Bio-fuelization of herbaceous lignocelluloses through a simultaneous saccharification and fermentation process (SSF) and photocatalytic reforming (photo-Reform) was examined. The SSF of the alkali-pretreated bamboo, rice straw, and silvergrass was performed in an acetate buffer (pH 5.0) using cellulase, xylanase, and Saccharomyces cerevisiae at 34 °C. Ethanol was produced in 63%-85% yields, while xylose was produced in 74%-97% yields without being fermented because xylose cannot be fermented by S. cerevisiae. After the removal of ethanol from the aqueous SSF solution, the SSF solution was subjected to a photo-Reform step where xylose was transformed into hydrogen by a photocatalytic reaction using Pt-loaded TiO 2 (2 wt % of Pt content) under irradiation by a high pressure mercury lamp. The photo-Reform process produced hydrogen in nearly a yield of ten theoretical equivalents to xylose. Total energy was recovered as ethanol and hydrogen whose combustion energy was 73.4%-91.1% of that of the alkali-pretreated lignocelluloses (holocellulose). OPEN ACCESSEnergies 2014, 7 4088

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Biodiesel (BDF) has gained much attention as new sustainable energy alternative to petroleum-based fuels. In particular, BDF market has significantly increased in Europe to adhere energy and climate policies. Therefore, the increased BDF production requires new utilization of glycerol which is by product of BDF synthesis. We have focused on photocatalytic reforming using titanium oxide (TiO2) photocatalyst using glycerol as sacrificial agent (SaH). Recently we have found that SaH with all of the carbon attached oxygen atoms such as glycerol and methanol continued to serve as an electron source until their sacrificial ability was exhausted in photocatalyzed hydrogen evolution using a Pt-loaded TiO2 (Pt/TiO2) catalyst. Here we investigated the utilization of residual glycerol in BDF synthesis by photocatalytic reforming.BDF (methyl alkanoate) preparation by transesterification of commercially-available vegetable oil (136.5 g) was performed by heating with MeOH (23.8 g) in the presence of NaOH (0.485 g) at 61 ℃ for 2 h. After cooling, standard follow-up operation was performed as follows. The products were separated into a lower layer (Solution A) and an upper layer. The upper layer was washed with water and separated into a BDF layer and an aqueous washing solution (Solution B). Glycerol (10.4 g) was obtained from Solution A in 73.3% yield along with methanol (6.85 g). BDF (114.5 g) was isolated in 83.7% yield. Solution B contained methanol in 4.38 g. The residual glycerol and unreacted methanol were turned to hydrogen by TiO2-photocatalytic reforming of Solutions A and B using Pt/TiO2 (100 mg) in aqueous solution (150 mL) under irradiation by high-pressure mercury lamp. Hydrogen was evolved in 2.82 g and 0.28 g from Solutions A and B, respectively. The combustion energy (ΔH) of the evolved H2 corresponded to 100.8% based on the total ΔH of glycerol and methanol involved in Solutions A and B. Similar experiment was performed using pre-used vegetable oil. Hydrogen was recovered from Solutions A and B as 69.6% of ΔH. Presence of sodium alkanoate disturbed the hydrogen evolution.

Fuelization of Italian ryegrass and Napier grass was examined by the combination of biological treatments and photocatalytic reforming (photo-Reform). The alkali-pretreated Italian ryegrass and Napier grass were subjected to the enzymatic saccharification using cellulase and xylanase. Xylose and glucose were produced in 56.6% and 71.1% from Italian ryegrass and in 49.5% and 67.3% from Napier grass, respectively. Xylose and glucose were converted to hydrogen by the photo-Reform using a Pt-loaded titanium oxide (Pt/TiO2) under UV irradiation. Moreover, a lowmoisture anhydrous ammonia (LMAA) pretreatment was performed for Italian ryegrass and Napier grass by keeping moist powdered biomass under NH3 gas atmosphere at room temperature for four weeks. The Italian ryegrass and Napier grass which were pretreated by LMAA method were subjected to simultaneous saccharification and fermentation (SSF) using a mixture of cellulase and xylanase as well as Saccharomyces cerevisiae in acetate buffer (pH 5.0). Ethanol and xylose were produced in 91.6% and 51.6% from LMAA-pretreated Italian ryegrass and 78.6% and 68.8% from Napier grass, respectively. After the evaporation of ethanol, xylose was converted to hydrogen by the photo-Reform. In the case of saccharification→photo-Reform, energy was recovered as hydrogen from the alkali-pretreated Italian ryegrass and Napier grass in 71.9% and 77.0% of energy recovery efficiency, respectively. In the case of SSF→photo-Reform, the energy was recovered in 82.7% and 77.2% as ethanol and hydrogen from the LMAA-pretreated Italian ryegrass and Napier grass, respectively.

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