Skip to main content

Advertisement

SpringerLink
Log in

Application of distributed activation energy model and Coats-Redfern integration method in the study of industrial lignin pyrolysis kinetics

  • Original Article
  • Published:
Biomass Conversion and Biorefinery Aims and scope Submit manuscript

Abstract

This study addressed the kinetics characteristics and pyrolysis behavior of waste industrial lignin in a thermogravimetric analyzer. DAEM and Coats-Redfern integration methods were employed to evaluate the kinetic parameters at varying heating rates (10–30 °C/min). The physicochemical inspection showed that the industrial lignin had excellent prospects to produce finest chemicals. The TGA results illustrated that the pyrolysis process of industrial lignin could be divided into three stages, including the water loss stage, massive decomposition stage (255–376℃), and charring stage (392–508℃). The activation energies calculated by DAEM are 12.7–23.9 kJ/mol as V/V* rose and 21–27 kJ/mol by the Coats-Redfern integration method of different pyrolysis stages. In addition, the average activation energy of the massive decomposition stage was higher than that of the charring stage. The similar activation energies calculated by both DAEM and Coats-Redfern methods confirmed the accuracy of the kinetic calculations.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. Acar C, Dincer I (2015) Impact assessment and efficiency evaluation of hydrogen production methods. Int J Energy Res 39:1757–1768

    Article  Google Scholar 

  2. Lee H-C, Chang C-T (2018) Comparative analysis of MCDM methods for ranking renewable energy sources in Taiwan. Renew Sustain Energy Rev 92:883–896

    Article  Google Scholar 

  3. Watkins D, Nuruddin M, Hosur M, Tcherbi-Narteh A, Jeelani S (2015) Extraction and characterization of lignin from different biomass resources. J Mater Res Technol 4:26–32

    Article  Google Scholar 

  4. Wu F, Chen L, Hu P, Wang Y, Deng J, Mi B (2021) Industrial alkali lignin-derived biochar as highly efficient and low-cost adsorption material for Pb(II) from aquatic environment. Bioresour Technol 322:124539

    Article  Google Scholar 

  5. Li C, Zhao X, Wang A, Huber GW, Zhang T (2015) Catalytic transformation of lignin for the production of chemicals and fuels. Chem Rev 115:11559–11624

    Article  Google Scholar 

  6. Bajwa DS, Pourhashem G, Ullah AH, Bajwa SG (2019) A concise review of current lignin production, applications, products and their environmental impact. Ind Crops Prod 139:111526

    Article  Google Scholar 

  7. Zhu JY, Pan XJ (2010) Woody biomass pretreatment for cellulosic ethanol production: technology and energy consumption evaluation. Bioresour Technol 101:4992–5002

    Article  Google Scholar 

  8. Chio C, Sain M, Qin W (2019) Lignin utilization: a review of lignin depolymerization from various aspects. Renew Sustain Energy Rev 107:232–249

    Article  Google Scholar 

  9. Mahmood N, Yuan Z, Schmidt J, Xu C (2016) Depolymerization of lignins and their applications for the preparation of polyols and rigid polyurethane foams: A review. Renew Sustain Energy Rev 60:317–329

    Article  Google Scholar 

  10. Ahmad UM, Ji N, Li H, Wu Q, Song C, Liu Q, Ma D, Lu X (2021) Can lignin be transformed into agrochemicals? Recent advances in the agricultural applications of lignin. Ind Crops Prod 170:113646

    Article  Google Scholar 

  11. Baghel S, Sahariah BP, Anandkumar J (2020): Bioremediation of lignin-rich pulp and paper industry effluent. In: Shah M , Banerjee A (Editors), Combined Application of Physico-Chemical & Microbiological Processes for Industrial Effluent Treatment Plant. Springer Singapore, Singapore, 261–278

