Microscopic reaction mechanism of the production of methanol during the thermal aging of cellulosic insulating paper

  • 31 Accesses


Cellulose is the main component of transformer insulating paper. In this paper, the pyrolysis mechanism of cellulose is studied by means of computational chemistry. This study is aimed at exploring the generation process of the methanol from cellulosic insulating paper at the atomic level. A simulation scheme of cellulose pyrolysis with detailed reaction pathways for methanol production has been obtained that is not readily accessible by experiments. The molecular dynamics method based on reactive force field (ReaxFF) is adopted to simulate the pyrolysis of cellobiose. A model composed of 40 cellobioses simulated at 500–3000 K was established, and the force biased monte-carlo is mixed into ReaxFF to make it closer to the actual situation and ensure the reliability. The result reveals that the –CH2– group from the C5 (or \({\text{C}}_{ 5}^{{\prime }}\)) group in cellobioses grabbed the nearby H atom to form methanol. In the pyrolysis process of cellobioses, methanol is stable at the early stage but unstable even disappeared in the later stage. The pre-exponential factor A and activation energy Ea of the ReaxFF-MD simulation are consistent with previous experimental results. Thus, this study provides an effective theory of the methanol as an indicator to evaluate the aging condition of cellulosic insulating paper in the early stage at the atomic level.

Graphic abstract

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

Access options

Buy single article

Instant unlimited access to the full article PDF.

US$ 39.95

Price includes VAT for USA

Subscribe to journal

Immediate online access to all issues from 2019. Subscription will auto renew annually.

US$ 199

This is the net price. Taxes to be calculated in checkout.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8


  1. Arroyo OH, Fofana I, Jalbert J, Ryadi M (2015) Relationships between methanol marker and mechanical performance of electrical insulation papers for power transformers under accelerated thermal aging. IEEE Trans Dielectr Electr Insul 22:3625–3632

  2. Ashraf C, Shabnam S, Jain A et al (2019) Pyrolysis of binary fuel mixtures at supercritical conditions: a ReaxFF molecular dynamics study. Fuel 235:194–207

  3. Bruzzoniti MC, Maina R, De Carlo RM et al (2014) GC methods for the determination of methanol and ethanol in insulating mineral oils as markers of cellulose degradation in power transformers. Chromatographia 77:1081–1089

  4. Cao Y, Liu C, Xu X et al (2019) Influence of water on HFO-1234yf oxidation pyrolysis via ReaxFF molecular dynamics simulation. Mol Phys.

  5. Chen W, Kuo P (2011) Isothermal torrefaction kinetics of hemicellulose, cellulose, lignin and xylan using thermogravimetric analysis. Energy 36:6451–6460

  6. Chen Z, Sun W, Zhao L (2019) Initial mechanism and kinetics of diesel incomplete combustion: ReaxFF molecular dynamics based on a multicomponent fuel model. J Phys Chem C 123:8512–8521

  7. Chenoweth K, Van Duin ACT, Goddard WA (2008) ReaxFF reactive force field for molecular dynamics simulations of hydrocarbon oxidation. J Phys Chem A 112:1040–1053

  8. Ding J, Zhang L, Zhang Y et al (2013) A reactive molecular dynamics study of n-heptane pyrolysis at high temperature. J Phys Chem A 117:3266–3278

  9. Fernández-Diego C, Ortiz A, Carrascal IA et al (2019) Damage assessment of transformer Kraft paper insulation aged in mineral and vegetable oils. Cellulose 26:2653–2672

  10. Friesner RA (2005) Ab initio quantum chemistry: methodology and applications. Proc Natl Acad Sci 102:6648–6653

  11. Gao Y, Wang X, Yang H et al (2012) Characterization of products from hydrothermal treatments of cellulose. Energy 42:457–465

  12. Gao M, Li X, Ren C et al (2019) Construction of a multicomponent molecular model of fugu coal for ReaxFF-MD pyrolysis simulation. Energy Fuels 33:2848–2858

  13. Hameed S, Sharma A, Pareek V et al (2019) A review on biomass pyrolysis models: kinetic, network and mechanistic models. Biomass Bioenerg 123:104–122

  14. Hong D, Cao Z, Guo X (2019) Effect of calcium on the secondary reactions of tar from Zhundong coal pyrolysis: a molecular dynamics simulation using ReaxFF. J Anal Appl Pyrolysis 137:246–252

  15. Jalbert J, Gilbert R, Denos Y et al (2012) Methanol: a novel approach to power transformer asset management. IEEE Trans Power Deliv 27:514–520

  16. Leibfried T, Jaya M, Majer N et al (2013) Postmortem investigation of power transformers—profile of degree of polymerization and correlation with furan concentration in the oil. IEEE Trans Power Deliv 28:886–893

  17. Lin Y, Cho J, Tompsett GA et al (2009) Kinetics and mechanism of cellulose pyrolysis. J Phys Chem C 113:20097–20107

  18. Liu J, Fan X, Zhang Y et al (2019a) Condition prediction for oil-immersed cellulose insulation in field transformer using fitting fingerprint database. IEEE Trans Dielectr Electr Insul.

  19. Liu J, Fan X, Zhang Y et al (2019b) Quantitative evaluation for moisture content of cellulose insulation material in paper/oil system based on frequency dielectric modulus technique. Cellulose.

