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Fermentative hydrogen production via dark fermentation with the application of lignocellulosic biomass requires a multistep pre-treatment procedure, due to the complexed structure of the raw material. Hence, the comparison of the hydrogen productivity potential of different lignocellulosic materials (LCMs) in relation to the lignocellulosic biomass composition is often considered as an interesting field of research. In this study, several types of biomass, representing woods, cereals and grass were processed by means of mechanical pre-treatment and alkaline and enzymatic hydrolysis. Hydrolysates were used in fermentative hydrogen production via dark fermentation process with Enterobacter aerogenes (model organism). The differences in the hydrogen productivity regarding different materials hydrolysates were analyzed using chemometric methods with respect to a wide dataset collected throughout this study. Hydrogen formation, as expected, was positively correlated with glucose concentration and total reducing sugars amount (YTRS) in enzymatic hydrolysates of LCMs, and negatively correlated with concentrations of enzymatic inhibitors i.e., HMF, furfural and total phenolic compounds in alkaline-hydrolysates LCMs, respectively. Interestingly, high hydrogen productivity was positively correlated with lignin content in raw LCMs and smaller mass loss of LCM after pre-treatment step. Besides results of chemometric analysis, the presented data analysis seems to confirm that the structure and chemical composition of lignin and hemicellulose present in the lignocellulosic material is more important to design the process of its bioconversion than the proportion between the cellulose, hemicellulose and lignin content in this material. For analyzed LCMs we found remarkable higher potential of hydrogen production via bioconversion process of woods i.e., beech (24.01 mL H2/g biomass), energetic poplar (23.41 mL H2/g biomass) or energetic willow (25.44 mL H2/g biomass) than for cereals i.e., triticale (17.82 mL H2/g biomass) and corn (14.37 mL H2/g biomass) or for meadow grass (7.22 mL H2/g biomass).

Fermentative Conversion of Two-Step Pre-Treated Lignocellulosic Biomass to Hydrogen