  12. Ahmad RK, Sulaiman SA, Dol SS, Umar HA (2021): The potential of coconut shells through pyrolysis technology in Nigeria. In: Sulaiman SA (Editor), Clean Energy Opportunities in Tropical Countries. Springer Singapore, Singapore, 151–175

  13. Koul B, Yakoob M, Shah MP (2022) Agricultural waste management strategies for environmental sustainability. Environ Res 206:112285

    Article  Google Scholar 

  14. Haghighat M, Majidian N, Hallajisani A, Samipourgiri M (2020) Production of bio-oil from sewage sludge: a review on the thermal and catalytic conversion by pyrolysis. Sustain Energy Technol Assess 42:100870

    Google Scholar 

  15. Yang Z, Zhang L, Zhang Y, Bai M, Zhang Y, Yue Z, Duan E (2020) Effects of apparent activation energy in pyrolytic carbonization on the synthesis of MOFs-carbon involving thermal analysis kinetics and decomposition mechanism. Chem Eng J 395:124980

    Article  Google Scholar 

  16. Du J, Gao L, Yang Y, Chen G, Guo S, Omran M, Chen J, Ruan R (2021) Study on thermochemical characteristics properties and pyrolysis kinetics of the mixtures of waste corn stalk and pyrolusite. Bioresour Technol 324:124660

    Article  Google Scholar 

  17. Bach Q-V, Chen W-H (2017) A comprehensive study on pyrolysis kinetics of microalgal biomass. Energy Convers Manage 131:109–116

    Article  Google Scholar 

  18. Suriapparao DV, Vinu R (2018) Effects of biomass particle size on slow pyrolysis kinetics and fast pyrolysis product distribution. Waste Biomass Valorization 9:465–477

    Article  Google Scholar 

  19. Wu J, Liao Y, Lin Y, Tian Y, Ma X (2019) Study on thermal decomposition kinetics model of sewage sludge and wheat based on multi distributed activation energy. Energy 185:795–803

    Article  Google Scholar 

  20. Bhutto AW, Bazmi AA, Zahedi G (2013) Underground coal gasification: from fundamentals to applications. Progr Energy Combust Sci 39:189–214

    Article  Google Scholar 

  21. Garcia-Maraver A, Perez-Jimenez JA, Serrano-Bernardo F, Zamorano M (2015) Determination and comparison of combustion kinetics parameters of agricultural biomass from olive trees. Renew Energy 83:897–904

    Article  Google Scholar 

  22. Álvarez A, Pizarro C, García R, Bueno JL, Lavín AG (2016) Determination of kinetic parameters for biomass combustion. Bioresour Technol 216:36–43

    Article  Google Scholar 

  23. Mian I, Li X, Jian Y, Dacres OD, Zhong M, Liu J, Ma F, Rahman N (2019) Kinetic study of biomass pellet pyrolysis by using distributed activation energy model and Coats Redfern methods and their comparison. Bioresour Technol 294:122099

    Article  Google Scholar 

  24. Xiao R, Yang W, Cong X, Dong K, Xu J, Wang D, Yang X (2020) Thermogravimetric analysis and reaction kinetics of lignocellulosic biomass pyrolysis. Energy 201:117537

    Article  Google Scholar 

  25. Fernandez A, Mazza G, Rodriguez R (2018) Thermal decomposition under oxidative atmosphere of lignocellulosic wastes: different kinetic methods application. J Environ Chem Eng 6:404–415

    Article  Google Scholar 

  26. Sajdak M, Słowik K (2014) Use of plastic waste as a fuel in the co-pyrolysis of biomass: Part II. Variance analysis of the co-pyrolysis process. J Anal Appl Pyrolysis 109:152–158

    Article  Google Scholar 

  27. Huang S, Qin J, Chen T, Yi C, Zhang S, Zhou Z, Zhou N (2022) Co-pyrolysis of different torrefied Chinese herb residues and low-density polyethylene: kinetic and products distribution. Sci Total Environ 802:149752

