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- Hydrogenation of rapeseed oil for production of liquid bio-chemicalsPublication . Pinto, Filomena; Martins, Susana; Gonçalves, Maria Margarida; Costa, Paula; Gulyurtlu, Ibrahim; Alves, Andreia; Mendes, BenildeThe main objective of rapeseed oil hydrogenation tests was the production of liquid bio-chemicals to be used as renewable raw material for the production of several chemicals and in chemical synthesis to substitute petroleum derived stuff. As, hydrogenation of vegetable oils is already applied for the production of biofuels, the work done focused in producing aromatic compounds, due to their economic value. The effect of experimental conditions on rapeseed oil hydrogenation was studied, namely, reaction temperature and time with the aim of selecting the most favourable conditions to convert rapeseed oil into liquid valuable bio-chemicals. Rapeseed oil was hydrogenated at a hydrogen initial pressure of 1.10 MPa. Reaction temperature varied in the range from 200 C to 400 C, while reaction times between 6 and 180 min were tested. The performance of a commercial cobalt and molybdenum catalyst was also studied. The highest hydrocarbons yields were obtained at the highest temperature and reaction times tested. At a temperature of 400 C and at the reaction time of 120 min hydrocarbons yield was about 92% in catalyst presence, while in the absence of the catalyst this value decreased to 85%. Hydrocarbons yield was even higher when the reaction time of 180 min was used in the presence of catalyst, as the yield of 97% was observed. At these conditions hydrocarbons formed had a high content of aromatic compounds, around 50%. For this reason, the viscosity values of hydrogenated oils were lower than that established by EN590, which together with hydrogenated liquids composition prevented its use as direct liquid fuel to substitute fossil gas oil for transport sector. However, hydrocarbons analysis showed the presence of several valuable compounds that encourages their use as a raw material for the production of several chemicals and in chemical synthesis.
- Resultados e conclusões do GTAER : Grupo de Trabalho para a definição das Áreas de Aceleração de Energias RenováveisPublication . Simoes, Sofia; Barbosa, Juliana; Oliveira, Paula; Quental, Lídia; Simões, Teresa; Catarino, Justina; Rodrigues, Carlos; Costa, Paula; Patinha, Pedro; Picado, AnaRESUMO: Este documento apresenta os resultados e conclusões do GTAER (Grupo de Trabalho para a definição das áreas de Aceleração de Energias Renováveis) criado pelo Despacho n.º 11912/2023. Uma parte importante do documento foca o objetivo de consolidar e robustecer o trabalho realizado na identificação das áreas com menor sensibilidade para a localização de unidades de produção de eletricidade renovável. Este trabalho desenvolve-se na sequência do trabalho anteriormente realizado pelo grupo de trabalho informal em atividade entre setembro de 2022 e janeiro de 2023 e que foi alvo de atualização pelo LNEG em junho de 2023. São também apresentados elementos no que respeita a: • potencial de implementação de unidades de geração em superfícies artificializadas; • proposta das áreas de aceleração de energias renováveis; • proposta de regras adequadas à implementação dos projetos de energias renováveis nestas áreas e as medidas de mitigação aplicáveis; • proposta de método de disponibilização pública das áreas de aceleração de energias renováveis a designar, bem como a metodologia para a sua revisão e a periodicidade associada.
- Co-liquefaction of wastes and coal mixtures to produce added value liquid compoundsPublication . Pinto, Filomena; Costa, Paula; Paradela, Filipe; Silva, Pedro; Meredith, Will; Stevens, Lee; Snape, ColinABSTRACT: Nowadays there is an increasing need to find alternative fuels to reduce the dependency on imported ones and to decrease the negative environmental impact of wastes accumulation. Plastics are an important components of urban biowaste, thus their conversion into liquid fuels, in mixtures with other solid fuels still remains an important research goal. After the large experience obtained from coal gasification, it was found that co-liquefaction of coal and wastes may be a good solution to produce liquid fuels and raw materials for several industries. Co-liquefaction of coal blended with biomass gave unfavourable results, but co-liquefaction of coal mixed with PE (polyethylene) wastes led to encouraging results. The results obtained showed that the rise of PE content in coal blends led to an increase in liquid yield. As the main objective was the formation of liquid products, the mixture of coal with 50 wt% of PE was selected, as substantial total liquid yields were obtained, while using significant coal content. This blend was used to study the effect of initial hydrogen pressure, reaction temperature and time on products yields, using Response Surface Methodology (RSM) approach. Liquid yields were most affected by reaction temperature and pressure. The rise of temperature decreased liquid yields, while pressure had a positive effect, but the interaction between these two parameters showed a negative influence. Theoretical equations were used to calculate total and direct liquids yield (%daf). Total liquids are the sum of the liquids directly recovered from the autoclave (direct liquids) and the liquids extracted from the solid product. Both the theoretical model and the experimental results showed that the highest total liquids yields were obtained at 380 ºC, 1.4 MPa and 90 minutes.
