Enhanced Catalytic Activity of Nano-Fe2O3–MCM-48–SO4 as a Green Catalyst for the Esterification of Acetic Acid with Methanol

  • Navdeep Sharma
  • Disha Guliani
  • Kamalpreet Kaur
  • Anoop Verma
  • Amit Sobti
  • Amrit Pal ToorEmail author
Research Paper
Part of the following topical collections:
  1. Chemistry


Coupling of sulphated iron oxide with MCM-48 was carried out to prepare an efficient heterogeneous catalyst for the esterification reaction of acetic acid with methanol to produce methyl acetate as desired product. The prepared catalyst has shown a remarkable acid conversion of about 90% under optimized reaction conditions, which has resulted in an approximate 71% enhancement in catalyst activity using Fe2O3–MCM-48–SO4 catalyst over bare MCM-48. The effect of various reaction parameters like calcination temperature and time, amount of metal oxide and active species, catalyst loading and reaction temperature were also studied to optimize the catalytic activity of Fe2O3–MCM-48–SO4. The prepared catalyst was characterized using SEM–EDS, FT-IR, XRD and BET techniques. In addition, a detailed kinetics of esterification reaction has been carried out and a possible reaction pathway is also proposed.


Sulphated iron oxide Esterification MCM-48 Acetic acid Methanol Kinetics 



Financial support received from TEQIP-III, DST PURSE Grant-II of Dr. SSB University Institute of Chemical Engineering and Technology, Panjab University, Chandigarh, is gratefully acknowledged.


