• Energy Research

Today microalgae represent a viable alternative source for high-value products. The specie Chlorella protothecoides (Cp), heterotrophically grown, has been widely studied and provides a high amount of lutein and fatty acids (FA) and has a good profile for biodiesel production. This work studies carotenoid and FA production by autotrophic grown Cp. Cp was grown until the medium's nitrogen was depleted, then diluted in NaCl solution, resulting in nutritional, luminosity, and salinity stresses. Different NaCl concentrations were tested (10, 20, 30 g/L) at two different dilutions. After dilution, a color shifting from green to orange-red was noticed, showing carotenoid production. The best production of both carotenoids and FA was attained with a 20 g/L NaCl solution. The total carotenoid content was 0.8 % w/w (canthaxanthin (23.3 %), echinenone (14.7 %), free astaxanthin (7.1 %), and lutein/zeaxanthin (4.1 %)). Furthermore, the total lipid content reached 43.4 % w/w, with a FA composition of C18:1 (33.64 %), C16:0 (23.30 %), C18:2 (11.53 %), and less than 12 % of C18:3, which is needed to fulfill the biodiesel quality specifications (EN 14214).

Chrypthecodinium cohnii lipids have been almost exclusively used as a source of Docosahexaenoic acid (DHA). Such an approach wastes the remaining microalgal lipid fraction. The present work presents a novel process to produce C. cohnii biomass, using low-cost industrial by-products (raw glycerol and corn steep liquor), in a 7L-bioreactor, under fed-batch regime. At the end of the fermentation, the biomass concentration reached 9.2 g/L and the lipid content and lipid average productivity attained 28.0% (w/w dry cell weight) and 13.6 mg/L h, respectively. Afterwards the microalgal biomass underwent a saponification reaction to produce fatty acid (FA) soaps, which were further converted into FA ethyl ester (FA EE). C. cohnii FA EE mixture was then fractionated, using the urea complexation method at different temperatures, in order to obtain a polyunsaturated fatty acid ethyl ester (PUFA EE) rich fraction, that could be used for food/pharmaceutical/cosmetic purposes, and a saturated fatty acid ethyl ester (SAT EE) rich fraction, which could be used as biodiesel. The temperature that promoted the best separation between PUFA and SAT EE, was −18 °C, resulting in a liquid fraction with 91.6% (w/w) DHA, and a solid phase with 88.2% of SAT and monounsaturated fatty acid ethyl ester (MONOUNSAT), which could be used for biodiesel purposes after a hydrogenation step.

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.

This work evaluates the environmental performance of using pulp and paper sludge as feedstock for the production of second generation ethanol. An ethanol plant for converting 5400 tons of dry sludge/year was modelled and evaluated using a cradle-to-gate life cycle assessment approach. The sludge is a burden for pulp and paper mills that is mainly disposed in landfilling. The studied system allows for the valorisation of the waste, which due to its high polysaccharide content is a valuable feedstock for bioethanol production. Eleven impact categories were analysed and the results showed that enzymatic hydrolysis and neutralisation of the CaCO3 are the environmental hotspots of the system contributing up to 85% to the overall impacts. Two optimisation scenarios were evaluated: (1) using a reduced HCl amount in the neutralisation stage and (2) co-fermentation of xylose and glucose, for maximal ethanol yield. Both scenarios displayed significant environmental impact improvements.

Wastewater biological treatment with microalgae can be an effective technology, removing nutrients and other contaminants while reducing chemical oxygen demand. This can be particularly interesting for the meat producing industry which produces large volumes of wastewater from the slaughtering of animals and cleaning of their facilities. The main purpose of this research was the treatment of poultry wastewater using Scenedesmus obliquus in an economical and environmentally sustainable way. Two wastewaters were collected from a Portuguese poultry slaughterhouse (poultry raw - PR and poultry flocculated - PF) and the bioremediation was evaluated. The performance of microalga biomass growth and biochemical composition were assessed for two illumination sources (fluorescent vs LEDs). S. obliquus achieved positive results when grown in highly contaminated agro-industrial wastewater from the poultry industry, independently of the light source. The wastewater bioremediation revealed results higher than 97% for both ammonium and phosphate removal efficiency, for a cultivation time of 13 days. The saponifiable matter obtained from the biomass of the microalga cultures was, on average, 11% and 27% (m/malga) with PR and PF wastewater, respectively. In opposition, higher sugar content was obtained from microalgae biomass grown in PR wastewater (average 34% m/malga) in comparison to PF wastewater (average 23% m/malga), independently of the illumination source. Therefore, biomass obtained with PR wastewater will be more appropriate as a raw material for bioethanol/biohydrogen production (higher sugar content) while biomass produced in PF wastewater will have a similar potential as feedstock for both biodiesel and bioethanol/biohydrogen production (similar lipid and sugar content).

