Nutrient Recovery from Algae Using Mild Oxidative Treatment and Ion Exchange
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Engineering topics
Christensen, Earl D.
Publications and source records attributed to Christensen, Earl D..
Water Contamination Impacts on Biodiesel Antioxidants and Storage Stability
Biodiesel (fatty acid methyl esters) can oxidize in storage to form acids and gums that negatively impact engine performance and durability. Antioxidant additives are used to increase biodiesel storage stability, and previous studies that evaluated the effectiveness of antioxidants demonstrated that more polar antioxidants tend to be the most effective (provide the largest improvement in stability per unit of antioxidant added). However, polar antioxidants have significant water solubility, and diesel fuel storage tanks are commonly contaminated with water (forming a layer of water under the fuel). This study investigates whether nonpolar antioxidants, which are less effective in dry environments, might be more effective under wet conditions simulating real-world storage. Biodiesel blends treated with polar and nonpolar antioxidants were subjected to accelerated aging using the ASTM D4625 protocol (storage at 43 °C, open to air, for up to 24 weeks) both with and without added water. Fuels treated with polar/higher-effectiveness compounds and stored in contact with water (simulating water in a storage tank) or high humidity showed accelerated loss of stability compared to dry storage. The same fuel treated with a nonpolar antioxidant and stored in the same conditions did not exhibit accelerated stability loss and thus had higher storage stability over the long term despite treatment with an initially less effective additive. Analysis of the fuels during aging showed that this loss of stability was not due to oxidation but rather extraction of the polar antioxidant into the water layer. Antioxidant additives that are incompatible with wet or humid storage conditions were found to cause faster-than-anticipated loss of stability, which was preventable with use of nonpolar additives.
09 BIOMASS FUELS↗
Analytical Evaluation of Lead Iodide Precursor Impurities Affecting Halide Perovskite Device Performance
Not Available
14 SOLAR ENERGY↗
Lignin alkaline oxidation using reversibly-soluble bases
When excess base is required to drive desired reactions, such as in lignin alkaline oxidation, Sr(OH) 2 can offer a reversibly-soluble alternative to NaOH that allows simple recycle of the excess base with concomitant cost and environmental benefits.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Screening and evaluation of biomass upgrading strategies for sustainable transportation fuel production with biomass-derived volatile fatty acids
Biomass conversion to fuels and chemicals is crucial to decarbonization, but choosing an advantageous upgrading pathway out of many options is challenging. Rigorously evaluating all candidate pathways (process simulation, product property testing) requires a prohibitive amount of research effort; even simple upgrading schemes have hundreds of possible permutations. We present a method enabling high-throughput screening by approximating upgrading unit operations and drop-in compatibility of products (e.g., fuel properties) and apply it to volatile fatty acid (VFA) conversion to liquid transportation fuels via a MATLAB script, VFA Upgrading to Liquid Transportation fUels Refinery Estimation (VULTURE). VULTURE selects upgrading configurations that maximize fuel blend bio-derived content. We validate VULTURE's approximations through surrogate fuel property testing and process simulation. Techno-economic and life cycle analyses suggest that VFA upgrading processes down-selected by VULTURE are profitable and have low carbon intensities, demonstrating the potential for the strategy to accelerate process development timelines at decreased costs.
09 BIOMASS FUELS↗
Continuous hydrodeoxygenation of lignin to jet-range aromatic hydrocarbons
Sustainable aviation fuel (SAF) is essential to decrease the carbon footprint of the aviation industry. Although many strategies have been developed to provide the branched, aliphatic components of SAF, few viable strategies have been demonstrated to supply the aromatic and cycloalkane fraction of SAF at the necessary scale from bio-based feedstocks. Lignin is the largest natural source of renewable aromatic compounds, yet major challenges in deoxygenation have prevented its use as a feedstock for SAF. Here we report a continuous, two-stage catalytic process using molybdenum carbide to deoxygenate lignin from poplar into aromatic hydrocarbons with 87.5% selectivity towards aromatic hydrocarbons at 86% of the theoretical carbon recovery. This work demonstrates an effective approach to convert lignin into aromatic SAF blendstocks.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
A separations and purification process for improving yields and meeting fuel contaminant specifications for high-octane gasoline produced from dimethyl-ether over a Cu/BEA catalyst
In this work, we have been developing a three-step conversion of biomass-derived syngas to methanol to dimethyl-ether (DME) to non-aromatic hydrocarbons for use as high-octane gasoline and sustainable aviation fuel. This process produces branched alkanes from DME using a Cu/BEA catalyst and is a promising alternative to other syngas conversion processes such as Fischer-Tropsch to linear alkanes and traditional ZSM-5 catalyzed methanol to aromatic gasoline. In this short article we describe some advances in our understanding related to separations and purification via the use of more detailed experimental speciation in an updated process model involving multiple phase equilibrium-based separation steps. Primary modeled reactor outlet constituents (and weight %) are: C3 and lighter hydrocarbon gases (11.1%), C4s (54.5%), H 2 (1.2%), CO 2 (2.9%), water (5.0%), unreacted DME (16.5%), methanol (2.3%), and C5+ hydrocarbons (6.4%). DME (the primary reactant) and H 2 recycle and reuse are important for the overall process efficiency, and the recycle of C4s is important to increase the C5+ yield via reactivation and homologation. Thus H 2 , C4s, and DME are targeted for recycle, while methanol and water need to be removed from the product to conform with fuel specifications. Model predictions from Aspen Plus using the NRTL-RK property method indicate a fuel composition with C5+ content of 97.1 wt%, with minor constituents: 2.4 wt% C4s, 0.3 wt% methanol, 0.1 wt% DME, 0.03 wt% water, and 0.01 wt% C3s. These ranges of minor components conform with fuel quality requirements, and the modeled product is amenable for unconstrained blending to boost gasoline octane ratings.
