Pyrolysis GC–MS as a novel analysis technique to determine the biochemical composition of microalgae

The biochemical composition of microalgae is a major factor in the feasibility of microalgae biofuel systems. Currently full compositional analysis entails tedious, costly and time consuming analysis methods. In the current research, an attempt has been made to use Analytical Pyrolysis Gas Chromatography Mass Spectrometry (Py–GC–MS) to determine the biochemical composition of microalgae. By identifying pyrolysis marker compounds of each main biochemical component of microalgae, the composition of algae samples could be estimated. This was aided by performing Py–GC–MS of a model protein, carbohydrate and lipid. Indole was shown to be a decomposition product from the protein fraction and its levels were consistent with the changing protein content. The lipid content of the microalgae could be estimated from the presence of alkanes and the carbohydrate fraction by the presence of 1,2-cyclopentanedione, 3-methyl-. A total of 26 different microalgae and cyanobacteria strains were investigated for their protein, carbohydrate and lipid levels using established analysis techniques. The biochemical compositions are compared to the results from the novel technique using Py–GC–MS and are shown to correspond well; R2 values were found to be 0.6–0.9. The results suggest that Py–GC–MS can be used as a rapid test for studying levels and changes in biochemical composition of different algae using one fast technique with minimal sample preparation

Hydrothermal microwave processing of microalgae as a pre-treatment and extraction technique for bio-fuels and bio-products

Microalgae are regarded as a promising source of lipids for bio-diesel production and bio-products. The current paper investigates the processing of microalgal slurries under controlled microwave irradiation. Microwave power was applied to reach temperatures of 80, 100, 120 and 140. °C at a constant residence time of 12. min. Microwave irradiation led to disruption of the algal cell walls which facilitated lipid extraction. The influence of inorganic material on microwave heating was assessed for three strains including, Nannochloropsis occulata, Chlorogloeopsis fritschii and Pseudochoricystis ellipsoidea. Mass balances were calculated and showed that the amount of carbon, nitrogen and total mass recovered in the residue was highly dependent on process conditions and algae strain. Hydrothermal microwave processing (HMP) was found to be an effective pre-treatment for hydrothermal liquefaction and extraction of lipids and phytochemicals

The Influence of pH on the Combustion Properties of Bio-Coal Following Hydrothermal Treatment of Swine Manure

The application of excessive amounts of manure to soil prompted interest in using alternative approaches for treating slurry. One promising technology is hydrothermal carbonisation (HTC) which can recover nutrients such as phosphorus and nitrogen while simultaneously making a solid fuel. Processing manure under acidic conditions can facilitate nutrient recovery; however, very few studies considered the implications of operating at low pH on the combustion properties of the resulting bio-coal. In this work, swine manure was hydrothermally treated at temperatures ranging from 120 to 250 °C in either water alone or reagents including 0.1 M NaOH, 0.1 M H2SO4, and finally 0.1 M organic acid (CH3COOH and HCOOH). The influence of pH on the HTC process and the combustion properties of the resulting bio-coals was assessed. The results indicate that pH has a strong influence on ash chemistry, with decreasing pH resulting in an increased removal of ash. The reduction in mineral matter influences the volatile content of the bio-coal and its energy content. As the ash content in the final bio-coal reduces, the energy density increases. Treatment at 250 °C results in a more “coal like” bio-coal with fuel properties similar to that of lignite coal and a higher heating value (HHV) ranging between 21 and 23 MJ/kg depending on pH. Processing at low pH results in favourable ash chemistry in terms of slagging and fouling. Operating at low pH also appears to influence the level of dehydration during HTC. The level of dehydration increases with decreasing pH, although this effect is reduced at higher temperatures. At higher-temperature processing (250 °C), operating at lower pH increases the yield of bio-coal; however, at lower temperatures (below 200 °C), the reverse is true. The lower yields obtained below 200 °C in the presence of acid may be due to acid hydrolysis of carbohydrate in the manure, whereas, at the higher temperatures, it may be due to the acid promoting polymerisation

The seasonal variation of fucoidan within three species of brown macroalgae

Fucoidan is comprised of a fucose backbone with sulphate groups, whose variation is important to the functionality of the polysaccharide. The structure of fucoidan has been reported to vary according to species, season, location and maturity; however there is currently little published data to support this. Understanding the seasonal variation of fucoidan is important for industrial applications to identify optimum harvesting times and ensure consistent product composition. This study explores the seasonal variation of three species of brown macroalgae, Fucus serratus (FS), Fucus vesiculosus (FV) and Ascophyllum nodosum (AN), harvested monthly off the coast of Aberystwyth, UK. Average fucoidan content is 6.0, 9.8 and 8.0 wt% respectively for FS, FV and AN, with highest quantities extracted in autumn and lowest in spring. Fucose content, varied between 18 and 28, 26–39 and 35–46 wt% and sulphate content between 30 and 40, 9–35 and 6–22 wt% for FS, FV and AN respectively, with both fluctuating inversely to the total fucoidan content. Size exclusion chromatography (SEC) has provided insight into the structural differences between the species. Based on the molecular weight (MW) distribution, and in line with previous research, it is hypothesised that fucoidan in FS has a more complex structure, with a higher degree of associated sulphate ions than in FV and AN which have a simpler, linear structure with less associated sulphate ions

Improving the biomethane yield from food waste by boosting hydrogenotrophic methanogenesis

