Skip to main content
SpringerLink
Log in

Mechanistic investigation on the Hg0 elimination ability of MnOx–CeOx nanorod adsorbents: effects of Mn/Ce molar ratio

  • Article
  • Published:
Waste Disposal & Sustainable Energy Aims and scope Submit manuscript

Abstract

Mercury pollution is created by coal combustion processes in multi-component systems. Adsorbent injection was identified as a potential strategy for capturing Hg0 from waste gases, with adsorbents serving as the primary component. The hydrothermal approach was used to synthesize a series of MnOx–CeOx nanorod adsorbents with varying Mn/Ce molar ratios to maximize the Hg0 capture capabilities. Virgin CeOx had weak Hg0 elimination activity; <8% Hg0 removal efficiency was obtained from 150 °C to 250 °C. With the addition of MnOx, the amount of surface acid sites and the relative concentration of Mn4+ increased. This ensured the sufficient adsorption and oxidation of Hg0 while overcoming the limitations of restricted adsorbate-adsorbent interactions caused by the lower surface area, endowing MnOx–CeOx with increased Hg0 removal capacity. When the molar ratio of Mn/Ce reached 6/4, the adsorbent’s Hg0 removal efficiency remained over 92% at 150 °C and 200 °C. As the molar ratio of Mn/Ce grew, the adsorbent’s Hg0 elimination capacity declined due to decreased surface area, weakened acidity, and decreased activity of Mn4+; <75% Hg0 removal efficiency was reached between 150 °C and 250 °C for virgin MnOx. Throughout the overall Hg0 elimination reactions, Mn4+ and Oα were in charge of oxidizing Hg0 to HgO, with Ce4+ acting as a promoter to aid in the regeneration of Mn4+. Because of its limited adaptability to flue gas components, further optimization of the MnOx–CeOx nanorod adsorbent is required.

Graphical abstract

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12

Similar content being viewed by others

Abbreviations

M :

Usage of the examined sample (g)

f :

Flow rate of the simulated flue gas (mL/min)

t :

Hg0 elimination time (min)

q t :

Capture capacity of Hg0 (μg/g)

ƞ :

Removal efficiency of Hg0 (%)

X out :

Outlet Hg0 concentration (μg/m3)

X in :

Inlet Hg0 concentration (μg/m3)

B :

Potential mass transfer index (mg/g)

b :

Adsorbate–adsorbent affinity parameter (g·h/mg)

[k L a]f :

External mass transfer factor (h−1)

[k L a]g :

Global mass transfer factor (h−1)

[k L a]d :

Internal mass transfer factor (h−1)

k 1 :

Pseudo-first-order rate constant (min−1)

k 2 :

Pseudo-second-order rate constant (min−1)

q e :

Theoretical Hg0 capture capacity (μg/g)

k p :

Intraparticle diffusion coefficient (μg/(g·min1/2))

c :

Constant corresponding to the boundary conditions (μg/g)

α :

Initial adsorption rate constant (μg/(g·min1/2))

β :

Desorption rate constant (g/μg)

References

  1. Wang, T., Wu, J., and Zhang, Y. 2018. Increasing the chlorine active sites in the micropores of biochar for improved mercury adsorption. Fuel 229: 60–67.

    Article  CAS  Google Scholar 

  2. Liu, H., Chang, L., Liu, W., et al. 2020. Advances in mercury removal from coal-fired flue gas by mineral adsorbents. Chemical Engineering Journal 379: 122263.

    Article  CAS  Google Scholar 

  3. Li, G., Wu, Q., Wang, S., et al. 2020. Promoting SO2 resistance of a CeO2-WO3/TiO2 catalyst for Hg0 oxidation via adjusting the basicity and acidity sites using a CuO doping method. Environmental Science and Technology 54 (3): 1889–1897.

    Article  CAS  Google Scholar 

  4. Hao, R., Luo, Y., Qian, Z., et al. 2020. Simultaneous removal of SO2, NO and Hg0 using an enhanced gas phase UV-AOP method. Science of the Total Environment 734: 139266.

    Article  CAS  Google Scholar 

  5. An, J., Lou, J., Meng, Q., et al. 2017. Non-thermal plasma injection-CeO2-WO3/TiO2 catalytic method for high-efficiency oxidation of elemental mercury in coal-fired flue gas. Chemical Engineering Journal 325: 708–714.

    Article  CAS  Google Scholar 

  6. Yang, J., Wang, Q., Zhou, J., et al. 2020. Electrochemical removal of gaseous elemental mercury in liquid phase with a novel foam titanium-based DSA anode. Separation and Purification Technology 250: 117162.

