The Mechanism Study of Degradative Solvent Extraction of Biomass by Liquid Membrane-Fourier Transform Infrared Spectroscopy
Degradative solvent extraction is the method developed for biomass upgrading by dewatering and fractionation of biomass under the mild condition. However, the conversion mechanism of the degradative solvent extraction method has not been fully understood so far. The rice straw was treated in 1-methylnaphthalene (1-MN) at a different solvent-treatment temperature varied from 250 to 350 oC with the residence time for 60 min. The liquid membrane-Fourier Transform Infrared Spectroscopy (FTIR) technique is applied to study the processing mechanism in-depth without separation of the solvent. It has been found that the strength of the oxygen-hydrogen stretching (3600-3100 cm-1) decreased slightly with increasing temperature in the range of 300-350 oC. The decrease of the hydroxyl group in the solvent soluble suggested dehydration reaction taking place between 300 and 350 oC. FTIR spectra in the carbonyl stretching region (1800-1600 cm-1) revealed the presence of esters groups, carboxylic acid and ketonic groups in the solvent-soluble of biomass. The carboxylic acid increased in the range of 200 to 250 oC and then decreased. The prevailing of aromatic groups showed that the aromatization took place during extraction at above 250 oC. From 300 to 350 oC, the carbonyl functional groups in the solvent-soluble noticeably decreased. The removal of the carboxylic acid and the decrease of esters into the form of carbon dioxide indicated that the decarboxylation reaction occurred during the extraction process.
Digital Object Identifier (DOI): doi.org/10.5281/zenodo.1316101Procedia APA BibTeX Chicago EndNote Harvard JSON MLA RIS XML ISO 690 PDF Downloads 515
 Edenhofer O., Pichs-Madruga R., Sokona Y., Seyboth K., Matschoss P., Kadner S., Zwickel T., Eickemeier P., Hansen G., Schlömer S., Stechow von C., IPCC, 2011: Summary for Policymakers. In: IPCC Special Report on Renewable Energy Sources and Climate Change Mitigation. Cambridge: Cambridge University Press.
 Bridgwater AV., “Renewable fuels and chemicals by thermal processing of biomass”, Chem. Eng, vol. 91, pp.87-102, 2003.
 Brenes M. D., Biomass and Bioenergy New Research, New York: Nova Science Publisher Inc., 2006, ch. 4.
 Mckendry P., “Energy production from biomass (part 2): Conversion Technologies,” Bioresour Technol, vol. 83, no. 1, pp. 47–54, 2002.
 Lv D., Xu M., Liu X., Zhan Z., Li Z., Yao H., “Effect of cellulose, lignin, alkali and alkaline earth metallic species on biomass pyrolysis and gasification,” Fuel Process Technol, vol. 91, pp. 903–909, 2010.
 Liu Y., Aziz M., Fushimi C., Kansha Y., Mochidzuki K., Kaneko S., Tsutsumi A., Yokohama K., Myoyo K., Oura K., Matsuo K., Sawa S., Shinoda K., “Exergy analysis of biomass drying based on self-heat recuperation technology and its application to industry : a simulation and experimental study,” Industrial and Engineering Chemistry Research, vol. 51, pp. 9997-10007, 2012.
 Janewit W., Li X., Nakorn W., Ashida R., Miura K., “Production of high-grade carbonaceous materials and fuel having similar chemical and physical properties from various types of biomass by degradative solvent extraction,” Energy Fuels, vol. 26, pp. 4521–31, 2012.
 Li X., Ashida R., Miura K., “Preparation of high-grade carbonaceous materials having similar chemical and physical properties from various low-rank coals by degradative solvent extraction,” Energy Fuels, vol.26, 11, pp. 6897–6904, 2012.
 Fujitsuka H., Ashida R., Miura K., “Upgrading and dewatering of low rank coals through solvent treatment at around 350°C and low temperature oxygen reactivity of the treated coals.” Fuel, vol. 114, pp. 16–20, 2013.
 Li X., Zhu X., Xiao L., Ashida R., Miura K., Luo G., Yao H., “Degradative solvent extraction of demineralized and ion-exchanged low-rank coals,” J Fuel Chem Technol, vol. 42, 8, pp. 897–904, 2014.
 Li X., Ashida R., Makino M., Nishida A., Yao H., Miura K., “Enhancement of gasification reactivity of low-rank coal through high-temperature solvent treatment,” Energy Fuels, vol. 28, 9, pp. 5690–5695, 2014.
 Ashida R., Takahashi R., Kawase M., Miura K., “Upgrading mechanism in degradative solvent extraction of biomass wastes,” 12thEMSES, 2015.
