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Thermo-kinetic analysis, thermodynamic parameters and comprehensive pyrolysis index of Melia azedarach sawdust as a genesis of bioenergy

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Abstract

Energy demands are dynamic and intensifying demand of energy led to execute this study in order to analyze the thermal degradation characteristics of Melia azedarach sawdust (MAS) collected from sawmill intending to examine its pyrolytic performance for biofuel production. The inceptive characterizations which include proximate, ultimate, component analysis and higher heating value (HHV) were carried out so as to scrutinize its worth for pyrolysis. Furthermore, thermogravimetric (TG) experiments were performed in temperature hovering from ambient to 900 ℃ at three different slow rates of heating (10, 20 and 30 ℃ min−1) under inert condition. Findings of TG analysis revealed 210 to 480 ℃ as the maximum devolatilization temperature range during thermal degradation of MAS. Kinetic and thermodynamic parameters were estimated using three iso-conversional models, i.e. Kissinger–Akahira–Sunose (KAS), Flynn–Wall–Ozawa (FWO) and Starink and average activation energy was found to be 161.18, 162.68 and 161.41 kJ mol−1, respectively. The obtained values of Gibbs free energy (ΔG) were 185.98, 185.91 and 185.97 kJ mol−1 and that of change in enthalpy (ΔH) were 155.91, 157.47 and 156.19 kJ mol−1 for KAS, FWO and Starink models, respectively. Master plot along with Criado method revealed a complex mechanism of the reaction. Average and maximum decomposition rates, as well as initial devolatilization and peak temperatures, shifted to higher values with an increase in heating rate. Comprehensive pyrolysis index (CPI) exhibited higher value at higher heating rate which indicates the suitability of pyrolysis of MAS at a high heating rate. All these findings coupled with 15.43 MJ kg−1 HHV inferred the suitability of MAS for pyrolysis as it exhibits remarkably high potential for biofuel generation. Thus, it can be a concrete step towards clean energy generation along with a balance between economy and ecology with desire to strengthen our energy self-sufficiency.

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Data availability

Data are available on request to the corresponding author.

Abbreviations

t :

Time (s)

α :

Fractional conversion

β :

Rate of heating (°C min−1)

k :

Rate constant

Wi :

Initial mass of sample (mg)

Wt :

Mass of sample at time t (mg)

W f :

Final mass of the sample left as residue after reaction (mg)

T :

Temperature (K)

R :

Universal gas constant (J k−1 mol−1)

E :

Activation energy (kJ mol−1)

A :

Pre-exponential or frequency factor (s−1)

ΔG :

Change in Gibbs free energy (kJ mol−1)

ΔH :

Change in enthalpy (kJ mol−1)

ΔS :

Change in entropy (J mol−1 K−1)

h :

Plank’s constant (6.626 × 10 − 34 J s)

K B :

Boltzmann constant (1.381 × 10 − 23 J K−1

References

  1. Owusu PA, Asumadu-Sarkodie S (2016) A review of renewable energy sources, sustainability issues and climate change mitigation. Cogent Eng 3(1):1167990

    Article  Google Scholar 

  2. Rapier R (2020) Fossil fuels still supply 84 percent of the world’s energy-and other eye opener from BP’s annual review. Forbes https://www.forbes.com/sites/rrapier/2020/06/20/bp-review-newhighs-in-global-energy-consumption-and-carbon-emissions-in2019/?sh=2d26a63766a1. Accessed 10 Apr 2021

  3. Hussain M, Zhao Z, Ren J, Rasool T, Raza S (2019) Biomass and bioenergy thermokinetics and gaseous product analysis of banana peel pyrolysis for its bioenergy potential. Biomass Bioenergy 122:193–201

    Article  Google Scholar 

  4. Shahid A, Ishfaq M, Ahmad MS, Farooq M, Hui Z, Batawi AH, 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 289:121701

  5. Wang T, Meng D, Zhu J, Chen X (2020) Effects of pelletizing conditions on the structure of rice straw-pellet pyrolysis char. Fuel 264:116909

  6. Mukherjee A, Lal R, Zimmerman AR (2014) Effects of biochar and other amendments on the physical properties and greenhouse gas emissions of an artificially degraded soil. Sci Total Environ 487:26–36

