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DOE OSTI2019

One-pot transformation of lignocellulosic biomass into crude bio-oil with metal chlorides via hydrothermal and supercritical ethanol processing

Grape seeds were deconstructed in both hydrothermal and supercritical ethanol media with a combination of two metal chlorides (TiCl 4 :MgCl 2 ) to produce bio-oils. The use of metal chloride additives in supercritical ethanol achieved the highest bio-oil yield of 49.2 wt% (300 °C, 30 min). Both the hydrothermal and supercritical ethanol deconstruction with the additives (TiCl 4 :MgCl 2 = 4 mmol:4mmol) produced the bio-oils with a higher heating value (HHV) of 35 MJ/Kg. Here, gas chromatography-mass spectrometry (GC-MS) analysis of the bio-oils showed that the major products in bio-oils from the hydrothermal deconstruction were acids while the majority products in bio-oils form the supercritical ethanol deconstruction were esters. Nuclear magnetic resonance (NMR) data of the bio-oils suggested that both hydrothermal and supercritical ethanol deconstruction with metal chlorides significantly reduced the non-condensed OH and oxygenated lignin sub-units in bio-oils; while only supercritical ethanol deconstruction with metal chlorides reduced the aliphatic OH and O-alkylated structures in bio-oils.

09 BIOMASS FUELS↗

DOE OSTI2018

A screening-level life cycle greenhouse gas analysis of CO 2 enhanced oil recovery with CO 2 sourced from the Shute Creek natural gas-processing facility

This life cycle analysis (LCA) evaluates life cycle greenhouse gas (GHG) emissions associated with a system that produces both natural gas and crude oil. Two systems are defined: System 1, which independently produces natural gas and oil, and System 2, which captures carbon dioxide (CO 2 ) from the natural gas-processing plant and utilizes this captured CO 2 for enhanced oil recovery (EOR). The LCA uses customized spreadsheet models with emission factors from peer-reviewed literature and publications of the National Energy Technology Laboratory of the U.S. Department of Energy. The modeling results show that the CO 2 EOR scenario using captured CO 2 produces both natural gas and oil with lower life cycle GHG emissions than alternative systems producing natural gas and oil independently. Sensitivity analyses show that the model results are most sensitive to the fraction of CO 2 captured (or equivalently, the fraction of CO 2 vented) at the natural gas-processing facility and the incremental oil recovery factor and net CO 2 utilization factor of the EOR operations. The input variable driving the relative difference in life cycle GHG emissions between these two systems is the fraction of CO 2 captured at the natural gas-processing facility (i.e., the capture rate). Here, the results of this study highlight the necessity of linking processes in the life cycle modeling, as a change to one process can affect other processes within the coupled energy system comprised of natural gas and oil. In addition, this analysis shows, as prior work has also suggested, that CO 2 EOR using captured anthropogenic CO 2 provides a viable means for offsetting carbon emissions from oil production and combustion via the associated storage of CO 2 that occurs incidentally during this tertiary method of oil recovery.

02 PETROLEUM↗

DOE OSTI2020

Conversion of Loblolly pine biomass residues to bio-oil in a two-step process: Fast pyrolysis in the presence of zeolite and catalytic hydrogenation

In this work, Loblolly pine biomass residue was converted to bio-oil in a two-step process, consisting of 1) fast pyrolysis in the presence of zeolite ZSM-5 as a catalyst to produce pyrolysis oil, 2) hydrogenation of pyrolysis oil using formic acid as the hydrogen source in presence of Ru/activated carbon catalyst. Pyrolysis oils were analyzed by 13 C, 31 P and HSQC-NMR and the results revealed that the zeolite-induced catalytic fast pyrolysis process led to effective demethoxylation, producing more catechol and p-hydroxy-phenyl hydroxyl groups in the bio-oils, resulting in a decrease in the methoxyl group content by about 85 % and rich aromatic structures in the pyrolysis oils. The properties of pyrolysis oil with and without zeolite were in the bio-oil range. Hydrogenated pyrolysis oil showed that 79 % of the aromatic protons are eliminated and 87 % of protons are aliphatic in nature, with no oxygen attached to the α-carbon.

09 BIOMASS FUELS↗

DOE OSTI2020

Historic and modern approaches for discovery of abandoned wells for methane emissions mitigation in Oil Creek State Park, Pennsylvania

