THERMAL SCIENCE

International Scientific Journal

Thermal Science - Online First

online first only

Thermodynamic model and kinetic compensation effect of oil sludge pyrolysis based on thermogravimetric analysis

ABSTRACT
Oil sludge (OS) is an organic solid waste in the petrochemical industry and improper treatment of OS will cause environmental pollution. Pyrolysis is an effective way to realize its resource reuse. In order to understand the pyrolysis behavior and thermodynamic characteristics of OS, four OS samples from storage tanks were used as the research object, and pyrolysis experiments were carried out at heating rates of 5, 10, and 15℃/min under a nitrogen atmosphere. The kinetic parameters of pyrolysis of OS are calculated by three equal conversion methods (Friedman method (FR), Flynn-Wall-Ozawa method (FWO) and Distributed activation energy model (DAEM)), and the most possible thermodynamic models for the main pyrolysis phase were analyzed and discussed by introducing the Malek method. The results show: High heating rate can promote the pyrolysis of OS; In the pyrolysis stage, the apparent activation energy increases with the increase of the conversion rate. The apparent activation energy calculated by the FR method is more reliable. The average apparent activation energies of the four OS are 221.23, 84.71, 94.67 and 116.56 kJ/mol, respectively. The apparent activation energy and the pre-exponential factor are positively correlated, indicating that there is a kinetic compensation effect in the pyrolysis process. The thermodynamic models of the four OS samples are all three-dimensional diffusion models, but their integral functions are different. The research results can provide theoretical support for the industrialization, harmlessness and resource utilization of OS pyrolysis.
KEYWORDS
PAPER SUBMITTED: 2020-09-26
PAPER REVISED: 2020-12-05
PAPER ACCEPTED: 2020-12-06
PUBLISHED ONLINE: 2021-01-02
DOI REFERENCE: https://doi.org/10.2298/TSCI200926350L
REFERENCES
  1. Liu, J., et al., Devolatilization of oil sludge in a lab-scale bubbling fluidized bed. Journal of Hazardous Materials, 185(2011), 2-3, pp.1205-1213.
  2. Mutyala, S., et al., Microwave applications to oil sands and petroleum: A review. Fuel Processing Technology, 91(2010), 2, pp.127-135.
  3. Ning, X., et al., Effects of ultrasound on oily sludge deoiling. Journal of Hazardous Materials, 171(2009), 1-3, pp. 914-917.
  4. Chen, J., et al., Co-combustion of sewage sludge and coffee grounds under increased O2/CO2 atmospheres: Thermodynamic characteristics, kinetics and artificial neural network modeling. Bioresource Technology, 250(2018), pp. 230-238.
  5. Gao, B., et al., Performance of dithiocarbamate-type flocculant in treating simulated polymer flooding produced water. Journal of Environmental Sciences, 23(2011), 1, pp. 37-43.
  6. Hou, S. S., et al., Experimental study of the combustion characteristics of densified refuse derived fuel (RDF-5) produced from oil sludge. Fuel, 116(2014), pp.201-207.
  7. Zhou, L, et al., Characteristics of oily sludge combustion in circulating fluidized beds. Journal of Hazardous Materials, 170(2009), 1, pp.175-179.
  8. Cano, R, et al., Energy feasibility study of sludge pretreatments: A review. Applied Energy, 149(2015), pp.176-185.
  9. Gong, Z. Q., et al., Experimental Study on Pyrolysis Characteristics of Oil Sludge with a Tube Furnace Reactor. Energy & Fuels, 31(2017),8, pp.8102-8108.
  10. Hossain, M. K., et al., Thermal characterisation of the products of wastewater sludge pyrolysis. Journal of Analytical & Applied Pyrolysis, 85(2009),1-2, pp.442-446.