    Article  CAS  Google Scholar 

  7. Li, J., Xu, H., Liao, Y., et al. 2020. Atomically dispersed manganese on a carbon-based material for the capture of gaseous mercury: Mechanisms and environmental applications. Environmental Science and Technology 54 (8): 5249–5257.

    Article  CAS  Google Scholar 

  8. Ye, D., Wang, X., Wang, R., et al. 2021. Recent advances in MnO2-based adsorbents for mercury removal from coal-fired flue gas. Journal of Environmental Chemical Engineering 9 (5): 105993.

    Article  CAS  Google Scholar 

  9. Zhao, H., Ezeh, C.I., Yin, S., et al. 2020. MoO3-adjusted δ-MnO2 nanosheet for catalytic oxidation of Hg0 to Hg2+. Applied Catalysis, B: Environmental 263: 117829.

    Article  CAS  Google Scholar 

  10. Zhang, H., Wang, T., Liu, J., et al. 2020. Promotional effect of sulfur trioxide (SO3) on elemental mercury removal over Cu/ZSM-5 catalyst. Applied Surface Science 511: 145604.

    Article  CAS  Google Scholar 

  11. Ye, D., Wang, X., Wang, R., et al. 2022. Review of elemental mercury (Hg0) removal by CuO-based materials. Journal of Zhejiang University-SCIENCE A 23 (7): 505–526.

    Article  CAS  Google Scholar 

  12. Dong, L., Wang, H., Huang, Y., et al. 2021. Elemental mercury removal from coal-fired flue gas using recyclable magnetic Mn-Fe based attapulgite sorbent. Chemical Engineering Journal 407: 127182.

    Article  CAS  Google Scholar 

  13. Li, H., Zhang, J., Cao, Y., et al. 2020. Enhanced activity and SO2 resistance of Co-modified CeO2–TiO2 catalyst prepared by facile co-precipitation for elemental mercury removal in flue gas. Applied Organometallic Chemistry 34: e5463. 

    Article  CAS  Google Scholar 

  14. Ye, D., Wang, R., Wang, X., et al. 2022. Effects of synthesis methods on the physicochemical properties and Hg0 capture capability of MnO2–CeO2 mixed oxides. Applied Surface Science 578: 151998.

    Article  CAS  Google Scholar 

  15. Zhang, Z., Wu, J., Li, B., et al. 2019. Removal of elemental mercury from simulated flue gas by ZSM-5 modified with Mn-Fe mixed oxides. Chemical Engineering Journal 375: 121946.

    Article  CAS  Google Scholar 

  16. Ye, D., Gao, S., Wang, Y., et al. 2023. New insights into the morphological effects of MnOx–CeOx binary mixed oxides on Hg0 capture. Applied Surface Science 613: 156035.

    Article  CAS  Google Scholar 

  17. Wang, D., Peng, Y., Yang, Q., et al. 2019. NH3-SCR performance of WO3 blanketed CeO2 with different morphology: Balance of surface reducibility and acidity. Catalysis Today 332: 42–48.

    Article  CAS  Google Scholar 

  18. Zhang, X., Zhang, H., Song, X., et al. 2021. Co3O4-based catalysts derived from natural wood with hierarchical structure for elemental mercury oxidation. Journal of the Energy Institute 94: 285–293.

    Article  CAS  Google Scholar 

  19. Yang, L., Wu, J., Li, B., et al. 2021. Defective molybdenum disulfide nanosheet for elemental mercury capture in simulated flue gas. Journal of the Energy Institute 94: 120–128.

    Article  CAS  Google Scholar 

  20. Ye, D., Hu, Y., Jiang, Z., et al. 2023. Mechanistic investigation on Hg0 capture over MnOx adsorbents: Effects of the synthesis methods. Journal of Zhejiang University-SCIENCE A 24 (1): 80–90.

    Article  CAS  Google Scholar 

  21. Ye, D., Gao, S., Hu, Y., et al. 2023. Promotional effect of PVP-modification on Hg0 removal over CrOx monometallic oxide. Colloids and Surfaces A 676: 132219.

    Article  CAS  Google Scholar 

  22. Ye, D., Wang, R., Wang, X., et al. 2022. Improvement in the Hg0 removal performance of CeO2 by modifying with CuO. Applied Surface Science 579: 152200.

    Article  CAS  Google Scholar 

  23. Wang, R., Wang, Y., Liu, X., et al. 2022. Revealing insights into the mechanism of Hg0 removal over MnO2 hollow sphere adsorbents: Effect of calcination temperatures. Industrial and Engineering Chemistry Research 61: 18720–18728.

    Article  CAS  Google Scholar 

  24. Chalkidis, A., Jampaiah, D., Hartley, P.G., et al. 2019. Regenerable α-MnO2 nanotubes for elemental mercury removal from natural gas. Fuel Processing Technology 193: 317–327.

