Catalytic Pyrolysis of Geodae-Uksae 1 over MCM-48 Bull. Korean Chem. Soc. 2014, Vol. 35, No. 7 1951 http://dx.doi.org/10.5012/bkcs.2014.35.7.1951 Catalytic Upgrading of Geodae-Uksae 1 over Mesoporous MCM-48 Catalysts Ki-Joon Jeon, a Sung Ho Jin, †,a Sung Hoon Park, ‡ Jong-Ki Jeon, § Sang-Chul Jung, ‡ Changkook Ryu, # and Young-Kwon Park †,* Department of Environmental Engineering, Inha University, Incheon 402-751, Korea † Graduate School of Energy and Environmental System Engineering, University of Seoul, Seoul 130-743, Korea * E-mail: catalica@uos.ac.kr ‡ Department of Environmental Engineering, Sunchon National University, Suncheon 540-950, Korea § Department of Chemical Engineering, Kongju National University, Cheonan 330-717, Korea # School of Mechanical Engineering, Sungkyunkwan University, Suwon 440-746, Korea Received February 5, 2014, Accepted March 5, 2014 Catalytic pyrolysis of Geodae-Uksae 1, a kind of miscanthus found in Korea, was carried out over mesoporous MCM-48 catalysts. For rapid product analysis and catalyst evaluation, pyrolysis-gas chromatography/mass spectrometry was used. X-ray diffraction, nitrogen sorption, pyridine adsorbed Fourier transform infrared, and NH3 temperature programmed desorption were utilized to analyze the properties of the catalysts. Compared to non-catalytic reaction, catalytic upgrading over mesoporous Al-MCM-48 catalysts produced a higher-quality bio-oil with a high stability and low oxygen content. Al-MCM-48 exhibited higher deoxygenation ability than Si-MCM-48 due to its higher acidity. Key Words : Geodae-Uksae 1, Catalytic pyrolysis, MCM-48, Bio-oil Introduction Since industrial revolution, the demand for fossil fuel such as coal and oil has greatly increased accompanied by the development of the chemical industry. Because the con- tinuous supply and utilization of fossil fuel inhibits the sustainable growth of living environment, a large attention is paid to the renewable energy. At this moment, biomass conversion process is a strong candidate due to the capability of large energy production. 1 Bioenergy from biomass can provide 30% of global energy demand in 2020. Especially, the pyrolysis of biomass is the most suitable for the pro- duction of a lot of bioenergy among the various biomass conversion processes. Pyrolysis is a thermal process to pro- duce bio-oil in an oxygen-free atmosphere. 2-10 Fast pyrolysis is an optimized process for bio-oil production because its yield is over 50%. However, there is a difficulty for its commercial utilization due to the low heating value and high acidity of the product bio-oil. Therefore, bio-oil should be reformed with catalyst to use it in transport fuel applications. Also, it is essential to use catalyst in order to enhance the yield of valuable products such as furans, phenolics and mono-aromatics from bio-oil. 1,11,12 Mesoporous materials like Al-SBA-15 and Al-MCM-41 have been proved to be effective for the catalytic pyrolysis of biomass. 13-16 Among various biomass materials, energy crops refer to the plants that are cultivated for dedicated energy produc- tion. Geodae-Uksae 1 (giant miscanthus found in Korea) is a sort genotype of Miscanthus sacchariflorus (Amur silver- grass) recently discovered Korea. 17,18 It grows as tall as 4 m with an average stalk diameter of 1 cm, which produces dry mass of approximately 30 ton/ha/yr. Due to the doubled yield compared to the common miscanthus, Geodae-Uksae 1 is now cultivated for bioenergy in large scale. Various con- version methods for this crop is being investigated, includ- ing biological fermentation, thermal combustion, and thermal fast pyrolysis. 17 However, few papers were reported about the catalytic pyrolysis of miscanthus, especially none with Geodae-Uksae 1. In this study, the catalytic pyrolysis of Geodae-Uksae 1 was carried out. Al-MCM-48, which is known to be effec- tive for the conversion of large-molecular-mass biomass to bio-oil due to its large pore size, was applied as the catalyst. Al-MCM-48 was more effective than Al-MCM-41 for the pyrolysis of miscanthus in a previous study. 1 An in-situ analysis of the product of the catalytic pyrolysis was done using pyrolysis gas chromatography/mass spectroscopy (Py- GC/MS). To investigate the effect of acid sites, Si-MCM-48 without acidity was also used. Experimental Geodae-Uksae 1 which was obtained from Korean Rural Development Administration was ground into powders and it was dried at 110 °C in an oven for at least 24 h before experiment. The proximate analysis result of Geodae-Uksae1 was moisture (7.3 wt %), volatile matter (73.2 wt %), fixed carbon (15.9 wt %), and ash (3.6 wt %). 17 The elemental composition analysis of Geodae-Uksae1 on the dry-ash-free basis reveals 47.6%, 5.5%, 46.1% and 0.8% of carbon, hydrogen, oxygen, and nitrogen, respectively. 17 The cellu- lose, hemicellulose and lignin contents of Geodae-Uksae 1 a These authors contributed equally to this work.