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  1. Co-processing catalytic fast pyrolysis oil in an FCC reactor

    Here, studies of co-processing catalytic fast pyrolysis (CFP) oil with vacuum gas oil (VGO) are conducted in a Davison Circulating Riser (DCR). The CFP oil (CFPO) for this study was produced by upgrading fast-pyrolysis vapors from pine in an ex-situ fixed-bed reactor. CFPOs were co-processed at up to a volume fraction of 0.05 with VGO at 521 degrees C and 257 kPa. The yields of oil, aqueous phase, tail gas, and coke were measured. The amount of coke was determined from the carbon containing components in the regenerator flue gas. A compositional analysis was conducted with gas chromatography and elementalmore » analyzers. The organic liquids were distilled into gasoline, jet-fuel, diesel, and resid fractions. A biocarbon analysis was conducted on the organic phase and its individual boiling-point fractions. The results show a small decrease in liquid yield and a generally increased gas yield when co-processing CFPO with VGO. The experiments showed that 75%-100% of biocarbon is incorporated into liquid fuels relative to fossil carbon, depending on catalyst and CFPO. The measurements indicate that cracked CFPO components are predominantly included in the jet-fuel and diesel fractions. A techno-economic analysis (TEA) estimated the minimum fuel selling price (MSFP) for fuel-range products derived from FCC co-processing of CFPO at 24 to 29 $$\$$$$/GJ ($$\$$$$2.90 to $$\$$$$3.50 per gasoline-gallon equivalent; GGE) at a yield of 4.87-7.14 GJ/t(biomass) or 40-58 GGE/t.« less
  2. Model-based compositional predictions for a differential scanning calorimetry/thermogravimetric analysis-mass spectrometry system used for heat of vaporization measurements

    A Differential Scanning Calorimetry/Thermogravimetric Analysis (DSC/TGA) procedure for determination of Heat of Vaporization (HOV) of fuel and surrogate fuel mixtures has been previously utilized for evaluation of oxygenate impacts on spark ignition fuels. This analysis has been further leveraged with mass spectrometry (MS) to elucidate vapor phase compositional changes during evaporation. In this study we focus on a simple system of three compounds (ethanol, n-hexane, and n-octane) to provide a model-based understanding of the evaporation process under these experimental conditions. An Aspen Plus model was set up to provide liquid and vapor phase concentration predictions during mixture evaporation using themore » initial mixture composition, and measured temperature and mass loss profiles from DSC/TGA experiments. Agreements between the trends of the MS ion count profiles and model composition predictions provide a degree of validation of this modeling approach that can allow the interpretation and extrapolation of DSC/TGA measurements for more complex fuel mixtures.« less
  3. Supercritical Methanol Solvolysis and Catalysis for the Conversion of Delignified Woody Biomass into Light Alcohol Gasoline Bioblendstock

    Supercritical methanol (SCM) solvolysis and catalysis has recently emerged as a promising pathway to produce gasoline-range light alcohols from woody biomass through staged depolymerization and hydro-deoxygenation (DHDO). Here, structure-property relationships of Cu"M"AlOx catalysts (M = Mg, Zr, and Ce) are examined for upgrading delignified hybrid poplar via SCM-DHDO. CuCeAlOx displays the highest activity, increasing the C2-C7 alcohol production rate and selectivity by twofold in batch reactions, and >50% in semicontinuous reactions relative to the current state-of-the-art CuMgAlOx. The performance of CuCeAlOx is correlated with its high reducibility and acidity. Cu sintering and biogenic impurity poisoning are identified as possible deactivationmore » mechanisms over 60 h of continuous testing. The gasoline-range SCM-DHDO products are comprised of primarily aliphatic alcohols that result in improved energy density and favorably reduced vapor pressure, relative to ethanol, with the tradeoff of nonsynergistic octane blending with conventional gasoline and lower oxidation stability. Overall, this work highlights the potential to produce suitable light oxygenates by SCM-DHDO processing for gasoline bioblendstock applications.« less
  4. Efficacy, economics, and sustainability of bio-based insecticides from thermochemical biorefineries

    The efficacy, economics, and sustainability of a bio-based insecticide produced from the catalytic fast pyrolysis of biomass is reported. This synergistic approach to fuels and agrochemical production can improve both energy and food sectors.
  5. Catalyst design to direct high-octane gasoline fuel properties for improved engine efficiency

    The paraffin-to-olefin (P/O) ratio in gasoline fuel is a critical metric affecting fuel properties and engine efficiency. In the conversion of dimethyl ether (DME) to high-octane hydrocarbons over BEA zeolite catalysts, the P/O ratio can be controlled through catalyst design. Here in this paper, we report bimetallic catalysts that balance the net hydrogenation and dehydrogenation activity during DME homologation. The Cu-Zn/BEA catalyst exhibited greater relative dehydrogenation activity attributed to higher ionic site density, resulting in a lower P/O ratio (6.6) versus the benchmark Cu/BEA (9.4). The Cu-Ni/BEA catalyst exhibited increased hydrogenation due to reduced Ni species, resulting in a highermore » P/O ratio (19). The product fuel properties were estimated with an efficiency merit function and compared against finished gasolines and a typical alkylate blendstock. Merit values for the hydrocarbon product from all three BEA catalysts exceeded those of the comparison fuels (0–5.3), with the product from Cu-Zn/BEA exhibiting the highest merit value (9.7).« less
  6. A Review and Perspective on Particulate Matter Indices Linking Fuel Composition to Particulate Emissions from Gasoline Engines