    Article  CAS  Google Scholar 

  25. Ye, D., Wang, X., Hu, Y., et al. 2022. Mechanistic study on the role of VOx in the acidity, oxidizability, and Hg0 capture capability of FeOx-VOx binary mixed oxides. Applied Surface Science 602: 154324.

    Article  CAS  Google Scholar 

  26. Liu, D., Zhang, Z., Luo, F., et al. 2020. Elemental mercury capture from simulated flue gas by graphite-phase carbon nitride. Energy & Fuels 34 (6): 6851–6861.

    Article  CAS  Google Scholar 

  27. Zhang, Z., Liu, J., Wang, Z., et al. 2021. Efficient capture of gaseous elemental mercury based on novel copper-based metal–organic frameworks. Fuel 289: 119791.

    Article  CAS  Google Scholar 

  28. Zhang, Z., Liu, J., Wang, Z., et al. 2021. Bimetallic Fe-Cu-based metal-organic frameworks as efficient adsorbents for gaseous elemental mercury removal. Industrial and Engineering Chemistry Research 60 (1): 781–789.

    Article  CAS  Google Scholar 

  29. Ma, W., Ye, D., and Wang, H. 2022. Experimental study on the elemental mercury removal performance and regeneration ability of CoOx–FeOx-modified ZSM-5 adsorbents. Applied Sciences 12 (8): 3769.

    Article  CAS  Google Scholar 

  30. Ye, D., Gao, S., Jiang, Z., et al. 2023. Revealing insights into the correlations between structure and performance of CrOx monometallic oxide for Hg0 capture. Journal of the Energy Institute 107: 101185.

    Article  CAS  Google Scholar 

  31. Ye, D., Wang, X., Wang, R., et al. 2022. Relationship between Hg0 capture performance and physicochemical properties of CeO2-CrOx mixed oxides. Journal of Environmental Chemical Engineering 10 (5): 108252.

    Article  CAS  Google Scholar 

  32. Mei, J., Wang, C., Kong, L., et al. 2019. Outstanding performance of recyclable amorphous MoS3 supported on TiO2 for capturing high concentrations of gaseous elemental mercury: Mechanism, kinetics, and application. Environmental Science and Technology 53 (8): 4480–4489.

    Article  CAS  Google Scholar 

  33. Mei, J., Wang, C., Kong, L., et al. 2020. Remarkable improvement of Ti incorporation on Hg0 capture from smelting flue gas by sulfurated γ-Fe2O3: Performance and mechanism. Journal of Hazardous Materials 381: 120967.

    Article  CAS  Google Scholar 

  34. Wang, C., Hu, Q., Zhang, Q., et al. 2020. Novel synergetic effect of Fe and W in FeWx/TiO2 on capturing high concentrations of gaseous Hg0 from smelting flue gas: Adsorption kinetics and structure-activity relationship. Industrial and Engineering Chemistry Research 59 (7): 2745–2753.

    Article  CAS  Google Scholar 

Download references

Funding

This work is supported by the Fundamental Research Funds in China Jiliang University, the Zhejiang Provincial Department of Education General Research Project in 2023 (No. Y202353660), and the Zhejiang Provincial Natural Science Foundation of China (No. LQ22E060003).

Author information

Authors and Affiliations

  1. College of Quality and Safety Engineering, China Jiliang University, Hangzhou, 310018, China

    Shujie Gao, Kai Zhu & Dong Ye

  2. Key Laboratory of Biomass Chemical Engineering of Ministry of Education, Institute of Industrial Ecology and Environment, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, 310027, China

    Xiaoxiang Wang

  3. Department of Electrical Engineering and Electronics, University of Liverpool, Liverpool, L69 3GJ, UK

    Yaolin Wang

  4. Ningbo Tech University, No. 1 Qianhu South Road, Ningbo, 315100, China

    Changxing Hu

Authors
  1. Shujie Gao
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Xiaoxiang Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yaolin Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Kai Zhu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Changxing Hu
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Dong Ye
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

SG: investigation, validation, writing—original draft. YH: Investigation. ZJ: Investigation. XW: Validation. YW: Writing—review and editing. HW: Writing—review and editing. DY: Conceptualization, writing—review and editing, supervision.

Corresponding author

Correspondence to Dong Ye.

Ethics declarations

Conflict of interest

The authors declare that there is no competing interest.

Additional information

Publisher's Note

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

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (DOCX 29 KB)

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Gao, S., Wang, X., Wang, Y. et al. Mechanistic investigation on the Hg0 elimination ability of MnOx–CeOx nanorod adsorbents: effects of Mn/Ce molar ratio. Waste Dispos. Sustain. Energy (2024). https://doi.org/10.1007/s42768-023-00181-z

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s42768-023-00181-z

Keywords

Search

Navigation