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- Fermentative hydrogen production from microalgal biomass by a single strain of bacterium Enterobacter aerogenes: effect of operational conditions and fermentation kineticsPublication . Batista, Ana Paula; Gouveia, Luisa; Marques, PaulaABSTRACT: Biohydrogen production through dark fermentation is a promising technology for generating renewable energy, while using microalgal biomass as a third generation feedstock can further increase the sustainability of the process. In the present study, Scenedesmus obliquus was used as model microalga substrate for studying the impact of operational parameters in batch dark fermentation trials using a strain of Enterobacter aerogenes bacteria. (i) The initial gas-liquid ratio in the bioreactor (from 13 to 8.2) was tested, resulting in higher bioH(2) yields for ratios above 5. (ii) Different bacterial growth, inoculation procedures and fermentation media were tested in combined experiments. The best conditions were chosen by maximising bioH(2) yield and minimising production time and costs. (iii) The autoclave sterilization effect on sugar extraction and bioH(2) yield was tested for different microalga concentrations (2.5-50 g/L) with best results attained for 2.5 g/L (81.2% extraction yield, 40.9 mL H-2/g alga). For the best operational conditions, fermentation kinetics were monitored and adjusted to the Modified Gompertz model, with t(95) (time required for bioH(2) production to attain 95% of the maximum yield) below 4.5 h. The maximum hydrogen production was higher when using wet algal biomass enabling the energy Consuming biomass drying step to be skipped.
- 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.
- Biological hydrogen production by Anabaena sp. – Yield, energy and CO2 analysis including fermentative biomass recoveryPublication . Ferreira, Ana F.; Marques, Ana C.; Batista, Ana Paula; Marques, Paula; Gouveia, Luisa; Silva, Carla M.This paper presents laboratory results of biological production of hydrogen by photoautrotophic cyanobacterium Anabaena sp. Additional hydrogen production from residual Cyanobacteria fermentation was achieved by Enterobacter aerogenes bacteria. The authors evaluated the yield of H2 production, the energy consumption and CO2 emissions and the technological bottlenecks and possible improvements of the whole energy and CO2 emission chain. The authors did not attempt to extrapolate the results to an industrial scale, but to highlight the processes that need further optimization. The experiments showed that the production of hydrogen from cyanobacteria Anabaena sp. is technically viable. The hydrogen yield for this case was 0.0114 kgH2/kgbiomass which had a rough energy consumption of 1538 MJ/MJH2 and produced 114640 gCO2/MJH2. The use of phototrophic residual cyanobacteria as a substrate in a dark-fermentation process increased the hydrogen yield by 8.1% but consumed 12.0% more of energy and produced 12.1% more of CO2 showing that although the process increased the overall efficiency of hydrogen production it was not a viable energy and CO2 emission solution. To make cyanobacteria-based biofuel production energy and environmentally relevant, efforts should be made to improve the hydrogen yield to values which are more competitive with glucose yields (0.1 kgH2/kgbiomass). This could be achieved through the use of electricity with at least 80% of renewables and eliminating the unessential processes (e.g.pre-concentration centrifugation).
- A biorefinery from Nannochloropsis sp. microalga – Extraction of oils and pigments. Production of biohydrogen from the leftover biomassPublication . Nobre, B. P.; Villalobos, Fidel; Barragan, Blanca E; Oliveira, Ana Cristina; Batista, Ana Paula; Marques, Paula; Mendes, Rui L.; Sovová, H.; Palavra, António F.; Gouveia, LuisaThe microalga Nannochloropsis sp. was used in this study, in a biorefinery context, as biomass feedstock for the production of fatty acids for biodiesel, biohydrogen and high added-value compounds. The microalgal biomass, which has a high lipid and pigment content (mainly carotenoids), was submitted to supercritical CO2 extraction. The temperature, pressure and solvent flow-rate were evaluated to check their effect on the extraction yield. The best operational conditions to extract 33 glipids/100 gdry biomass were found to be at 40 °C, 300 bar and a CO2 flow-rate of 0.62 g/min. The effect of adding a co-solvent (ethanol) was also studied. When supercritical CO2 doped with 20% (w/w) ethanol was used, it was possible to extract 45 glipids/100 gdry biomass of lipids and recover 70% of the pigments. Furthermore, the remaining biomass after extraction was effectively used as feedstock to produce biohydrogen through dark fermentation by Enterobacter aerogenes resulting in a hydrogen production yield of 60.6 mL/gdry biomass.
