PYROLYSIS OF ISOCHRYSIS MICROALGAE WITH METAL OXIDE CATALYSTS FOR BIO-OIL PRODUCTION
Pyrolysis of Isochrysis microalgae was carried out in a fixed-bed reactor without and with metal oxide catalysts (CeO2, TiO2, Al2O3) at the temperatures of 450, 500 and 550 oC with a constant heating rate of 40 oC/min. The pyrolysis conditions including catalyst and temperature were studied in terms of their effects on the yields of pyrolysis products and quality. The amount of bio-char, bio-oil and gas products was calculated. The composition of the produced bio-oils was determined by Elemental analysis (EA), Fourier transform infrared spectroscopy (FT-IR), proton nuclear magnetic resonance (1H NMR) and Gas chromatography/mass spectrometry (GC–MS) techniques. As a result of the pyrolysis experiments, it is shown that there have been significant effects of both catalyst and temperature on the conversion of Isochrysis microalgae into solid, liquid (bio-oil) and gas products. The highest bio-oil yield (24.30 %) including aqueous phase was obtained in the presence of TiO2 (50%) as catalyst at 500 °C. 98 different compounds were identified by GC-MS in bio-oils obtained at 500 oC. According to 1H NMR analysis, bio-oils contained ∼60-64 % aliphatic and ∼17-19 % aromatic structural units. EA showed that the bio-oils contained ∼66-69 % C and having 31-34 MJ/kg higher heating values.
Le TA, Ly HV, Kim J, Kim S-S, Choi JH, Woo H-C, et al. Hydrodeoxygenation of 2-furyl methyl ketone as a model compound in bio-oil from pyrolysis of Saccharina Japonica Alga in fixed-bed reactor. Chemical Engineering Journal. 2014 Aug 15;250:157–63. DOI: 10.1016/j.cej.2014.04.003.
Babich IV, van der Hulst M, Lefferts L, Moulijn JA, O’Connor P, Seshan K. Catalytic pyrolysis of microalgae to high-quality liquid bio-fuels. Biomass and Bioenergy. 2011 Jul;35(7):3199–207. DOI: 10.1016/j.biombioe.2011.04.043.
Helwani Z, Othman MR, Aziz N, Fernando WJN, Kim J. Technologies for production of biodiesel focusing on green catalytic techniques: A review. Fuel Processing Technology. 2009 Dec;90(12):1502–14. DOI: 10.1016/j.fuproc.2009.07.016.
Neveux N, Yuen AKL, Jazrawi C, Magnusson M, Haynes BS, Masters AF, et al. Biocrude yield and productivity from the hydrothermal liquefaction of marine and freshwater green macroalgae. Bioresource Technology. 2014 Mar;155:334–41. DOI: 10.1016/j.fuproc.2014.08.014.
Duman G, Uddin MA, Yanik J. Hydrogen production from algal biomass via steam gasification. Bioresource Technology. 2014 Aug;166:24–30. DOI: 10.1016/j.biortech.2014.04.096.
Chisti Y. Biodiesel from microalgae beats bioethanol. Trends Biotechnol. 2008 Mar;26(3):126–31. DOI: 10.1016/j.tibtech.2007.12.002.
Nautiyal P, Subramanian KA, Dastidar MG. Production and characterization of biodiesel from algae. Fuel Processing Technology. 2014 Apr;120:79–88. DOI: 10.1016/j.fuproc.2013.12.003.
Wahlen BD, Barney BM, Seefeldt LC. Synthesis of Biodiesel from Mixed Feedstocks and Longer Chain Alcohols Using an Acid-Catalyzed Method. Energy Fuels. 2008 Nov 19;22(6):4223–8. DOI: 10.1021/ef800279t.
Yusuf NNAN, Kamarudin SK, Yaakub Z. Overview on the current trends in biodiesel production. Energy Conversion and Management.
Jul;52(7):2741–51. DOI: 10.1016/j.enconman.2010.12.004.
Kim S-S, Ly HV, Kim J, Lee EY, Woo HC. Pyrolysis of microalgae residual biomass derived from Dunaliella tertiolecta after lipid extraction and carbohydrate saccharification. Chemical Engineering Journal. 2015 Mar 1;263:194–9. DOI:10.1016/j.cej.2014.11.045.
Umdu ES, Tuncer M, Seker E. Transesterification of Nannochloropsis oculata microalga’s lipid to biodiesel on Al2O3 supported CaO and MgO catalysts. Bioresource Technology. 2009 Jun;100(11):2828–31. DOI: 10.1016/j.biortech.2008.12.027.
Xu H, Miao X, Wu Q. High quality biodiesel production from a microalga Chlorella protothecoides by heterotrophic growth in fermenters. Journal of Biotechnology. 2006 Dec 1;126(4):499–507. DOI: 10.1016/j.energy.2013.01.059.
