10.57647/ijc.2026.1603.23

A Novel Solid Acid Catalyst for the Esterification Reaction of n-butanol and Acetic Acid: Sulfated Ceria and Amorphous Silica

Show Details XML PDF
  • Kum-Hyok Song1,
  • Myong Yun1,
  • Un-Ha Kim*1,
  • Se-Ok Pak1,
  1. Faculty of Chemistry, Kim Il Sung University, Pyongyang, Democratic People’s Republic of Korea

Received: 2026-01-13

Revised: 2026-04-02

Accepted: 2026-04-16

Published Online: 2026-07-28

Copyright (c) 2025 Ali Sobhani-Nasaba, Mohammad Eghbali-Arani, Seyed Mostafa Hosseinpour-Mashkani, Farhad Ahmadi, Mehdi Rahimi-Nasrabadi, Vahid Ameri (Author)

Creative Commons License

This work is licensed under a Creative Commons Attribution 4.0 International License.

How to Cite

Song, K.-H., Yun, M., Kim, U.-H., & Pak, S.-O. (2026). A Novel Solid Acid Catalyst for the Esterification Reaction of n-butanol and Acetic Acid: Sulfated Ceria and Amorphous Silica. Iranian Journal of Catalysis, 2026. https://doi.org/10.57647/ijc.2026.1603.23
Crossref
Scopus
Google Scholar
Europe PMC

PDF views: 8

Abstract

A novel solid acid catalyst based on ceria and amorphous silica was successfully prepared by coprecipitation-impregnation method with ceric sulfate and sodium metasilicate. This research aimed to examine the availability of sulfated ceria and amorphous silica catalyst for the synthesis of n-butyl acetate. The catalyst was characterized by means of XRD, N2 sorption, SEM, Hammett Indicator titration, FT-IR, TG-DTA. The experimental results show that this catalyst has the high catalytic activity and reusability because of the strong acidity and good thermal stability of sulfated ceria. With the catalyst, the maximum conversion of acetic acid was obtained as 97.3% under the optimum conditions (molar ratio of n-butanol to acetic acid 1.6, catalyst amount 2.3 wt%, reaction temperature 120 °C, reaction time 120 min). Moreover, even at temperatures higher than 120 °C, any by-products were not formed and the conversion of acetic acid was up to 90% for five cycles. We confirmed that sulfated ceria and amorphous silica-based solid acid catalyst could be used effectively for the esterification reaction.

Highlights

·       A novel solid acid catalyst based on ceria and amorphous silica was prepared.

·       Sulfated ceria accounts for acidity of the prepared catalyst.

·       In the esterification reaction of n-butanol with acetic acid, the maximum conversion of acetic acid reached 97.3% under the optimum conditions.

·       For five cycles of the catalyst, the conversion of acetic acid reached more than 90%. 

