Abstract
In the present paper, the development of new heterogeneous catalytic processes to produce high commodity chemicals of industrial interest such as acetaldehyde, ethyl acetate, and pure hydrogen by bioethanol has been discussed. All the reactions were performed in a conventional packed bed tubular reactor and in a wide range of temperature 50–500°C, pressure 1–30 bar, and space time W/F = 0.1–100 g h mol−1. The aim of this research is to demonstrate that by varying properly the operative range of residence time and pressure, it is possible to obtain with high selectivity acetaldehyde or ethyl acetate from ethanol in a single reaction step. The performances of a series of commercial copper-based catalysts have been studied in the ethanol dehydrogenation/oxidative reforming reactions. In particular, very promising results have been obtained by using a commercial catalyst of copper/copper chromite containing barium chromite as a promoter. In a low range of residence time 0.1–1 g h mol−1 and at low pressure, very high performances in terms of ethanol conversion (60 %) and acetaldehyde selectivity (90 %) have been obtained. On the contrary, by operating at high residence time, at a pressure higher than 10 bar, and by feeding 25 cm3/min of a mixture of 6 % H2 in N2, a very high selectivity to ethyl acetate (98.9 %) was observed. The examined catalysts were characterized by using ex situ methods such as X-ray photoelectron spectroscopy and in situ EXAFS and FTIR with the aim to evaluate their physical properties and to correlate them with the catalysts' performances.
Similar content being viewed by others
References
Rass-Hansen J, Falsig H, Jørgensen B, Christensen CH (2007) Perspective bioethanol: fuel or feedstock. J Chem Technol Biotechnol 82:329–333. doi:10.1002/jctb.16645
Champagne P (2007) Resour Conserv Recycl 50:211–230
Lynd LR, Wyman CE, Gerngross TU (1999) Biotechnol Prog 15(5):777–793. doi:10.1021/bp990109e
Chladek P, Croiset E, Epling W, Hudgins RR (2007) Characterization of copper foam as catalytic material in ethanol dehydrogenation. Can J Chem Eng 85:917. doi:10.1002/cjce.5450850613
Colley SW, Tabatabaei J, Waugh KC, Wood MA (2005) J Catal 236:21–33
Inui K, Kurabayashi T, Sato S (2002) Appl Catal Gen 237(729):53–61
Inui K, Kurabayashi T, Sato S, Ichikawa N (2004) J Mol Catal 216(731):147–156
Inui K, Kurabayashi T, Sato S (2002) J Catal 212(732):207–215
Gaspar AB, Barbosa FG, Letichevsky S, Appel LG (2010) Appl Catal A: Gen 380(734):113–117
Colley SW, Fawcett CR, Sharif M, Tuck MWM, Watson DJ, Wood MA(2004) US 6, 809, 217 B1 October 6, Process for the preparation of ethyl acetate
Colley SW, Fawcett CR, Sharich M, Tuck M, Watson DJ, Wood MA et al. (2009) United States Patent 7,553,397, B1 June 30, process. 761
Colley SW, Fawcett CR, Sharich M, Tuck M, Watson DJ, Wood MA, Davy (1978) Process Tech., Republic of South Africa 2004/9535–18,7,05
Church JM, Joshi HK (1951) Acetaldehyde by dehydrogenation of ethyl alcohol. Ind Eng Chem 43:1804–1811
Franckaerts J, Froment GF (1964) Kinetic study of the dehydrogenation of ethanol. Chem Eng Sci 19:807–818
Carotenuto G, Di Serio M, Santacesaria E, Tesser R (2010) New process for the production of ethyl acetate and pure hydrogen from ethanol: Italian patent NA2010A000009; WO2011/104738A2 assigned to EUROCHEM Engineering
Carotenuto G, Di Serio M, Santacesaria E, Tesser R (2011) Production of pure hydrogen by ethanol dehydrogenation. OIL GAS European Magazine 2, ISSN 0342-562
Zhang M, Li G, Jiang H (2011) Catal Lett 141:1104–1110
Brooks AR, Clayton CR, Doss K, Lu YCJ (1986) Electrochem Soc 133:2459
Philip G, Harrison et al (2000) Chem Mater 12:3113–3122
Llorca J et al (2004) J Catal 227:556–560
Millar GJ et al (1991) J Chem Soc Faraday Trans 1(87):2785
Borrello E (1967) J Phys Chem 71:2938
Yee A, Morrison SJ, Idriss H (1999) J Catal 186:279
Deacon GB, Phillips RJ (1980) J Coord Chem Rev 33:227
Idriss H, Diagne C, Hindermann JP, Kiennemann A, Barteau MA (1995) J Catal 155:219
Kumar A, Mukasyan AS, Wolf EE (2011) App Catal 401(1–2):20–28
Santacesaria E, Carotenuto G, Tesser R, Di Serio M (2012) Ethanol dehydrogenation to ethyl acetate by using copper and copper chromite catalysts. Chem Eng J 179:209–220
Fujita SI, Iwasa N, Tani H, Nomura W, Arai M, Takezawa N (2001) Dehydrogenation of ethanol over Cu/ZnO catalysts prepared from various coprecipitated precursors. React Kinet Catal Lett 73:367–372
Carotenuto G, Tesser R, Di Serio M, Santacesaria E (2012) Kinetic study of ethanol dehydrogenation to ethyl acetate promoted by a copper/copper-chromite based catalyst. Catal Today. doi:10.1016/j.cattod.2012.02.054
Khasin AA, Yur’eva TM, Plyasova LM, Kustova GN, Jobic H, Ivanov A, Chesalov YA, Zaikovskii VI, Khasin AV, Davydova LP, Parmon VN (2008) Russ J Gen Chem 78(11):2203–2213
Yurieva TM, Plyasova LM, Makarova OV, Krieger TA (1996) J Mol Catal A: Chem 113:455
Frusteri F, Freni S, Chiodo V, Spadaro L, Di Blasi O, Bonura G, Cavallaro S (2004) Appl. Catal A: Gen 270:1
Acknowledgments
We gratefully acknowledge Prof. E. E. Wolf of the University of Notre Dame (IN, USA) for the interesting and useful discussions and Dr. Jeff Miller from Argonne National Laboratory of Chicago for the XANES measurements.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Carotenuto, G., Tesser, R., Di Serio, M. et al. Bioethanol as feedstock for chemicals such as acetaldehyde, ethyl acetate and pure hydrogen. Biomass Conv. Bioref. 3, 55–67 (2013). https://doi.org/10.1007/s13399-012-0045-3
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s13399-012-0045-3