Prior to the commissioning of a new industrial biorefinery it is deemed necessary to evaluate if the new project will be beneficial or detrimental to climate change, one of the main drivers for the sustainable development goals (SDG) of the United Nations. In particular, how SDG 7, Clean and Efficient Energy, SDG 3, Good Health and Well Being, SDG 9, Industry Innovation and Infrastructure, and SDG 12, Responsible Production and Consumption, would engage in a new biorefinery design, beneficial to climate change, i.e., fostering SDG 13, Climate Action. This study uses life cycle assessment methodology (LCA) to delve in detail into the Global Warming Impact category, project scenario GHG savings, using a conventional and a dynamic emission flux approach until 2060 (30-year lifetime). Water, heat and electricity circularity are in place by using a water recirculation process and a combined heat and power unit (CHP). A new historical approach to derive low and higher-end commodity prices (chemicals, electricity, heat, jet/maritime fuel, DHA, N-fertilizer) is used for the calculation of the economic indicators: Return of investment (ROI) and inflation-adjusted return (IAR), based upon the consumer price index (CPI). Main conclusions are: supercritical fluid extraction is the hotspot of energy consumption; C. cohnii bio-oil without DHA has higher sulfur concentration than crude oil based jet fuel requiring desulfurization, however the sulfur levels are compatible with maritime fuels; starting its operation in 2030, by 2100 an overall GHG savings of 73% (conventional LCA approach) or 85% (dynamic LCA approach) is projected; economic feasibility for oil productivity and content of 0.14 g/L/h and 27% (w/w) oil content, respectively (of which 31% is DHA), occurs for DHA-cost 100 times higher than reference fish oil based DHA; however future genetic engineering achieving 0.4 g/L/h and 70% (w/w) oil content (of which 31% is DHA), reduces the threshold to 20 times higher cost than reference fish oil based DHA; N-fertilizer, district heating and jet fuel may have similar values then their fossil counterparts.

This work proposes a valorization route for spent coffee grounds (SCG), a widespread lignocellulosic residue, encompassing the production of: biomethane, lignin, and oligosaccharides as value-added products obtained simultaneously during a mild alkaline (NaOH) pretreatment. The studied operational variables were the reaction time (60–240 min), temperature (25–75 °C), and the NaOH concentration (0–2.5 M). The severity factor suitably describes the global process kinetics, with higher severities (log Mo = 5.5) yielding high product yields, 18.02% and 13.25% (on dry SCG basis) for lignin and oligosaccharides (XGMOS), respectively. Solid yield is negatively impacted by all studied variables (at the 95% confidence level). Conversely, XGMOS yield is positively influenced both by time and catalyst concentration, whereas lignin yield is only (positively) influenced by catalyst concentration. Optimal balance between product formation and potential operational costs is putatively achieved when using 0.625 M NaOH, at 50 °C for 60 min. The mild alkaline pretreated biomass (MAP-SCG) was compared to untreated SCG for biomethane production by anaerobic co-digestion with pig slurry (PS), using a ratio of biomass/PS = 1/3 (volatile solids (VS) basis). The proposed valorization route enabled the sequential production of 6.25 kg lignin, 6.36 kg oligosaccharides, and 138.05 kg biomethane per 100 kg of non-extracted SCG (and 287.60 kg pig slurry), in an integrated process that is technically feasible and promotes the circular bioeconomy.