Keywords

  • Ceria,
  • Silica,
  • Solid acid,
  • Esterification
PDF

References

  1. H. Pan, Q. Xia, Y. Wang, Z. Shen, H. Huang, Z. Ge, X. Li, J. He, X. Wang, L. Li, Y. Wang, Recent advances in biodiesel production using functional carbon materials as acid/base catalysts, Fuel Process. Technol. 237 (2022) 107421. https://doi.org/10.1016/j.fuproc.2022.10742
  2. N. S. Lani, N. Ngadi, I. Mohammed Inuwa, L. Anako Opotu, Z. Y. Zakaria, S. Haron, A cleaner approach with magnetically assisted reactor setup over CaO-zeolite/Fe₃O₄ catalyst in biodiesel production: evaluation of catalytic performance, reusability and life cycle assessment studies, J. Clean. Prod. 419 (2023) 138329. https://doi.org/10.1016/j.jclepro.2023.13832
  3. W. B. Widayatno, G. Guan, J. Rizkiana, X. Du, X. Hao, Z. Zhang, Selective catalytic conversion of bio-oil over high-silica zeolites, Bioresour. Technol. 179 (2015) 518-523. http://dx.doi.org/10.1016/j.biortech.2014.12.04
  4. J. Yu, J. Luo, Y. Zhang, J. Cao, C.-C. Chang, R. J. Gorte, W. Fan, An examination of alkali-exchanged BEA zeolites as possible Lewis-acid catalysts, Microporous Mesoporous Mater. 225 (2016) 472-481. http://dx.doi.org/10.1016/j.micromeso.2016.01.03
  5. V. S. Marakatti, A. B. Halgeri, G. V. Shanbhag, Metal ion-exchanged zeolites as solid acid catalysts for the green synthesis of nopol from Prins reaction, Catal. Sci. Technol. 4 (2014) 4065-4074. https://doi.org/10.1039/c4cy00596
  6. N. Rinaldi, N. D. E. Purba, A. Kristiani, E. Agustian, R. R. Widjaya, A. A. Dwiatmoko, Bentonite pillarization using sonication in a solid acid catalyst preparation for the oleic acid esterification reaction, Catal. Commun. 174 (2023) 106598. https://doi.org/10.1016/j.catcom.2022.10659
  7. H. Rahimzadeh, M. Tabatabaei, M. Aghbashlo, H. K. S. Panahi, A. Rashidi, S. A. H. Goli, M. Mostafaei, M. Ardjmand, A. S. Nizami, Potential of acid-activated bentonite and SO₃H-functionalized MWCNTs for biodiesel production from residual olive oil under biorefinery scheme, Front. Energy Res. 6 (2018) 1–10. https://doi.org/10.3389/fenrg.2018.0013
  8. G. Nagendrappa, R. R. Chowreddy, Organic Reactions Using Clay and Clay-Supported Catalysts: A Survey of Recent Literature, Catal. Surv. Asia 25 (2021). https://doi.org/10.1007/s10563-021-09333-
  9. X. Guo, F. Guo, Y. Li, Z. Zheng, Z. Xing, Z. Zhu, T. Liu, X. Zhang, Y. Jin, Dehydration of D-xylose into furfural over bimetallic salts of heteropolyacid in DMSO/H₂O mixture, Appl. Catal. A 558 (2018) 18–25. https://doi.org/10.1016/j.apcata.2018.03.02
  10. F. Huang, Y. Su, Y. Tao, W. Sun, W. Wang, Preparation of 5-hydroxymethylfurfural from glucose catalyzed by silica supported phosphotungstic acid heterogeneous catalyst, Fuel 226 (2018) 417-422. https://doi.org/10.1016/j.fuel.2018.03.193
  11. X. Cao, J. Ren, C. Xu, K. Zhang, J. Lan, Preparation, Characterization of Dawson-type Heteropoly Acid Cerium (III) Salt and Its Catalytic Performance on the Synthesis of n-Butyl Acetate, Chin. J. Chem. Eng. 21 (2013) 500-506. https://doi.org/10.1016/S1004-9541(13)60493-0
  12. S. M. Ibrahim, A. Mustafa, Synthesis and characterization of new bifunctional SnZrSi oxide catalysts for biodiesel production, J. Mol. Liq. 354 (2022) 118811. https://doi.org/10.1016/j.molliq.2022.118811
  13. J. Wang, H. Pan, A. Wang, X. Tian, X. Wu, Y. Wang, Synthesis and characterization of S₂O₈²⁻/ZnFexAl₂₋xO₄ solid acid catalysts for the esterification of acetic acid with n-butanol, Catal. Commun. 62 (2015) 29-33. http://dx.doi.org/10.1016/j.catcom.2015.01.009
  14. F. Yang, Y. Li, Q. Zhang, X. F. Sun, H. X. Fan, N. Xu, Selective conversion of cotton cellulose to glucose and 5-hydroxymethyl furfural with SO₄²⁻/MxOy solid superacid catalyst, Carbohydr. Polym. 131 (2015) 9-14. http://dx.doi.org/10.1016/j.carbpol.2015.05.036
  15. X. Li, S. Ren, L. Liu, X. Xing, L. Chen, J. Li, J. Yang, Q. Liu, Superior PbO-resistance of CeO₂/ZrO₂ catalyst promoted by solid superacid SO₄²⁻/ZrO₂ for selective catalytic reduction of NOx with NH₃, Fuel 332 (2023) 126103. https://doi.org/10.1016/j.fuel.2022.126103
  16. S. Cai, T. Xu, P. Wang, L. Han, S. Impeng, Y. Li, Self-protected CeO₂-SnO₂@SO₄²⁻/TiO₂ catalysts with extraordinary resistance to alkali and heavy metals for NOx reduction, Environ. Sci. Technol. 54 (2020) 12752–12760. https://doi.org/10.1021/acs.est.0c04911
  17. Z. Han, X. Li, X. Wang, Y. Gao, S. Yang, L. Song, Insight into the promoting effect of support pretreatment with sulfate acid on selective catalytic reduction performance of CeO₂/ZrO₂ catalysts, J. Colloid Interface Sci. 608 (2022) 2718–2729. https://doi.org/10.1016/j.jcis.2021.10.191
