Over the past few decades, life cycle assessment (LCA) has been established as a critical tool for the evaluation of the environmental burdens of chemical processes and materials cycles. The increasing amount of plastic solid waste (PSW) in landfills has raised serious concern worldwide for the most effective treatment. Thermochemical post-treatment processes, such as pyrolysis, seem to be the most appropriate method to treat this type of waste in an effective manner. This is because such processes lead to the production of useful chemicals, or hydrocarbon oil of high calorific value (i.e. bio-oil in the case of pyrolysis). LCA appears to be the most appropriate tool for the process design from an environmental context. However, addressed limitations including initial assumptions, functional unit and system boundaries, as well as lack of regional database and exclusion of socio-economic aspects, may hinder the final decision. This review aims to address the benefits of pyrolysis as a method for PSW treatment and raise the limitations and gaps of conducted research via an environmental standpoint.

Virgin linear low-density polyethylene was subjected to pyrolysis in a fluidized bed reactor pilot plant segmented into three heating zones with both sand and Magnofil BT 80 catalyst as bed materials. The pyrolysis oil and wax products were extracted at an average bed temperature of 600 and 700 °C. The oil yield decreased between 600 (8.7 wt %) and 700 °C (8.1 wt %) in an inverse relationship with the reaction time (358 and 384 min, respectively). This was attributed to an increase in the vibration of the polyolefin polymer matrix as a result of the absorbed thermal energy with an increase in temperature. The experiments performed at 700 °C showed no wax formation but high yields of gaseous products and oils, which are more lucrative in managing accumulated plastic waste, of which polyethylene constitutes large proportions, via thermochemical conversion technologies. The estimated calorific value at 600 °C was 45.5 MJ kg–1, which is in the acceptable range for both diesel and gasoline fuel market specifications. The sulfur content in the pyrolysis oil was estimated to be 0.013% and was not affected by changes in the temperature of the fluidized reactor. However, desulfurization will be required in the future to obtain oil within acceptable ranges of clean fuels. In addition, to support this work’s results in obtaining fuels from such feedstock materials, the fuel range hydrocarbons were also analyzed. The diesel fuel hydrocarbon range (C10–C19) was between 37 and 60% in the pyrolysis oils examined. The results determined experimentally from the pilot-plant work herein are quite promising for sustainable fuel integration plans in the near future with existing petroleum refining complexes.

The use of hydrogen as a renewable fuel has gained increasing attention in recent years due to its abundance and efficiency. The decomposition of formic acid for hydrogen production under mild conditions of 30 °C has been investigated using a 5 wt.% Pd/C catalyst and a fixed bed microreactor. Furthermore, a comprehensive heterogeneous computational fluid dynamic (CFD) model has been developed to validate the experimental data. The results showed a very good agreement between the CFD studies and experimental work. Catalyst reusability studies have shown that after 10 reactivation processes, the activity of the catalyst can be restored to offer the same level of activity as the fresh sample of the catalyst. The CFD model was able to simulate the catalyst deactivation based on the production of the poisoning species CO, and a sound validation was obtained with the experimental data. Further studies demonstrated that the conversion of formic acid enhances with increasing temperature and decreasing liquid flow rate. Moreover, the CFD model established that the reaction system was devoid of any internal and external mass transfer limitations. The model developed can be used to successfully predict the decomposition of formic acid in microreactors for potential fuel cell applications.

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This review paper provides an in-depth review of microreactors for the intensification of the liquid fuel production processes.