Green Diesel: Biomass Feedstocks, Production Technologies, Catalytic Research, Fuel Properties and Performance in Compression Ignition Internal Combustion Engines

The present investigation provides an overview of the current technology related to the green diesel, from the classification and chemistry of the available biomass feedstocks to the possible production technologies and up to the final fuel properties and their effect in modern compression ignition internal combustion engines. Various biomass feedstocks are reviewed paying attention to their specific impact on the production of green diesel. Then, the most prominent production technologies are presented such as the hydro-processing of triglycerides, the upgrading of sugars and starches into C15–C18 saturated hydrocarbons, the upgrading of bio-oil derived by the pyrolysis of lignocellulosic materials and the “Biomass-to-Liquid” (BTL) technology which combines the production of syngas (H2 and CO) from the gasification of biomass with the production of synthetic green diesel through the Fischer-Tropsch process. For each of these technologies the involved chemistry is discussed and the necessary operation conditions for the maximum production yield and the best possible fuel properties are reviewed. Also, the relevant research for appropriate catalysts and catalyst supports is briefly presented. The fuel properties of green diesel are then discussed in comparison to the European and US Standards, to petroleum diesel and Fatty Acid Methyl Esters (FAME) and, finally their effect on the compression ignition engines are analyzed. The analysis concludes that green diesel is an excellent fuel for combustion engines with remarkable properties and significantly lower emissions

Energy and Exergy-Based Screening of Various Refrigerants, Hydrocarbons and Siloxanes for the Optimization of Biomass Boiler–Organic Rankine Cycle (BB–ORC) Heat and Power Cogeneration Plants

The cogeneration of power and heat was investigated for Biomass Boiler–Organic Rankine Cycle (BB–ORC) plants with the characteristics of typical units, such as the 1 MWel Turboden ORC 10 CHP. The thermodynamic analysis of the ORC unit was undertaken considering forty-two (42) dry and isentropic candidate pure working fluids. Only subcritical Rankine cycles were considered, and the pinch point temperature differences for the evaporation and condensation heat exchangers were kept constant at 10 °C in all cases. The study provides an original and unique screening of almost all pure working fluids that are considered appropriate in the literature under the same operation and optimization conditions and compiles them into a single reference. In its conclusions, the study provides useful fluid selection and design guidelines, which may be easily followed depending on the optimization objective of the ORC designer or operator. In general, hydrocarbons are found to lie in the optimum middle range of the fluid spectrum, between the siloxanes that maximize the production of mechanical power and the refrigerants that maximize the production of heat. Specific hydrocarbon fluids, such as cyclopentane, heptane, hexane, benzene, and toluene, are found as rational options for maximum mechanical efficiency when operating with practically feasible condensation pressures between 10 and 200 kPa. At condensation pressures below 10 kPa, ethylbenzene, o-xylene, m-xylene, p-xylene, and nonane are also found to be feasible options. Finally, cyclopentane, hexane, and MM (hexamethyldisiloxane) are selected as the most appropriate options for cogeneration plants aiming simultaneously at high mechanical power and maximum temperature water production

Effect of operating parameters on the selective catalytic deoxygenation of palm oil to produce renewable diesel over Ni supported on Al2O3, ZrO2 and SiO2 catalysts

The present work investigated the production of Green Diesel through the deoxygenation of palm oil over Ni catalysts supported on γ-Αl2O3, ZrO2 and SiO2 for a continuous flow fixed bed reactor. A comprehensive experimental study was carried out in order to examine the effects of temperature, pressure, LHSV and H2/oil feed ratio on catalytic activity during short (6 h) and long (20 h) time-on-stream experiments. The catalysts were prepared through the wet impregnation method (8 wt% Ni) and were extensively characterized by N2 adsorption/desorption, XRD, NH3-TPD, CO2-TPD, H2-TPD, H2-TPR, XPS, TEM/HR-TEM and Raman. The characterization of the materials prior to reaction revealed that although relatively small Ni nanoparticles were achieved for all catalysts (4.3 ± 1.6 nm, 6.1 ± 1.8 nm and 6.0 ± 1.8 nm for the Ni/Al2O3, Ni/ZrO2 and Ni/SiO2 catalysts, respectively), NiO was better dispersed on the Ni/ZrO2 catalyst, while the opposite was true for the Ni/SiO2 sample. In the case of Ni/Al2O3, part of Ni could not participate in the reaction due to its entrapment in the NiAl2O4 spinel phase. Regarding performance, although an increase in H2 pressure led to increases in paraffin conversion, the increase of temperature was beneficial only up to a critical value which differed for each catalytic system under consideration (375 °C, 300 °C and 350 °C for the Ni/Al2O3, Ni/ZrO2 and Ni/SiO2 catalysts, respectively). All catalysts favored the deCO2 and deCO deoxygenation paths much more extensively than HDO, irrespective of testing conditions. Time-on-stream experiments showed that all catalysts deactivated after about 6 h, which was attributed to the sintering of the Ni particles and/or their covering by a thin graphitic carbon shell.KNP is grateful for the support of the Hellenic Foundation for Research and Innovation (HFRI) and the General Secretariat for Research and Technology (GSRT), under the HFRI PhD Fellowship grant (GA. no. 359). MAG and NDC gratefully acknowledge that this researched was co-financed by Greece and the European Union (European Social Fund- ESF) through the Operational Programme “Human Resources Development, Education and Lifelong Learning” (MIS-5050170). SD is thankful for financial assistance provided by the Research Committee of the University of Western Macedonia (grant number 70277). KP acknowledges the financial support from the Abu Dhabi Department of Education and Knowledge (ADEK) under the AARE 2019-233 grant and the support from Khalifa University under the RCII-2018-024.Peer reviewe

