Co-hydrothermal carbonization of microalgae and digested sewage sludge: Assessing the impact of mixing ratios on the composition of primary and secondary char.

The role of microalgae cultivation in wastewater treatment and reclamation has been studied extensively, as has the potential utility of the resulting algal biomass. Most methods for processing such biomass generate solid residues that must be properly managed to comply with current sustainable resource utilization requirements. Hydrothermal carbonization (HTC) can be used to process both individual wet feedstocks and mixed feedstocks (i.e., co-HTC). Here, we investigate co-HTC using microalgae and digested sewage sludge as feedstocks. The objectives were to (i) study the material's partitioning into solid and liquid products, and (ii) characterize the products' physicochemical properties. Co-HTC experiments were conducted at 180-250°C using mixed microalgae/sewage sludge feedstocks with the proportion of sewage sludge ranging from 0 to 100 %. Analyses of the hydrochar composition and the formation and composition of secondary char revealed that the content of carbonized material in the product decreased as the proportion of sewage sludge in the feedstock increased under fixed carbonization conditions. The properties of the hydrochars and the partitioning of material between the liquid phase and the hydrochar correlated linearly with the proportion of microalgae in mixed feedstocks, indicating that adding sewage sludge to microalgae had weak or non-existent synergistic effects on co-HTC outcomes. However, the proportion of sewage sludge in the feedstock did affect the secondary char. For example, adding sewage sludge reduced the abundance of carboxylic acids and ketones as well as the concentrations of higher molecular weight cholesterols. Such changes may alter the viable applications of the hydrochar.

Comparative characterisation and phytotoxicity assessment of biochar and hydrochar derived from municipal wastewater microalgae biomass.

Microalgae, originating from a tertiary treatment of municipal wastewater, is considered a sustainable feedstock for producing biochar and hydrochar, offering great potential for agricultural use due to nutrient content and carbon storage ability. However, there are risks related to contamination and these need to be carefully assessed to ensure safe use of material from wastewater microalgae. Therefore, this study compared the properties and phototoxicity of biochar and hydrochar produced via pyrolysis and hydrothermal carbonisation (HTC) of microalgae under different temperatures and residence times. While biochar promoted germination and seedling growth by up to 11.0% and 70.0%, respectively, raw hydrochar showed strong phytotoxicity, due to the high content of volatile matter. Two post-treatments, dichloromethane (DCM) washing and further pyrolysis, proved to be effective methods for mitigating phytotoxicity of hydrochar. Additionally, biochar had 35.8-38.6% fixed carbon, resulting in higher carbon sequestration potential compared to hydrochar.

Influence of hydrothermal carbonization conditions on the porosity, functionality, and sorption properties of microalgae hydrochars.

Green microalgae is a possible feedstock for the production of biofuels, chemicals, food/feed, and medical products. Large-scale microalgae production requires large quantities of water and nutrients, directing the attention to wastewater as a cultivation medium. Wastewater-cultivated microalgae could via wet thermochemical conversion be valorised into products for e.g., water treatment. In this study, hydrothermal carbonization was used to process microalgae polycultures grown in municipal wastewater. The objective was to perform a systematic examination of how carbonization temperature, residence time, and initial pH affected solid yield, composition, and properties. Carbonization temperature, time and initial pH all had statistically significant effects on hydrochar properties, with temperature having the most pronounced effect; the surface area increased from 8.5 to 43.6 m2 g-1 as temperature was increased from 180 to 260 °C. However, hydrochars produced at low temperature and initially neutral pH generally had the highest capacity for methylene blue adsorption. DRIFTS analysis of the hydrochar revealed that the pH conditions changed the functional group composition, implying that adsorption was electrostatic interactions driven. This study concludes that un-activated hydrochars from wastewater grown microalgae produced at relatively low hydrothermal carbonization temperatures adsorb methylene blue, despite having low surface area.

Predicting the drying properties of sludge based on hydrothermal treatment under subcritical conditions.

The effects of hydrothermal treatment on the drying properties of sludge were determined. Sludge was hydrothermally treated at 180-260 °C for 0.5-5 h using NaOH and HCl as additives to influence reaction conditions. Untreated sludge and attained hydrochar samples were then dried under identical conditions with a laboratory microdryer and an X-ray microtomograph was used to follow changes in sample dimensions. The effective moisture diffusivities of sludge and hydrochar samples were determined and the effect of process conditions on respective mean diffusivities evaluated using multiple linear regression. Based on the results the drying time of untreated sludge decreased from approximately 80 min to 37-59 min for sludge hydrochar. Drying of untreated sludge was governed by the falling rate period where drying flux decreased continuously as a function of sludge moisture content due to heat and mass transfer limitations and sample shrinkage. Hydrothermal treatment increased the drying flux of sludge hydrochar and decreased the effect of internal heat and mass transfer limitations and sample shrinkage especially at higher treatment temperatures. The determined effective moisture diffusivities of sludge and hydrochar increased as a function of decreasing moisture content and the mean diffusivity of untreated sludge (8.56·10(-9) m(2) s(-1)) and sludge hydrochar (12.7-27.5·10(-9) m(2) s(-1)) were found statistically different. The attained regression model indicated that treatment temperature governed the mean diffusivity of hydrochar, as the effects of NaOH and HCl were statistically insignificant. The attained results enabled prediction of sludge drying properties through mean moisture diffusivity based on hydrothermal treatment conditions.

Hydrothermal carbonization of industrial mixed sludge from a pulp and paper mill.

Mixed sludge from a pulp and paper mill was hydrothermally carbonized at 180-260°C for 0.5-5h with the use of HCl or NaOH for determining the effect of acid and base additions during sludge carbonization. Based on the results carbonization was mainly governed by dehydration, depolymerization and decarboxylation of sludge components. Additive type had a statistically significant effect on hydrochar carbon content and carbon and energy yield, of which especially energy yield increased through the use of HCl. The theoretical energy efficiencies of carbonization increased with decreasing reaction temperature, retention time and the use of HCl and suggested that the energy requirement could be covered by the energy content of attained hydrochar. The BOD5/COD-ratios of analyzed liquid samples indicated that the dissolved organic components could be treated by conventional biological methods.