Abstract
The current research article addresses the ability of heterogeneous Amberlyst 16 to catalyze the esterification reaction between acetic acid and ethanol, as well as the modelling of the chemical kinetics. The effects of pretreatment, reaction temperature, ethanol-to-acid molar ratio, catalyst dose and time on the rate of ethyl acetate production were systematically investigated. Furthermore, the recyclability of Amberlyst 16 to accelerate the esterification reaction was carefully examined. Amberlyst 16 was found to be a suitable catalyst for this process giving a final acid conversion of 93.3% using reaction temperature of 60 °C, ethanol-to-acid molar ratio of 6:1, catalyst dose of 10 wt% and 200 rpm stirring intensity after 1680 min, and can be successfully utilized for 4 recycle tests. A detailed kinetic model has been developed and tested for the described process, which was based on a four-step mechanism equivalent to the Langmuir–Hinshelwood one. It was found that that the esterification reaction occurred between ethoxide ions and acetic acid chemisorbed on the neighboring catalytic surfaces, whereas, the overall process was controlled by the surface reaction step.
Similar content being viewed by others
References
Gaspar AB, Esteves AML, Mendes FMT, Barbosa FG, Appel LG (2009) Chemicals from ethanol—the ethyl acetate one-pot synthesis. Appl Catal A 1–2:109
Nielsen M, Junge H, Kammer A, Beller M (2012) Towards a green process for bulk-scale synthesis of ethyl acetate: efficient acceptorless dehydrogenation of ethanol. Angew Chem Int Ed 23:5711
PRWEB (2015) Global ETAC production to exceed 3.5 Mln Tonnes in 2015. http://www.prweb.com/releases/2014/02/prweb11619424.htm. Accessed 21 August 2018
Merchant Research & Consulting Ltd. Ethyl Acetate (ETAC) (2016) World market outlook and forecast up to 2020. https://mcgroup.co.uk/researches/ethyl-acetate-etac. Accessed 21 August 2018
Inui K, Kurabayashi T, Sato S (2002) Direct synthesis of ethyl acetate from ethanol over Cu-Zn-Zr-Al-O catalyst. Appl Catal A 1–2:53
Inui K, Kurabayashi T, Sato S (2002) Direct synthesis of ethyl acetate from ethanol carried out under pressure. J Catal 212(2):207
Manayil JC, Inocencio CVM, Lee AF, Wilson K (2016) Mesoporous sulfonic acid silicas for pyrolysis bio-oil upgrading via acetic acid esterification. Green Chem 18:1387
Bennett JA, Parlett CMA, Isaacs MA, Durndell LJ, Olivi L, Lee AF, Wilson K (2017) Acetic acid ketonization over Fe3O4/SiO2 for pyrolysis bio-oil upgrading. ChemCatChem 9(9):1648
Rönnback R, Salmi T, Vuori A, Haario H, Lehtonen J, Sundqvist A, Tirronen E (1997) Development of a kinetic model for the esterification of acetic acid with methanol in the presence of a homogeneous acid catalyst. Chem Eng Sci 52(19):3369
Mäki-Arvela P, Salmi T, Sundell M, Ekman K, Peltonen R, Lehtonen J (1999) Comparison of polyvinylbenzene and polyolefin supported sulphonic acid catalysts in the esterification of acetic acid. Appl Catal A 184(1):25
Jafar JJ, Budd PM, Hughes R (2002) Enhancement of esterification reaction yield using zeolite A vapour permeation membrane. J Membr Sci 199(1–2):117
Marchetti JM, Errazu AF (2008) Esterification of free fatty acids using sulfuric acid as catalyst in the presence of triglycerides. Biomass Bioenerg 32(9):892
Marchetti JM, Pedernera MN, Schbib NS (2011) Production of biodiesel from acid oil using sulfuric acid as catalyst: kinetics study. Int J Low-Carbon Technol 6(1):38
Avhad MR, Marchetti JM (2016) Innovation in solid heterogeneous catalysis for the generation of economically viable and ecofriendly biodiesel: a review. Catal Rev Sci Eng 58(2):157