  1. Battiston CSZ, Ficanha AMM, Levandoski KLD, da Silva BA, Battiston S, Dallago RM, Mignoni ML (2017) Immobilization of lipase on mesoporous molecular sieve MCM-48 obtained using ionic solid as a structure director and esterification reaction on solvent free. Quim Nova 40:293–298Google Scholar
  2. Castillo MLG, Herrera HA, Cervantes AT, Acosta DR, Castillo PS, De la Funte AM, Rodriguez AV (2002) The effect of sulfate ion on the synthesis and stability of mesoporous materials. Stud Surf Sci Catal 142:1039–1046CrossRefGoogle Scholar
  3. Chen CL, Cheng S, Lin HP, Wong ST, Mou CY (2001) Sulfated zirconia catalyst supported on MCM-41 mesoporous molecular sieve. Appl Catal A Gen 215:21–30CrossRefGoogle Scholar
  4. Choi S, Wang Y, Nie Z, Liu J, Peden CHF (2000) Cs-substituted tungstophosporic acid salt supported on mesoporous silica. Catal Today 55:117–124CrossRefGoogle Scholar
  5. Dong C, Tian B (1999) Studies on preparation and emulsifying properties of guar galactomannan ester of palmitic acid. J Appl Polym Sci 72(5):639–645CrossRefGoogle Scholar
  6. Guliani D, Kaur K, Singh N, Sobti A, Toor AP (2019) Catalytic performance of sulfate-grafted graphene oxide for esterification of acetic acid with methanol. Chem Eng Commun 206(5):592–604CrossRefGoogle Scholar
  7. Hoffmann F, Cornelius M, Morell J, Froba M (2006) Silica based mesoporous organic-inorganic hybrid materials. Angew Chem Int Ed 45:3216–3251CrossRefGoogle Scholar
  8. JagadeeshBabu PE, Sandesh K, Saidutta MB (2011) Kinetics of esterification of acetic acid with methanol in the presence of ion exchange resin catalysts. Ind Eng Chem Res 50:7155–7160CrossRefGoogle Scholar
  9. Jiang L, Wang L, Zhang J (2010) A direct route for the synthesis of nanometer sized Bi2WO6 particles loaded on a spherical MCM-48 mesoporous molecular sieve. Chem Commun 46:8067–8069CrossRefGoogle Scholar
  10. Kaur K, Wanchoo RK, Toor AP (2015) Sulfated iron oxide: a proficient catalyst for esterification of butanoic acid with glycerol. Ind Eng Chem Res 54(13):3285–3292CrossRefGoogle Scholar
  11. Kaur K, Wanchoo RK, Toor AP (2016) Facile synthesis of tributyrin catalyzed by versatile sulfated iron oxide: reaction pathway and kinetic evaluation. Ind Eng Chem Res 55(9):2534–2542CrossRefGoogle Scholar
  12. Kaur K, Wanchoo RK, Toor AP (2017) Elementary transformation of glycerol to trivalerin: design of an experimental approach. ACS Sustain Chem Eng 5(1):802–808CrossRefGoogle Scholar
  13. Kefayati H, Golshekan M, Shariati S, Bagheri M (2015) Fe3O4@MCM-48-SO3H: an efficient magnetically separable nanocatalyst for the synthesis of benzo[f]chromeno[2,3-d]pyrimidinones. Chin J Catal 36:572–578CrossRefGoogle Scholar
  14. Kim JM, Kim SK, Ryoo R (1998) Synthesis of MCM-48 single crystals. Chem Commun (2):259–260CrossRefGoogle Scholar
  15. Labrecque LV, Kumar RA, Dave V, Gross RA, McCarthy SP (1997) Citrate esters as plasticizers for poly (lactic acid). J Appl Polym Sci 66(8):1507–1513CrossRefGoogle Scholar
  16. Maneesuwan H, Longloilert R, Chaisuwan T, Wongkasemjit S (2013) Synthesis and characterization of Fe–Ce–MCM-48 from silatrane precursor via sol–gel process. Mater Lett 94:65–68CrossRefGoogle Scholar
  17. Marcelli T, Hammar P, Himo F (2008) Phosphoric acid catalyzed enantio selective transfer hydrogenation of imines: a density functional theory study of reaction mechanism and the origins of enantioselectivity. Chem Eur J14:8562–8571CrossRefGoogle Scholar
  18. Marchetti JM, Errazu AF (2008) Esterification of free fatty acids using sulfuric acid as catalyst in the presence of triglycerides. Biomass Bioenergy 32:892–895CrossRefGoogle Scholar
  19. Miao S, Shanks BH (2011) Mechanism of acetic acid esterification over sulfonic acid-functionalized mesoporous silica. J Catal 279:136–143CrossRefGoogle Scholar
  20. Miller DL, Samsel EP, Cobler JG (1961) Determination of acrylate and maleate esters in polymers by combined zeisel and gas chromatographic analysis. Anal Chem 33(6):677–680CrossRefGoogle Scholar
  21. Mishra MK, Liu S, Kellogg DS (2013) U.S. Patent No. 8,541,401. Washington, DC: U.S. Patent and Trademark OfficeGoogle Scholar
  22. Peng R, Zhao D, Dimitrijevic NM, Rajh T, Koodali RT (2012) Room temperature synthesis of Ti–MCM-48 and Ti–MCM-41 mesoporous materials and their performance on photocatalytic splitting of water. J Phys Chem C116:1605–1613Google Scholar
