A Brief Literature Overview of Various Routes to Biorenewable Fuels from Lipids for the National Alliance for Advanced Biofuels and Bio-products (NAABB) Consortium

Renewable methods of producing transportation fuels are currently the focus of numerous large research efforts across the globe. Renewable fuel produced from algal lipids is one aspect of this research that could have profound implications on future transportation fuel requirements. However, technical challenges remain in several areas of algal-lipid-based fuels. These challenges include the identification and development of robust and productive algal species as well as extraction methods to recover the produced lipids. Not the least of these technical challenges is the conversion of the algae lipids to fungible fuels. This brief literature review focuses primarily on state-of-the-art “downstream” applications of producing fuel from fats and lipids, which can be applied to ongoing research with algae-derived lipids

Individual Reactions of Permanganate and Various Reductants - Student Report to the DOE ERULF Program for Work Conducted May to July 2000

Tank waste on the Hanford Site contains radioactive elements that need to be removed from solution prior to disposal. One effective way to do this is to precipitate the radioactive elements with manganese solids, produced by permanganate oxidation. When added to tank waste, the permanganate reacts quickly producing manganese (IV) dioxide precipitate. Because of the speed of the reaction it is difficult to tell what exactly is happening. Individual reactions using non-radioactive reductants found in the tanks were done to determine reaction kinetics, what permanganate was reduced to, and what oxidation products were formed. In this project sodium formate, sodium nitrite, glycolic acid, glycine, and sodium oxalate were studied using various concentrations of reductant in alkaline sodium hydroxide solutions. It was determined that formate reacted the quickest, followed by glycine and glycolic acid. Oxalate and nitrite did not appear to react with the permanganate solutions. The products of the oxidation reaction were examined. Formate was oxidized to carbonate and water. Glycolic acid was oxidized slower producing oxalate and water. Glycine reactions formed some ammonia in solution, oxalate, and water. The research reported by Amber Gauger in this report was part of a DOE ERULF student intern program at Pacific Northwest National Laboratory under the direction of Richard Hallen in the summer of 2000

Single-Step Syngas-to-Distillates (S2D) Synthesis via Methanol and Dimethyl Ether Intermediates: Final Report

The objective of the work was to enhance price-competitive, synthesis gas (syngas)-based production of transportation fuels that are directly compatible with the existing vehicle fleet (i.e., vehicles fueled by gasoline, diesel, jet fuel, etc.). To accomplish this, modifications to the traditional methanol-to-gasoline (MTG) process were investigated. In this study, we investigated direct conversion of syngas to distillates using methanol and dimethyl ether intermediates. For this application, a Pd/ZnO/Al2O3 (PdZnAl) catalyst previously developed for methanol steam reforming was evaluated. The PdZnAl catalyst was shown to be far superior to a conventional copper-based methanol catalyst when operated at relatively high temperatures (i.e., >300°C), which is necessary for MTG-type applications. Catalytic performance was evaluated through parametric studies. Process conditions such as temperature, pressure, gas-hour-space velocity, and syngas feed ratio (i.e., hydrogen:carbon monoxide) were investigated. PdZnAl catalyst formulation also was optimized to maximize conversion and selectivity to methanol and dimethyl ether while suppressing methane formation. Thus, a PdZn/Al2O3 catalyst optimized for methanol and dimethyl ether formation was developed through combined catalytic material and process parameter exploration. However, even after compositional optimization, a significant amount of undesirable carbon dioxide was produced (formed via the water-gas-shift reaction), and some degree of methane formation could not be completely avoided. Pd/ZnO/Al2O3 used in combination with ZSM-5 was investigated for direct syngas-to-distillates conversion. High conversion was achieved as thermodynamic constraints are alleviated when methanol and dimethyl are intermediates for hydrocarbon formation. When methanol and/or dimethyl ether are products formed separately, equilibrium restrictions occur. Thermodynamic relaxation also enables the use of lower operating pressures than what would be allowed for methanol synthesis alone. Aromatic-rich hydrocarbon liquid (C5+), containing a significant amount of methylated benzenes, was produced under these conditions. However, selectivity control to liquid hydrocarbons was difficult to achieve. Carbon dioxide and methane formation was problematic. Furthermore, saturation of the olefinic intermediates formed in the zeolite, and necessary for gasoline production, occurred over PdZnAl. Thus, yield to desirable hydrocarbon liquid product was limited. Evaluation of other oxygenate-producing catalysts could possibly lead to future advances. Potential exists with discovery of other types of catalysts that suppress carbon dioxide and light hydrocarbon formation. Comparative techno-economics for a single-step syngas-to-distillates process and a more conventional MTG-type process were investigated. Results suggest operating and capital cost savings could only modestly be achieved, given future improvements to catalyst performance. Sensitivity analysis indicated that increased single-pass yield to hydrocarbon liquid is a primary need for this process to achieve cost competiveness

