiSO4 on the Carbothermal Reduction Process of Phosphate Rock and SiO2. Silicon 12, 1985–1994 (2020). https://doi.org/10.1007/s12633-019-00311-5

Download citation

Keywords

  • Silica
  • K2CO3-NiSO4
  • Catalytic
  • Energy saving
  • Phosphorus
  • Carbothermal reduction