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- 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.
- 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.
- 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.
- 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.
- Effects of experimental conditions and of addition of natural minerals on syngas production from lignin by oxy-gasification: comparison of bench- and pilot scale gasificationPublication . Pinto, Filomena; Andre, Rui N.; Carolino, Carlos; Miranda, Miguel; Abelha, Pedro; Direito, Daniel; Dohrup, Jesper; Sorensen, Hanne Risbjerg; Gírio, FranciscoGasification of spent lignin pellets was used to obtain a gas suitable for energy production. Spent lignin was obtained from second-generation cellulosic ethanol demo plant using wheat straw as feedstock. Gasification of lignin did not give rise to any feeding problems, thus no significant changes were needed in the existing gasification installation. The rise of temperature and steam flow rate favoured the formation of H2, while hydrocarbons (CnHm) and tar contents decreased. The increase of equivalent ratio (ER) also decreased hydrocarbons and tar contents, but syngas higher heating value (HHV) was reduced. The use of natural minerals improved lignin gasification. The presence of dolomite led to the highest H2 and to the lowest CnHm and tar contents. Results obtained at bench-scale were confirmed at pilot-scale, as similar trends were obtained. However, as the residence time in pilot gasifier was higher, greater gas yields with higher H2 and CH4 concentrations were obtained, while tar contents decreased. After syngas hot cleaning and upgrading, the final syngas composition showed to be suitable for a wide range of applications (e.g. energy production and synthesis of chemicals), since it was substantially enriched in hydrogen, whereas tar and heavier gaseous hydrocarbons were completely destroyed.
- Biocatalytic performance of Butyribacterium methylotrophicum in the long-term conversion of synthesis gas produced from low-grade lignin gasification by Butyribacterium methylotrophicum [Resumo]Publication . Pacheco, Marta; Pinto, Filomena; Andre, Rui N.; Marques, Paula; Gírio, Francisco; Moura, PatríciaABSTRACT: Second-generation biorefineries produce large streams of low-grade lignin. Its thermochemical conversion, through gasification, enables the carbon recovery from an otherwise recalcitrant by-product. The main product of gasification is producer synthesis gas (PS), which is mainly composed by carbon monoxide (CO), carbon dioxide (CO2), hydrogen (H2), methane (CH4) and minor impurities. Carboxydotrophic acetogenic bacteria can utilize CO and CO2 as carbon and energy source, and convert them into biomass, biofuels and biochemicals through the Wood-Ljungdahl pathway.
- Integration of gasification and solid oxide fuel cells (SOFCs) for combined heat and power (CHP)Publication . Costa, Paula; Pinto, Filomena; Andre, Rui N.; Marques, PaulaABSTRACT: This paper reviews the most recent information about the main operations to produce energy from carbonaceous materials, namely biomass and wastes through the integration of gasification, syngas cleaning and solid oxide fuel cells (SOFCs), which have shown to be a good option for combined heat and power (CHP) production, due to high efficiency and low environmental impact. However, some challenges still need to be overcome, mainly when mixed feedstocks with high contents of hazardous contaminants are used, thus syngas cleaning and conditioning is of major importance. Another drawback is SOFC operation, hence new materials especially for the anode has been proposed and tested. An overall process to produce CHP by gasification integration with SOFC is proposed.
- Co-gasification of rice production wastesPublication . Andre, Rui N.; Pinto, Filomena; Miranda, Miguel; Carolino, Carlos; Costa, PaulaRice production is one of the major food sources in the world and unavoidably generates large amounts of wastes, mainly husk and straw that must be dealt in an environmentally sound and sustainable way. Traditional solutions, like burning in open fields or soil incorporation, may contribute for local pollution. Even the use of these wastes as animal food is not an appropriate solution. Plastics are also an additional waste arising from the life cycle of rice production, manufacturing and distribution. The co-gasification of these wastes was easily accomplished in a fluidized bed installation using steam mixed with air or oxygen as gasifying and fluidisation agents. By changing the gasifying agent composition it is possible to select the best conditions to co-gasify rice husks and PE wastes blends. For rice husks gasification, highest H2/hydrocarbons molar ratios were obtained using a mixture of air and steam and an equivalent ratio of 0.2. These conditions correspond to low tar emissions and very good gas yields and gas higher heating values (HHV). Co-gasification of rice husk mixed with PE enables to increase gas HHV, but also generates more tar. Nevertheless using up to 20 % of PE can be considered a promising solution to deal with this kind of wastes. Pollutants like H2S and NH3 were formed in the gasification process in acceptable amounts. Co-gasification with PE enables to decrease these pollutants. Depending on the gas end-use, the installation of a hot gas conditioning system could be needed to further decrease the contents of tar, H2S and NH3, while also promoting the conversion of hydrocarbons into H2 and CO.
- Hot treatment and upgrading of syngas obtained by co-gasification of coal and wastesPublication . Pinto, Filomena; Andre, Rui N.; Carolino, Carlos; Miranda, MiguelNowadays there is a great interest in producing energy through co-gasification of low grade coals and waste blends to increase the use of alternative feedstocks with low prices. The experimental results showed that the viability of co-gasification to process such blends and that by the right manipulation of coal and biomass or waste blends, syngas treatment and upgrading may be simplified and the cost of the overall process may be reduced. Blends of three different coal grades (sub-bituminous coal from Puertollano mines, South African bituminous coal and German brown coal) with two different types of biomass (pine and olive oil bagasse) or polyethylene (PE) were co-gasified. Blend co-gasification showed to be beneficial to reduce the negative characteristics of some coals, such as the high ash and sulphur contents, especially of Puertollano coal. Syngas obtained by these blends was hot cleaned and undesirable syngas components (tar, NH3 and H2S) were measured along the hot treatment tested, which proved to be suitable to treat syngas produced by a wide range of feedstocks. Different routes for syngas cleaning were analysed to reduce unsuitable components to values required by most common end-uses. The results obtained showed that the type of feedstock to be gasified is a key outcome on initial syngas composition, affecting greatly syngas cleaning needs, its application and the economic viability of the overall process.
- Benefits and drawbacks of energetic valorisation of Eucalyptus Globulus stumps by thermochemical processesPublication . Pinto, Filomena; Andre, Rui N.; Lopes, Helena; Neves, Diogo; Varela, Francisco; Santos, João Navalho; Miranda, Migueln the pulp and paper industry in Iberian Peninsula there is an intensive use of eucalyptus globulus that has a fast growth and a high productivity. There are large areas of forest dedicated to its growth. After 9 to 12 year rotation cycles trees are cut and the stumps are left in the fields. After 2 or 3 harvesting cycles these tree stumps are removed from the fields and considered low value biomass wastes. This corresponds to depletion on organic matter and of valuable minerals related to soil fertility. The use of these biomass wastes in thermochemical conversion processes like gasification or combustion may be a valuable alternative solution as it allows taking profit of these wastes energetic content. The solid by-products obtained by thermal conversion (ashes) may be incorporated in soils to return the valuable minerals and to ensure a good forest management system. Stumps removed from eucalyptus stands were used in combustion trials to improve the burning conditions and in gasification tests with different experimental conditions to obtain syngas suitable to be used in furnaces (chemical recover) of pulp industries. Stumps combustion and gasification processes were compared in terms of stumps energetic valorisation, gaseous emissions and gasification gas utilisation.
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