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Study of thermal cracking kinetics and co-processing of biocrude in thermal residual upgradation unit for converting ‘waste to energy’

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Abstract

In order to reduce dependence on imported crude oil and to progress towards self-reliance in energy, it is desirable to develop processes for producing fuels from renewable resources like bio-based feedstocks. However, it is observed that use of biocrude in a Petroleum Refinery is limited by extensive corrosion of Refinery equipment due to the presence of Naphthenic acids at high levels to the tune of > 90 mg KOH/gm. As part of the study, detailed study on biocrude is carried out and found that 46 vol% fraction of biocrude is having boiling range of 643.15°K–753.15°K and has a high tendency of coke formation. To investigate the behaviour of thermal cracking and extract kinetic parameters, different model-free techniques such as the Friedman, Flynn–Wall–Ozawa and Kissinger–Akahira–Sunose method are employed from the Thermogravimetric and Differential Scanning Calorimetry analysis. The experimental results showed that activation energy obtained from isoconversional methods showed good agreement, but Friedman method was considered to be the best among the model-free methods to evaluate kinetic parameters of highly stable materials like biocrude and VR with activation energy ranging from 53 to 92 kJ mol−1 and 159 to 234 kJ mol−1, respectively, for extent of conversion from 10 to 50 mass%. A thermal cracking study in laboratory scale Micro-coker unit was also carried out by co-processing the biocrude with vacuum residue, to study the feasibility of co-processing in Delayed Coker Unit. Thermal decomposition of biocrude also showed considerable reduction in the Total Acid Number from 90 to 18 mg KOH/gm.

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Acknowledgements

We acknowledge IOCL R&D Centre for providing state of art analytical facilities and granting permission to publish this paper relevant feed and coke samples.

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Authors and Affiliations

  1. Indian Oil Corporation Limited, R & D Centre, Sector-13, Faridabad, India

    B. Jitumoni, Shivam A. Dixit, P. R. Pradeep, K. Ravindra, Satyen K. Das, Jayaraj Christopher, Madhusudan Sau, Gurpreet S. Kapur & S. S. V. Ramakumar

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  1. B. Jitumoni
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  2. Shivam A. Dixit
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Contributions

JB contributed to conceptualization, data curation, visualization, investigation, and writing—original draft, reviewing and editing. SAD contributed to data curation, visualization, and supervision. PPR contributed to data curation, visualization, supervision, and validation. RK contributed to formal analysis (TGA). SKD contributed to supervision, validation, approval and editing of the manuscript in various domains and occasions. JC contributed to supervision, validation, approval and editing of the manuscript in various domains and occasions. MS contributed to supervision, validation, approval and editing of the manuscript in various domains and occasions. GSK contributed to supervision, validation, approval and editing of the manuscript in various domains and occasions. SSVR contributed to supervision, validation, approval and editing of the manuscript in various domains and occasions.

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Correspondence to Satyen K. Das.

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Jitumoni, B., Dixit, S.A., Pradeep, P.R. et al. Study of thermal cracking kinetics and co-processing of biocrude in thermal residual upgradation unit for converting ‘waste to energy’. J Therm Anal Calorim 148, 3439–3456 (2023). https://doi.org/10.1007/s10973-023-11941-8

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