- Admissibility Grid to Support the Decision for the Preferential Routing of Portuguese Endogenous Waste Biomass for the Production of Biogas, Advanced Biofuels, Electricity and HeatPublication . Crujeira, Teresa; Trancoso, Maria Ascensão; Eusebio, Ana; Oliveira, Ana Cristina; Passarinho, Paula; Abreu, Mariana; Marques, Isabel Paula; Marques, Paula; Marques, Susana; Albergaria, Helena; Pinto, Filomena; Costa, Paula; Andre, Rui N.; Girio, Francisco; Moura, PatríciaABSTRACT: A methodology was developed to assess the allocation of different types of endogenous waste biomass to eight technologies for producing electricity, heat, biogas and advanced biofuels. It was based on the identification of key physicochemical parameters for each conversion process and the definition of limit values for each parameter, applied to two different matrices of waste biomass. This enabled the creation of one Admissibility Grid with target values per type of waste biomass and conversion technology, applicable to a decision process in the routing to energy production. The construction of the grid was based on the evaluation of 24 types of waste biomass, corresponding to 48 sets of samples tested, for which a detailed physicochemical characterization and an admissibility assessment were made. The samples were collected from Municipal Solid Waste treatment facilities, sewage sludges, agro-industrial companies, poultry farms, and pulp and paper industries. The conversion technologies and energy products considered were (trans)esterification to fatty acid methyl esters, anaerobic digestion to methane, fermentation to bioethanol, dark fermentation to biohydrogen, combustion to electricity and heat, gasification to syngas, and pyrolysis and hydrothermal liquefaction to bio-oils. The validation of the Admissibility Grid was based on the determination of conversion rates and product yields over 23 case studies that were selected according to the best combinations of waste biomass type versus technological solution and energy product.
- Electrical driven pyrolysis reactor retrofit for indirect concentrated solar heatPublication . Azevedo, Pedro; Costa, PaulaABSTRACT: Aiming for a climate-neutral economy, and the associated transition towards fuels produced from alternative feedstock, and to overcome some biomass pyrolysis unsuitable properties for the conventional combustion devices, plastics pyrolysis also produces oils, whose main compounds are also hydrocarbons, that can be used in conventional engines without so complex and costly upgrading processes. Most of the chemical reactions found in a pyrolysis process are endothermal thus, to fulfill that energy demand, the retrofit of a 4 kW electrical furnace pyrolysis reactor to indirect solar driven energy was assessed aiming to adapt it to a central receiver solar tower with up to 100 kWth-peak, using air as heat transfer fluid. The heat demand along a typical pyrolysis test was experimentally assessed and a heat transfer mathematical model was defined to address the working constraints of the reactor. Additional analysis considering new design parameters were performed, namely sensitive analysis to the length of the new heating coil and its overall heat transfer coefficient, the reactor temperature set point, the inlet and outlet (to the atmosphere) gas temperature and working mass flow rates and temperatures were found to provide the same heat demand and minimize the waste heat. Considering both the heat source facility and the reactor constraints, it was found that the retrofit is possible providing that the product of surface area by the overall heat transfer coefficient (A·U) yields more than 17.7 W/K, for a reactor temperature set point of 450 °C and a maximum temperature inlet of 700 °C.
- Production of liquid compounds by co-pyrolysis of different pre-treated biomasses mixed with plastic wastesPublication . Pinto, Filomena; Duarte, Luís C.; Carvalheiro, Florbela; Paradela, Filipe; Costa, Paula; Marques, Joana; Andre, Rui N.; Marques, Paula; Costa, Diogo; Sampaio, BrunoABSTRACT: As an innovation to conventional biomass pyrolysis to produce liquid biofuels, different types of biomass wastes were pre-treated by autohydrolysis, prior to pyrolysis. Eucalyptus forestry waste, corn cobs agricultural residue, and miscanthus (an energy crop) were autohydrolysed. Autohydrolysis led to valuable sugar-rich stream that may be used in fermentation and to solids rich in lignin that were pyrolysed. Pyrolysis of autohydrolysed eucalyptus led to an increase in liquids yields of 24 % in relation to untreated eucalyptus, as autohydrolysis weakened initial macromolecular structure and thus helped chemical bonds breakdown during pyrolysis. However, similar pyrolysis liquid yields were obtained by autohydrolysed or untreated corn cobs and miscanthus, thus feedstock composition is an important issue. Nevertheless, the production of added value products by autohydrolysis may still justify this pre-treatment. Otherwise, more severe pre-treatments of these biomasses might improve co-pyrolysis as it happened with eucalyptus. As polyethylene (PE) is easier to pyrolyse than biomass and greatly favours the production of liquid hydrocarbons, autohydrolysed and untreated biomass was mixed with PE wastes to be used in co-pyrolysis. The rise of PE content in the blend clearly favoured the production of liquid products of pre-treated and untreated biomass. 75 %wt. of PE in the blend led to liquid yields of 72 %wt. for untreated eucalyptus and of 82 %wt. for autohydrolysed eucalyptus.
