Abstract
The evaluation of microalgal wastes has gained importance both economically and environmentally since microalgae have a wide range of use and their use in industry has increased rapidly in recent years. In this context, one of the most effective and efficient processes for the evaluation of waste microalgal pulp is pyrolysis. This study aims to determine the thermal behavior and pyrolysis kinetics under different parameters of various types of freshwater and marine microalgae wastes using the thermogravimetric method. Concordantly, pyrolysis processes of freshwater microalgae Chlorella minutissima and Botryococcus braunii wastes and marine microalgae Tetraselmis suecica and Nannochloropsis oculata wastes were investigated. As a result of the thermogravimetric analysis, mass loss of about 75% for freshwater types and 55% for marine types was observed. Pyrolysis activation energy values determined by the Coats–Redfern method using different models were also calculated between 14.223 and 54.687 kJ/mol with a regression coefficient of more than 0.90. According to these results, it is seen that the most suitable models for pyrolysis of waste microalgal pulp were D3, R2 and R1 for all microalgae species. When all the results obtained as a result of this study are analyzed, it can be said that the pyrolysis process is an appropriate way to evaluate microalgal waste pulp and the obtained products have a stable structure and are more energy-efficient.
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References
Agrawal A, Chakraborty S (2013) A kinetic study of pyrolysis and combustion of microalgae Chlorella vulgaris using thermo-gravimetric analysis. Bioresour Technol 128:72–80. https://doi.org/10.1016/j.biortech.2012.10.043
Ahmad MS, Mehmood MA, Taqvi STH et al (2017) Pyrolysis, kinetics analysis, thermodynamics parameters and reaction mechanism of Typha latifolia to evaluate its bioenergy potential. Bioresour Technol 245:491–501. https://doi.org/10.1016/j.biortech.2017.08.162
Allen MM (1968) Simple conditions for growth of unicellular blue-green algae on plates. J Phycol 4:1–4. https://doi.org/10.1111/j.1529-8817.1968.tb04667.x
Alves JLF, Da Silva JCG, Costa RL et al (2019) Investigation of the bioenergy potential of microalgae Scenedesmus acuminatus by physicochemical characterization and kinetic analysis of pyrolysis. J Therm Anal Calorim 135:3269–3280. https://doi.org/10.1007/s10973-018-7506-2
Azizi K, Keshavarz Moraveji M, Abedini Najafabadi H (2017) Characteristics and kinetics study of simultaneous pyrolysis of microalgae Chlorella vulgaris, wood and polypropylene through TGA. Bioresour Technol 243:481–491. https://doi.org/10.1016/j.biortech.2017.06.155
Barbanera M, Cotana F, Di Matteo U (2018) Co-combustion performance and kinetic study of solid digestate with gasification biochar. Renew Energy 121:597–605. https://doi.org/10.1016/j.renene.2018.01.076
Bohutskyi P, Ketter B, Chow S et al (2015) Anaerobic digestion of lipid-extracted Auxenochlorella protothecoides biomass for methane generation and nutrient recovery. Bioresour Technol 183:229–239. https://doi.org/10.1016/j.biortech.2015.02.012
Cao B, Sun Y, Guo J et al (2019) Synergistic effects of co-pyrolysis of macroalgae and polyvinyl chloride on bio-oil/bio-char properties and transferring regularity of chlorine. Fuel 246:319–329. https://doi.org/10.1016/j.fuel.2019.02.037
Ceylan S, Kazan D (2015) Pyrolysis kinetics and thermal characteristics of microalgae Nannochloropsis oculata and Tetraselmis sp. Bioresour Technol 187:1–5. https://doi.org/10.1016/j.biortech.2015.03.081
Chen C, Ma X, He Y (2012) Co-pyrolysis characteristics of microalgae Chlorella vulgaris and coal through TGA. Bioresour Technol 117:264–273. https://doi.org/10.1016/j.biortech.2012.04.077
Coats AW, Redfern JP (1964) Kinetic parameters from thermogravimetric data [12]. Nature 201:68–69
Demirbaş A (1997) Calculation of higher heating values of biomass fuels. Fuel 76:431–434. https://doi.org/10.1016/S0016-2361(97)85520-2
Dilek (Yalcin) Duygu (2012) Fourier transform infrared (FTIR) spectroscopy for identification of Chlorella vulgaris Beijerinck 1890 and Scenedesmus obliquus (Turpin) Kützing 1833. African J Biotechnol 11. https://doi.org/10.5897/ajb11.1863