    Article  Google Scholar 

  28. Van Soest PJ, Wine RH (1968) Determination of lignin and cellulose in acid-detergent fiber with permanganate. J Assoc Off Anal Chem 51:780–785

    Google Scholar 

  29. Miura K, Maki T (1998) A simple method for estimating f(E) and k0(E) in the distributed activation energy model. Energy Fuels 12:864–869

    Article  Google Scholar 

  30. Fang S, Lin Y, Lin Y, Chen S, Shen X, Zhong T, Ding L, Ma X (2020) Influence of ultrasonic pretreatment on the co-pyrolysis characteristics and kinetic parameters of municipal solid waste and paper mill sludge. Energy 190:116310

    Article  Google Scholar 

  31. Miura K (1995) A new and simple method to estimate f (E) and k0 (E) in the distributed activation energy model from three sets of experimental data. Energy Fuels 9:302–307

    Article  Google Scholar 

  32. Shen DK, Gu S, Jin B, Fang MX (2011) Thermal degradation mechanisms of wood under inert and oxidative environments using DAEM methods. Bioresour Technol 102:2047–2052

    Article  Google Scholar 

  33. Yeo JY, Chin BLF, Tan JK, Loh YS (2019) Comparative studies on the pyrolysis of cellulose, hemicellulose, and lignin based on combined kinetics. J Energy Inst 92:27–37

    Article  Google Scholar 

  34. Çepelioğullar Ö, Pütün AE (2013) Thermal and kinetic behaviors of biomass and plastic wastes in co-pyrolysis. Energy Convers Manage 75:263–270

    Article  Google Scholar 

  35. Cheng G, He P-w, Xiao B, Hu Z-q, Liu S-m, Zhang L-g, Cai L (2012) Gasification of biomass micron fuel with oxygen-enriched air: thermogravimetric analysis and gasification in a cyclone furnace. Energy 43:329–333

    Article  Google Scholar 

  36. Mishra RK, Mohanty K (2020) Kinetic analysis and pyrolysis behaviour of waste biomass towards its bioenergy potential. Bioresour Technol 311:123480

    Article  Google Scholar 

  37. 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 

  38. 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

    Article  Google Scholar 

  39. Mishra RK, Mohanty K (2018) Characterization of non-edible lignocellulosic biomass in terms of their candidacy towards alternative renewable fuels. Biomass Convers Biorefinery 8:799–812

    Article  Google Scholar 

  40. Li C, Sun Y, Zhang L, Wang C, Zhang S, Li Q, Xu L, Hu X (2021) Cross-interaction of volatiles from co-pyrolysis of lignin with pig manure and their effects on properties of the resulting biochar. Biochar 3:391–405

    Article  Google Scholar 

  41. Shen Z, Hou D, Jin F, Shi J, Fan X, Tsang DCW, Alessi DS (2019) Effect of production temperature on lead removal mechanisms by rice straw biochars. Sci Total Environ 655:751–758

    Article  Google Scholar 

  42. Shi J, Fan X, Tsang DCW, Wang F, Shen Z, Hou D, Alessi DS (2019) Removal of lead by rice husk biochars produced at different temperatures and implications for their environmental utilizations. Chemosphere 235:825–831

    Article  Google Scholar 

  43. Streubel JD, Collins HP, Garcia-Perez M, Tarara J, Granatstein D, Kruger CE (2011) Influence of contrasting biochar types on five soils at increasing rates of application. Soil Sci Soc Am J 75:1402–1413

    Article  Google Scholar 

  44. Hua M-Y, Li B-X (2016) Co-pyrolysis characteristics of the sugarcane bagasse and Enteromorpha prolifera. Energy Convers Manage 120:238–246

    Article  Google Scholar 

  45. Wang X, Sheng L, Yang X (2017) Pyrolysis characteristics and pathways of protein, lipid and carbohydrate isolated from microalgae Nannochloropsis sp. Bioresour Technol 229:119–125

