Algae from Cr-containing infiltrate bioremediation for valorised chemical production - Seasonal availability, composition, and screening studies on hydrothermal conversion.

Integrating bioremediation of toxic wastewater with value-added production is increasing interest, but - due to some essential problems - it is hardly applied in industrial practice. The aim of the study was an annual observation of the taxonomic and biochemical composition of various Cr-resistant algal communities grown in the existing Cr-containing infiltrate treatment system, selection of the most suitable algal biomass for infiltrates bioremediation and chromium-loaded algae conversion under mild subcritical conditions. Considering continuous availability and relatively constant chemical composition, Cladophora sp. was selected for utilisation in the chromium bioremediation system, simultaneously as a waste biomass source suitable for hydrothermal conversion. Screening studies conducted in a continuous pilot plant confirmed the possibility of selective extraction of saccharides and their separation from the metals remaining in the solid residual. The negligible concentration of metals in the obtained sugar-rich aqueous phase is essential for its further use in biotechnological processes.

Hydrothermal fractionation of woody biomass: Lignin effect on sugars recovery.

Subcritical water was employed to fractionate woody biomass into carbohydrates and lignin. Nine urban trees species (hardwood and softwood) from Spain were studied. The experiments were carried out in a semi-continuous reactor at 250 °C for 64 min. The hemicellulose and cellulose recovery yields were between 30%wt. and 80%wt. while the lignin content in the solid product ranged between 32%wt. and 92%wt. It was observed that an increment of solubilized lignin disfavored the hydrolysis of hemicelluloses. It was determined that the maximum extraction of hemicellulose was achieved at 20 min of solid reaction time while the extraction of celluloses not exhibited a maximum value. The hydrolysis of hemicellulose and cellulose would be governed by the hydrolysis kinetic and the polymers accessibility. In addition, the extraction of hemicellulose was negatively affected by the lignin content in the raw material while cellulose hydrolysis was not affected by this parameter.

Governing chemistry of cellulose hydrolysis in supercritical water.

At extremely low reaction times (0.02 s), cellulose was hydrolyzed in supercritical water (T=400 °C and P=25 MPa) to obtain a sugar yield higher than 95 wt%, whereas the 5-hydroxymethylfurfural (5-HMF) yield was lower than 0.01 wt %. If the reaction time was increased to 1 s, the main product was glycolaldehyde (60 wt%). Independently of the reaction time, the yield of 5-HMF was always lower than 0.01 wt%. To evaluate the reaction mechanism of biomass hydrolysis in pressurized water, several parameters (temperature, pressure, reaction time, and reaction medium) were studied for different biomasses (cellulose, glucose, fructose, and wheat bran). It was found that the H(+) and OH(-) ion concentration in the reaction medium as a result of water dissociation is the determining factor in the selectivity. The reaction of glucose isomerization to fructose and the further dehydration to 5-HMF are highly dependent on the ion concentration. By an increase in the pOH/pH value, these reactions were minimized to allow control of 5-HMF production. Under these conditions, the retroaldol condensation pathway was enhanced, instead of the isomerization/dehydration pathway.

Energetic approach of biomass hydrolysis in supercritical water.

Cellulose hydrolysis can be performed in supercritical water with a high selectivity of soluble sugars. The process produces high-pressure steam that can be integrated, from an energy point of view, with the whole biomass treating process. This work investigates the integration of biomass hydrolysis reactors with commercial combined heat and power (CHP) schemes, with special attention to reactor outlet streams. The innovation developed in this work allows adequate energy integration possibilities for heating and compression by using high temperature of the flue gases and direct shaft work from the turbine. The integration of biomass hydrolysis with a CHP process allows the selective conversion of biomass into sugars with low heat requirements. Integrating these two processes, the CHP scheme yield is enhanced around 10% by injecting water in the gas turbine. Furthermore, the hydrolysis reactor can be held at 400°C and 23 MPa using only the gas turbine outlet streams.

High glucose selectivity in pressurized water hydrolysis of cellulose using ultra-fast reactors.

A new reactor was developed for the selective hydrolysis of cellulose. In this study, the glucose selectivity obtained from cellulose was improved by using ultra-fast reactions in which a selective medium was combined with an effective residence time control. A selective production of glucose, fructose and cellobiose (50%) or total mono-oligo saccharides (>96%) was obtained from the cellulose in a reaction time of 0.03 s. Total cellulose conversion was achieved with a 5-hydroxymethylfural concentration lower than 5 ppm in a novel micro-reactor. Reducing the residence time from minutes to milliseconds opens the possibility of moving from the conventional m(3) to cm(3) reactor volumes.