O presente trabalho buscou avaliar o processo de co-pirólise de resíduos de polipropileno com gasóleo, variando a temperatura e a quantidade de polipropileno no meio reacional. A co-pirólise é uma rota promissora, uma vez que minimiza o impacto ambiental causado pela disposição do plástico de maneira inadequada, evita seu acúmulo em lixões e permite um melhor aproveitamento de um recurso natural não-renovável, o petróleo, matéria-prima importante para a geração de energia e obtenção de produtos químicos. As amostras de polipropileno e gasóleo foram submetidas à co-pirólise térmica em atmosfera inerte, em sistema de leito fixo, sob fluxo constante de nitrogênio, variando a temperatura de 400C a 500C e a quantidade de PP no meio reacional de 0,1 a 1,0 g. A influência do gasóleo no meio foi avaliada pelos testes na ausência de PP. Os líquidos pirolíticos obtidos foram caracterizados por cromatografia gasosa modificada, com o objetivo de avaliar a geração de frações na faixa da destilação do diesel. De uma maneira geral, pôde-se observar que o aumento da quantidade de PP no meio reacional favorece a redução do rendimento de líquido pirolítico e o aumento da quantidade de sólido gerado, efeito inverso ao do aumento da temperatura. Com relação ao rendimento geral de produtos na faixa de destilação do diesel na co-pirólise, a adição de PP ao meio não interfere muito no resultado. Já o aumento de temperatura favorece o aumento do rendimento de produtos nessa faixa de destilação. Os resultados obtidos comprovam o potencial da co-pirólise como método de reciclagem química de artefatos de polipropileno pós-consumo / In this study, the process of co-pyrolysis of polypropylene (PP) residues with gas-oil was evaluated, varying the temperature and the amount of polypropylene fed to the reactor. The co-pyrolysis is a promising route to minimize the environmental impact caused by the inadequate disposal of plastics, preventing its accumulation in landfields and giving a better use of the non renewable raw material (oil). The polypropylene samples and gas-oil were submitted to the thermal co-pyrolysis in an inert atmosphere, varying the temperature from 400C to 500C and the amount of PP from 0,1 to 1,0g. The influence of the gas-oil was evaluated carrying the co-pyrolysis in the absence of PP. The pyrolysed liquids produced by this thermal treatment were characterized by modified gaseous chromatography in order to evaluate the yield in the range of distillation of diesel. As a result, the increase of PP amount lead to a reduction in the yield of the pyrolytic liquid and to an increase of the amount of solid generated. The effect of temperature increase showed an inverse result. The addition of PP in the reactor showed little influence in the yield of diesel in the co-pyrolysis. On the other hand, an increase in temperature favors the increase of products in this range of destillation. The results show that plastic residue co-pyrolysys is a potential method for chemical recycling of plastic products

O presente trabalho buscou avaliar o processo de co-pirólise de resíduos de polipropileno com gasóleo, variando a temperatura e a quantidade de polipropileno no meio reacional. A co-pirólise é uma rota promissora, uma vez que minimiza o impacto ambiental causado pela disposição do plástico de maneira inadequada, evita seu acúmulo em lixões e permite um melhor aproveitamento de um recurso natural não-renovável, o petróleo, matéria-prima importante para a geração de energia e obtenção de produtos químicos. As amostras de polipropileno e gasóleo foram submetidas à co-pirólise térmica em atmosfera inerte, em sistema de leito fixo, sob fluxo constante de nitrogênio, variando a temperatura de 400C a 500C e a quantidade de PP no meio reacional de 0,1 a 1,0 g. A influência do gasóleo no meio foi avaliada pelos testes na ausência de PP. Os líquidos pirolíticos obtidos foram caracterizados por cromatografia gasosa modificada, com o objetivo de avaliar a geração de frações na faixa da destilação do diesel. De uma maneira geral, pôde-se observar que o aumento da quantidade de PP no meio reacional favorece a redução do rendimento de líquido pirolítico e o aumento da quantidade de sólido gerado, efeito inverso ao do aumento da temperatura. Com relação ao rendimento geral de produtos na faixa de destilação do diesel na co-pirólise, a adição de PP ao meio não interfere muito no resultado. Já o aumento de temperatura favorece o aumento do rendimento de produtos nessa faixa de destilação. Os resultados obtidos comprovam o potencial da co-pirólise como método de reciclagem química de artefatos de polipropileno pós-consumo / In this study, the process of co-pyrolysis of polypropylene (PP) residues with gas-oil was evaluated, varying the temperature and the amount of polypropylene fed to the reactor. The co-pyrolysis is a promising route to minimize the environmental impact caused by the inadequate disposal of plastics, preventing its accumulation in landfields and giving a better use of the non renewable raw material (oil). The polypropylene samples and gas-oil were submitted to the thermal co-pyrolysis in an inert atmosphere, varying the temperature from 400C to 500C and the amount of PP from 0,1 to 1,0g. The influence of the gas-oil was evaluated carrying the co-pyrolysis in the absence of PP. The pyrolysed liquids produced by this thermal treatment were characterized by modified gaseous chromatography in order to evaluate the yield in the range of distillation of diesel. As a result, the increase of PP amount lead to a reduction in the yield of the pyrolytic liquid and to an increase of the amount of solid generated. The effect of temperature increase showed an inverse result. The addition of PP in the reactor showed little influence in the yield of diesel in the co-pyrolysis. On the other hand, an increase in temperature favors the increase of products in this range of destillation. The results show that plastic residue co-pyrolysys is a potential method for chemical recycling of plastic products