A Brief Literature Overview of Various Routes to Biorenewable Fuels from Lipids for the National Alliance for Advanced Biofuels and Bio-products (NAABB) Consortium

Renewable methods of producing transportation fuels are currently the focus of numerous large research efforts across the globe. Renewable fuel produced from algal lipids is one aspect of this research that could have profound implications on future transportation fuel requirements. However, technical challenges remain in several areas of algal-lipid-based fuels. These challenges include the identification and development of robust and productive algal species as well as extraction methods to recover the produced lipids. Not the least of these technical challenges is the conversion of the algae lipids to fungible fuels. This brief literature review focuses primarily on state-of-the-art “downstream” applications of producing fuel from fats and lipids, which can be applied to ongoing research with algae-derived lipids

Individual Reactions of Permanganate and Various Reductants - Student Report to the DOE ERULF Program for Work Conducted May to July 2000

Tank waste on the Hanford Site contains radioactive elements that need to be removed from solution prior to disposal. One effective way to do this is to precipitate the radioactive elements with manganese solids, produced by permanganate oxidation. When added to tank waste, the permanganate reacts quickly producing manganese (IV) dioxide precipitate. Because of the speed of the reaction it is difficult to tell what exactly is happening. Individual reactions using non-radioactive reductants found in the tanks were done to determine reaction kinetics, what permanganate was reduced to, and what oxidation products were formed. In this project sodium formate, sodium nitrite, glycolic acid, glycine, and sodium oxalate were studied using various concentrations of reductant in alkaline sodium hydroxide solutions. It was determined that formate reacted the quickest, followed by glycine and glycolic acid. Oxalate and nitrite did not appear to react with the permanganate solutions. The products of the oxidation reaction were examined. Formate was oxidized to carbonate and water. Glycolic acid was oxidized slower producing oxalate and water. Glycine reactions formed some ammonia in solution, oxalate, and water. The research reported by Amber Gauger in this report was part of a DOE ERULF student intern program at Pacific Northwest National Laboratory under the direction of Richard Hallen in the summer of 2000

Hydrothermal Liquefaction Biocrude Compositions Compared to Petroleum Crude and Shale Oil

We provide a direct and detailed comparison of the chemical composition of petroleum crude oil (from the Gulf of Mexico), shale oil, and three biocrudes (i.e., clean pine, microalgae <i>Chlorella</i> sp., and sewage sludge feedstocks) generated by hydrothermal liquefaction (HTL). Ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) reveals that HTL biocrudes are compositionally more similar to shale oil than petroleum crude oil and that only a few heteroatom classes (e.g., N₁, N₂, N₁O₁, and O₁) are common to organic sediment- and biomass-derived oils. All HTL biocrudes contain a diverse range of oxygen-containing compounds when compared to either petroleum crude or shale oil. Overall, petroleum crude and shale oil are compositionally dissimilar to HTL oils, and >85% of the elemental compositions identified within the positive-ion electrospray (ESI) mass spectra of the HTL biocrudes were not present in either the petroleum crude or shale oil (>43% for negative-ion ESI). Direct comparison of the heteroatom classes that are common to both organic sediment- and biomass-derived oils shows that HTL biocrudes generally contain species with both smaller core structures and a lower degree of alkylation relative to either the petroleum crude or the shale oil. Three-dimensional plots of carbon number versus molecular double bond equivalents (with observed abundance as the third dimension) for abundant molecular classes reveal the specific relationship of the composition of HTL biocrudes to petroleum and shale oils to inform the possible incorporation of these oils into refinery operations as a partial amendment to conventional petroleum feeds