Abstract
In the base catalyzed ethanol condensation reactions, the calcined MgO–Al2O3 derived hydrotalcites used broadly as catalytic material and the calcination temperature plays a big role in determining the catalytic activity. The characteristics of the hydrotalcite material treated between catalytically relevant temperatures 450 and 800 °C have been studied with respect to the physical, chemical, and structural properties and compared with catalytic activity testing. With the increasing calcination temperature, the total measured catalytic basicity dropped linearly with the calcination temperature and the total measured acidity stayed the same for all the calcination temperatures except 800 °C. However, the catalyst activity testing does not show any direct correlation between the measured catalytic basicity and the catalyst activity to the ethanol condensation reaction to form 1-butanol. The highest ethanol conversion of 44 % with 1-butanol selectivity of 50 % was achieved for the 600 °C calcined hydrotalcite material.
Similar content being viewed by others
References
Sun J, Wang Y (2014) Recent advances in catalytic conversion of ethanol to chemicals. ACS Catal 4(4):1078–1090. doi:10.1021/cs4011343
Tews IJ, Jones SB, Santosa DM, Dai Z, Ramasamy K, Zhu Y (2010) A survey of opportunities for microbial conversion of biomass to hydrocarbon compatible fuels. vol PNNL-19704. PNNL, Richland
Ramasamy KK, Wang Y (2014) Ethanol conversion to hydrocarbons on HZSM-5: effect of reaction conditions and Si/Al ratio on the product distributions. Catal Today 237:89–99. doi:10.1016/j.cattod.2014.02.044
Ramasamy KK, Zhang H, Sun JM, Wang Y (2014) Conversion of ethanol to hydrocarbons on hierarchical HZSM-5 zeolites. Catal Today 238:103–110. doi:10.1016/j.cattod.2014.01.037
Ni M, Leung DYC, Leung MKH (2007) A review on reforming bio-ethanol for hydrogen production. Int J Hydrog Energy 32(15):3238–3247. doi:10.1016/j.ijhydene.2007.04.038
Angelici C, Weckhuysen BM, Bruijnincx PC (2013) Chemocatalytic conversion of ethanol into butadiene and other bulk chemicals. Chem Sus Chem 6(9):1595–1614. doi:10.1002/cssc.201300214
Ramasamy KK, Wang Y (2013) Thermochemical conversion fermentation-derived oxygenates to fuels. In: Zhang B, Wang Y (eds) Biomass processing, conversion and biorefinery. Nova Science Publishers Inc, New York, pp 289–300
Zheng J, Tashiro Y, Wang Q, Sonomoto K (2015) Recent advances to improve fermentative butanol production: genetic engineering and fermentation technology. J Biosci Bioeng 119(1):1–9. doi:10.1016/j.jbiosc.2014.05.023
Ndou AS, Plint N, Coville NJ (2003) Dimerisation of ethanol to butanol over solid-base catalysts. Appl Catal A 251(2):337–345. doi:10.1016/s0926-860x(03)00363-6
Kozlowski JT, Davis RJ (2013) Heterogeneous catalysts for the Guerbet coupling of alcohols. ACS Catal 3(7):1588–1600. doi:10.1021/cs400292f
Carvalho DL, Borges LEP, Appel LG, Ramírez de la Piscina P, Homs N (2013) In situ infrared spectroscopic study of the reaction pathway of the direct synthesis of n-butanol from ethanol over MgAl mixed-oxide catalysts. Catal Today 213:115–121. doi:10.1016/j.cattod.2013.03.034
Debecker DP, Gaigneaux EM, Busca G (2009) Exploring, tuning, and exploiting the basicity of hydrotalcites for applications in heterogeneous catalysis. Chemistry 15(16):3920–3935. doi:10.1002/chem.200900060
Roelofs JCAA, Bokhoven JAV, Dillen AJV, John WG, Jong KPD (2002) The thermal decomposition of Mg ± Al hydrotalcites: effects of interlayer anions and characteristics of the final structure. Chem Eur J 8(24):5571–5579
Xie W, Peng H, Chen L (2006) Calcined Mg–Al hydrotalcites as solid base catalysts for methanolysis of soybean oil. J Mol Catal A: Chem 246(1–2):24–32. doi:10.1016/j.molcata.2005.10.008
Chimentao R, Abello S, Medina F, Llorca J, Sueiras J, Cesteros Y, Salagre P (2007) Defect-induced strategies for the creation of highly active hydrotalcites in base-catalyzed reactions. J Catal 252(2):249–257. doi:10.1016/j.jcat.2007.09.015
Liu Y, Lotero E, Goodwin JG, Mo X (2007) Transesterification of poultry fat with methanol using Mg–Al hydrotalcite derived catalysts. Appl Catal A 331:138–148. doi:10.1016/j.apcata.2007.07.038