    Article  Google Scholar 

  46. Jiang Y, Zong P, Ming X, Wei H, Zhang X, Bao Y, Tian B, Tian Y, Qiao Y (2021) High-temperature fast pyrolysis of coal: an applied basic research using thermal gravimetric analyzer and the downer reactor. Energy 223:119977

    Article  Google Scholar 

  47. Chen D, Zhou J, Zhang Q (2014) Effects of heating rate on slow pyrolysis behavior, kinetic parameters and products properties of moso bamboo. Bioresour Technol 169:313–319

    Article  Google Scholar 

  48. Müsellim E, Tahir MH, Ahmad MS, Ceylan S (2018) Thermokinetic and TG/DSC-FTIR study of pea waste biomass pyrolysis. Appl Therm Eng 137:54–61

    Article  Google Scholar 

  49. Zuba D (2012) Identification of cathinones and other active components of ‘legal highs’ by mass spectrometric methods. TrAC. Trends Anal Chem 32:15–30

    Article  Google Scholar 

  50. Wan Z, Sun Y, Tsang DCW, Hou D, Cao X, Zhang S, Gao B, Ok YS (2020) Sustainable remediation with an electroactive biochar system: mechanisms and perspectives. Green Chem 22:2688–2711

    Article  Google Scholar 

  51. Naqvi SR, Tariq R, Hameed Z, Ali I, Naqvi M, Chen W-H, Ceylan S, Rashid H, Ahmad J, Taqvi SA, Shahbaz M (2019) Pyrolysis of high ash sewage sludge: kinetics and thermodynamic analysis using Coats-Redfern method. Renew Energy 131:854–860

    Article  Google Scholar 

  52. Raza M, Abu-Jdayil B, Al-Marzouqi AH, Inayat A (2022) Kinetic and thermodynamic analyses of date palm surface fibers pyrolysis using Coats-Redfern method. Renew Energy 183:67–77

    Article  Google Scholar 

  53. Yao Z, Cai D, Chen X, Sun Y, Jin M, Qi W, Ding J (2022): Thermal behavior and kinetic study on the co-pyrolysis of biomass with polymer waste. Biomass Convers. Biorefinery

  54. Yao Z, Yu S, Su W, Wu W, Tang J, Qi W (2020) Kinetic studies on the pyrolysis of plastic waste using a combination of model-fitting and model-free methods. Waste Manag Res 38:77–85

    Article  Google Scholar 

  55. Mui ELK, Cheung WH, Lee VKC, McKay G (2008) Kinetic study on bamboo pyrolysis. Ind Eng Chem Res 47:5710–5722

    Article  Google Scholar 

  56. Guo Z, Zhang L, Wang P, Liu H, Jia J, Fu X, Li S, Wang X, Li Z, Shu X (2013) Study on kinetics of coal pyrolysis at different heating rates to produce hydrogen. Fuel Process Technol 107:23–26

    Article  Google Scholar 

  57. Fahmi R, Bridgwater AV, Darvell LI, Jones JM, Yates N, Thain S, Donnison IS (2007) The effect of alkali metals on combustion and pyrolysis of Lolium and Festuca grasses, switchgrass and willow. Fuel 86:1560–1569

    Article  Google Scholar 

  58. Bui H-H, Tran K-Q, Chen W-H (2016) Pyrolysis of microalgae residues – a kinetic study. Bioresour Technol 199:362–366

    Article  Google Scholar 

  59. Gai C, Liu Z, Han G, Peng N, Fan A (2015) Combustion behavior and kinetics of low-lipid microalgae via thermogravimetric analysis. Bioresour Technol 181:148–154

    Article  Google Scholar 

  60. Domínguez JC, Oliet M, Alonso MV, Gilarranz MA, Rodríguez F (2008) Thermal stability and pyrolysis kinetics of organosolv lignins obtained from Eucalyptus globulus. Ind Crops Prod 27:150–156