With 220 billion dry tons available, biomass is one of the world’s most abundant energy source; it also could be a reliable energy source. The human population annual rate of production is 275 million tons of plastic waste as of the year 2019, which has to be managed to facilitate circular carbon economy. Pyrolysis of biomass has emerged as an attractive option for converting waste into bioenergy. Because of its high oxygen content, acidity and viscosity, pyrolysis bio-oil is generally a low-quality product that requires upgrading before being used directly as a drop-in fuel and a fuel additive; this upgrade is achieved by co-pyrolysis of biomass with waste polymers. Since polymers are a rich source of hydrogen, pyrolysis vapors are upgrade; the advantage of co-pyrolysis is that a separate hydroprocessing unit becomes unnecessary after process optimization. Machine learning is emerging as a growing field to predict and optimize the energy related processes. The process can be finetuned using the models trained on the existing experimental data. In this research, machine learning models were developed to predict product yields from the co-pyrolysis of biomass and polymers. Data from the literature on co-pyrolysis of lignocellulosic biomass and polymer co-pyrolysis provided a tool to predict these outcomes. Machine learning algorithms were examined and trained with datasets acquired for biochar and bio-oil yields, with cross-validation and hyperparameters to fit the ultimate and proximate analysis of the reactants and physical conditions of the reactions. XGBoost predicted a biochar yield with RMSE of 1.77 and R$^2$ of 0.96, and a dense neural network predicted a bio-oil yield with RMSE 2.6 and R$^2$ of 0.96. Proximate analysis features were a necessary addition to the bio-oil model. SHAP (SHapley Additive exPlanations) analysis for the DNN liquid model found biomass fixed carbon, biomass moisture and biomass volatile matter with 0.11, 0.09, and 0.06 mean absolute SHAP values, respectively. The machine learning models provided a convenient and predictive tool for co-pyrolysis reaction within the range of the model’s errors and training features. These models also offered insight into the development of municipal solid waste pyrolysis in a circular carbon economy.

Waste recycling is gaining prominence and acceptance compared to landfilling to reduce greenhouse gas emissions. Municipal solid waste (MSW), the largest source of solid waste, is primarily composed of food waste, plastics packaging and papers. Thermochemical recycling technique, such as pyrolysis, is considered as a promising alternative for producing value-added products. Pyrolysis is a process occurring in inert environments at moderate temperatures controlled by parameters such as the reaction temperature, heating rate and residence time to produce bio-oil and biochar. It is also known for its high tolerance for mixed waste stream. In this thesis, fruit waste (FW) consisted of bananas, apples, oranges and cucumbers peels and commercial high density polyethylene (HDPE) as co-pyrolysis feedstock were investigated. Co-pyrolysis experiments were performed in a tubular furnace reactor to investigate the effect of polymer composition, temperature and CO2 atmosphere. HDPE composition was varied between 33–67% to investigate the effect of feedstock composition at 500 ˚C. A composition was fixed and then effect of temperature was assessed in the range 500–700 ˚C. Finally, in CO2 atmosphere, co-pyrolysis experiments were performed with 50% HDPE at 600 ˚C. The collected bio-oil and biochar were thoroughly characterized via different analytical techniques. The effect of different process parameters on bio-oil was studied by gas chromatography-mass spectrometry (GC/MS), proton nuclear magnetic resonance (1H NMR) and Fourier-transform ion cyclotron resonance mass spectroscopy (FT-ICR MS). Biochar samples are analyzed using scanning electron microscopy (SEM), CHNS elemental analysis and Fourier-transform infrared (FTIR). Detailed product composition revealed that formation of hydrocarbons was promoted with increasing HDPE, while significant deoxygenation was observed with increased temperature. In addition, heavier molecules in the bio-oil were studied via FT-ICR MS. HDPE loading and CO2 atmosphere stabilized the biochar by reducing the oxygen content. The results demonstrated the potential use of HDPE as a co-feed with FW in a pyrolysis system to produce valuable products.

As a carbon neutral and renewable source of energy, biomass carries a high potential to help sustain the future energy demand. The co-firing of coal and biomass mixtures is an alternative fuel route for the existing coal based reactors. The main challenges associated with co-firing involves proper understanding of the co-firing behavior of blended coal-biomass fuels, and proper understanding of advanced gasification systems used for converting such blended fuels to energy. The pyrolysis and combustion behavior of coal-biomass mixtures was quantified by devising laboratory experiments and mathematical models. The pyrolysis-combustion behavior of blended fuels was quantified on the basis of their physicochemical, kinetic, energetic and evolved gas behavior during pyrolysis/combustion. The energetic behavior of fuels was quantified by applying mathematical models onto the experimental data to obtain heat of pyrolysis and heat of combustion. Fuel performance models were developed to compare the pyrolysis and combustion performance of non-blended and blended fuels. The effect of blended fuel briquetting was also analyzed to find solutions related to coal and biomass co-firing by developing a bench scale fuel combustion setup. The collected data was analyzed to identify the effects of fuel blending and briquetting on fuel combustion performance, ignitability, flammability and evolved pollutant gases. A further effort was made in this research to develop the understanding of fluidized bed hydrodynamics. A lab scale cold-flow fluidized bed setup was developed and novel non-intrusive techniques were applied to quantify the hydrodynamics behavior. Particle Image Velocimetry and Digital Image Analysis algorithms were used to investigate the evolution of multiple inlet gas jets located at its distributor base. Results were used to develop a comprehensive grid-zone phenomenological model and determine hydrodynamics parameters such as jet particle entrainment velocities and void fraction among others. The results were further used to study the effect of fluidization velocity, particle diameter, particle density, distributor orifice diameter and orifice pitch on the solid circulation in fluidized beds. / Ph. D.