  18. B. Zheng, L. Chen, L. He, H. Wang, H. Li, H. Zhang, S. Yang, Facile synthesis of chitosan-derived sulfonated solid acid catalysts for realizing highly effective production of biodiesel, Ind. Crops Prod. 210 (2024) 118058. https://doi.org/10.1016/j.indcrop.2024.118058
  19. Z. Xu, G. Zhang, K. Wang, Efficient conversion of biomass derivatives to furfural with a novel carbon-based solid acid catalyst, Catal. Commun. 175 (2023) 106608. https://doi.org/10.1016/j.catcom.2023.106608
  20. Y. Mao, J. Cheng, H. Guo, Y. Shao, L. Qian, W. Yang, Sulfamic acid–modified zeolitic imidazolate framework (ZIF-90) with synergetic Lewis and Brønsted acid sites for microalgal biodiesel production, Fuel 331 (2023) 125795. https://doi.org/10.1016/j.fuel.2022.125795
  21. T. Ma, C. Xu, C. Song, W. Li, G. Chen, Z. Yun, J. Qian, Sulfated zirconium metal-organic frameworks as highly efficient catalysts for the green synthesis of n-amyl acetate, Sustain. Chem. Pharm. 43 (2025) 101919. https://doi.org/10.1016/j.scp.2025.101919
  22. T. Ma, D. Liu, Z. Liu, J. Xu, Y. Dong, G. Chen, Z. Yun, 12-Tungstophosphoric acid-encapsulated metal-organic framework UiO-66: A promising catalyst for the esterification of acetic acid with n-butanol, J. Taiwan Inst. Chem. Eng. 133 (2022) 104277. https://doi.org/10.1016/j.jtice.2022.104277
  23. T. Ma, C. Song, H. Chen, M. Yin, C. Su, N. Guo, Y. Yao, M. Yu, Y. Wang, G. Chen, Z. Yun, Green catalysis for the production of n-butyl acetate over phosphotungstic acid-encapsulated metal-organic framework UiO-67 catalyst: Catalyst preparation, characterization and reaction kinetics, Sustain. Chem. Pharm. 37 (2024) 101389. https://doi.org/10.1016/j.scp.2023.101389
  24. B. Viswanadham, J. Pedada, N. Mameda, B. Putrakumar, Enhanced Catalytic Activity and Reusability of Porous Niobium Oxide for Esterification of Acetic Acid With Butanol, J. Chem. (2025). https://onlinelibrary.wiley.com/doi/10.1155/joch/8896509
  25. L. Hu, Y. Liu, M. Liu, P. Zhang, H. Cui, J. He, Enhanced esterification performance by SO₄²⁻/ZrO₂ anchored Nb₂O₅ nanotube, J. Ind. Eng. Chem. 129 (2023) 321-330. https://doi.org/10.1016/j.jiec.2023.08.046
  26. C. L. Chen, S. Cheng, H. P. Lin, S. T. Wong, C. Y. Mou, Sulfated zirconia catalyst supported on MCM-41 mesoporous molecular sieve, Appl. Catal. A 215 (2001) 21-30. https://doi.org/10.1016/S0926-860X(01)00504-X
  27. Q. H. Xia, K. Hidajat, S. Kawi, Effect of ZrO₂ loading on the structure, acidity, and catalytic activity of the SO₄²⁻/ZrO₂/MCM-41 acid catalyst, J. Catal. 205 (2002) 318-331. https://doi.org/10.1006/jcat.2001.3424
  28. T. Lei, J. S. Xu, Y. Tang, W. M. Hua, Z. Gao, New solid superacid catalysts for n-butane isomerization: γ-Al₂O₃ or SiO₂ supported sulfated zirconia, Appl. Catal. A 192 (2000) 181-188. https://doi.org/10.1016/S0926-860X(99)00404-4
  29. Y. Wang, Y. Gan, R. Whiting, G. Lu, Synthesis of sulfated titania supported on mesoporous silica using direct impregnation and its application in esterification of acetic acid and n-butanol, J. Solid State Chem. 182 (2009) 2530-2534. https://doi.org/10.1016/j.jssc.2009.07.003
  30. B. M. Reddy, P. M. Sreekanth, P. Lakshmanan, Sulfated zirconia as an efficient catalyst for organic synthesis and transformation reactions, J. Mol. Catal. A 237 (2005) 93-100. https://doi.org/10.1016/j.molcata.2005.04.039
  31. J. Wang, H. Pan, D. Meng, X. Wu, Y. Wang, X. Meng, Synthesis, characterization and catalytic performances of S₂O₈²⁻/Al-x wt%Ce–Zn–O solid acid catalysts, React. Kinet. Mech. Catal. 102 (2011) 331-341. https://doi.org/10.1007/s11144-010-0276-x
  32. X. Shi, Y. Wu, P. Li, H. Yi, M. Yang, G. Wang, Catalytic conversion of xylose to furfural over the solid acid SO₄²⁻/ZrO₂–Al₂O₃/SBA-15 catalysts, Carbohydr. Res. 346 (2011) 480-487. https://doi.org/10.1016/j.carres.2011.01.001
  33. X. Han, M. Bian, K. Liu, X. Yang, D. Zheng, X. Yang, Y. Zhang, Influence of Particle Size of CeO₂ Nanospheres Encapsulated in SBA-15 Mesopores on SO₂ Tolerance during NH₃-SCR Reaction, Catalysts 14 (2024) 151. https://doi.org/10.3390/catal14020151
  34. J. L. Ropero-Vega, A. Aldana-Pérez, R. Gómez, M. E. Nino-Gómez, Sulfated titania [TiO₂/SO₄²⁻]: A very active solid acid catalyst for the esterification of free fatty acids with ethanol, Appl. Catal. A 379 (2010) 24-29. https://doi.org/10.1016/j.apcata.2010.02.02
  35. H. H. Salam Al-Jaberi, U. Rashid, F. A. J. Al-Doghachi, G. Abdulkareem-Alsultan, Y. H. Taufiq-Yap, Synthesis of MnO-NiO-SO₄²⁻/ZrO₂ solid acid catalyst for methyl ester production from palm fatty acid distillate, Energy Convers. Manage. 139 (2017) 166-174. http://dx.doi.org/10.1016/j.enconman.2017.02.05