Shen JY, Tu M, Hu C (1998) Structural and surface acid/base properties of hydrotalcite-derived MgAlO oxides calcined at varying temperatures. J Solid State Chem 137(2):295–301. doi:10.1006/jssc.1997.7739
Rey F, Fornes V, Rojo JM (1992) Thermal-decomposition of hydrotalcites—an infrared and nuclear-magnetic-resonance spectroscopic study. J Chem Soc Faraday Trans 88(15):2233–2238. doi:10.1039/Ft9928802233
Cosimo JID, D´ıez VK, Xu M, Iglesia E, Apesteguia CR (1998) Structure and surface and catalytic properties of Mg-Al basic oxides. J Catal 178:499–510
Kuśtrowski P, Chmielarz L, Bożek E, Sawalha M, Roessner F (2004) Acidity and basicity of hydrotalcite derived mixed Mg–Al oxides studied by test reaction of MBOH conversion and temperature programmed desorption of NH3 and CO2. Mater Res Bull 39(2):263–281. doi:10.1016/j.materresbull.2003.09.032
Hibino T, Tsunashima A (1997) Formation of spinel from a hydrotalcite-like compound at low temperature: reaction between edges of crystallites. Clays Clay Miner 45(6):842–853. doi:10.1346/Ccmn.1997.0450608
Akitt JW (1989) Multinuclear studies of aluminum compounds. Prog Nucl Magn Reson Spectrosc 21:1–149. doi:10.1016/0079-6565(89)80001-9
MacKenzie KJD, Meinhold RH, Sherriff BL, Xu Z (1993) 27Al and 25 Mg solid-state magic-angle spinning nuclear magnetic resonance study of hydrotalcite and its thermal decomposition sequence. J Mater Chem 3(12):1263–1269
Park T-J, Choi S-S, Kim Y (2009) 27Al solid-state NMR structural studies of hydrotalcite compounds calcined at different temperatures. Bull Korean Chem Soc 30(1):149–152
Corma A, Fornes V, Rey F (1994) Hydrotalcites as base catalysts—influence of the chemical-composition and synthesis conditions on the dehydrogenation of isopropanol. J Catal 148(1):205–212. doi:10.1006/jcat.1994.1202
Díez V (2003) Effect of the chemical composition on the catalytic performance of MgyAlOx catalysts for alcohol elimination reactions. J Catal 215(2):220–233. doi:10.1016/s0021-9517(03)00010-1
Erickson KL, Bostrom TE, Frost RL (2005) A study of structural memory effects in synthetic hydrotalcites using environmental SEM. Mater Lett 59(2–3):226–229. doi:10.1016/j.matlet.2004.08.035
Ramasamy KK, Gerber MA, Flake M, Zhang H, Wang Y (2014) Conversion of biomass-derived small oxygenates over HZSM-5 and its deactivation mechanism. Green Chem 16(2):748–760. doi:10.1039/C3gc41369a
Rao KK, Gravelle M, Valente JS, Fc Figueras (1998) Activation of Mg–Al hydrotalcite catalysts for aldol condensation reactions. J Catal 173:115–121
Constantino VRL, Pinnavaia TJ (1994) Structure-reactivity relationships for basic catalysts derived from a Mg2+/A13+/CO layered double hydroxide. Catal Lett 23:361–367
Kozlowski JT, Davis RJ (2013) Sodium modification of zirconia catalysts for ethanol coupling to 1-butanol. J Energy Chem 22(1):58–64. doi:10.1016/s2095-4956(13)60007-8
Birky TW, Kozlowski JT, Davis RJ (2013) Isotopic transient analysis of the ethanol coupling reaction over magnesia. J Catal 298:130–137. doi:10.1016/j.jcat.2012.11.014
Acknowledgments
The Pacific Northwest National Laboratory is operated by the Battelle Memorial Institute for the U.S. Department of Energy under Contract No. DE-AC05-76RL01830. This work was supported by the U.S. Department of Energy’s Bioenergy Technology Office. The SEM imaging portion of the work was done as a part of chemical imaging initiative, a laboratory directed research and development program at Pacific Northwest National Laboratory. The SEM imaging was conducted in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by DOE’s Office of Biological and Environmental Research and located at PNNL. The authors wish to express thanks to Robert A. Dagle and Michael A. Lilga for the valuable technical discussions, Colin D. Smith for the XRD analysis, and Satish Nune for the TG analysis.
Author information
Authors and Affiliations
Corresponding authors
Rights and permissions
About this article
Cite this article
Ramasamy, K.K., Gray, M., Job, H. et al. Role of Calcination Temperature on the Hydrotalcite Derived MgO–Al2O3 in Converting Ethanol to Butanol. Top Catal 59, 46–54 (2016). https://doi.org/10.1007/s11244-015-0504-8
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11244-015-0504-8