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Energies 2019, 12, 809 17 of 41 of woods but other feedstocks have also been tested such as forest residues and agricultural residues such as straw, willow, olive pits and nut shells [159,160]. The pyrolysis products are biochar (a black solid residue), syngas (a mixture of H2 and CO), and bio-oil (a brown liquid). Bio-char is a high carbon, fine-grained solid residue. It has potential as a solid fuel for the generation of heat and power or as a soil improver and a ground storage medium for the atmospheric greenhouse gases. It was found to benefit soil health by retaining both water and water soluble nutrients [161]. This can increase crop production in soils that are degraded and nutrient poor and can provide cost benefits decreasing the needs for irrigation and fertilizers [162]. Land bio-char applications are also environmentally desirable as they remove CO2 from the atmosphere and facilitate long term carbon sequestration. Bio-char can also store large amounts of greenhouse gases in the ground [163–166]. Apart from H2 and CO, the pyrolysis syngas also contains small amounts of CO2, H2O(g)), N2, CH4, ethylene (C2H4), ethane (C2H6), tar and ash in a quantitative composition that depends on the process conditions and the biomass feedstock. H2 production is due to the thermal cracking and gaseous reforming of hydrocarbons and generally increases with temperature. On the other hand, CO and CO2 are produced by the thermal cracking of oxygenated organic compounds such as cellulose. Methane, ethylene and ethane are also formed by the thermal cracking of higher hydrocarbons. The syngas formed by pyrolysis may be combusted to provide heat or may be used as a fuel in industrial processes, internal combustion engines and Solid Oxide Fuel Cells (SOFCs). Moreover, syngas may be used as the reactant mixture for the production of synthetic chemicals and fuels through the well-known Fischer-Tropsch process, especially when the H2/CO molar ratio is close to 2. Bio-oil contains highly oxygenated organic molecules such as carbohydrates, phenols, alcohols, aldehydes, organic acids and lignin-derived oligomers with a specific composition which depends on the biomass feedstock as shown for some typical cases in Table 6 [94,167–169]. Table 6. Comparison of the properties of pyrolysis bio-oil produced by various lignocellulosic feedstocks and common distillate fuels. Data taken from [94,167,169]. Properties Wood Water Content, wt% 15–30 Carbon, wt% 54–58 Hydrogen, wt% 5.5–7 Oxygen, wt% 35–40 Nitrogen, wt% 0–0.2 Ash, wt% 0–0.2 pH 2–3 2.68 3.45 Willow Straw Sweet Grass Petroleum Distillate Fuel 24.7 0.1 38.3 85 7.42 11 54.08 1 0.1 0.3 0.1 Viscosity, mm2 /s 40–100 53.2 Density, kg/m3 1.2 Higher Heating Value (HHV), MJ/kg 16–19 18.4 Solid Particulates, wt% 0.2–1 Distillation Residue, wt% up to 50 2.87 - 17.2 34.2 2.39 0.94 13.6 16.4 40 1 1 17.4 47.4 43.17 28.2 7.15 8.78 49.49 62.83 0.1 0.1 It is also shown that bio-oil is significantly different to any petroleum distillate fuel. Bio-oil has a high content of water which is produced during pyrolysis through chemical dehydration of cellulose and hemicellulose and also it is acidic with a pH of approximately 2–3 due to the presence of organic acids [167]. The elemental composition of bio-oil is close to the composition of biomass and as a result it has a similar heating value of 16–19 MJ/kg which is, however, significantly lower than the heating value of petroleum fuels [94]. Due to low heating value, high viscosity, low pH and high water content crude bio-oil is generally regarded as inappropriate for direct use in CI engines or turbines. Bio-oil’s acidity is corrosive to the engine parts (injection nozzles, fuel pumps, pressure valves, seals, gaskets etc.) and its high water content impedes autoignition. For this reason it is generally agreed that bio-oil is not appropriate in high speed engines. Furthermore, various tests have shown that crude bio-oil produces also a number of engine problems such as excessive carbon deposition inside the engine cylinders, poor atomization during injection and increased engine wear. Although bio-oil is aPDF Image | Green Diesel: Biomass Feedstocks, Production Technologies
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