09 BIOMASS FUELS↗
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 elemental 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.
09 BIOMASS FUELS↗
Elemental Analysis of Bio-Oils by Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). Laboratory Analytical Procedure (LAP), Issue Date: May 13, 2022
Concentrations of inorganic elements is a key quality metric for bio-oils as certain elements impact upgrading processes and product quality. Unless reduced or removed during production and processing, alkali and alkaline metals native to lignocellulosic biomass can carry over into bio-oils contributing to ash content and degraded catalyst performance during upgrading to hydrocarbon fuels or chemical products. Non-metallic elements such as sulfur and phosphorus can also negatively impact upgrading catalysts and product quality. Inductively coupled plasma optical emission spectroscopy (ICP-OES) can be used to measure inorganic elements of interest in bio-oils. This procedure covers the preparation and analysis of fast pyrolysis (FP) and catalytic fast pyrolysis (CFP) bio-oils. The concentrations of these elements can indicate potential bio-oil quality from the perspective of deoxygenation processes. The implications of elemental composition will depend on process parameters such as upgrading catalyst sensitivities. This Laboratory Analytical Procedure (LAP) covers two methods for quantification of inorganic elements by ICP-OES: Procedure A uses microwave assisted digestion with concentrated nitric acid, and Procedure B is an organic ICP-OES method utilizing a diglyme solvent.
09 BIOMASS FUELS↗
Corrosivity Screening of Pyrolysis Bio-Oils by Short-Term Alloy Exposures. Laboratory Analytical Procedure (LAP), Issue Date: May 12, 2022
Bio-oils contain organic acids and oxygenated compounds that can lead to corrosion issues during bio-oil processing and storage. This Laboratory Analytical Procedure (LAP) allows for rapid screening of a bio-oil's corrosivity without the need for complex equipment and long-term exposures. A robust and repeatable method for assessing the corrosivity of bio-oils is necessary in order to remove materials degradation as an obstacle to research, upgrading, use and storage of bio-oils. This LAP involves the incubation of a representative alloy, 410 stainless steel (410 SS), specimen in bio-oil over a period of 48 hours at 50 degrees C in a sealed container. The corrosive species in the bio-oil react with and deplete alloy elements such as iron (Fe) and/or chromium (Cr) from the specimen into the bio-oil solution. The depletion of Fe and Cr from the specimen results in a significant mass loss that can be recorded. The mass loss is directly correlated to the corrosivity of a bio-oil. Examples of bio-oils in scope include the ones produced by fast pyrolysis and catalytic fast pyrolysis, as well as liquids produced from hydrothermal liquefaction.
09 BIOMASS FUELS↗
Determination of Phenolic Groups in Bio-Oils Using Revised Folin-Ciocalteu Methods: Single Cuvette and Plate Reader. Laboratory Analytical Procedure (LAP), Issue Date: May 12, 2022
Phenol components are ubiquitous in wood-derived bio-oils and biocrudes. Their reaction with other functional groups (e.g., aldehydes) may contribute to the formation of carbonaceous species and the expected thermal instability of pyrolysis oils. During hydrotreating, phenols can be recalcitrant species, requiring higher reaction temperatures than other oxygen-containing functional groups. Phenols are also present in upgraded products and have been shown to lead to catalyst deactivation during hydrotreating. They also are the first oxygenated functional group to re-appear in the upgraded product, signaling catalyst deactivation. This procedure covers the determination of phenolic compounds in fast pyrolysis oils. This Laboratory Analytical Procedure (LAP) includes two methods, the first allowing for shorter analysis time at increased reaction temperature, while the second employs a longer analysis time but at room temperature. Additionally, the use of both a single cuvette and of a plate reader are also presented.
