Abstract
Fast pyrolysis is a potential technology for converting lignocellulosic biomass into bio-oil, a potential substitute for crude oil and a source of chemicals. Nevertheless, the high amounts of acid, oxygenated compounds, and water content cause the bio-oil to be unsuitable for direct usage. Catalytic fast pyrolysis (CFP) is able to improve bio-oil properties so that downstream upgrading processes may be economically feasible. The catalytic effects of calcium oxide (CaO), magnesium oxide (MgO), and zinc oxide (ZnO) on the pyrolysis of lignocellulosic biomass were investigated and were found to be attractive. However, the reaction pathways involved have not been comprehensively compiled to our knowledge. This study aimed to study the change in physical properties of bio-oils at the simplest form upon the addition of the oxides and to provide an understanding on the catalytic reaction pathways. Such study is beneficial to further explore the potential of selected oxides in enhancing the properties of bio-oil from biomass with different lignocellulosic compositions. Experiments were carried out in a fixed-bed reactor at laboratory scale to mimic large-scale processes in a controlled environment. The catalysts exhibited strengths at different bases. CaO catalyst showed the most favorable physical effects in terms of reducing the acidity of cellulose-derived bio-oils without increasing the water content significantly and without compromising with the yield. As for deoxygenation ability, ZnO catalyst exhibited better performance.
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Bhagiyalakshmi M, Lee JY, Jang HT (2010) Synthesis of mesoporous magnesium oxide: its application to CO2 chemisorption. Int J Greenh Gas Control 4:51–56. https://doi.org/10.1016/j.ijggc.2009.08.001
Carlson TR, Tompsett GA, Conner WC, Huber GW (2009) Aromatic production from catalytic fast pyrolysis of biomass-derived feedstocks. Top Catal 52:241–252. https://doi.org/10.1007/s11244-008-9160-6
Chen X, Chen Y, Yang H et al (2017) Fast pyrolysis of cotton stalk biomass using calcium oxide. Bioresour Technol 233:15–20. https://doi.org/10.1016/j.biortech.2017.02.070
Coates J (2006) Interpretation of infrared spectra: a practical approach. In: Encyclopedia of analytical chemistry. Wiley, New York
Czernik S, Bridgwater AV (2004) Overview of applications of biomass fast pyrolysis oil. Energy Fuels 18:590–598. https://doi.org/10.1021/ef034067u
Dobele G, Rossinskaja G, Dizhbite T et al (2005) Application of catalysts for obtaining 1,6-anhydrosaccharides from cellulose and wood by fast pyrolysis. J Anal Appl Pyrolysis 74:401–405
Dorado J, Almendros G, Field JA, Sierra-Alvarez R (2001) Infrared spectroscopy analysis of hemp (Cannabis sativa) after selective delignification by Bjerkandera sp. at different nitrogen levels. Enzyme Microb Technol 28:550–559. https://doi.org/10.1016/S0141-0229(00)00363-X
Fabbri D, Torri C, Baravelli V (2007) Effect of zeolites and nanopowder metal oxides on the distribution of chiral anhydrosugars evolved from pyrolysis of cellulose: an analytical study. J Anal Appl Pyrolysis 80:24–29. https://doi.org/10.1016/j.jaap.2006.12.025
Fanchiang WL, Lin YC (2012) Catalytic fast pyrolysis of furfural over H-ZSM-5 and Zn/H-ZSM-5 catalysts. Appl Catal A Gen 419–420:102–110. https://doi.org/10.1016/j.apcata.2012.01.017
Hosoya T, Kawamoto H, Saka S (2007) Cellulose-hemicellulose and cellulose-lignin interactions in wood pyrolysis at gasification temperature. J Anal Appl Pyrolysis 80:118–125. https://doi.org/10.1016/j.jaap.2007.01.006
Hwang H, Oh S, Choi IG, Choi JW (2015) Catalytic effects of magnesium on the characteristics of fast pyrolysis products—bio-oil, bio-char, and non-condensed pyrolytic gas fractions. J Anal Appl Pyrolysis 113:27–34. https://doi.org/10.1016/j.jaap.2014.09.028
Khromova SA, Smirnov AA, Selishcheva SA et al (2013) Magnesium-containing catalysts for the decarboxylation of bio-oil. Catal Ind 5:260–268. https://doi.org/10.1134/S2070050413030069
Kumar S, Saxena SK (2014) A comparative study of CO2 sorption properties for different oxides. Mater Renew Sustain Energy 3:30. https://doi.org/10.1007/s40243-014-0030-9
