Fuel oil production from thermal decomposition of the model and waste polystyrene: Comparative kinetics and product distribution

Ghulam Ali, J. Nisar, Muhammad Arshad
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Abstract

The thermal degradation of model polystyrene (MPS) and waste polystyrene (WPS) was performed in a thermobalance system at four heating rates (β) i.e., 5, 10, 15 and 20 °C/min  in an inert atmosphere. The apparent activation energy (Ea) and frequency factor (A) for the MPS and the WPS were calculated using Ozawa-Flynn-Wall (OFW), Kissinger-Akahira-Sunose (KAS), and Augis-Bennetis (AB) methods. It has been determined that Ea and A vary according to fraction conversion, heating rates, and applied models. The activation energy determined for MPS was found to be in the range of 91-106, 90-105, and 114-133 kJ/mol, while, for WPS, Ea was determined in the range of 82-160, 79-159 and 102-202 kJ/mol by applying OFW, KAS, and AB models, respectively. From the results obtained, it was concluded that the Ea determined by all of these methods increases with fraction conversion, indicating that the decomposition of polystyrene follows a complex mechanism of the solid-state reaction. Hence, the kinetic parameters, i.e., Ea and A, seem to play a key role in investigating the mechanism of solid-state reactions and will provide an opportunity to develop the mechanism of the industrial decomposition reactions. The results show that the MPS has a lower activation energy compared to WPS. This high Ea of WPS may be due to the additives used in the manufacturing of different polystyrene products. Pyrolysis GC/MS of WPS indicates that the main components of pyrolysis oil are 1-hydroxy-2-propanone, styrene, α-methyl styrene, toluene, and 1,2-dimethyl benzene. The presence of some oxygenated compounds in the fuel oil of WPS may be due to contamination or additives used during polystyrene processing, as the WPS samples were collected from a garbage dump near a local market. WPS can be utilized as fuel if the fuel oil collected from the pyrolysis of WPS is properly upgraded to make it equivalent to commercial fuel oil.
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从模型和废弃聚苯乙烯的热分解中生产燃料油:比较动力学和产品分布
模型聚苯乙烯(MPS)和废聚苯乙烯(WPS)的热降解是在热平衡系统中,在惰性气氛中以4种加热速率(β)进行的,即5、10、15和20°C/min。使用Ozawa Flynn Wall(OFW)、Kissinger Akahira Sunose(KAS)和Augis-Bennetis(AB)方法计算MPS和WPS的表观活化能(Ea)和频率因子(A)。已经确定Ea和A根据馏分转化率、加热速率和应用模型而变化。通过应用OFW、KAS和AB模型,发现MPS的活化能在91-106、90-105和114-133 kJ/mol的范围内,而WPS的Ea分别在82-160、79-159和102-202 kJ/mol范围内。从获得的结果可以得出结论,通过所有这些方法测定的Ea随着馏分转化率的增加而增加,表明聚苯乙烯的分解遵循复杂的固态反应机制。因此,动力学参数,即Ea和A,似乎在研究固态反应的机理中发挥着关键作用,并将为发展工业分解反应的机理提供机会。结果表明,与WPS相比,MPS具有更低的活化能。WPS的这种高Ea可能是由于在制造不同的聚苯乙烯产品中使用的添加剂。WPS的热解GC/MS表明,热解油的主要成分为1-羟基-2-丙酮、苯乙烯、α-甲基苯乙烯、甲苯和1,2-二甲基苯。WPS燃料油中存在一些含氧化合物可能是由于聚苯乙烯加工过程中使用的污染或添加剂,因为WPS样品是从当地市场附近的垃圾场收集的。如果从WPS热解收集的燃料油经过适当升级,使其相当于商业燃料油,则WPS可以用作燃料。
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