Applied Chemistry for Engineering (공업화학)

The Korean Society of Industrial and Engineering Chemistry (한국공업화학회)
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Improved Toluene Oxidation over Dealuminated Zeolite under Low Temperatures and Humid Conditions

제올라이트 내 탈알루미늄을 통한 저온 다습 환경의 톨루엔 산화 반응 증진 연구

  • Younghee Jang (Department of Environmental Energy Engineering, Graduate School of Kyonggi University) ;
  • Sung Su Kim (Department of Environmental Energy Engineering, Kyonggi University)
  • 장영희 (경기대학교 일반대학원 환경에너지공학과) ;
  • 김성수 (경기대학교 환경에너지공학과)
  • Received : 2025.05.21
  • Accepted : 2025.05.25
  • Published : 2025.08.10
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Abstract

In this study, Pd-based catalysts were prepared to enhance toluene (C7H8) removal efficiency under humid conditions, with a focus on identifying factors that promote oxidation activity at low temperatures. The physical property changes (crystal structure and surface area) induced by the dealumination of the support were examined using X-ray diffraction and Brunauer-Emmett-Teller analyses. Pd dispersion and redox characteristics were evaluated through CO-chemisorption, temperature-programmed reduction, and temperature-programmed reduction-oxidation analyses. The oxidation behavior of toluene was assessed by temperature-programmed desorption and Fourier transform infrared spectroscopy analyses, as well as by measuring toluene conversion under various humidity conditions. As a result, the modification of the support effectively promoted high Pd dispersion and oxygen reactivity, which were identified as the main factors responsible for enhancing toluene adsorption and oxidation at low temperatures.

본 연구에서는 수분이 존재하는 환경에서 톨루엔(toluene, C7H8) 제거 효율 향상을 위해 Pd계 촉매를 제조하였고, 저온에서 산화 활성을 향상시킬 수 있는 촉매 인자를 확인하고자 하였다. 탈알루미늄으로 인한 촉매의 물리적 특성변화(결정구조, 비표면적)는 X-ray diffraction, Brunauer-Emmett-Teller 분석을 통해 확인하였고, CO-chemisorption, temperature programmed reduction, temperature programmed reduction-oxidation 분석을 통하여 Pd의 분산정도와 redox 특성을 조사하였다. 톨루엔 산화 반응 특성은 temperature programmed desorption, Fourier transform infrared spectroscopy 분석 및 다양한 수분 조건에서의 톨루엔 전환율을 통해 평가하였다. 그 결과, 지지체 개질이 Pd의 고분산화와 산소 반응성 증진에 효과적이었으며, 이는 저온에서의 톨루엔 흡착 및 산화 반응을 향상시키는 주요한 촉매 인자임을 확인하였다.

Keywords

Acknowledgement

본 연구는 2022학년도 경기대학교 학술연구비(일반연구과제) 지원에 의하여 수행되었으며, 이에 감사드립니다.