 Zhu X., Zhang Z., Zhou Qi, Cai T., Qiao E., Li X, Yao H. “Upgrading and multistage separation of rice straw by degradative solvent extraction,” J Fuel Chem Technol, vol. 43, 4, pp. 422-428, 2015.
 Zhu X., Xue Y., Li X., Zhang Z., Sun W., Ashida R., Miura K., Yao H., “Mechanism study of degradative solvent extraction of biomass,” Fuel, vol. 165, pp. 10-18, 2016.
 Painter P. C., Snyder R. W., Starsinic M., Coleman M. M., Kuehn D. W., Davis A., “Concerning the Application of FT-IR to the Study of Coal: A Critical Assessment of Band Assignments and the Application of Spectral Analysis Programs,” Applied Spectroscopy, vol. 35, 5, pp. 475-485, 1981.
 Painter P. C., Starsinic M., Squires E., Davis A., “Concerning the 1600 cm−1 region in the i.r. spectrum of coal,” Fuel, vol. 62, 6, pp. 742-744, 1983.
 Solomon P. R., “Relation between coal aromatic carbon concentration and proximate analysis fixed carbon,” Fuel, vol. 60, 1, pp. 3-61981.
 Solomon P.R., Carangelo R.M., “FT-ir analysis of coal: 2. Aliphatic and aromatic hydrogen concentration,” Fuel, vol. 67, pp. 949, 1988.
 Sobkowiak M., Painter P.A., “A comparison of drift and KBr pellet methodologies for the quantitative analysis of functional groups in coal by infrared spectroscopy,” Energy & Fuels, vol. 9, pp.359, 1995.
 Solomon P.R., Carangelo R.M., “FTIR analaysis of coal. 1. Techniques and determination of hydroxyl concentrations,” Fuel, vol. 61, 1982.
 Sobkowiak M., Painter P.A., “A comparison of drift and KBr pellet methodologies for the quantitative analysis of functional groups in coal by infrared spectroscopy,” Energy Fuels, vol. 9, pp. 359, 1995.
 Glover G., van der Walt T.J., Glasser D., Prinsloo N.M., Hildebrandt D., “DRIFT spectroscopy and optical reflectance of heat-treated coal from a quenched gasifier,” Fuel, vol. 74, pp. 1216, 1995.
 Thomasson J., Coin C., Kahraman H., Fredericks P.M., “Attenuated total reflectance infrared microspectroscopy of coal,” Fuel, vol. 79, 685, 2000.
 Jorge A., Orrego-Ruiz, Rafael C., Enrique Mejía-O., “Study of colombian coals using photoacoustic Fourier transform infrared spectroscopy,” Int J of Coal Geology, vol. 85, pp. 307–310, 2011.
 Watcharakorn K., Trirat M., Janewit W., Zen H., Kii T., Miura K., Ohgaki H., “Proposal of Liquid Membrane-FTIR Spectroscopy to Quantify the Oxygen Content in Soluble Fraction of Degradative Solvent-Extraction,” Int. J. Exp. Spectroscopic Tech., pp. 2-10, 2017.
 Painter P.C., Sobkowiak M., Youtcheff J., “FT-i.r. study of hydrogen bonding in coal,” Fuel, vol. 66, pp. 973-978, 1987.
 Miura K., Mae K., Li W., Kusakawa T., Morozumi F., Kumano A., “Estimation of hydrogen bond distribution in coal through the analysis of OH stretching bands in Diffuse Reflectance Infrared Spectrum Measured by in-situ technique,” Energy Fuels, vol. 15, pp. 599-610, 2001.
 Ibarra J.V., Munoz E., Moliner R., “FTIR study of the evolution of coal structure during the coalification process,” Org. Geochem., vol. 24, pp. 725–735, 1996.
 Murakami K., Shirato H., Nishiyama Y., “In situ infrared spectroscopic study of the effects of exchanged cations on the thermal decomposition of a brown coal,” Fuel, vol. 76, pp. 655-661, 1997.
 Supaluknari S., Larkins F.P., “An FTIR study of Australian coals: characterization of oxygen functional groups,” Fuel Processing Technology, vol. 19, pp. 123-140, 1988.
 Wenhua Geng, Tsunemori Nakajima, Hirokazu Takanashi, Akira Ohki, “Analysis of carboxyl group in coal and coal aromaticity by Fourier transform infrared (FT-IR) spectroscopy,” Fuel, vol. 88, pp.139-144, 2009.
 Wang Y., Wu J., Xue Sh., Wang J., Zhang Y., “Experimental Study on the Molecular Hydrogen Release Mechanism during Low-Temperature Oxidation of Coal,” Energy Fuel, vol. 31, pp. 5498-5506, 2017.