Loading...
54 results
Search Results
Now showing 1 - 10 of 54
- 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.
- Avaliação do potencial de valorização de sobrantes agroflorestais por um processo organosolv baseado em propilenoglicolPublication . Sampaio, Bruno; Pinto, Filomena; Carvalheiro, Florbela; Duarte, Luís C.RESUMO: Os processos de fracionamento da biomassa são ainda responsáveis por uma parcela substancial dos custos de operação das biorrefinarias, tendo também um impacto muito significativo no desempenho ambiental, pelo que são considerados uma etapa chave para aumentar a competitividade destas instalações industriais. Neste trabalho propõe-se um processo organosolv inovador, baseado em propilenoglicol (PG) um solvente alternativo, não-inflamável, não-tóxico, e que apresenta uma reduzida pressão de vapor, o que permite a operação a pressões próximas da atmosférica, mesmo a temperaturas moderadamente elevadas (até aproximadamente 190ºC). Os resultados obtidos permitem confirmar o elevado potencial do processo organosolv com PG para a desconstrução da palha de trigo, com as vantagens de apresentar uma operação mais segura e económica em comparação com a utilização dos solventes convencionais. São também apresentados e discutidos quais os caminhos mais adequados para a intensificação do processo.
- Gasification study of cynara cardunculus to produce hydrogen rich gasPublication . Franco, Carlos; Lopes, Helena; Pinto, Filomena; Andre, Rui N.; Gulyurtlu, Ibrahim; Cabrita, IsabelThe need to substitute fossil fuel feedstocks with endogeneous biomass to produce energy with lower environmental impact makes necessary to develop innovative and technologically more advanced processes for energy production. Gasification of Cynara cardunculus L. (cardoon) alone and mixed with Eucalyptus was carried out in a bench scale fluidized bed gasifier to study the influence of operating parameters that could lead to a gas rich in hydrogen. The gasification tests were carried out using a mixture of oxygen and steam, as gasifying agent, to avoid the dilution effect of nitrogen that exists in air. The effect of catalysts addition to the bed on gas composition was analyzed as well as the influence in the level of contaminants like H2S, HCl, NH3 and tars in the gas produced. Steam and temperature had a positive effect by promoting the hydrogen production. The higher heating value of the gas produced was determined to be in the range 12 – 15 kJ/nm3 in a dry-nitrogen-free basis. Cardoon contains N, S and Cl which may give rise to problems during the gasification process and to the eventual use of the syngas produced. The results obtained showed that the presence of contaminants could be decreased through retention in the solid phase and by employing a condensation system to separate out pollutants in the liquid phase. This paper will fully present and discuss the results obtained with the gasification of cynara cardunculus and eucalyptus in a fluidized bed gasifier.
- 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.
- Recovery of wastes by pyrolysis: effect of experimental conditionsPublication . Paradela, Filipe; Pinto, Filomena; Ramos, Ana M.; Gulyurtlu, Ibrahim; Cabrita, IsabelThis work aimed to study the recovery of three types of waste by the process of pyrolysis: biomass, plastics and used tyres. The effects of experimental conditions in products yield and composition were studied. The increase of reaction time increased alkane content both in gas phase from 53% to 70% v/v and in liquid fraction from 48% to 60% w/w. The rise of reaction temperature led to a decrease of liquid yield (from 82% to 73% w/w), which was followed by the increase of solids and gases. The increase of reaction temperature also allowed the increase of the alkane content in gas phase from 39% to 70% v/v. The increase of initial pressure did not lead to appreciable variations in product yields or composition. The parameter that most affected products yield and composition was plastics content on the wastes initial mixture. The enhancement of this parameter increased liquids yield from 33% to 92% w/w, at the expenses of solids and gases contents and also decreased aromatics contents from 52% to 28% w/w.
- 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.