- Geologia e Energia [Comunicação oral]Publication . Quental, Lídia; Gonçalves, Pedro; Simões, Teresa; Costa, Paula; Couto, António; de Oliveira, Daniel Pipa Soares; Dias, Ruben Pereira
- Produção de hidrocarbonetos líquidos e gasosos por pirólise de resíduos plásticosPublication . Costa, PaulaA sociedade moderna está bastante dependente do petróleo, quer em termos de combustível, quer como matéria prima fundamental para numerosas indústrias. Perante esta situação é urgente gerir de forma mais eficaz os recursos petrolíferos que ainda nos restam, quer por técnicas de optimização de eficiência energética pela utilização de fontes alternativas para obtenção de combustíveis, quer ainda por processos de reciclagem e reutilização dos recursos provenientes do petróleo, de modo a diminuir o recurso crescente ao petróleo. Por outro lado os resíduos plásticos, sofreram um enorme crescimento, sendo por isso uma das principais preocupações da União Europeia. A necessidade de encontrar soluções urgentes para os problemas mencionados, conduziu ao estudo da pirólise para efectuar o aproveitamento energético dos resíduos plásticos. A pirólise é especialmente adequada para a reciclagem de misturas de resíduos plásticos uma vez que, contrariamente à reciclagem física ou mecânica, não exige a presença de um único tipo de plástico e permite a existência de contaminantes ao contrário da reciclagem física, constituindo este aspecto a principal vantagem da pirólise. Este trabalho teve como principal objectivo estudar a pirólise de resíduos plásticos para efectuar o seu aproveitamento energético sem recorrer ao uso de catalisadores, e com condições experimentais economicamente mais favoráveis, nomeadamente temperaturas mais baixas. O trabalho teve como fase inicial o estudo das condições experimentais nomeadamente, o tempo e temperatura de reacção e a pressão inicial, a fim de optimizar os rendimentos e a qualidade dos produtos. Foram estudados os três tipos de plásticos mais utilizados: PE (polietileno), PP (polipropileno) e PS (poliestireno). Este estudo revelou os seguintes valores para condições mais favoráveis: tempo reacção 30 minutos, pressão inicial de 0,41 MPa e temperatura 400ºC. Estas condições foram utilizadas para estudar o efeito da composição dos resíduos plásticos e do aumento de escala nos rendimentos e composição dos produtos. Verificou-se que a composição das misturas de resíduos foi o parâmetro que mais afectou os resultados obtidos. Esse efeito foi mais notório na composição dos produtos líquidos, tendo-se detectado que a presença de maiores teores de polietileno nas misturas favoreceu a formação de alcanos, a presença de polipropileno aumentou a concentração de alcenos e a de poliestireno favoreceu a formação de compostos aromáticos. Foi também estudada a ocorrência de eventuais interacções durante a pirólise de misturas de resíduos plásticos. Para tal, foram comparados os resultados obtidos na pirólise de várias 2 misturas dos três tipos de plásticos estudados com os resultados obtidos por pirólise dos plásticos usados individualmente. Apenas na composição dos produtos líquidos foram detectadas interacções entre os produtos formados por pirólise. Verificou-se que a presença de poliestireno parece ter um efeito predominante em relação aos outros plásticos, uma vez que, a existência de maiores teores deste plástico aumentou significativamente a concentração de compostos aromáticos na fracção líquida e diminuiu a de alcenos. O efeito do aumento de escala no processo de pirólise de resíduos plásticos também foi estudado, utilizando-se três reactores com diferentes capacidades, tendo este efeito sido diverso consoante a mistura de resíduos plásticos testada, o que não permitiu estabelecer claramente o efeito das dimensões do reactor no processo de pirólise. Provavelmente o efeito da composição das misturas sobrepôs-se ao da influência das características do reactor. A razão entre o volume do reactor e a quantidade de mistura utilizada também parece ter sido um parâmetro importante, uma vez que, esta razão teve de ser igual ou superior a 10, caso contrário não ocorria a formação de compostos líquidos. Por último foram efectuados estudos cinéticos destes três tipos de plásticos usados individualmente e de uma mistura contendo igual percentagem de todos eles. Com base nos resultados obtidos nos diversos ensaios, a diferentes temperaturas e tempos de reacção, foram propostos mecanismos reaccionais para todos os plásticos testados e para a mistura. Baseado no esquema reaccional proposto, foram desenvolvidos modelos cinéticos para a pirólise de PE, PP e PS e da mistura. Verificou-se que os resultados obtidos pelos modelos se ajustaram satisfatoriamente aos resultados experimentais, permitindo explicar os diversos resultados obtidos na pirólise. Os parâmetros cinéticos foram estimados verificando-se, em todos os casos, a possível dependência da energia de activação e do factor pré-exponencial da temperatura, não exibindo, por isso, algumas constantes de velocidade, uma dependência linear com a temperatura, na sua forma logarítmica. A composição das várias fracções obtidas na pirólise também foi analisada e com base nos resultados obtidos foram propostos esquemas reaccionais para a degradação dos três tipos de plástico e da mistura destes. Os resultados obtidos demonstraram que a pirólise de resíduos plásticos poderá, no futuro, desempenhar um papel importante no aproveitamento energético destes resíduos, embora o seu estudo deva ser continuado de forma a melhorar os aspectos económicos desta tecnologia e a demonstrar a sua viabilidade à escala industrial.