  20. Lu Q, Zhang Y, Dong C et al (2014) The mechanism for the formation of levoglucosenone during pyrolysis of β-d-glucopyranose and cellobiose: a density functional theory study. J Anal Appl Pyrolysis 110:34–43

  21. Matharage SY, Liu Q, Davenport E et al (2014) Methanol detection in transformer oils using gas chromatography and ion trap mass spectrometer. In: 2014 IEEE 18th international conference on dielectric liquids (ICDL). IEEE, pp 1–4

  22. Matharage SY, Liu Q, Wang Z (2016) Aging assessment of kraft paper insulation through methanol in oil measurement. IEEE Trans Dielectr Electr Insul 23:1589–1596

  23. Matharage SY, Liu Q, Wang Z et al (2017) Generation of methanol and ethanol from inhibited mineral oil. In: 2017 INSUCON-13th international electrical insulation conference (INSUCON). IEEE, pp 1–4

  24. Mazeau K, Heux L (2003) Molecular dynamics simulations of bulk native crystalline and amorphous structures of cellulose. J Phys Chem B 107:2394–2403

  25. Neyts EC, Bogaerts A (2009) Numerical study of the size-dependent melting mechanisms of nickel nanoclusters. J Phys Chem C 113:2771–2776

  26. Neyts EC, Shibuta Y, Van Duin ACT et al (2010) Catalyzed growth of carbon nanotube with definable chirality by hybrid molecular dynamics–force biased Monte Carlo simulations. ACS Nano 4:6665–6672

  27. Neyts EC, Van Duin ACT, Bogaerts A (2011) Changing chirality during single-walled carbon nanotube growth: a reactive molecular dynamics/Monte Carlo study. J Am Chem Soc 133:17225–17231

  28. Paajanen A, Vaari J (2017) High-temperature decomposition of the cellulose molecule: a stochastic molecular dynamics study. Cellulose 24:2713–2725

  29. Qiu Y, Zhong W, Shao Y et al (2019) Reactive force field molecular dynamics (ReaxFF MD) simulation of coal oxy-fuel combustion. Powder Technol.

  30. Rodriguez-Celis EM, Duchesne S, Jalbert J et al (2015) Understanding ethanol versus methanol formation from insulating paper in power transformers. Cellulose 22:3225–3236

  31. Schaut A, Autru S, Eeckhoudt S (2011) Applicability of methanol as new marker for paper degradation in power transformers. IEEE Trans Dielectr Electr Insul 18:533–540

  32. Shi L, Zhao T, Shen G et al (2016) Molecular dynamics simulation on generation mechanism of water molecules during pyrolysis of insulating paper. In: 2016 IEEE international conference on high voltage engineering and application (ICHVE). IEEE, pp 1–4

  33. Sørensen MR, Voter AF (2000) Temperature-accelerated dynamics for simulation of infrequent events. J Chem Phys 112:9599–9606

  34. Standard BOI (2006) IEC-60599-2007 Edition 2.1 Mineral oil-impregnated electrical equipment in services—guide to the interpretation of dissolved and free gases analysis

  35. Sun W, Yang L, Zare F et al (2019) Improved method for aging assessment of winding hot-spot insulation of transformer based on the 2-FAL concentration in oil. Int J Electr Power Energy Syst 112:191–198

  36. Timonova M, Groenewegen J, Thijsse BJ (2010) Modeling diffusion and phase transitions by a uniform-acceptance force-bias Monte Carlo method. Phys Rev B 81:144107

  37. Urquiza D, Garcia B, Burgos JC (2015) Statistical study on the reference values of furanic compounds in power transformers. IEEE Electr Insul Mag 4:15–23

  38. Van Duin ACT, Dasgupta S, Lorant F et al (2001) ReaxFF: a reactive force field for hydrocarbons. J Phys Chem A 105:9396–9409

  39. Wang Q, Wang J, Li J et al (2011) Reactive molecular dynamics simulation and chemical kinetic modeling of pyrolysis and combustion of n-dodecane. Combust Flame 158:217–226

  40. Wang S, Dai G, Ru B et al (2017) Influence of torrefaction on the characteristics and pyrolysis behavior of cellulose. Energy 120:864–871

  41. Wang D, Zhu Z, Zhang L et al (2019) Influence of metal transformer materials on oil-paper insulation after thermal aging. IEEE Trans Dielectr Electr Insul 26(2):554–560

  42. Westmoreland PR (2019) Pyrolysis kinetics for lignocellulosic biomass-to-oil from molecular modeling. Curr Opin Chem Eng 23:123–129

  43. Zhang Y, Liu C, Chen X (2015) Unveiling the initial pyrolytic mechanisms of cellulose by DFT study. J Anal Appl Pyrolysis 113:621–629

  44. Zhang Y, Li X, Zheng H et al (2019) A fault diagnosis model of power transformers based on dissolved gas analysis features selection and improved Krill Herd algorithm optimized support vector machine. In: IEEE Access

  45. Zheng M, Wang Z, Li X et al (2016) Initial reaction mechanisms of cellulose pyrolysis revealed by ReaxFF molecular dynamics. Fuel 177:130–141

Download references


This work was supported by the National Natural Science Foundation of China (51907034, 51867003, 61473272), the Natural Science Foundation of Guangxi (2018JJB160056, 2018JJB160064, 2018JJA160176), the Basic Ability Promotion Project for Yong Teachers in Universities of Guangxi (2019KY0046, 2019KY0022), the Guangxi Thousand Backbone Teachers Training Program, the Boshike Award Scheme for Young Innovative Talents and the Guangxi Bagui Young Scholars Special Funding.

Author information

Correspondence to Hanbo Zheng.

Additional information

Publisher's Note

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

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 811 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Zhang, Y., Li, Y., Zheng, H. et al. Microscopic reaction mechanism of the production of methanol during the thermal aging of cellulosic insulating paper. Cellulose (2020).

Download citation


  • Methanol
  • Cellulose
  • ReaxFF
  • Pyrolysis