    Article  Google Scholar 

  7. Al-Layla NMT, Saleh LA, Fadhila AB (2021) Liquid bio-fuels and carbon adsorbents production via pyrolysis of non-edible feedstock. J Anal Appl Pyrolysis 156:105088. https://doi.org/10.1016/j.jaap.2021.105088

    Article  Google Scholar 

  8. Tarek MAF, Mohamed EM, Somia BA, Matthew DH, James WL, Sandeep K (2015) Biochar from woody biomass for removing metal contaminants and carbon sequestration. J Ind Eng Chem 22:103–109

    Article  Google Scholar 

  9. Jinshuai Y, Yicheng Z, Yongdan L (2014) Utilization of corn cob biochar in a direct carbon fuel cell. J Power Sour 270:312–317

    Article  Google Scholar 

  10. Rakesh KG, Mukul D, Parashu K, Zhengrong G, Qi HF (2015) Biochar activated by oxygen plasma for super capacitors. J Power Sources 274:1300–1305

    Article  Google Scholar 

  11. Fadhil AB, Kareem BA (2021) Co-pyrolysis of mixed date pits and olive stones: identification of bio-oil and the production of activated carbon from bio-char. J Anal Appl Pyrol 158:105249. https://doi.org/10.1016/j.jaap.2021.105249

    Article  Google Scholar 

  12. Gupta GK, Mondal MK (2018) Iso-conversional kinetic and thermodynamic studies of Indian sagwan sawdust pyrolysis for its bioenergy potential. Environ Prog Sustain Energy 38(4):13131

    Article  Google Scholar 

  13. Mahin DB (1999) Industrial energy and electric power from wood residues. Arlington, VA, USA: Winrock International Institute for Agricultural Development

  14. Altamer DH, Al-Irhayim AN, Saeed LI (2021) Saeed bio-based liquids and solids from sustainable feedstock: production and analysis. J Anal Appl Pyrolysis 157:105224. https://doi.org/10.1016/j.jaap.2021.105224

    Article  Google Scholar 

  15. Wang Q, Wang C, Huang Y, Ding M, Wang J, Yang J (2021) Pyrolysis chemistry of n-propylcyclohexane via experimental and modeling approaches. Fuel 283:118847

  16. Fadhila AB (2020) Production and characterization of liquid biofuels from locally available nonedible feedstocks. Asia-Pac J Chem Eng 16:2572–2591. https://doi.org/10.1002/apj.2572

    Article  Google Scholar 

  17. Yasmin T, Asghar A, Ahmad MS, Mehmood MA, Nawaz M (2021) Biorefnery potential of Typha domingensis biomass to produce bioenergy and biochemicals assessed through pyrolysis, thermogravimetry, and TG-FTIR-GCMS-based study. Biomass Conv Bioref. https://doi.org/10.1007/s13399-021-01892-1

    Article  Google Scholar 

  18. Alves JLF, Silva JCG, Languer MP, Batistella L, Domenico MD, Filho VFS et al (2020) Assessing the bioenergy potential of high-ash anaerobic sewage sludge using pyrolysis kinetics and thermodynamics to design a sustainable integrated biorefinery. Biomass Conv Bioref. https://doi.org/10.1007/s13399-020-01023-2

    Article  Google Scholar 

  19. Braga RM, Melo DMA, Aquino FM, Freitas JCO, Melo MAF, Barros JMF et al (2020) Characterization and comparative study of pyrolysis kinetics of the rice husk and the elephant grass. J Therm Anal Calorim 115:1915–1920

    Article  Google Scholar 

  20. Magdziarz A, Wilk M, Wkadrzyk M (2020) Pyrolysis of hydrochar derived from biomass–experimental investigation. Fuel 267:117246

  21. Wu W, Mei Y, Zhang L, Liu R, Cai J (2015) Kinetics and reaction chemistry of pyrolysis and combustion of tobacco waste. Fuel 156:71–80

    Article  Google Scholar 

  22. Maia AAD, de Morais LC (2016) Kinetic parameters of red pepper waste as biomass to solid biofuel. Bioresour Technol 204:157–163

    Article  Google Scholar 

  23. Ahmad MS, Mehmood MA, Ayed OSA, Ye G, Luo H, Ibrahim M et al (2017) Kinetic analyses and pyrolytic behavior of Para grass (Urochloa mutica) for its bioenergy potential. Bioresour Technol 224:708–713

