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Energies 2019, 12, 809 29 of 41 diesel and six a blend of 85% green diesel and 15% petroleum diesel. Results showed that in all these Euro 2 to Euro 4 engines the operation with green diesel reduced the emissions of CO, CO2, unburned hydrocarbons (HC), nitrogen oxides (NOx) and solid particulates. CO emissions were on average 27, 38 and 45% lower than the EN 590 levels in the case of trucks-buses, passenger cars with pure fuel and passenger cars with blend fuel, respectively. At the same vehicle categories CO2 emissions were on average lower by about 4, 5 and 6%, respectively, HC were lower by 31, 55 and 40%, respectively, NOx were lower by 9, 1 and 1% and solid particulates were lower by 27, 30 and 13% respectively. The reduction of CO usually means higher CO2 due to more complete combustion, but Neste claims that CO2 emissions also reduce due to the higher H/C atomic ratio on the green diesel fuel. However, Neste also reported that the difference between individual engines was so large that some bus or truck engines showed lower solid particulates by 47% and a slight increase of the NOx emissions. In a similar study Kumar et al. [230] reported 25–30% lower CO emissions at part load, almost constant CO2 emissions at all loads, 25–30% lower HC emissions at low and part load, 5–15% lower NOX emissions at all loads and 49–75% lower smoke at all loads. Two phenomena were considered responsible for the lower emissions. At one hand, the mixing of green diesel with air is better since the fuel is comprised by hydrocarbons in narrow carbon atom (C15–C18) and narrow molecular length chain ranges. This reduces the emissions of CO, HC and smoke by promoting more complete combustion. Secondly, the higher cetane number of green diesel reduces the heat release rate and the maximum flame temperature in the cylinder. Reduced flame temperatures are known to inhibit both the thermal dissociation of CO2 into CO at the late combustion phase and also the Zeldovich mechanism of thermal NOx formation which is responsible for the production of the majority of NOx emissions in an internal combustion engine. The flame temperature with green diesel is also lower due to the higher H/C atomic ratio of the fuel. The reduction of NOx emissions is an advantage of green diesel over biodiesel and petroleum diesel and it was verified experimentally also in other communications [226,227,231,239–243]. However, some ambiguity exists since other communications have reported unchanged or increased green diesel NOx emissions [232,233,236,237,244]. Finally, most communications [228,232,235–237,239,241–243] claim that green diesel reduces the emission of the solid particulates by up to 45%, in agreement to the Neste report [216] mentioned previously. This is attributed to the higher cetane number of green diesel and also to the lower content in sulfur and aromatics. 8. Conclusions The hydro-processing of triglyceride oils and fats has been investigated as the most commonly used technology for the production of green diesel throughout the world. As shown, the appropriate selection of the operating conditions and the utilization of an optimally acidic catalyst and catalyst support is able to provide high yields of C15–C18 saturated hydrocarbons with the desired isomer/normal composition ratios which determine the cetane number and cold flow properties of the biofuel. The review of the relevant research has shown that such appropriate options are the sulfided Ni–Mo/Al2O3 and Co–Mo/Al2O3 catalysts which are the most common choice in the industrial production facilities, together with the sulfided Ni–Mo/SiO2 and the non-sulfided Pd/Al2O3, Pd/SAPO-31, ZnO/α-Al2O3 and Ni–Cu/Al2O3 catalysts which were found highly active in the hydrotreatment of various feedstocks. The catalytic upgrading of sugars and starches into green diesel was also examined paying specific attention on Virent’s BioForming® platform and the relative liquid phase processes of aqueous phase reforming, hydrogenation, hydrogenolysis, catalytic dehydration and alkene oligomerization. Although innovative, the method has found great success on the production of green diesel of sufficiently high cetane number (>50) and also opened a valuable new route of production from sugars obtained by the treatment of crops or lignocellulosic matter which, however, must be susceptible to the existed lignin pretreatment methods. Due to this disadvantage the upgrading of bio-oil or bio-crude and the BTL production technologies seem more promising as they can exploit the entire variety of biomass feedstocks through pyrolysis, hydrothermal liquefactionPDF Image | Green Diesel: Biomass Feedstocks, Production Technologies
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