09 BIOMASS FUELS↗
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 the 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.
33 ADVANCED PROPULSION SYSTEMS↗
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"AlO x catalysts (M = Mg, Zr, and Ce) are examined for upgrading delignified hybrid poplar via SCM-DHDO. CuCeAlO x displays the highest activity, increasing the C 2 -C 7 alcohol production rate and selectivity by twofold in batch reactions, and >50% in semicontinuous reactions relative to the current state-of-the-art CuMgAlO x . The performance of CuCeAlOx is correlated with its high reducibility and acidity. Cu sintering and biogenic impurity poisoning are identified as possible deactivation 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.
09 BIOMASS FUELS↗
Synthesis of Hydrophilic Derivative Surfactants From Algae-Derived Unsaponifiable Lipids
In the context of decarbonizing the economy, the utilization of biologically sourced feedstocks to produce replacements for petroleum-derived materials is becoming more urgent. Improving renewable biomass production and utilization is imperative for commercializing future biorefineries. Algae-derived biomass is a particularly promising feedstock thanks to its attractive oil content and composition; specifically, the high-value products in the unsaponifiable lipids have not been included in a conversion process. Here we demonstrate surfactant synthesis from a complex oil fraction as the hydrophobic donor moieties, yielding products that are similar to commercially available surfactants such as the linear alkyl benzene sulfonates. Unsaponifiable lipids extracted from algae were derivatized to non-ionic surfactants using a green chemical synthesis route based on a double esterification with succinic acid and polyethylene glycol. The in-depth molecular and structural surfactant characterization is included and indicates that the resulting properties fall between those of pure cholesterol and phytol used as surrogates for the reaction synthesis demonstration. This is the first demonstration of an effective and potentially high-value synthesis of functional surfactants with properties that can be tailored based on the relative composition of the resulting hydrocarbon alcohol components in the mixture. This novel green chemistry synthesis approach provides a route to high-value product synthesis from algae.
09 BIOMASS FUELS↗
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 identified 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.
33 ADVANCED PROPULSION SYSTEMS↗
Determination of Carbon, Hydrogen, Nitrogen, and Oxygen in Bio-Oils: Laboratory Analytical Procedure (LAP)
The determination of total carbon, hydrogen, and nitrogen in bio-oils is important as these values can be used to track the carbon balance of production processes as well as calculate total oxygen content by difference. Oxygen content of bio-oils is a key metric for production and upgrading strategies as these are typically aimed at reducing oxygen. Oxygenates in bio-oils contribute to poor hydrocarbon miscibility, high acidity, high viscosity, and poor stability. Upgrading of bio-oils via deoxygenation produces hydrocarbons which can be used to generate feedstocks for renewable fuels and chemicals. In this Laboratory Analytical Procedure (LAP), combustion-based ultimate analysis is used to determine the weight percent (wt%) of C, H, and N in bio-oils and upgraded products. Ultimate analysis uses high temperatures and a pure oxygen environment to completely combust organic samples to carbon dioxide (CO 2 ), water (H 2 O), and nitrogen oxides (NO x ). In this procedure the amount of C and H in the sample are quantified by measuring resultant CO 2 and H 2 O with Fourier-transform infrared spectroscopy (FTIR). For N, NO x is reduced to nitrogen (N 2 ) which is measured with a thermal conductivity detector (TCD), providing total N content.
09 BIOMASS FUELS↗
Determination of Water Content in Bio-Oils by Volumetric Karl Fischer Titration: Laboratory Analytical Procedure (LAP)
The water content of bio-oils is a key metric for several reasons. Water is typically the most concentrated single component of fast pyrolysis oils, though this will be much lower in catalytic fast pyrolysis and upgraded products. Reduced water content is preferable in bio-oil as water can contribute to phase separation, corrosivity, and instability. Additionally, lower water is beneficial for physical properties such as energy density. The percentage of water can also be used to correct the calculation for organic oxygen when determining total oxygen content of bio-oils via combustion-based ultimate analysis. The procedure described here is specifically written for the analysis of bio-oils, and is based on ASTM E203, Standard Test Method for Water Using Volumetric Karl Fischer Titration. This standard test method is specified for measuring the mass % water in pyrolysis liquid biofuels in ASTM D7544, Standard Specification for Pyrolysis Liquid Biofuel. Although the standard method is prescribed for the analysis of pyrolysis liquids for use in industrial and commercial burners, the method is not specifically written for this product. The method described with this Laboratory Analytical Procedure (LAP) provides specific guidance for the analysis of bio-oils. Both organic and aqueous phases can be measured with this technique.
09 BIOMASS FUELS↗