    Article  Google Scholar 

  24. Alves JLF, Gomes da Silva JC, Domenico MD, Galdino WVDA, Andersen SLF, Alves RF et al (2021) Exploring açaí seed (Euterpe oleracea) pyrolysis using multi-component kinetics and thermodynamics assessment towards its bioenergy potential. Bioenergy Res 14:209–225

    Article  Google Scholar 

  25. Kissinger HE (1957) Reaction kinetics of differential thermal analysis. Anal Chem 29:1702–1706

    Article  Google Scholar 

  26. Akahira T, Sunose T (1971) Method of determining activation deterioration constant of electrical insulating materials. Research Report: Chiba Inst of Technol 16:22–23

    Google Scholar 

  27. Ozawa T (1965) A new method of analyzing thermogravimetric data. Bull Chem Soc Jpn 38(11):1881–1886

    Article  Google Scholar 

  28. Flynn J, Wall L (1966) A quick, direct method for the determination of activation energy from thermogravimetric data. J Polymer Sci 4(5):323–328

    Article  Google Scholar 

  29. Doyle CD (1965) Series approximations to the equation of thermogravimetric data. Nature 207(4994):290–291

    Article  Google Scholar 

  30. Galwey AK, Brown ME (1999) Chapter 3 kinetic models for solid state reactions. In: Galwey AK, Brown ME (eds) Studies in physical and theoretical chemistry. Elsevier, New York, pp 75–115

    Google Scholar 

  31. Starink MJ (1996) A new method for the derivation of activation energies from experiments permormed at constant heating rate. Thermochim Acta 288:97–104

    Article  Google Scholar 

  32. Luo L, Zhang Z, Li C, Nishu, He F, Zhang X, et al. (2021) Insight into master plots method for kinetic analysis of lignocellulosic biomass pyrolysis. Energy 233: 121194

  33. Pérez-Maqueda LA, Popescu C, Vyazovkin S, Burnham AK, Sbirrazzuoli N, Criado JM (2011) ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data. Thermochim Acta 520:1–19

    Article  Google Scholar 

  34. Pérez-Maqueda LA, Criado JM, Gotor FJ, Málek J (2019) Advantages of combined kinetic analysis of experimental data obtained under any heating profile. J Phys Chem 106(12):2862–2868

    Article  Google Scholar 

  35. Mishra G, Kumar J, Bhaskar T (2015) Kinetic studies on the pyrolysis of pinewood. Bioresour Technol 182:282–288

    Article  Google Scholar 

  36. Singh S, Chakraborty JP, Mondal MK (2020) Intrinsic kinetics, thermodynamic parameters and reaction mechanism of non-isothermal degradation of torrefied Acacia nilotica using isoconversional methods. Fuel 259:116263

  37. Gupta GK, Gupta PK, Mondal MK (2019) Experimental process parameters optimization and in-depth product characterizations for teak sawdust pyrolysis. Waste Mang 87:499–511

    Article  Google Scholar 

  38. Laouge ZB, Merdun H (2021) Investigation of thermal behavior of pine sawdust and coal during co-pyrolysis and co-combustion. Energy 231:120895

  39. Mishra RK, Mohanty K (2018) Pyrolysis kinetics and thermal behavior of waste sawdust biomass using thermogravimetric analysis. Bioresour Technol 251:63–74

    Article  Google Scholar 

  40. Asadullah M, Rahman MA, Ali MM, Rahman MS, Motin MA, Sultan MB et al (2007) Production of bio-oil from fixed bed pyrolysis of bagasse. Fuel 86:2514–2520

    Article  Google Scholar 

  41. Reed TB (1981) Biomass gasification: principles and technology. Noyes Data Corporation, Park Ridge, NJ, pp 154–182

    Google Scholar 

  42. Nanda S, Mohanty P, Kozinski JA, Dalai AK (2014) Physicochemical properties of bio-oils from pyrolysis of lignocellulosic biomass with high and slow heating rate. Energy Environ Res 4:569–577

    Article  Google Scholar 

  43. Shen D, Jin W, Hu J, Xiao R, Luo K (2015) An overview on fast pyrolysis of the main constituents in lignocellulosic biomass to value-added chemicals: structures, pathways and interactions. Renew Sust Energ Rev 51:761–774