ElFar OA, Chang CK, Leong HY, et al (2020) Prospects of Industry 5.0 in algae: customization of production and new advance technology for clean bioenergy generation. Energy Convers Manag X. https://doi.org/10.1016/j.ecmx.2020.100048
Fernández FGA, Reis A, Wijffels RH et al (2021) The role of microalgae in the bioeconomy. N Biotechnol 61:99–107. https://doi.org/10.1016/j.nbt.2020.11.011
García R, Pizarro C, Lavín AG, Bueno JL (2012) Characterization of Spanish biomass wastes for energy use. Bioresour Technol 103:249–258. https://doi.org/10.1016/j.biortech.2011.10.004
Guillard RR, Ryther JH (1962) Studies of marine planktonic diatoms. I. Cyclotella nana Hustedt, and Detonula confervacea (cleve) Gran. Can J Microbiol 8:229–239. https://doi.org/10.1139/m62-029
Hong Y, Xie C, Chen W et al (2020) Kinetic study of the pyrolysis of microalgae under nitrogen and CO2 atmosphere. Renew Energy 145:2159–2168. https://doi.org/10.1016/j.renene.2019.07.135
Huang L, Liu J, He Y et al (2016) Thermodynamics and kinetics parameters of co-combustion between sewage sludge and water hyacinth in CO2/O2 atmosphere as biomass to solid biofuel. Bioresour Technol 218:631–642. https://doi.org/10.1016/j.biortech.2016.06.133
Karakaş C, Özçimen D, İnan B (2017) Potential use of olive stone biochar as a hydroponic growing medium. J Anal Appl Pyrolysis 125:17–23. https://doi.org/10.1016/j.jaap.2017.05.005
Kassim MA, Kirtania K, De La Cruz D et al (2014) Thermogravimetric analysis and kinetic characterization of lipid-extracted Tetraselmis suecica and Chlorella sp. Algal Res 6:39–45. https://doi.org/10.1016/j.algal.2014.08.010
Kebelmann K, Hornung A, Karsten U, Griffiths G (2013) Intermediate pyrolysis and product identification by TGA and Py-GC/MS of green microalgae and their extracted protein and lipid components. Biomass Bioenerg 49:38–48. https://doi.org/10.1016/j.biombioe.2012.12.006
Koçer AT, Özçimen D (2018) Investigation of the biogas production potential from algal wastes. Waste Manag Res 36:1100–1105. https://doi.org/10.1177/0734242X18798447
Koçer AT, Özçimen D (2021) Determination of combustion characteristics and kinetic parameters of Ulva lactuca and its biochar. Biomass Convers Biorefinery. https://doi.org/10.1007/s13399-020-01245-4
Koçer AT, Mutlu B, Özçimen D (2020) Investigation of biochar production potential and pyrolysis kinetics characteristics of microalgal biomass. Biomass Convers Biorefinery 10:85–94. https://doi.org/10.1007/s13399-019-00411-7
Lambert JB, Lightner DA, Shurvell HF, Cooks RG (1987) Introduction to organic spectroscopy. Macmillan
Li S, Liu L, Cheng JJ, Yang X (2020) Comparison study on potential syngas produced by mild thermoconversion of microalgal residues through proton nuclear magnetic resonance and thermogravimetric analysis-fourier transform infrared spectroscopy. Biomass Convers Biorefinery. https://doi.org/10.1007/s13399-019-00591-2
Marcilla A, Gómez-Siurana A, Gomis C et al (2009) Characterization of microalgal species through TGA/FTIR analysis: Application to nannochloropsis sp. Thermochim Acta 484:41–47. https://doi.org/10.1016/j.tca.2008.12.005
Maurya R, Ghosh T, Saravaia H et al (2016) Non-isothermal pyrolysis of de-oiled microalgal biomass: kinetics and evolved gas analysis. Bioresour Technol 221:251–261. https://doi.org/10.1016/j.biortech.2016.09.022
Miao X, Wu Q, Yang C (2004) Fast pyrolysis of microalgae to produce renewable fuels. J Anal Appl Pyrolysis 71:855–863. https://doi.org/10.1016/j.jaap.2003.11.004
Naqvi SR, Tariq R, Hameed Z et al (2019) Pyrolysis of high ash sewage sludge: kinetics and thermodynamic analysis using coats-redfern method. Renew Energy 131:854–860. https://doi.org/10.1016/j.renene.2018.07.094
Nithya K, Sathish A, Pradeep K, Kiran Baalaji S (2019) Algal biomass waste residues of Spirulina platensis for chromium adsorption and modeling studies. J Environ Chem Eng. https://doi.org/10.1016/j.jece.2019.103273
Özçimen D, İnan B, Akış S, Koçer AT (2015) Utilization alternatives of algal wastes for solid algal products. Algal Biorefineries. Springer, Cham, pp 393–418
Özyurtkan MH, Özçimen D, Meriçboyu AE (2008) Investigation of the carbonization behavior of hybrid poplar. Fuel Process Technol 89:858–863. https://doi.org/10.1016/j.fuproc.2008.02.005