  11. Chen, J. B., et al., TG/DSC-FTIR and Py-GC investigation on pyrolysis characteristics of petrochemical wastewater sludge. Bioresource Technology, 192(2015), pp.1-10.
  12. Moliner, R., et al., Valorization of Lube Oil Waste by Pyrolysis. Energy & Fuels, 11(1997),6, pp.1165-1170.
  13. Lin, B., et al., Co-pyrolysis of oily sludge and rice husk for improving pyrolysis oil quality. Fuel Processing Technology, 177(2018), pp.275-282.
  14. Shie, J. L., et al., Pyrolysis of oil sludge with additives of catalytic solid wastes. Journal of Analytical & Applied Pyrolysis, 71(2004), 2, pp.695-707.
  15. Liu, J., et al., Pyrolysis treatment of oil sludge and model-free kinetics analysis. Journal of Hazardous Materials, ,161(2009), 2-3, pp. 1208-1215.
  16. Punnaruttanakun, P, et al., Pyrolysis of API separator sludge. Journal of Analytical & Applied Pyrolysis, 68(2003), pp.547-560.
  17. Shao, J, et al., Pyrolysis Characteristics and Kinetics of Sewage Sludge by Thermogravimetry Fourier Transform Infrared Analysis. Energy & Fuels, 22(2008),1, pp.38-45.
  18. Lin, Y., et al., The investigation of co-combustion of sewage sludge and oil shale using thermogravimetric analysis. Thermochimica Acta, 653(2008), pp. 71-78.
  19. Liu, H., et al., Thermal decomposition kinetics analysis of the oil sludge using model-based method and model-free method. Process Safety and Environmental Protection, 141(2020), pp.167-177
  20. Hu, R. Z., et al., Thermal analysis kinetics. Science Press, Beijing, China, 2008.
  21. Moukhina, E., Determination of kinetic mechanisms for reactions measured with thermoanalytical instruments. Journal of Thermal Analysis and Calorimetry, 109(2012) ,3, pp.1203-1214.
  22. Han, Y., et al., A modified Ortega method to evaluate the activation energies of solid state reactions. Journal of Thermal Analysis and Calorimetry, 112(2013), 2, pp.683-687.
  23. Popescu, C., et al., Critical considerations on the methods for evaluating kinetic parameters from nonisothermal experiments. International Journal of Chemical Kinetics, 30(2015),5, pp.313-327.
  24. Malek, J., Kinetic Analysis of Crystallization Processes in Amorphous Materials. Thermochimica Acta, 355(2000), 1-2, pp.239-253.
  25. Yang, X., et al., Kinetic studies of overlapping pyrolysis reactions in industrial waste activated sludge. Bioresource Technology, 99(2009), 14, pp.3663-3668.
  26. Quan, C., et al., Thermogravimetric analysis and kinetic study on large particles of printed circuit board wastes. Waste Management, 29(2009), 8, pp.2353-2360.
  27. Vyazovkin, S., Computational aspects of kinetic analysis.: Part C. The ICTAC Kinetics Project — the light at the end of the tunnel. Thermochimica Acta, 355(2000), 1, pp.155-163.
  28. Cepeliogullar, O., et al., Thermal and kinetic behaviors of biomass and plastic wastes in co-pyrolysis. Energy Conversion & Management, 75(2013), pp.263-270.
  29. Vyazovkin, S., Modification of the integral isoconversional method to account for variation in the activation energy. Journal of Computational Chemistry, 22(2001), 2, pp.178-183.
  30. Xiang, C. L., et al., Thermodynamic model and kinetic compensation effect of spontaneous combustion of sulfur concentrates. ACS OMEGA, 5(2020), pp.20618-20629.
  31. Koga, N., A review of the mutual dependence of Arrhenius parameters evaluated by the thermoanalytical study of solid-state reactions: The kinetic compensation effect. Thermochimica Acta, 244(1994), pp.1-20.
  32. Tian, B., et al., Pyrolysis behavior and kinetics of the trapped small molecular phase in a lignite. Energy Conversion & Management, 140(2017), pp.109-120.