    Article  Google Scholar 

  44. Doshi P, Srivastava G, Pathak G, Dikshit M (2014) Physicochemical and thermal characterization of nonedible oilseed residual waste as sustainable solid biofuel. Waste Manage 34:1836–1846

    Article  Google Scholar 

  45. Font R, Fullana A, Conesa J (2005) Kinetic models for the pyrolysis and combustion of two types of sewage sludge. J Anal Appl Pyrol 74(1–2):429–438

    Article  Google Scholar 

  46. Gašparoviè L (2012) Calculation of kinetic parameters of the thermal decomposition of wood by distributed activation energy model (DAEM). Chem Biochem Eng Q 26:45–53

    Google Scholar 

  47. Misse SE, Brillard A, Brilhac JF, Obonou M, Ayina LM, Schonnenbeck C et al (2018) Thermogravimetric analyses and kinetic modeling of three Cameroonian biomass. J Therm Anal Calorim 132:1979–1994

    Article  Google Scholar 

  48. Yang H, Yan R, Chen H, Lee DH, Cheng C (2007) Characteristics of hemicellulose, cellulose and lignin pyrolysis. Fuel 86(12–13):1781–1788

    Article  Google Scholar 

  49. Fan Y, Lu D, Wang J, Kawamoto H (2022) Thermochemical behaviors, kinetics and bio-oils investigation during co-pyrolysis of biomass components and polyethylene based on simplex-lattice mixture design. Energy 239:122235. https://doi.org/10.1016/j.energy.2021.122234

    Article  Google Scholar 

  50. Khan AS, Man Z, Bustam MA, Kait CF, Ullah Z, Nasrullah A et al (2016) Kinetics and thermodynamic parameters of ionic liquid pretreated rubber wood biomass. J Mol Liq 223:754–762

    Article  Google Scholar 

  51. Knoetze, JH, Görgens JF, Thomas Johannes Hugo (2010) Pyrolysis of sugarcane bagasse. Department of Process Engineering at the University of Stellenbosch, Msc Thesis

  52. Šimon P (2004) Isoconversional methods J Therm Anal Calorim 76:123

    Article  Google Scholar 

  53. Vyazovkin S, Burnham AK, Criado JM, P´erez-Maqueda LA, Popescu C, Sbirrazzuoli N, (2011) ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data. Thermochim Acta 520(1–2):1–19

    Article  Google Scholar 

  54. Doddapaneni TRKC, Konttinen J, Hukka TI, Moilanen A (2016) Infuence of torrefaction pretreatment on the pyrolysis of eucalyptus clone: a study on kinetics, reaction mechanism and heat fow. Ind Crop Prod 92:244–254

    Article  Google Scholar 

  55. Nam HV, Tam TT, Tho VDS (2019) Kinetic modelling of thermal decomposition of sugarcane bagasse in the inert gas environment. Vietnam J Chem 57(5):574–580

    Article  Google Scholar 

  56. Junges J, Silvestre WP, Conto DD, Baldasso C, Osório E, Godinho M (2002) Non-isothermal kinetic study of fodder radish seed cake pyrolysis: performance of model-free and model-ftting methods. Braz J Chem Eng 37:139–155

    Article  Google Scholar 

  57. Zheng C, Li D, Ek M (2019) Mechanism and kinetics of thermal degradation of insulating materials developed from cellulose fiber and fire retardants. J Therm Anal Calorim 135:3015–3027

    Article  Google Scholar 

  58. Yuan X, He T, Cao H (2017) Yuan Q (2017) Cattle manure pyrolysis process: kinetic and thermodynamic analysis with iso-conversional methods. Renew Energy 107:489–496

    Article  Google Scholar 

  59. Cao H, Xin Y, Wang D, Yuan Q (2014) Pyrolysis characteristics of cattle manures using a discrete distributed activation energy model. Bioresour Technol 172:219–225

    Article  Google Scholar 

  60. EL-Sayed S, Mostafa ME, (2021) Kinetics, thermodynamics, and combustion characteristics of Poinciana pods using TG/DTG/DTA techniques. Biomass Conv Bioref. https://doi.org/10.1007/s13399-021-02021-8

    Article  Google Scholar 

  61. Ahmad MS, Kleme JJ, Alhumade H, Elkamel A, Mahmood A, Shen B, et al. (2021) Thermo-kinetic study to elucidate the bioenergy potential of Maple Leaf Waste (MLW) by pyrolysis, TGA and kinetic modelling. Fuel 293:120349