Peng W, Wu Q, Tu P, Zhao N (2001) Pyrolytic characteristics of microalgae as renewable energy source determined by thermogravimetric analysis. Bioresour Technol 80:1–7. https://doi.org/10.1016/S0960-8524(01)00072-4
Phukan MM, Chutia RS, Konwar BK, Kataki R (2011) Microalgae Chlorella as a potential bio-energy feedstock. Appl Energy 88:3307–3312. https://doi.org/10.1016/j.apenergy.2010.11.026
Sanchez-Silva L, López-González D, Garcia-Minguillan AM, Valverde JL (2013) Pyrolysis, combustion and gasification characteristics of Nannochloropsis gaditana microalgae. Bioresour Technol 130:321–331. https://doi.org/10.1016/j.biortech.2012.12.002
Sathasivam R, Radhakrishnan R, Hashem A, Abd_Allah EF (2019) Microalgae metabolites: a rich source for food and medicine. Saudi J Biol Sci 26:709–722
Shahid A, Ishfaq M, Ahmad MS et al (2019) Bioenergy potential of the residual microalgal biomass produced in city wastewater assessed through pyrolysis, kinetics and thermodynamics study to design algal biorefinery. Bioresour Technol. https://doi.org/10.1016/j.biortech.2019.121701
Shuping Z, Yulong W, Mingde Y et al (2010) Pyrolysis characteristics and kinetics of the marine microalgae Dunaliella tertiolecta using thermogravimetric analyzer. Bioresour Technol 101:359–365. https://doi.org/10.1016/j.biortech.2009.08.020
Soria-Verdugo A, Goos E, García-Hernando N, Riedel U (2018) Analyzing the pyrolysis kinetics of several microalgae species by various differential and integral isoconversional kinetic methods and the distributed activation energy model. Algal Res 32:11–29. https://doi.org/10.1016/j.algal.2018.03.005
Sukarni S, Hamidi N et al (2014) Potential and properties of marine microalgae Nannochloropsis oculata as biomass fuel feedstock. Int J Energy Environ Eng 5:279–290. https://doi.org/10.1007/s40095-014-0138-9
Tarhan SZ, Koçer AT, Özçimen D, Gökalp İ (2021) Cultivation of green microalgae by recovering aqueous nutrients in hydrothermal carbonization process water of biomass wastes. J Water Process Eng 40:101783. https://doi.org/10.1016/j.jwpe.2020.101783
Tibbetts SM, Milley JE, Lall SP (2015) Chemical composition and nutritional properties of freshwater and marine microalgal biomass cultured in photobioreactors. J Appl Phycol 27:1109–1119. https://doi.org/10.1007/s10811-014-0428-x
Wang L, Lei H, Liu J, Bu Q (2018) Thermal decomposition behavior and kinetics for pyrolysis and catalytic pyrolysis of Douglas fir. RSC Adv 8:2196–2202. https://doi.org/10.1039/c7ra12187c
Watanabe H, Li D, Nakagawa Y et al (2014) Characterization of oil-extracted residue biomass of Botryococcus braunii as a biofuel feedstock and its pyrolytic behavior. Appl Energy 132:475–484. https://doi.org/10.1016/j.apenergy.2014.07.037
Wellinger A (2009) Algal biomass does it save the world ? Short reflections. IEA Bioenergy Task 37
Yang X, Wang X, Zhao B, Li Y (2014) Simulation model of pyrolysis biofuel yield based on algal components and pyrolysis kinetics. Bioenergy Res 7:1293–1304. https://doi.org/10.1007/s12155-014-9467-z
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The authors would like to acknowledge that this paper is submitted in partial fulfillment of the requirements for PhD degree at Yildiz Technical University. The first author of this paper received financial support from The Scientific and Technological Research Council of Turkey (TUBITAK—BIDEB 2211 National Scholarship Programme for PhD Students) and 100/2000 The Council of Higher Education (YÖK) Doctorate Scholarship Programme.
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All authors contributed to the study conception and design. Material preparation, data collection and analysis were performed by Anıl Tevfik Koçer and Didem Özçimen. The first draft of the manuscript was written by Anıl Tevfik Koçer. All authors read and approved the final manuscript.
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Koçer, A.T., Özçimen, D. Experimental investigation on thermal behavior and thermo-kinetic study on pyrolysis of de-oiled microalgae. Int. J. Environ. Sci. Technol. 19, 12279–12288 (2022). https://doi.org/10.1007/s13762-022-03933-2
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DOI: https://doi.org/10.1007/s13762-022-03933-2