- 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.
- Carbon dioxide biofixation and lipid accumulation by green microalgae species at different CO2 concentrations [Resumo]Publication . Leonardo, Joana; Batista, Ana Paula; Manoel, João; Reis, Alberto; Marques, Paula; Gouveia, Luisa
- Lead bioremoval by cork residues as biosorbentPublication . Mota, Dora; Marques, Paula; Rosa, Maria Fernanda; Gil, Luís; Marques, Carlos PereiraThe intensification of industrial activity during the last few years has greatly contributed to the increase of heavy metals in the environment, mainly in the aquatic systems [1]. Conventional technologies traditionally used for the removal of heavy metals from aqueous solutions are expensive and inefficient at low metal concentrations [2]. Biosorption, which is a property of different types of biomass (biosorbents) to bind and concentrate heavy metals from even very dilute aqueous solutions, is one of the most promising technologies that can be used for this purpose [3]. The goal of this work was to study the bioremoval process of Pb(II) ions from aqueous dilute solutions by cork granulates (1-2 mm) from a Portuguese cork processing company. The effect of physico-chemical parameters such as initial metal solution, pH, biomass cork pre-treatments and initial metal and biosorbent concentrations on the metal removal efficiency were investigated. The maximum Pb(II) uptake capacity (Qmax) of cork biomass was also determined from the Langmuir isotherm. The results obtained showed that the optimum initial pH for Pb(II) removal was in the range 3-4, leading to removal yields of about 90-100% for initial metal concentrations of 10-100 mg/L. Cork biomass without treatment provided a higher removal yield (93%) than the biomass submitted to previous extraction with deionised water (80%), ethyl acetate (83%) and ethanol (88 %). The Langmuir model showed a very good correlation with experimental results (r2=0.995) and the Qmax was determined as being 5.3 mg Pb(II)/g cork. The optimisation of continuous bioremoval of Pb(II) (10 mg/L) from 25 L of influent, regarding metal uptake yield and volume of effluent containing a Pb(II) concentration 1 mg/L (MAV), was carried out by the factorial design methodology, leading to the establishment of the best operating conditions. In these conditions, two fixed bed-reactors (operational liquid volume of each reactor containing 20g of biosorbent=138 mL) running in sequential mode (feed flow rate - 590 mL/h) were more efficient (effluent volume with [Pb(II)] 1 mg/L=10 L) than one reactor alone (effluent volume with [Pb(II)] 1 mg/L=5 L). Finally, the chemical characterization in terms of CQO, TOC and phenolic compounds of the effluent before discharge showed that all values were lower than the ones allowed by environmental legislation.
- 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.
- Bioconversion of Jatropha curcas seed cake to hydrogen by a strain of Enterobacter aerogenesPublication . Lopes, Sofia Lewis; Fragoso, Rita; Duarte, Elisabeth; Marques, PaulaHydrogen (H2) gas is considered the future energy carrier as a clean fuel. Biological processes to produce hydrogen are very attractive due to less energy expenditures and the possibility to use organic wastes as substrate. In this work, Jatropha curcas L. seed cake (JSC), a solid residue remaining after oil extraction from J. curcas seeds for biodiesel production, was used as substrate in a dark fermentation process by a pure strain of the bacteria Enterobacter aerogenes. Batch assays were performed using the substrate (2.5 gVolatile Solid/LFermentation Medium) submitted to thermal pretreatment in an autoclave for two different exposure times (15 and 30 min) and the results were compared with the ones obtained when the JSC was used without pretreatment. The best specific biohydrogen production (68.2 mL H2/gVSiJSC) was attained for the conditions of no substrate pretreatment, which is an advantage from the view point of energy saving. In the best conditions, the increase of the initial JSC concentration from 2.5 to 10 gVS/LFM led to the increase of the cumulative hydrogen production and to higher bioH2 production rates. However a decrease on the specific H2 production from 68.2 to 23.5 mL H2/gVSiJSC was observed.
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