    Particulate matter (PM) indices - those linking PM emissions from gasoline engines to the composition and properties of the fuel - have been a topic of significant study over the last decade. It has long been known that fuel composition has a significant impact on particulate emissions from gasoline engines. Since gasoline direct injection (GDI) engines have become the market-leading technology, this has become more significant because the evaporative behavior of fuel increases in importance. Several PM indices have been developed to provide metrics describing this behavior and correlating PM emissions. In this article, 16 different PM indices are identifiedmore » and collected - to the authors' knowledge, all of the indices are available at the time of writing. The indices are reviewed and discussed in the context of the information required to calculate them, as well as their utility. Additionally, the authors believe that there is a need for indices that provide both a detailed and robust correlation, as well as those that are less sophisticated yet sufficient for specific use cases. Future research is suggested to guide the technical community toward improvements in the indices' methods and equations for both high and low fidelity and high and low time investment.« less
  7. Toward net-zero sustainable aviation fuel with wet waste–derived volatile fatty acids

    Significance To meet the growing demand for sustainable aviation fuels (SAF), conversion pathways are needed that leverage wet waste carbon and meet jet fuel property specifications. Here, we demonstrate SAF production from food waste–derived volatile fatty acids (VFA) by targeting normal paraffins for a near-term path to market and branched isoparaffins to increase the renewable content long term. Combining these distinct paraffin structures was shown to synergistically improve VFA-SAF flash point and viscosity to increase the renewable blend limit to 70%. Life cycle analysis shows the dramatic impact on the carbon footprint if food waste is diverted from landfills tomore » produce VFA-SAF, highlighting the potential to meet jet fuel safety, operability, and environmental goals.« less
  8. Advanced spectrometric methods for characterizing bio-oils to enable refineries to reduce fuel carbon intensity during co-processing

    A promising approach for supplementing petroleum-derived fuels to support reductions in green-house gas emissions is to convert abundant biomass feedstocks into renewable carbon-rich oils using pyrolysis. However, the resultant bio-oils contain various oxygenated compounds that can impart acidity, chemical and thermal instability, and immiscibility with petroleum derived fuels, necessitating further upgrading to derive fuel blendstocks. Co-processing bio-oils and petroleum-derived liquids in existing refineries is a potentially near-term, cost-effective approach for upgrading bio-oils while reducing refinery carbon intensities. However, one cause for hesitation in co-processing bio-oils is limited comprehensive characterization and speciation of the bio-oil components. Advanced analytical techniques are currentlymore » under investigation to enable identification of elusive species in bio-oils, enabling researchers to develop strategies to mitigate catalyst deactivation agents and contaminants. This review provides a brief overview of several analytical methods commonly used to analyze bio-oils and their limitations. In addition, advanced techniques currently under development are discussed to further elucidate bio-oil components that may limit its end use. This will help inform the technical and economic feasibility of co-processing bio-oils with petroleum-derived liquids, therefore, improving the overall downstream processes for biofuels blendstock production.« less
  9. Synthesis of Butyl-Exchanged Polyoxymethylene Ethers as Renewable Diesel Blendstocks with Improved Fuel Properties

    Methyl-terminated polyoxymethylene ethers (MM-POMEs), having the formula CH3O–(CH2O)n–CH3 (n = 3–5), are a high-cetane, low-sooting group of oxygenates that have recently attracted attention as potential diesel blendstocks. Despite these attractive fuel properties, MM-POMEs have shortcomings due to their low energy density and high water solubility. Guided by a computational fuel property assessment for POMEs with longer end-groups, the most promising improvements in the desired compression ignition fuel properties were observed for butyl-terminated POMEs. Here, an acid-catalyzed transacetalization reaction was developed to exchange the methyl end-groups of MM-POMEs (n = 3–6) with butyl end-groups. The reaction utilizes an ion-exchange resin asmore » the acid catalyst at mild reaction conditions of 60 °C and atmospheric pressure. Approximately 100 mL of butyl-exchanged POMEs in the diesel boiling range were produced, enabling laboratory-scale fuel property testing. The butyl-terminated POME mixture possesses the advantaged fuel properties of the parent MM-POMEs (low-soot, high-cetane) while exhibiting improved energy density (lower heating value (LHV) of 30 MJ/kg) and substantially reduced water solubility (7.3 g/L) compared to the parent MM-POME mixture (LHV of 19 MJ/kg , water solubility of 258 g/L).« less
  10. Online Biogenic Carbon Analysis Enables Refineries to Reduce Carbon Footprint during Coprocessing Biomass- and Petroleum-Derived Liquids

    To mitigate green-house gas (GHG) emissions, governments around the world are enacting legislation to reduce carbon intensity in transportation fuels. Coprocessing biomass and petroleum-derived liquids in existing refineries is a near-term, cost-effective approach for introducing renewable carbon in fuels and enabling refineries to meet regulatory mandates. However, coprocessing biomass-derived liquids in refineries results in variable degrees of biogenic carbon incorporation, necessitating accurate quantification to verify compliance with mandates. Existing refinery control and instrumentation systems lack the means to measure renewable carbon accurately, reliably, and quickly. Furthermore, accurate measurement of biogenic carbon is key to ensuring refineries meet regulatory mandates. Inmore » this Perspective, we present existing methods for measuring biogenic carbon, point out their challenges, and discuss the need for new online analytical capabilities to measure biogenic carbon in fuel intermediates.« less
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