- Production of bio-hydrocarbons by hydrotreating of pomace oilPublication . Pinto, Filomena; Varela, Francisco; Gonçalves, Maria Margarida; Andre, Rui N.; Costa, Paula; Mendes, BenildeOlive pomace oil is a by-product from the olive oil industry that is still being used in the food industry as a low value vegetable oil. Crude olive pomace oil needs to be refined and is blended with virgin olive oils before being used as edible oil. The detection of toxic compounds led to more restricted legislation and to the search of alternative valorisation processes, such as hydrotreating to obtain bio-hydrocarbons. Hydrotreating of olive pomace oil at moderate temperatures (from 300 to 430 C) and in presence of initial hydrogen pressure of 1.1 MPa led to triglycerides destruction and to their conversion into a large range of organic compounds with predominance to hydrocarbons. Even without any catalyst, conversions into hydrocarbons were always higher than 90% (v/v). Catalyst presence, such as: CoMo/Al2O3, FCC (fluid catalytic cracking) or HZSM-5 changed hydrogenated liquids composition. The highest content of alkanes was obtained with CoMo catalyst, while FCC and HZSM-5 led to the highest contents of aromatic compounds. The results obtained showed that olive pomace oil can be efficiently converted into bio-hydrocarbons with a wide range of applications. It was also studied the effect of pyrolysing olive pomace oil prior to its hydrotreating. Pyrolysis pre-treatment seems to have favoured hydrotreating process by promoting initial cracking reactions. Thus, it was possible to increase the production of liquid compounds with a higher content of light molecules. However, the advantages of using a more complex two steps process still need to be proven.
- Carbon footprint assessment of microalgal biomass production, hydrothermal liquefaction and refining to sustainable aviation fuel (SAF) in mainland PortugalPublication . Pires, Renata; Silva, Tiago; Ribeiro, Cláudia; Costa, Luis; Matos, Cristina T.; Costa, Paula; Lopes, Tiago; Gírio, Francisco; Silva, CarlaABSTRACT: Industrial liquid effluents (e.g., from fertilizer industry) and flue gas streams (e.g., CO2-rich, from cement industry) arise as an opportunity for waste valorization. Microalgae are suitable biomass for assimilating both effluents at the cultivation stage. Under a biorefinery concept, given the urge for energy transition in the aviation sector, this research explores the transformation of a microalgae consortium grown at an industrial site in Portugal and its subsequent harvesting, hydrothermal liquefaction (HTL), and bio-oil refining. A life cycle assessment (LCA) approach is undertaken with two functional units (FU): 1 kg of microalgae dry-cell weight (dw) and 1 MJ of bio-jet fuel. The latter follows an attributional approach with energy allocation for comparison with the Carbon Offsetting and Reduction Scheme for International Aviation (CORSIA) guidelines. HTL is based on data from bench-scale experiments and literature, whereby the Petroleum Refinery Life Cycle Inventory Model (PRELIM) is used to mimic bio-oil refining. Following this approach, achieving Sustainable Aviation Fuel (SAF) compliance requires net-zero electricity (0 gCO2eq/kWh), with an HTL bio-oil yield of 55.6 % dw (the maximum observed), a minimum refining bio-jet fuel yield of at least 16 %. Alternatively, an HTL bio-oil yield of 36.9 % dw (the median observed) with a refining efficiency of at least 24.3 %.