Kwon EE, Lee T, Sik Y et al (2018) Effects of calcium carbonate on pyrolysis of sewage sludge. Energy 153:726–731. https://doi.org/10.1016/j.energy.2018.04.100
Li S, Lyons-Hart J, Banyasz J, Shafer K (2001) Real-time evolved gas analysis by FTIR method: an experimental study of cellulose pyrolysis. Fuel 80:1809–1817. https://doi.org/10.1016/S0016-2361(01)00064-3
Liao YF, Wang SR, Ma XQ (2004) Study of reaction mechanisms in cellulose pyrolysis. ACS Div Fuel Chem Prepr 49:407–411
Lievens C, Mourant D, He M et al (2011) An FT-IR spectroscopic study of carbonyl functionalities in bio-oils. Fuel 90:3417–3423. https://doi.org/10.1016/j.fuel.2011.06.001
Lin Y, Zhang C, Zhang M, Zhang J (2010) Deoxygenation of bio-oil during pyrolysis of biomass in the presence of CaO in a fluidized-bed reactor. Energy Fuels 24:5686–5695. https://doi.org/10.1021/ef1009605
Liu C, Wang H, Karim AM et al (2014) Catalytic fast pyrolysis of lignocellulosic biomass. Chem Soc Rev 43:7594–7623. https://doi.org/10.1039/C3CS60414D
Long Y, Yu Y, Chua YW, Wu H (2017) Acid-catalysed cellulose pyrolysis at low temperatures. Fuel 193:460–466. https://doi.org/10.1016/j.fuel.2016.12.067
Lu Q, Li WZ, Zhu XF (2009a) Overview of fuel properties of biomass fast pyrolysis oils. Energy Convers Manag 50:1376–1383. https://doi.org/10.1016/j.enconman.2009.01.001
Lu Q, Xiong W-M, Li W-Z et al (2009b) Catalytic pyrolysis of cellulose with sulfated metal oxides: a promising method for obtaining high yield of light furan compounds. Bioresour Technol 100:4871–4876. https://doi.org/10.1016/j.biortech.2009.04.068
Lu Q, Zhang ZF, Dong CQ, Zhu XF (2010) Catalytic upgrading of biomass fast pyrolysis vapors with nano metal oxides: an analytical Py-GC/MS study. Energies 3:1805–1820. https://doi.org/10.3390/en3111805
Lu Q, Ye XN, Zhang ZB et al (2014) Catalytic fast pyrolysis of cellulose and biomass to produce levoglucosenone using magnetic SO4(2-)/TiO2-Fe3O4. Bioresour Technol 171:10–15. https://doi.org/10.1016/j.biortech.2014.08.075
Luo Z, Wang S, Liao Y, Cen K (2004) Mechanism study of cellulose rapid pyrolysis. Ind Eng Chem Res 43:5605–5610. https://doi.org/10.1021/ie030774z
Mekhemer GAH, Halawy SA, Mohamed MA, Zaki MI (2005) Ketonization of acetic acid vapour over polycrystalline magnesia: in situ Fourier transform infrared spectroscopy and kinetic studies. J Catal 230:109–122. https://doi.org/10.1016/j.jcat.2004.09.030
Nokkosmäki MI, Kuoppala ET, Leppämäki EA, Krause AOI (2000) Catalytic conversion of biomass pyrolysis vapours with zinc oxide. J Anal Appl Pyrolysis 55:119–131. https://doi.org/10.1016/S0165-2370(99)00071-6
Oasmaa A, Elliott DC, Korhonen J (2010) Acidity of biomass fast pyrolysis bio-oils. Energy Fuels 24:6548–6554. https://doi.org/10.1021/ef100935r
Piskorz J, Radlein D, Scott DS (1986) On the mechanism of the rapid pyrolysis of cellulose. J Anal Appl Pyrolysis 9:121–137. https://doi.org/10.1016/0165-2370(86)85003-3
Pütün E (2010) Catalytic pyrolysis of biomass: effects of pyrolysis temperature, sweeping gas flow rate and MgO catalyst. Energy 35:2761–2766. https://doi.org/10.1016/j.energy.2010.02.024
Rajadurai S (2006) Pathways for carboxylic acid decomposition on transition metal oxides. Catal Rev 36:385–403. https://doi.org/10.1080/01614949408009466
Ronsse F, Bai X, Prins W, Brown RC (2012) Secondary reactions of levoglucosan and char in the fast pyrolysis of cellulose. Environ Prog Sustain Energy 31:256–260. https://doi.org/10.1002/ep.11633
Rutkowski P, Kubacki A (2006) Influence of polystyrene addition to cellulose on chemical structure and properties of bio-oil obtained during pyrolysis. Energy Convers Manag 47:716–731. https://doi.org/10.1016/j.enconman.2005.05.017
Scheer AM, Mukarakate C, Robichaud DJ et al (2010) Radical chemistry in the thermal decomposition of anisole and deuterated anisoles: an investigation of aromatic growth. J Phys Chem A 114:9043–9056. https://doi.org/10.1021/jp102046p
Shafizadeh F, Lai YZ (1966) Thermal degradation of 1,6-anhydro-p-D-glucopyranose. J Org Chem 1964:2139–2143. https://doi.org/10.1002/star.19630150503