Promoting effect of CaO-MgO mixed oxide on Ni/γ-Al2O3 catalyst for selective catalytic deoxygenation of palm oil

The study presented herein examines, for the first time in the literature, the role of CaO-MgO as a modifier of γ-Αl2O3 for Ni catalysts for the production of green diesel through the deoxygenation of palm oil. The characteristics of the catalytic samples were examined by N2 adsorption/desorption, XRD, NH3-TPD, CO2-TPD, H2-TPR, XPS and TEM analysis. The carbon deposited on the catalytic surfaces was characterized by TPO, Raman and TEM/HR-TEM. Experiments were conducted between 300 and 400 °C, at 30 bar. Maximum triglyceride conversion and the yield of the target n–C15–n–C18 paraffins increased with temperature up to 375 °C for both catalysts. Both samples promoted deCO2 and deCO deoxygenation reactions much more extensively than HDO. However, although both catalysts exhibited similar activity at the optimal temperature of 375 °C, the Ni/modAl was more active at lower reaction temperatures, which can be probably understood on the basis of the increased dispersion of Ni on its surface and its lower acidity, which suppressed hydrocracking reactions. Time-on-stream experiments carried out for 20 h showed that the Ni/modAl catalyst was considerably more stable than the Ni/Al, which was attributed to the lower amount and lower crystallinity of the carbon deposits and to the suppression of sintering due to the presence of the CaO-MgO modifiers.KNP is grateful for the support of the Hellenic Foundation for Research and Innovation (HFRI) and the General Secretariat for Research and Technology (GSRT), under the HFRI PhD Fellowship grant (GA. no. 359). MAG and NDC gratefully acknowledge that this researched was co-financed by Greece and the European Union (European Social Fund- ESF) through the Operational Programme «Human Resources Development, Education and Lifelong Learning» (MIS-5050170). SD is thankful for financial assistance provided by the Research Committee of the University of Western Macedonia (grant number 70277). KP acknowledges the financial support from the Abu Dhabi Department of Education and Knowledge (ADEK) under the AARE 2019-233 grant and support by the Khalifa University of Science and Technology under Award No. RC2-2018-024.Peer reviewe

The relationship between reaction temperature and carbon deposition on nickel catalysts based on Al2O3, ZrO2 or SiO2 supports during the biogas dry reforming reaction

This article belongs to the Special Issue Catalyst Deactivation in Hydrocarbon Processing.The tackling of carbon deposition during the dry reforming of biogas (BDR) necessitates research of the surface of spent catalysts in an effort to obtain a better understanding of the effect that different carbon allotropes have on the deactivation mechanism and correlation of their formation with catalytic properties. The work presented herein provides a comparative assessment of catalytic stability in relation to carbon deposition and metal particle sintering on un-promoted Ni/Al2O3, Ni/ZrO2 and Ni/SiO2 catalysts for different reaction temperatures. The spent catalysts were examined using thermogravimetric analysis (TGA), Raman spectroscopy, high angle annular dark field scanning transmission electron microscopy (STEM-HAADF) and X-ray photoelectron spectroscopy (XPS). The results show that the formation and nature of carbonaceous deposits on catalytic surfaces (and thus catalytic stability) depend on the interplay of a number of crucial parameters such as metal support interaction, acidity/basicity characteristics, O2– lability and active phase particle size. When a catalytic system possesses only some of these beneficial characteristics, then competition with adverse effects may overshadow any potential benefits.Peer reviewe