- Chemical and bioassay fractionation of chars obtained in the co-pyrolysis of different wastesPublication . Bernardo, Maria; Lapa, Nuno; Gonçalves, Maria Margarida; Mendes, Benilde; Pinto, FilomenaThe present work is devoted to the study chars obtained in the co-pyrolisis of plastics, biomass and tyres wastes. The composition of these chars is not yet well studied and only recent an attempt was made by the aithors to provide some information about the composition and risk assessment of these materials. The objectives of this work were to perform solvent extractions, using differents, in chars obtained in the co-pyrolysis process to evaluate the extraction efficiency by characterising the different solvent extracts obtained as well as the extracted chars, to perform a chemical ans bioassay franctionation in the most toxic crude extraction in order to study the chemical composition of the fractions as well as their individual contribution to the global toxicity of the crude extarct. The results will allow to conclude which solvent should be used in the decontamination of the pyrolysis chars.
- Evaluation of the environmental hazard of char residues produced in the co-pyrolysis of different wastes :chemical and ecotoxicological characterizationPublication . Bernardo, Maria; Lapa, Nuno; Gonçalves, Maria Margarida; Barbosa, Rui; Mendes, Benilde; Pinto, Filomena; Gulyurtlu, IbrahimChar residues produced in co-pyrolysis of different wastes were characterized through chemical and toxicity tests. A fraction of the solid chars was treated by extraction with dichloromethane. Different volatilit fractions present in the extracted and non extrated char were evaluated. A selected group of heavy metals was determined in both chars. Chars were subjected to the leaching test ISO/TS 21268-2 and resulting eluates were further characterized by determining a group of inorganic parameters and concentrations of several organic contaminants. An ecotoxicological characterization was performed by using the bio-indicator Vibrio fischeri. The chemical and ecotoxicological characterization led to a classification on the chars as ecotoxic
- Evaluation of the toxicity of char residues produced in the co-pyrolysis of different wastesPublication . Bernardo, Maria; Lapa, Nuno; Gonçalves, Maria Margarida; Barbosa, Rui; Mendes, Benilde; Pinto, FilomenaThe high amounts of solid waste produced in industrial installations and in urban centers is a complex problem of today's society. The traditional strategies for solid waste transformation and disposal include and filling or incineration. Other approaches are being exploited namely waste selective collection and recycling on the energetic valorization of solid wastes through pyrolysis. In the pyrolytic process, the wastes are converted into a gaseous and liquid phase that can be used in energy production or as feedstock in chemistry industries. A solid residue (char) is also produced in a proportion that depends on the pyrolysis conditions. Even when the operating condiions are optimized in order to minimize the solid fraction, a resonable amount of chars are obtained. Those chars are mainly composed of a carbon-rich matrix that contains the mineral matter initially present in the wastes as well as components of the liquid fraction. Therefore, these solid residues have a toxicity potential due to the presence of heavy metals or organic compounds that must be assessed in order to define their safe reutilization or disposal. In the present study, the chars produced in the co-pyrolysis of plastics, pine biomass and tyres were characterized through chemical and ecotoxicological tests. A fraction of the solid chars was treated by extraction with dichloromethane. Different volatibility groups of compounds present in the extracted and non extracted char were evaluated. A selected group of heavy metals was determined in both chars. Chars were subjected to the leaching test ISO/TS 21268-2 and the resulting eluates were further characterized by determining a group of inorganic and organic parameters. An ecotoxicological characterization was performed by using he bio-indicator Vibrio fischeri. The chemical and ecotoxicological results were compared and analysed according to the council Decision 2003/33/CE and the Criteria on the Evaluation Methods of Waste Ecotoxicity (CEMWE). The results of the chemical characterization indicate that the extraction of the char residues with an appropriate organic solvent allows the sufficient elimination of the volatile organic contaminants thus decreasing the potential toxicity of these chars. The semi-volatile and non-volatile fractions were not, apparently, affected by this pre-treatment. Regarding the release of heavy metals from extracted and non-extracted chars during the leaching tests, a strong contamination with Zn was found in both eluates, which contribute to a classification of the corresponding chars as hazardous and ecotoxic materials. Also the results of the ecotoxicological characterization of the eluates led to a classification of these chars as ecotoxic materials.
- 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.