Shafizadeh F, Yuan-Zong L (1975) Thermal degradation of 3-deoxy-D-erythro-hexosulose. Carbohydr Res 40:263–274. https://doi.org/10.1016/S0008-6215(00)82608-7
Shao J, Agblevor F (2015) New rapid method for the determination of total acid number (tan) of bio-oils. Am J Biomass Bioenergy 4:1–9. https://doi.org/10.7726/ajbb.2015.1001
Shen DK, Gu S (2009) The mechanism for thermal decomposition of cellulose and its main products. Bioresour Technol 100:6496–6504. https://doi.org/10.1016/j.biortech.2009.06.095
Shen DK, Gu S (2010) Pyrolytic behaviour of cellulose in a fluidized bed reactor. Cellul Chem Technol 44:79–87
Stefanidis SD, Kalogiannis KG, Iliopoulou EF et al (2011) In-situ upgrading of biomass pyrolysis vapors: catalyst screening on a fixed bed reactor. Bioresour Technol 102:8261–8267. https://doi.org/10.1016/j.biortech.2011.06.032
Stefanidis SD, Karakoulia SA, Kalogiannis KG et al (2016) Natural magnesium oxide (MgO) catalysts: a cost-effective sustainable alternative to acid zeolites for the in situ upgrading of biomass fast pyrolysis oil. Appl Catal B Environ 196:155–173. https://doi.org/10.1016/j.apcatb.2016.05.031
Vochozka M, Maroušková A, Straková J, Váchal J (2016) Techno-economic appraisal of waste cellulose processing. Clean Technol Environ Policy 18:1233–1237. https://doi.org/10.1007/s10098-015-1089-4
Vohs JM, Barteau MA (1988) Reaction pathways and intermediates in the decomposition of acetic and propionic acids on the polar surfaces of zinc oxide. Surf Sci 201:481–502. https://doi.org/10.1016/0039-6028(88)90499-2
Wang S, Liu Q, Luo Z et al (2007) Mechanism study on cellulose pyrolysis using thermogravimetric analysis coupled with infrared spectroscopy. Front Energy Power Eng China 1:413–419. https://doi.org/10.1007/s11708-007-0060-8
Wang D, Xiao R, Zhang H, He G (2010) Comparison of catalytic pyrolysis of biomass with MCM-41 and CaO catalysts by using TGA-FTIR analysis. J Anal Appl Pyrolysis 89:171–177. https://doi.org/10.1016/j.jaap.2010.07.008
Wang S, Yan S, Ma X, Gong J (2011) Recent advances in capture of carbon dioxide using alkali-metal-based oxides. Energy Environ Sci 4:3805–3819. https://doi.org/10.1039/c1ee01116b
Wang S, Guo X, Liang T, Zhou Y, Luo Z (2012) Mechanism research on cellulose pyrolysis by Py-GC/MS and subsequent density functional theory studies. Bioresour Technol 104:722–728. https://doi.org/10.1016/j.biortech.2011.10.078
Williams PT, Nugranad N (2000) Comparison of products from the pyrolysis and catalytic pyrolysis of rice husks. Energy 25:493–513. https://doi.org/10.1016/S0360-5442(00)00009-8
Zhang C, Lin Y, Zhang M, Zhang J (2015a) Experimental study of CaO facilitated cellulose pyrolysis in a drop tube pyrolyzer. Energy Sources Part A Recover Util Environ Eff 37:2662–2670. https://doi.org/10.1080/15567036.2012.721055
Zhang J, Choi YS, Yoo CG et al (2015b) Cellulose-hemicellulose and cellulose-lignin interactions during fast pyrolysis. ACS Sustain Chem Eng 3:293–301. https://doi.org/10.1021/sc500664h
Zhao C, Jiang E, Chen A (2017) Volatile production from pyrolysis of cellulose, hemicellulose and lignin. J Energy Inst 90:902–913. https://doi.org/10.1016/J.JOEI.2016.08.004
Zhou L, Yang H, Wu H et al (2013) Catalytic pyrolysis of rice husk by mixing with zinc oxide: characterization of bio-oil and its rheological behavior. Fuel Process Technol 106:385–391. https://doi.org/10.1016/j.fuproc.2012.09.003
Acknowledgements
The authors would like to express sincere gratitude to Ministry of Higher Education, Malaysia, for the realization of this research project under the Grant FRGS/1/2015/TK02/UNIM/02/1. However, only the authors are responsible for the opinion expressed in this paper and for any remaining errors.
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Chong, Y.Y., Thangalazhy-Gopakumar, S., Ng, H.K. et al. Catalytic pyrolysis of cellulose with oxides: effects on physical properties and reaction pathways. Clean Techn Environ Policy 21, 1629–1643 (2019). https://doi.org/10.1007/s10098-019-01737-6
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DOI: https://doi.org/10.1007/s10098-019-01737-6