  23. Peng R, Wu CM, Baltrusaitis J, Dimitrijevic NM, Rajh T, Koodali RT (2013) Ultra-stable CdS incorporated Ti–MCM-48 mesoporous materials for efficient photocatalytic decomposition of water under visible light illumination. Chem Commun 49:3221–3223CrossRefGoogle Scholar
  24. Pires LHO, de Oliveira AN, Monteiro Jr OV, Angélica RS, da Costa CEF, Zamian JR et al (2014) Esterification of a waste produced from the palm oil industry over 12-tungstophosphoric acid supported on kaolin waste and mesoporous materials. Appl Catal B Environ 160–161:122–128CrossRefGoogle Scholar
  25. Sakakibara S, Shimonishi Y, Kishida Y, Okada M, Sugihara H (1967) Use of anhydrous hydrogen fluoride in peptide synthesis—I behavior of various protective groups in anhydrous hydrogen fluoride. Bull Chem Soc Jpn 40:2164–2167CrossRefGoogle Scholar
  26. Sakthivel A, Komura K, Sugi Y (2008) MCM-48 supported tungstophosphoric acid: an efficient catalyst for the esterification of long-chain fatty acids and alcohols in supercritical carbon dioxide. Ind Eng Chem Res 47:2538–2544CrossRefGoogle Scholar
  27. Schumacher K, Grün M, Unger KK (1999) Novel synthesis of spherical MCM-48. Micropor Mesopor Mat 27:201–206CrossRefGoogle Scholar
  28. Singh S, Patel A (2014a) Selective green esterification and oxidation of glycerol over 12-tungstophosphoric acid anchored to MCM-48. Ind Eng Chem Res 53:14592–14600CrossRefGoogle Scholar
  29. Singh S, Patel A (2014b) 12-Tungstophoric acid supported on mesoporous molecular material: synthesis, characterization and performance in biodiesel production. J Clean Prod 72:46–56CrossRefGoogle Scholar
  30. Subramanian H, Nettleton EG, Budhi S, Koodali RT (2010) Baeyer–Villiger oxidation of cyclic ketones using Fe containing MCM-48 cubic mesoporous materials. J Mol Catal A Chem 330:66–72CrossRefGoogle Scholar
  31. Szűts A, Szabó-Révész P (2012) Sucrose esters as natural surfactants in drug delivery systems—a mini-review. Int J Pharm 433(1–2):1–9CrossRefGoogle Scholar
  32. Tsai YT, Lin H, Lee MJ (2011) Kinetics behavior of esterification of acetic acid with methanol over Amberlyst 36. Chem Eng J 171:1367–1372CrossRefGoogle Scholar
  33. Verma P, Kaur K, Toor AP, Wanchoo RK (2017) Esterification of acetic acid to methyl acetate using activated TiO2 under UV light irradiation at ambient temperature. J Photochem Photobiol A Chem 336:170–175CrossRefGoogle Scholar
  34. Wang LZ, Jiang L, Xu CC, Zhang JL (2012) Influence of Cr–MCM-48 and Cr–KIT-6 matrixes synthesized in alkaline and acidic conditions to the visible-light driven photocatalytic performance of loaded TiO2. J Phys Chem C116:16454–16460Google Scholar
  35. Wu HY, Zhang XL, Chen X, Chen Y, Zheng XC (2014) Preparation, characterization and catalytic properties of MCM-48 supported tungstophosphoric acid mesoporous materials for green synthesis of benzoic acid. J Solid State Chem 211:51–57CrossRefGoogle Scholar
  36. Yates TJV, Thomas JM, Fernandez JJ, Terasaki O, Ryoo R, Midgley PA (2006) Three-dimensional Real space crystallography of MCM-48 mesoporous silica revealed by scanning transmission electron tomography. Chem Phys Lett 418:540–543CrossRefGoogle Scholar
  37. Zhai D, Nie Y, Yue Y, He H, Hua W, Gao Z (2011) Esterification and transesterification on Fe2O3-doped sulfated tin oxide catalysts. Catal Commun 12:593–596CrossRefGoogle Scholar
  38. Zhan W, Guo Y, Wang Y, Liu X, Guo Y, Wang Y, Zhang Z, Lu G (2007) Synthesis of lanthanum doped MCM-48 molecular sieves and its catalytic performance for the oxidation of Styrene. J Phys Chem B 111:12103–12110CrossRefGoogle Scholar

Copyright information

© Shiraz University 2019

Authors and Affiliations

  • Navdeep Sharma
    • 1
  • Disha Guliani
    • 2
  • Kamalpreet Kaur
    • 1
  • Anoop Verma
    • 3
  • Amit Sobti
    • 1
  • Amrit Pal Toor
    • 1
    • 2
    Email author
  1. 1.Dr. SSB University Institute of Chemical Engineering and TechnologyPanjab UniversityChandigarhIndia
  2. 2.Energy Research CentrePanjab UniversityChandigarhIndia
  3. 3.School of Energy and EnvironmentThapar Institute of Engineering and Technology (Deemed to be University)PatialaIndia

Personalised recommendations