  62. Gupta GK, Mondal MK (2019) Kinetics and thermodynamic analysis of maize cob pyrolysis for its bio energy potential using thermogravimetric analyzer. J Therm Anal Calorim 137:1431–1441

    Article  Google Scholar 

  63. Akyurek Z (2019) Sustainable valorization of animal manure and recycled polyester: co-pyrolysis synergy. Sustainability 11:2280

    Article  Google Scholar 

  64. Daugaard DE, Brown RCD (2003) Enthalpy for pyrolysis for several types of biomass. Energy Fuels 17:934–939

    Article  Google Scholar 

  65. Ahmad MS, Mehmood MA, Taqvi STH, Elkamel A, Liu CG, Ren X et al (2017) Pyrolysis, kinetics analysis, thermodynamics parameters and reaction mechanism of Typha latifolia to evaluate its bioenergy potential. Bioresour Technol 245:491–501

    Article  Google Scholar 

  66. He Q, Ding L, Gong Y, Li W, Wei J, Yu G (2019) Effect of torrefaction on pinewood pyrolysis kinetics and thermal behavior using thermogravimetric analysis. Bioresour Technol 280:104–111

    Article  Google Scholar 

  67. Tahir MH, Çakman G, Goldfarb JL, Topcu Y, Naqvi SR, Ceylan S (2019) Demonstrating the suitability of canola residue biomass to biofuel conversion via pyrolysis through reaction kinetics, thermodynamics and evolved gas analyses. Bioresour Technol 279:67–73

    Article  Google Scholar 

  68. Mishra RK, Mohanty K, Wang X (2020) Pyrolysis kinetic behavior and Py-GC–MS analysis of waste dahlia flowers into renewable fuel and value-added chemicals. Fuel 260:116338

  69. Huang J, Liu J, Chen J, Xie W, Kuo J, Lu X et al (2018) Combustion behaviors of spent mushroom substrate using TG-MS and TG-FTIR: thermal conversion, kinetic, thermodynamic and emission analyses. Bioresour Technol 266:389–397

    Article  Google Scholar 

  70. Huanga H, Liua J, Liua H, Evrendilekb F, Buyukadad M (2020) Pyrolysis of water hyacinth biomass parts: bioenergy, gas emissions, and byproducts using TG-FTIR and Py-GC/MS analyses. Energy Convers Manag 207:112552

  71. Rasool T, Srivastava VC, Khan MNS (2018) Kinetic and thermodynamic analysis of thermal decomposition of Deodar sawdust and rice husk as potential for pyrolysis. Int J Chem React Eng 17

  72. Dave A, Gupta GK, Mondal MK (2021) Study on thermal degradation characteristics, kinetics, thermodynamic, and reaction mechanism analysis of Arachis hypogaea shell pyrolysis for its bioenergy potential. Biomass Conv Bioref. https://doi.org/10.1007/s13399-021-01749-7

    Article  Google Scholar 

  73. Slopiecka K, Bartocci P, Fantozzi F (2012) Thermogravimetric analysis and kinetic study of poplar wood pyrolysis. Appl Energy 97:491–549

    Article  Google Scholar 

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Acknowledgements

The authors would like to express their sincere gratitude to the Department of Chemical Engineering and Technology and CIFC, Indian Institute of Technology (Banaras Hindu University), Varanasi, for rendering all the indispensable support needed in this work.

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  1. Department of Chemical Engineering and Technology, Indian Institute of Technology (Banaras Hindu University), Varanasi, 221005, India

    Nidhi Agnihotri, Goutam Kishore Gupta & Monoj Kumar Mondal

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  1. Nidhi Agnihotri
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Nidhi Agnihotri—methodology, investigations, analysis and writing original draft; Goutam Kishore Gupta—formal analysis and editing; Monoj Kumar Mondal—resources, supervision and editing.

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Correspondence to Monoj Kumar Mondal.

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Agnihotri, N., Gupta, G.K. & Mondal, M.K. Thermo-kinetic analysis, thermodynamic parameters and comprehensive pyrolysis index of Melia azedarach sawdust as a genesis of bioenergy. Biomass Conv. Bioref. 14, 1863–1880 (2024). https://doi.org/10.1007/s13399-022-02524-y

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