Galadima A, Muraza O. Biodiesel production from algae by using heterogeneous catalysts: A critical review. Energy. 2014 Dec 15;78:72–83. DOI: 10.1016/j.energy.2014.06.018.
Grierson S, Strezov V, Shah P. Properties of oil and char derived from slow pyrolysis of Tetraselmis chui. Bioresource Technology. 2011 Sep;102(17):8232–40. DOI: 10.1016/j.biortech.2011.06.010.
Fatih Demirbas M. Biorefineries for biofuel upgrading: A critical review. Applied Energy. 2009 Nov;86, Supplement 1:S151–S161. DOI: 10.1016/j.apenergy.2009.04.043.
Miao X, Wu Q. High yield bio-oil production from fast pyrolysis by metabolic controlling of Chlorella protothecoides. Journal of Biotechnology. 2004 May 13;110(1):85–93. DOI: 10.1016/j.jbiotec.2004.01.013.
Hu Z, Zheng Y, Yan F, Xiao B, Liu S. Bio-oil production through pyrolysis of blue-green algae blooms (BGAB): Product distribution and bio-oil characterization. Energy. 2013 Apr 1;52:119–25. DOI: 10.1016/j.energy.2013.01.059.
Srirangan K, Akawi L, Moo-Young M, Chou CP. Towards sustainable production of clean energy carriers from biomass resources. Applied Energy. 2012 Dec;100:172–86. DOI: 10.1016/j.apenergy.2012.05.012.
Thangalazhy-Gopakumar S, Adhikari S, Chattanathan SA, Gupta RB. Catalytic pyrolysis of green algae for hydrocarbon production using H+ZSM-5 catalyst. Bioresource Technology. 2012 Aug;118:150–7. DOI: 10.1016/j.biortech.2012.05.080.
Chaiwong K, Kiatsiriroat T, Vorayos N, Thararax C. Study of bio-oil and bio-char production from algae by slow pyrolysis. Biomass and Bioenergy. 2013 Sep;56:600–6. DOI: 10.1016/j.biombioe.2013.05.035.
Campanella A, Harold MP. Fast pyrolysis of microalgae in a falling solids reactor: Effects of process variables and zeolite catalysts. Biomass and Bioenergy. 2012 Nov;46:218–32. DOI: 10.1016/j.biombioe.2012.08.023.
Harman-Ware AE, Morgan T, Wilson M, Crocker M, Zhang J, Liu K, et al. Microalgae as a renewable fuel source: Fast pyrolysis of Scenedesmus sp. Renewable Energy. 2013 Dec;60:625–32. DOI: 10.1016/j.renene.2013.06.016.
Aysu T. Catalytic pyrolysis of Eremurus spectabilis for bio-oil production in a fixed-bed reactor: Effects of pyrolysis parameters on product yields and character. Fuel Processing Technology. 2015 Jan;129:24–38. DOI: 10.1016/j.fuproc.2014.08.014.
Biller P, Ross AB. Potential yields and properties of oil from the hydrothermal liquefaction of microalgae with different biochemical content. Bioresource Technology. 2011 Jan;102(1):215–25. DOI: 10.1016/j.biortech.2010.06.028.
Marcilla A, Gómez-Siurana A, Gomis C, Chápuli E, Catalá MC, Valdés FJ. Characterization of microalgal species through TGA/FTIR analysis: Application to nannochloropsis sp. Thermochimica Acta. 2009 Feb 20;484(1–2):41–7. DOI: 10.1016/j.tca.2008.12.005.
Rover MR, Johnston PA, Whitmer LE, Smith RG, Brown RC. The effect of pyrolysis temperature on recovery of bio-oil as distinctive stage fractions. Journal of Analytical and Applied Pyrolysis. 2014 Jan;105:262–8. DOI: 10.1016/j.jaap.2013.11.012.
Naqvi SR, Uemura Y, Yusup SB. Catalytic pyrolysis of paddy husk in a drop type pyrolyzer for bio-oil production: The role of temperature and catalyst. Journal of Analytical and Applied Pyrolysis. 2014 Mar;106:57–62. DOI: 10.1016/j.jaap.2013.12.009.
Du S, Sun Y, Gamliel DP, Valla JA, Bollas GM. Catalytic pyrolysis of miscanthus × giganteus in a spouted bed reactor. Bioresource Technology. 2014 Oct;169:188–97. DOI: 10.1016/j.biortech.2014.06.104.
Akhtar J, Amin NAS. A review on process conditions for optimum bio-oil yield in hydrothermal liquefaction of biomass. Renewable and Sustainable Energy Reviews. 2011 Apr;15(3):1615–24. DOI: 10.1016/j.rser.2010.11.054.
Mullen CA, Strahan GD, Boateng AA. Characterization of Various Fast-Pyrolysis Bio-Oils by NMR Spectroscopy. Energy Fuels. 2009 May 21;23(5):2707–18. DOI: 10.1021/ef801048b.
J. Turk. Chem. Soc., Sect. A: Chem.