Marchetti JM, Errazu AF (2008) Comparison of different heterogeneous catalysts and different alcohols for the esterification reaction of oleic acid. Fuel 87(15–16):3477
Ilgen O (2014) Investigation of reaction parameters, kinetics and mechanism of oleic acid esterification with methanol by using Amberlyst 46 as a catalyst. Fuel Process Technol 124:134
Tsai Y-T, H-m Lin, Lee M-J (2011) Kinetics behavior of esterification of acetic acid with methanol over Amberlyst 36. Chem Eng J 171(3):1367
Jermy BR, Pandurangan A (2005) A highly efficient catalyst for the esterification of acetic acid using n-butyl alcohol. J Mol Catal A Chem 237(1–2):146
Miao S, Shanks BH (2011) Mechanism of acetic acid esterification over sulfonic acid-functionalized mesoporous silica. J Catal 279(1):136
Peters TA, Benes NE, Holmen A, Keurentjes JTF (2006) Comparison of commercial solid acid catalysts for the esterification of acetic acid with butanol. Appl Catal A 297(2):182
Corma A, Garcia H, Iborra S, Primo J (1989) Modified faujasite zeolites as catalysts in organic reactions: esterification of carboxylic acids in the presence of HY zeolites. J Catal 120(1):78
Verhoef MJ, Kooyman PJ, Peters JA, van Bekkum H (1999) A study on the stability of MCM-41-supported heteropoly acids under liquid- and gas-phase esterification conditions. Micropor Mesopor Mater 27(2–3):365
Izci A, Bodur F (2007) Liquid-phase esterification of acetic acid with isobutanol catalyzed by ion-exchange resins. React Funct Polym 67(12):1458
de la Iglesia Ó, Mallada R, Menéndez M, Coronas J (2007) Continuous zeolite membrane reactor for esterification of ethanol and acetic acid. Chem Eng J 131(1–3):35
Pöpken T, Götze L, Gmehling J (2000) Reaction kinetics and chemical equilibrium of homogeneously and heterogeneously catalyzed acetic acid esterification with methanol and methyl acetate hydrolysis. Ind Eng Chem Res 39(7):2601
Gangadwala J, Mankar S, Mahajani S, Kienle A, Stein E (2003) Esterification of acetic acid with butanol in the presence of ion-exchange resins as catalysts. Ind Eng Chem Res 42(10):2146
Hykkerud A, Marchetti JM (2016) Esterification of oleic acid with ethanol in the presence of Amberlyst 15. Biomass Bioenerg 95:40
Avhad MR, Sánchez M, Peña E, Bouaid A, Martínez M, Aracil J, Marchetti JM (2016) Renewable production of value-added jojobyl alcohols and biodiesel using a naturally-derived heterogeneous green catalyst. Fuel 179:332
Tesser R, Casale L, Verde D, Di Serio M, Santacesaria E (2010) Kinetics and modeling of fatty acids esterification on acid exchange resins. Chem Eng J 157(2–3):539
Özbay N, Oktar N, Tapan NA (2008) Esterification of free fatty acids in waste cooking oils (WCO): role of ion-exchange resins. Fuel 87(10–11):1789
Leveneur S, Murzin DY, Salmi T, Mikkola J-P, Kumar N, Eränen K, Estel L (2009) Synthesis of peroxypropionic acid and hydrogen peroxide over heterogeneous catalysts. Chem Eng J 147:323
Acknowledgement
The authors would like to express their gratitude to the Norwegian University of Life Sciences (Project No. 1301051406) for the financial support.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare no competing financial interests.
Rights and permissions
About this article
Cite this article
Avhad, M.R., Osborg, M.V. & Marchetti, J.M. Reusable Amberlyst 16 catalyst for acetic acid esterification relevant for pyrolysis bio-oil upgrading process. Reac Kinet Mech Cat 126, 181–197 (2019). https://doi.org/10.1007/s11144-018-1487-9
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11144-018-1487-9