Anaerobic digestion of food waste is usually impacted by high levels of VFAs, resulting in low pH and inhibited methane production from acetate (acetoclastic methanogenesis); however, this could be harnessed for improving methane production via hydrogenotrophic methanogenesis (biomethanation). In this study, batch anaerobic digestion of food waste was conducted to enhance biomethanation by supplying hydrogen gas (H2), using a gas mixture of 5%-H2 and 95%-N2. The addition of H2 influenced a temporal microbial shift in substrate utilisation from dissolved organic nutrients to H2 and CO2 and was perceived to have enhanced the hydrogenotrophic methanogenic activity. As a result, with the release of hydrogen as degradation progressed (secondary fermentation) hydrogenotrophic methanogenesis was further enriched. This resulted in an enhancement of the upgrading of the biogas, with a 12.1% increase in biomethane (from 417.6 to 468.3 NmL-CH4/gVSadded) and 38.9% reduction in CO2 (from 227.1 to 138.7 NmL-CO2/gVSadded). Furthermore, the availability of hydrogen gas at the start of the process promoted faster propionate degradation, by the enhanced activity of the H2-utilisers, thereby, reducing likely propionate-induced inhibitions. The high level of acidification from VFAs production helped to prevent excessive pH increases from the enhanced hydrogenotrophic methanogenic activity. Therefore, it was found that the addition of hydrogen gas to AD reactors treating food waste showed great potential for enhanced methane yield and biogas upgrade, supported by VFAs-induced pH buffer. This creates the possibility to optimise hydrogenotrophic methanogenesis towards obtaining biogas of the right quality for injection into the gas grid

Inorganic Salt Catalysed Hydrothermal Carbonisation (HTC) of Cellulose

The presence of inorganic salts either as part of the substrate or added to the reaction medium are known to significantly affect the reaction pathways during hydrothermal carbonisation (HTC) of biomass. This work aims to understand the influence of salts on hydrothermal carbonisation by processing cellulose in the presence of one or more inorganic salts with different valency. Batch experiments and Differential Scanning Calorimetry were used to investigate the change in reaction pathways during hydrothermal conversion. The effect of salts on the rate of HTC of cellulose can be correlated with the Lewis acidity of the cation and the basicity of the anion. The effect of the anion was more pH-dependent than the cation because it can protonate during the HTC process as organic acids are produced. The introduction of salts with Lewis acidity increases the concentration of low molecular weight compounds in the process water. The addition of a second salt can influence the catalytic effect of the first salt resulting in greater levulinic acid yields at the expense of hydrochar formation. Salts also play an important role in cellulose dissolution and can be used to modify the yield and composition of the hydrochars

Hydrothermal liquefaction of four brown macro-algae commonly found on the UK coasts: An energetic analysis of the process and comparison with bio-chemical conversion methods

Hydrothermal liquefaction (HTL) of four brown macro-algae was used to produce bio-crude and bio-char in an energy favorable way. Bio-crude yields between 9.8 wt% and 17.8 wt% (daf) with HHVs between 32 and 34 MJ/kg and bio-char yields between 10.9 wt% and 18.6 wt% (db) with HHVs between 15.7 and 26.2 MJ/kg were produced. A modification of the energy consumption ratio (ECR) index was attempted in order to include in the formula the calculation of the specific heat capacity of the feedstock used, as well as the increase of the specific heat capacity of water with temperature. A comparison in terms of energy output was made between the products from HTL and products from bio-chemical conversion of macro-algae such as anaerobic digestion (AD) and fermentation. The results indicate that HTL has higher energy output than fermentation and analogue of that from anaerobic digestion (7.91 MJ/kgseaweed and 8.25 MJ/kgseaweed from HTL and AD respectively)

Integration of Hydrothermal Carbonisation with Anaerobic Digestion; Opportunities for Valorisation of Digestate

Hydrothermal carbonisation (HTC) has been identified as a potential route for digestate enhancement producing a solid hydrochar and a process water rich in organic carbon. This study compares the treatment of four dissimilar digestates from anaerobic digestion (AD) of agricultural residue (AGR); sewage sludge (SS); residual municipal solid waste (MSW), and vegetable, garden, and fruit waste (VGF). HTC experiments were performed at 150, 200 and 250 °C for 1 h using 10%, 20%, and 30% solid loadings of a fixed water mass. The effect of temperature and solid loading to the properties of biocoal and biochemical methane potential (BMP) of process waters are investigated. Results show that the behaviour of digestate during HTC is feedstock dependent and the hydrochar produced is a poor-quality solid fuel. The AGR digestate produced the greatest higher heating value (HHV) of 24 MJ/kg, however its biocoal properties are poor due to slagging and fouling propensities. The SS digestate process water produced the highest amount of biogas at 200 °C and 30% solid loading. This study concludes that solely treating digestate via HTC enhances biogas production and that hydrochar be investigated for its use as a soil amender

Evidence for a core-shell structure of hydrothermal carbon

Hydrothermal carbonisation (HTC) has been demonstrated to be a sustainable thermochemical process, capable of producing functionalised carbon materials for a wide range of applications. In order to better apply such materials, the local chemistry and reaction pathways governing hydrothermal carbon growth must be understood. We report the use of scanning transmission X-ray microscopy (STXM) to observe chemical changes in the functionality of carbon between the interface and bulk regions of HTC. Spatially-resolved, element-specific X-ray photo-absorption spectra show the presence of differing local carbon chemistry between bulk “core” and interface “shell” regions of a glucose-derived hydrothermal carbon spherule. STXM provides direct evidence to suggest that mechanistic pathways differ between the core and shell of the hydrothermal carbon. In the shell region, at the water-carbon interface, more aldehyde and/or carboxylic species are suspected to provide a reactive interface for bridging reactions to occur with local furan-based monomers. In contrast, condensation reactions appear to dominate in the core, removing aryl-linking units between polyfuranic domains. The application of STXM to HTC presents opportunities for a more comprehensive understanding of the spatial distribution of carbon species within hydrothermal carbon, especially at the solvent-carbon interface