Innovative valorisation of microalgal by-products as feedstock for biorefineries

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Development of an innovative macroalgae biorefinery: Oligosaccharides as pivotal compounds

Publication . Andrade, Cristiana; Martins, Pedro L.; Duarte, Luís C.; Oliveira, Ana Cristina; Carvalheiro, Florbela

ABSTRACT: Macroalgae have significant advantages over land-living biomass resources and are promising pivotal feedstocks for the onset of the blue bioeconomy. Among these, Ulva lactuca has demonstrated a high potential due to its wide distribution and high productivity. In this work, a detailed chemical characterization of U. lactuca enabled the identification of polysaccharides as the main macromolecular component of the organic fraction. They present a high diversity of sugar constituents and hence can be a relevant source of added-value oligosaccharides for the food/feed industries. Four processes, with increasing operational temperatures, were compared for the selective production of oligosaccharides: Conventional Soxhlet Extraction, Accelerated Solvent Extraction, Hydrothermal treatment (HT) and Dilute Acid Hydrolysis (DAH). All processes presented high oligosaccharide/monosaccharide ratios, with HT and DAH exhibiting the highest oligosaccharides yields (10.6 and 16.6 g/100 g initial biomass, respectively). These oligosaccharides were obtained under milder, more economic conditions than the reported for lignocellulosic (land) plants and can represent an important added-value income of the algae biorefineries and thus contribute to their economic sustainability.

2022-07Journal article

Open access

Effective fractionation of microalgae biomass as an initial step for its utilization as a bioenergy feedstock

Publication . Martins, Pedro L.; Reis, Alberto; Duarte, Luís C.; Carvalheiro, Florbela

ABSTRACT: Scenedesmus obliquus, a biotechnologically relevant microalgae, was grown in 70 L vertical photobioreactors using non-supplemented secondary brewery wastewater as a culture medium. Upon collection, by mechanical means, the cells were subjected to hydrothermal (autohydrolysis) and dilute acid hydrolysis (0.5 % sulfuric acid) pre-treatments carried out using pressure micro-reactors under isothermal conditions up to 300 min. Both processes enabled a high recovery of soluble sugars (similar to 50 %) that were, in a great majority, present in the added-value oligomeric form (92 % and 90.5 % for autohydrolysis and dilute acid hydrolysis, respectively). Protein solubilization also presented relevant yields (35 % removal), with dilute acid hydrolysis allowing both higher oligosaccharides and protein productivities at a milder temperature. As compared to the current whole microalgae biomass-based upgrade strategies, the use of these mild processes is extremely promising, as they will enable the future co-production of added-value oligosaccharides, and protein, which can be relevant co-products of a biofuels-based biorefinery.

2022-12Journal article

Open access

Evaluation of different fractionation methods for the simultaneous protein and carbohydrate extraction from microalgae

Publication . Martins, Pedro L.; Duarte, Luís C.; Pereira, Helena; Reis, Alberto; Carvalheiro, Florbela

ABSTRACT: The production of high-value products from microalgae, one of the preferred emerging biorefineries' feedstocks, relies on the crucial step of biomass fractionation. In this work, the fractionation of Chlorella vulgaris and Scenedesmus obliquus biomass was tested for protein extraction using a wide range of physical, chemical, and enzymatic treatment combinations, including ultrasound, cell homogenizer, cellulase, and alcalase combinations in aqueous and alkali extraction conditions. The impact of these processes on biomass carbohydrates was also evaluated. Alkaline-assisted ultrasound treatments using alcalase presented the highest protein extraction yield, reaching 90 g/100 g protein on C. vulgaris, closely followed by the same treatment in aqueous conditions (85 g/100 g protein). The same aqueous treatment achieved the best performance on S. obliquus, reaching 82 g/100 g protein. All treatments on both microalgae partially solubilized the polysaccharide fraction with all alkaline treatments solubilizing over 50 g/100 g sugars for all conditions. Overall, all the treatments applied were effective methods for biomass fractionation, although they showed low selectivity regarding the individual extraction of protein or carbohydrates.

2024-01Journal article

Open access

Fractionation of macroalgae carbohydrates using hydrothermal and dilute inorganic salt pretreatments to produce oligosaccharides and furans

Publication . Martins, Pedro L.; Andrade, Cristiana; Duarte, Luís; Reis, Alberto; Pereira, Helena; Carvalheiro, Florbela

ABSTRACT: Furans are among the most important compounds derived from biomass, providing conversion pathways for sustainable alternatives to petroleum-based fuels and materials. Furfural, 5-hydroxymethylfurfural (5-HMF), and 5-methylfurfural (5-MF) are furans that can be obtained by carbohydrate dehydration under acidic conditions at elevated temperature and pressure. One of the mechanisms to produce these compounds from lignocellulosic materials relies on prior fractionation of biomass carbohydrates and further dehydration catalysis. However, this is a costly and technically challenging method and it would be advantageous to develop a one-pot conversion mechanism that facilitates simultaneous biomass fractionation and conversion to furans. Ulva lactuca is an alga that has the advantage of being lignin-free and rich in glucose, rhamnose, and xylose, which are ideal for producing 5-HMF, 5-MF, and furfural, respectively. The high diversity of sugar constituents is also relevant for the production of added-value oligosaccharides. Catalysis with inorganic salts has been reported as a successful tool for biomass upgrading to furans when combined with hydrothermal pretreatments, and could provide a cheap and environmentally friendly one-step methodology for furan production. This study therefore aimed to investigate the effect of hydrothermal and dilute acid pretreatments, as well as treatment with inorganic salt solutions (ferric chloride, ferric nitrate, and aluminium nitrate) on U. lactuca biomass to produce oligosaccharides, monosaccharides, and furans (furfural, 5-HMF, and 5-MF). These methods resulted in a maximum sugar solubilization of 65% in non-salt-assisted hydrothermal pretreatments and 84% in salt-assisted hydrothermal pretreatments, with inorganic salt catalysis also resulting in 100% xylose, 36% glucose, and 46% rhamnose conversion to the respective furans.

2025-07Journal article

Open access