References

  1. J. Kim, S. Jung, H. Kim, T. Jang, and K. Yoo, Evaluation of air quality with and without vapor recovery systems of Stage II, J. Korean Soc. Atmos. Environ., 29, 801-810 (2013). https://doi.org/10.5572/KOSAE.2013.29.6.801
  2. S. Shin, J. Park, J. Kim, P. Kim, C. Kim, K. Hwang, S. Park, J. Lee, J. Park, and J. Kim, Characteristics of volatile organic compounds distribution in downtown Ansan near industrial complexes, J. Environ. Anal. Health Toxicol., 27, 14-28 (2024). https://doi.org/10.36278/jeaht.27.1.14
  3. S. Kim, Y. Lee, K. Kang, and K. Yoo, The analysis on the VOCs contents and ozone production contribution of a marine paint in Korea, J. Korean Soc. Atmos. Environ., 30, 569-576 (2014). https://doi.org/10.5572/KOSAE.2014.30.6.569
  4. J. Cheong and S. You, Estimation on the contribution of VOCs and nitric oxides in creating photochemical ozone, J. Korean Soc. Environ. Eng., 32, 209-218 (2010).
  5. A. Clappier, P. Thunis, M. Beekmann, J. Putaud, and A. de Meij, Impact of SOx, NOx and NH3 emission reductions on PM 2.5 concentrations across Europe: Hints for future measure development, Environ. Int., 156, 106699 (2021).
  6. M. Song and H. Chun, Species and characteristics of volatile organic compounds emitted from an auto-repair painting workshop, Sci. Rep., 11, 16586 (2021). https://doi.org/10.1038/s41598-021-96163-4
  7. D. van der Vaart, E. Marchand, and A. Bagely-Pride, Thermal and catalytic incineration of volatile organic compounds, Crit. Rev. Environ. Sci. Technol., 24, 203-236 (1994). https://doi.org/10.1080/10643389409388466
  8. C. Yang, G. Miao, Y. Pi, Q. Xia, J. Wu, Z. Li, and J. Xiao, Abatement of various types of VOCs by adsorption/catalytic oxidation: A review, Chem. Eng. J., 370, 1128-1153 (2019). https://doi.org/10.1016/j.cej.2019.03.232
  9. H. Kim, H. Kim, J. Kim, J. Kim, S. Kang, J. Ryu, N. Park, D. Yun, and J. Bae, Noble-metal-based catalytic oxidation technology trends for volatile organic compound (VOC) removal, Catalysts, 12, 63 (2022). https://doi.org/10.3390/catal12010063
  10. M. Meena, P. Sonigra, and G. Yadav, Biological-based methods for the removal of volatile organic compounds (VOCs) and heavy metals, Environ. Sci. Pollut. Res. Int., 28, 2485-2508 (2021). https://doi.org/10.1007/s11356-020-11112-4
  11. Y. Xie, S. Lyu, Y. Zhang, and C. Cai, Adsorption and degradation of volatile organic compounds by metal–organic frameworks (MOFs): A review, Materials, 15, 7727 (2022).
  12. S. Chu, E. Wang, F. Feng, C. Zhang, J. Jiang, Q. Zhang, F. Wang, L. Bing, G. Wang, and D. Han, A review of noble metal catalysts for catalytic removal of VOCs, Catalysts, 12, 1543 (2022). https://doi.org/10.3390/catal12121543
  13. J. Liu, Y. Wang, Z. Dai, C. Q. Jia, L. Yang, J. Liu, Y. Chen, L. Yao, B. Wang, W. Huang, and W. Jiang, Recent advances in zeolite-based catalysts for volatile organic compounds decontamination by thermal catalytic oxidation, Sep. Purif. Technol., 330, 125339 (2024). https://doi.org/10.1016/j.seppur.2023.125339
  14. J. Li, Y. Liu, T. Zhang, and C. Tang, Advances in catalytic oxidation of volatile organic compounds, Front. Mater., 7, 595667 (2020). https://doi.org/10.3389/fmats.2020.595667
  15. R. Zhao, H. Wang, D. Zhao, R. Liu, J. Fu, Y. Zhang, and H. Ding, Review on catalytic oxidatioon of VOCs at ambient temperature, Mol. Sci., 23, 13739 (2022). https://doi.org/10.3390/ijms232213739
