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Biomass pre-treatments for bio-oil quality improvement are mainly based on thermal and chemical methods which are costly and hence reduce the sustainability of pyrolysis-based refineries. In this paper, anaerobic digestion (AD) and dark fermentation (DF) are proposed as alternative ‘green’ pre-treatments to improve this situation. For this purpose, three seaweeds namely Sargassum polycystum, (Phaephyta), Gracilaria tenuistipitata, (Rhodophyta) and Ulva reticulata, (Chlorophyta) with high ash and oxygen contents were pre-treated to improve their composition and structure prior to pyrolysis. The results reveal that both biological pre-treatments affected, positively, the composition and structure of the seaweed biomass with AD pre-treatment reducing N and S contents by 86% and 63%, respectively. DF was more efficient in terms of ash and moisture reduction with 25% and 70%, respectively. In addition, oxygen (O) reduction by 27% was observed after DF which was evidenced by FTIR spectroscopy indicating the reduction of most oxygen-containing functional groups in the biomass. On the other hand, the carbon (C) content increased in DF pre-treated seaweeds up to 42%, almost two times higher relative content than C in the raw seaweed. The changes in the composition of pre-treated seaweeds resulted in changes in their thermal degradation and the volatile profiles produced during pyrolysis. Interestingly, anhydrosugars and furans which account for some 70% (by area) in raw seaweeds markedly declined or become undetectable after DF pre-treatment and correspondingly more acetic acid and hydrocarbons were produced while after AD more aromatics with high toluene content (ca.17%) were generated. The results indicate that biooil with profiles more similar to petroleum-based composition i.e. rich in hydrocarbons and low in anhydrosugars, N and S can be generated by AD and DF pre-treatments and opens up the possibility of these approaches to effect cost reduction in the overall generation of bio-based fuels.
The valorization of macroalgae digestate as a secondary resource for high value chemicals and nutrients will promote the sustainability and circularity of anaerobic digestion based biorefinery. In this study, three digestates from A. nodosum C.linum and L. digitata were separated into liquid and solid fractions to investigate the production of high value added chemicals through pyrolysis using Pyrolysis Gas Chromatography Mass Spectroscopy (Py-GC/MS) while the filtered liquid fractions were tested as an alternative culture media to grow C. sorokiniana under mixotrophic conditions. The digestates showed different thermal degradation and an improvement of bio-oil profiles compared to the starter material. Pyrolyzates from raw macroalgae were characterized by a high anhydrosugar content in contrast to high aromatics observed in the case of their digestates. Toluene, benzofuran and vinylphenol, base chemicals for many industries, represented together 30–37% of the total chemicals produced during pyrolysis of the three macroalgae digestate. On the other hand, C. sorokiniana cultured on digestate-based media showed a higher lipid content with an increase in monounsaturated fatty acids and a lower poly-unsaturated fatty acid content in comparison to microalgae grown in standard tris-acetate-phosphate media. Thus, the acyl composition was shifted in a direction more suitable for biodiesel production by this process. In addition, the increase of Chemical Oxygen Demand and Volatile Fatty Acids concentration in the digestate was found to reduce ammonium toxicity. Finally, 94% of Chemical Oxygen Demand and 83% of ammonium were removed by microalgae from the digestate-based media which will reduce the pollution risk of the biorefinery. Overall, the results indicate that using macroalgae solid digestates can generate improvements in the quality of
products obtained by pyrolysis and the liquid digestate can positively influence microalgae growth and its products.
Hydroliquefaction is a possible pathway to produce liquid transportation fuels from solid feedstocks like coal or biomass. Though much effort has been put into the investigation of maximizing the oil yield using expensive catalysts and pasting oils in batch setups, little is known about how to commercialize the process. This work aims at the demonstration of lignin hydroliquefaction under conditions interesting for commercial operation. The results from hydroliquefaction experiments of two different lignin types using a cheap iron-based catalyst and anthracene oil as the pasting oil in a semibatch system are presented here. Oil yields of above 50% are reached without observing coke formation. Extensive analyses of the feedstocks and product oils were performed. The process supplies high-quality oil, while differences in the decomposition path of both lignin types are observed. An high heating value of 39 400 J/g and H/C and O/C ratios of up to 1.6 and 0.1, respectively, are detected for the produced bio-oils.
Flame retarded polymeric materials are used in various applications in which a certain fire behavior is demanded. Protection goals are defined, such as limited flammability in terms of hindered sustained ignition or limited contribution to a fire, and these protection levels are tested with defined specimens or components in defined fire scenarios, that is to say, different fire tests. Passing a specific fire test by meeting whatever its demands is often the most important development goal, so the parameters of the different fire tests vary widely to emphasize different fire properties. Some fire tests are used to screen or provide a general assessment of flame retardant polymers during development, while other fire tests and tailored experiments are performed to address special phenomena or understand the flame retardancy modes of action. For all fire testing, the devil is in the details – demanding know-how and crucial efforts to manage the quality of investigations and advanced interpretation. This chapter aims to offer a structured overview of all these aspects.