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To meet the increasing need for bioenergy several raw materials have to be considered for the production of e.g. bioethanol and biogas. In this study, three lignocellulosic raw materials were studied, i.e. (1) winter rye straw (Secale cereale L), (2) oilseed rape straw (Brassica napus L.) and (3) faba bean straw (Viciafaba L.). Their composition with regard to cellulose, hemicellulose, lignin, extractives and ash was evaluated, as well as their potential as raw materials for ethanol and biogas production. The materials were pretreated by wet oxidation using parameters previously found to be optimal for pretreatment of corn stover (195 1C, 15 min, 2 g l À1 Na 2 CO 3 and 12 bar oxygen). It was shown that pretreatment was necessary for ethanol production from all raw materials and gave increased biogas yield from winter rye straw. Neither biogas productivity nor yield from oilseed rape straw or faba bean straw was significantly affected by pretreatment. Ethanol was produced by the yeast Saccharomyces cerevisiae during simultaneous enzymatic hydrolysis of the solid material after wet oxidation with yields of 66%, 70% and 52% of theoretical for winter rye, oilseed rape and faba bean straw, respectively. Methane was produced with yields of 0.36, 0.42 and 0.44 l g À1 volatile solids for winter rye, oilseed rape and faba bean straw, respectively, without pretreatment of the materials. However, biogas productivity was low and it took over 50 days to reach the final yield. It could be concluded that all three materials are possible raw materials for either biogas or ethanol production; however, improvement of biogas productivity or ethanol yield is necessary before an economical process can be achieved. r

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Dark fermentation, also known as acidogenesis, involves the transformation of a wide range of organic substrates into a mixture of products, e.g. acetic acid, butyric acid and hydrogen. This bioprocess occurs in the absence of oxygen and light. The ability to synthesize hydrogen, by dark fermentation, has raised its scientific attention. Hydrogen is a nonpolluting energy carrier molecule. However, for energy generation, there is a variety of other sustainable alternatives to hydrogen energy, e.g. solar, wind, tide, hydroelectric, biomass incineration, or nuclear fission. Nevertheless, dark fermentation appears as an important sustainable process in another area: the synthesis of valuable chemicals, i.e. an alternative to petrochemical refinery. Currently, acetic acid, butyric acid and hydrogen are mostly produced by petrochemical reforming, and they serve as precursors of ubiquitous petrochemical derived products. Hence, the future of dark fermentation relies as a core bioprocess in the biorefinery concept. The present article aims to present and discuss the current and future status of dark fermentation in the biorefinery concept. The first half of the article presents the metabolic pathways, product yields and its technological importance, microorganisms responsible for mixed dark fermentation, and operational parameters, e.g. substrates, pH, temperature and head-space composition, which affect dark fermentation. The minimal selling price of dark fermentation products is also presented in this section. The second half discusses the perspectives and future of dark fermentation as a core bioprocess. The relationship of dark fermentation with other (bio)processes, e.g. liquid fuels and fine chemicals, algae cultivation, biomethane-biohythane-biosyngas production, and syngas fermentation, is then explored.

A pilot plant for hydrothermal treatment of wheat straw was compared in reactor systems of two steps (first, 80 degrees C; second, 190-205 degrees C) and of three steps (first, 80 degrees C; second, 170-180 degrees C; third, 195 degrees C). Fermentation (SSF) with Sacharomyces cerevisiae of the pretreated fibers and hydrolysate from the two-step system gave higher ethanol yield (64-75%) than that obtained from the three-step system (61-65%), due to higher enzymatic cellulose convertibility. At the optimal conditions (two steps, 195 degrees C for 6 min), 69% of available C6-sugar could be fermented into ethanol with a high hemicellulose recovery (65%). The concentration of furfural obtained during the pretreatment process increased versus temperature from 50 mg/l at 190 degrees C to 1,200 mg/l at 205 degrees C as a result of xylose degradation. S. cerevisiae detoxified the hydrolysates by degradation of several toxic compounds such as 90-99% furfural and 80-100% phenolic aldehydes, which extended the lag phase to 5 h. Acetic acid concentration increased by 0.2-1 g/l during enzymatic hydrolysis and 0-3.4 g/l during fermentation due to hydrolysis of acetyl groups and minor xylose degradation. Formic acid concentration increased by 0.5-1.5 g/l probably due to degradation of furfural. Phenolic aldehydes were oxidized to the corresponding acids during fermentation reducing the inhibition level.