  16. Z. Wang, J. Pei, and J. Zhang, Catalytic oxidization of indoor formaldehyde at room temperature - Effect of operation conditions, Build. Environ., 65, 49-57 (2013). https://doi.org/10.1016/j.buildenv.2013.03.007
  17. Y. Huang, L. Zhang, J. Liu, X. Wang, and Q. Chen, Hydrophobic USY zeolite for VOC adsorption under humid conditions: Effect of Si/Al ratio, Sustain. Environ. Res., 33, 173 (2023).
  18. Y. Li, Y. Ren, J. He, H. Xiao, and J. Li, Recent advances of the effect of H2O on VOC oxidation over catalysts: Influencing factors, inhibition/promotion mechanisms, and water resistance strategies, Environ. Sci. Technol., 59, 1034-1059 (2025). https://doi.org/10.1021/acs.est.4c08745
  19. X. Li, L. Wang, Q. Xia, Z. Liu, and Z. Li, Catalytic oxidation of toluene over copper and manganese based catalysts: Effect of water vapor, Catal. Commun., 14, 15-19 (2011). https://doi.org/10.1016/j.catcom.2011.07.003
  20. H. Yang, C. Ma, G. Wang, Y. Sun, J. Cheng, Z. Zhang, X. Zhang, and Z. Hao, Fluorine-enhanced Pt/ZSM-5 catalysts for low-temperature oxidation of ethylene, Catal. Sci. Technol., 8, 1988-1996 (2018). https://doi.org/10.1039/C8CY00130H
  21. Y. Jang, Y. Noh, S. Lee, and S. Kim, A study on the modification of NH4+ Y-zeolite for improving adsorption/desorption performance of benzene, Clean Technol., 25, 33-39 (2019).
  22. D. Li, L. Wang, Y. Lu, H. Deng, Z. Zhang, Y. Wang, Y. Ma, T. Pan, Q. Zhao, Y. Shan, X. Shi, J. Ma, and H. He, New insights into the catalytic mechanism of VOCs abatement over Pt/Beta with active sites regulated by zeolite acidity, Appl. Catal. B Environ., 334, 122811 (2023). https://doi.org/10.1016/j.apcatb.2023.122811
  23. Y. Jang, S. Lee, and S. Kim, Effect of a modified 13X zeolite support in Pd-based catalysts for hydrogen oxidation at room temperature, RSC Adv., 11, 38047-38053 (2021). https://doi.org/10.1039/D1RA06395B
  24. T. Zhang, J. Shi, J. Liu, D. Wang, Z. Zhao, K. Cheng, and J. Li, Enhanced hydrothermal stability of Cu-ZSM-5 catalyst via surface modification in the selective catalytic reduction of NO with NH3, Appl. Surf. Sci., 1, 186-195 (2016).
  25. J. Zhang, C. Rao, H. Peng, C. Peng, L. Zhang, X. Xu, W. Liu, Z. Wang, N. Zhang, and X. Wang, Enhanced toluene combustion performance over Pt loaded hierarchical porous MOR zeolite, Chem. Eng. J., 334, 10-18 (2018). https://doi.org/10.1016/j.cej.2017.10.017
  26. T. Kim, P. Balla, D. Shin, Y. Song, and S. Kim, Oxygen removal performance of M/γ-Al2O3 catalyst through H2-O2 recombination reaction and the effect of oxygen vacancies on the catalyst, J. Hydrogen New Energy, 34, 535-548 (2023). https://doi.org/10.7316/JHNE.2023.34.5.535
  27. M. Nielsen, A. Hafreager, R. Y. Brogaard, K. De Wispelaere, H. Falsig, P. Beato, V. Van Speybroeck, and S. Svelle, Collective action of water molecules in zeolite dealumination, Catal. Sci. Technol., 9, 5716-5724 (2019).
  28. D. Yang, S. Fu, S. Huang, W. Deng, Y. Wang, L. Guo, and T. Ishihara, The preparation of hierarchical Pt/ZSM-5 catalysts and their performance for toluene catalytic combustion, Micropor. Mesopor. Mater., 296, 109802 (2020). https://doi.org/10.1016/j.micromeso.2019.109802
  29. M. Liang, X. Zhu, and W. Ma, The propylene oxide rearrangement catalyzed by the lewis acid sites of zsm-5 catalyst with controllable surface acidity, Catal. Lett., 149, 942-949 (2019) https://doi.org/10.1007/s10562-019-02687-w