    Article  Google Scholar 

  61. Conner WC (1982) A general explanation for the compensation effect: the relationship between ΔS‡ and activation energy. J Catal 78:238–246

    Article  Google Scholar 

  62. Bu L, Tang Y, Gao Y, Jian H, Jiang J (2011) Comparative characterization of milled wood lignin from furfural residues and corncob. Chem Eng J 175:176–184

    Article  Google Scholar 

  63. Zhang Y, Huang M, Su J, Hu H, Yang M, Huang Z, Chen D, Wu J, Feng Z (2019) Overcoming biomass recalcitrance by synergistic pretreatment of mechanical activation and metal salt for enhancing enzymatic conversion of lignocellulose. Biotechnol Biofuels 12:12

    Article  Google Scholar 

  64. Li C, Sun Y, Dong D, Gao G, Zhang S, Wang Y, Xiang J, Hu S, Mortaza G, Hu X (2021) Co-pyrolysis of cellulose/lignin and sawdust: influence of secondary condensation of the volatiles on characteristics of biochar. Energy 226:120442

    Article  Google Scholar 

  65. Jalalabadi T, Drewery M, Tremain P, Wilkinson J, Moghtaderi B, Allen J (2020) The impact of carbonate salts on char formation and gas evolution during the slow pyrolysis of biomass, cellulose, and lignin. Sustain Energy Fuels 4:5987–6003

    Article  Google Scholar 

Download references

Funding

This work was supported by China postdoctoral science foundation [grant number 2018M640750]; Earmarked fund for China Agriculture Research System [grant number CARS-01–27]; Key scientific research project of Education Department of Hunan Province [grant number 20A245]; General project of Natural Science Foundation of Hunan Province [grant number 2021JJ30410]; General project of Natural Science Foundation of Hunan Province [grant number 2022JJ30348].

Author information

Author notes

  1. Long Chen and Jian Hu contributed equally to this work

Authors and Affiliations

  1. Hunan Engineering Research Center for Biochar, School of Chemistry and Materials Science, College of Agronomy, College of Bioscience and Biotechnology, Hunan Agricultural University, Changsha, Hunan, 410128, People’s Republic of China

    Long Chen, Jian Hu, Qian Han, Anqi Xie, Zhi Zhou, Jiankui Yang, Qiyuan Tang, Baobin Mi & Fangfang Wu

  2. Research Institute of Vegetables, Hunan Academy of Agriculture Sciences, Changsha, 410125, China

    Baobin Mi

Authors
  1. Long Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jian Hu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Qian Han
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Anqi Xie
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Zhi Zhou
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Jiankui Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Qiyuan Tang
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Baobin Mi
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Fangfang Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Long Chen: conceptualization, methodology, formal analysis, writing—review and editing, funding acquisition; Jian Hu: investigation, data curation, formal analysis, writing—original draft; Qian Han: investigation, data curation, validation; Anqi Xie: investigation, data curation; Jing Zhang: conceptualization, funding acquisition; Zhi Zhou: conceptualization, methodology, supervision; Qiyuan Tang: resources, funding acquisition, supervision; Baobin Mi*: Resources, methodology, supervision, validation; Fangfang Wu*: Funding acquisition, methodology, supervision, validation.

Corresponding authors

Correspondence to Baobin Mi or Fangfang Wu.

Ethics declarations

Competing Interests

The authors declare no competing interests.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (DOCX 169 KB)

Rights and permissions

Springer Nature or its licensor holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Chen, L., Hu, J., Han, Q. et al. Application of distributed activation energy model and Coats-Redfern integration method in the study of industrial lignin pyrolysis kinetics. Biomass Conv. Bioref. (2022). https://doi.org/10.1007/s13399-022-03132-6

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s13399-022-03132-6

Keywords

Search

Navigation