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Energies 2019, 12, 809 21 of 41 also in this case to avoid carbon deposition due to the bio-crude content in carbonyls but it was shown that the upgrading of HTL bio-crude may also proceed in a single step [191,192]. For example an oxygen removal higher than 95% was achieved in wood derived bio-crude at 300 ◦C over a sulfided CoMo/Al2O3 catalysts resistant to carbon formation due to its desalting pretreatment [192]. The second stage heavy hydrotreatment process may follow over the same catalysts proposed in Table 7. Grlic et al. [193] investigated the hydrotreatment of lignocellulosic biomass bio-crude over NiMo/Al2O3, Pd/Al2O3, Pd/C, Ni/SiO2-Al2O3 and bulk MoS2 at 300 ◦C, 80 bar and 60 min. Their results have shown that the sulfided NiMo/Al2O3 catalysts provide a liquid product with appropriate HHV, rheological properties and yield. The Pd/Al2O3 and Pd/C catalysts exhibited low catalytic activity and the bulk MoS2 catalysts was found promising for further investigation due to the low cost, relatively high activity and HDO selectivity. Duan and Savage [194–196] investigated the upgrading of bio-crude obtained from the non-catalytic liquefaction of Nannochlopris sp. at 320 or 340 ◦C and shown that Pt/C is an effective catalyst. At the same time, using 5 wt% Pd/C at 400 ◦C, they examined the effects of catalyst loading (5 to 80 wt%) and residence time (1 to 8 h) on the composition of the upgraded bio-crude and shown that an in increase of either of these parameters is beneficial causing the decrease of the O/C and N/C atomic ratios and an increase in the H/C ratio and the higher heating value (HHV) of the product [196]. Finally, only few studies have examined the catalytic cracking of HTL bio-crude. Adjaye and Bakshi [197] examined the upgrading of wood bio-crude at 330–410 ◦C, 1 bar, and 3.6 h−1 over HSZM-5, silicalite, H-mordenite, H-Y and SiO2-Al2O3. For HSZM-5 the maximum hydrocarbon yield was 39.3 wt% at 370 ◦C and included mostly hydrocarbons in the gasoline range. Over the rest catalysts the hydrocarbon yield was maximized at the maximum temperature examined (410 ◦C) following the order H-mordenite (27.5 wt%), SiO2-Al2O3 (26,1 wt%), silicalite (21.8 wt%), H-Y (21 wt%). Among these catalysts H-mordenite and H-Y have shown high selectivity of green jet fuel while the other catalysts mainly produced lighter hydrocarbons in the green naphtha boiling range. Gevert and Otterstedt [198] investigated two commercial catalysts, EKZ-4 and EKZ-2, and α-Al2O3 at 483, 500 and 562 ◦C for the upgrading of wood bio-crude which was then hydroprocessed over sulfided CoMo/Al2O3 at 370 ◦C and 100 bar. It was shown that EKZ-4 provides about 30.5 wt% gasoline and 20.1 wt% gas oil at 500 ◦C. The discussion above shows that the production of green diesel from the upgrading of HTL bio-crude has not been investigated in depth and therefore more research is needed. 6. Biomass to Liquid (BTL) Conversion of Lignocellulosic Biomass Gasification is the exothermal reaction which converts biomass or carbonaceous fuels into synthesis gas (syngas) by partial oxidation. It takes place by heating the material at temperatures above 700 ◦C with a controlled sub-stoichiometric amount of O2 and/or steam and leads to the production of mixtures containing syngas (i.e., CO and H2) and smaller amounts of CO2 and CH4. Syngas was previously introduced as one of the three products of the pyrolysis of biomass. Although pyrolysis may be optimized for the production of syngas, biomass gasification is considered a better route for its production as it provides higher yields of syngas without any significant byproduct competition. Gasification is an established process for the production of syngas from coal, char, oil sands, biogas and natural gas [199]. In a carbonaceous fuel the following reactions take place: C + 1/2O2→ CO ∆H = −111 kJ/mol (6) C + H2O → CO + H2 ∆H = +131 kJ/mol (7) where (6) is the exothermic partial oxidation of carbon and (7) is the endothermic water gas reaction. Both these reactions cause the conversion of carbon into H2 and CO. In the case of biogas or natural gas, which are already in the gas state, the endothermic catalytic steam reforming reaction is usually employed which is written as: CH4 +H2O↔CO+3H2 ∆H=+206kJ/mol (8)PDF Image | Green Diesel: Biomass Feedstocks, Production Technologies
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