Hundreds of oil wells were drilled along Oil Creek in Pennsylvania in the mid-16 1800s, birthing the modern oil industry. No longer in operation, many wells are now classified as abandoned, and, due to their age, their locations are either unknown or inaccurately recorded. These historic well sites present environmental, safety, and economic concerns in the form of possible methane leaks and physical hazards. Airborne magnetic and LiDAR surveys were conducted in the Pioneer Run watershed in Oil Creek State Park to find abandoned wells in a historically significant but physically challenging location. Wells were drilled in this area prior to modern geolocation and legal documentation. Although a large number of old wells were abandoned summarily without remediation of the site, much of the land area within Oil Creek State Park is now covered in trees and dense underbrush, which can obscure wellheads. The thick vegetation and steep terrain limited the possibility of ground-based surveys to easily find well sites for methane emissions studies. The data from remote sensing surveys were used to corroborate potential well locations from historic maps and photographs. Potential well sites were verified in a ground-based field survey and monitored for methane emissions. Two historic photographs documenting oil activity in the late 1800s were georeferenced using a combination of magnetic and LiDAR data. LiDAR data, which were more useful in georeferencing and in field verification, identified 290 field locations in the Pioneer Run watershed, 86% of which were possible well sites. Sixty-two percent of the ground-verified wells remained unplugged and comprised the majority of leaking wells. The mean methane emissions factor for unplugged wells was 0.027 ± 0.099 kg/day, lower than other Appalachian Basin methane emissions estimates. LiDAR was used for the first time, in combination with an airborne magnetic survey, to reveal underground oil industry features and inform well identification and remediation efforts in difficult-to-navigate regions. In the oldest oil fields, where well casing has been removed or wood conductor casing was installed, historic photographs provide additional lines of evidence for oil wells where ground disturbances have concealed surface features. Identification of well sites is necessary for mitigation efforts, as unplugged wells emit methane, a potent greenhouse gas.

02 PETROLEUM↗

DOE OSTI2014

Olive oil compounds inhibit vascular endothelial growth factor receptor-2 phosphorylation

Vascular endothelial growth factor (VEGF) triggers crucial signaling processes that regulate tumor angiogenesis and, therefore, represents an attractive target for the development of novel anticancer therapeutics. Several epidemiological studies have confirmed that abundant consumption of foods from plant origin is associated with reduced risk of developing cancers. In the Mediterranean basin, the consumption of extra virgin olive oil is an important constituent of the diet. Compared to other vegetable oils, the presence of several phenolic antioxidants in olive oil is believed to prevent the occurrence of a variety of pathological processes, such as cancer. While the strong antioxidant potential of these molecules is well characterized, their antiangiogenic activities remain unknown. The aim of this study is to investigate whether tyrosol (Tyr), hydroxytyrosol (HT), taxifolin (Tax), oleuropein (OL) and oleic acid (OA), five compounds contained in extra virgin olive oil, can affect in vitro angiogenesis. We found that HT, Tax and OA were the most potent angiogenesis inhibitors through their inhibitory effect on specific autophosphorylation sites of VEGFR-2 (Tyr951, Tyr1059, Tyr1175 and Tyr1214) leading to the inhibition of endothelial cell (EC) signaling. Inhibition of VEGFR-2 by these olive oil compounds significantly reduced VEGF-induced EC proliferation and migration as well as their morphogenic differentiation into capillary-like tubular structures in Matrigel. Our study demonstrates that HT, Tax and OA are novel and potent inhibitors of the VEGFR-2 signaling pathway. These findings emphasize the chemopreventive properties of olive oil and highlight the importance of nutrition in cancer prevention. - Highlights: • We investigated five compounds contained in extra virgin olive oil on angiogenesis. • Hydroxytyrosol, taxifolin and oleic acid are the best angiogenesis inhibitors. • Olive oil compounds affect endothelial cell functions essential for angiogenesis. • Olive oil compounds inhibit specific autophosphorylation sites of VEGFR-2. • Hydroxytyrosol, taxifolin and oleic acid inhibit VEGFR-2 signaling pathway.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2014

Comparison of electrical capacitance tomography and gamma densitometer measurement in viscous oil-gas flows

Multiphase flow is a common occurrence in industries such as nuclear, process, oil and gas, food and chemical. A prior knowledge of its features and characteristics is essential in the design, control and management of such processes due to its complex nature. Electrical Capacitance Tomography (ECT) and Gamma Densitometer (Gamma) are two promising approaches for multiphase visualization and characterization in process industries. In two phase oil and gas flow, ECT and Gamma are used in multiphase flow monitoring techniques due to their inherent simplicity, robustness, and an ability to withstand wide range of operational temperatures and pressures. High viscous oil (viscosity > 100 cP) is of interest because of its huge reserves, technological advances in its production and unlike conventional oil (oil viscosity < 100 cP) and gas flows where ECT and Gamma have been previously used, high viscous oil and gas flows comes with certain associated concerns which include; increased entrainment of gas bubbles dispersed in oil, shorter and more frequent slugs as well as oil film coatings on the walls of flowing conduits. This study aims to determine the suitability of both devices in the visualization and characterization of high-viscous oil and gas flow. Static tests are performed with both devices and liquid holdup measurements are obtained. Dynamic experiments were also conducted in a 1 and 3 inch facility at Cranfield University with a range of nominal viscosities (1000, 3000 and 7500 cP). Plug, slug and wavy annular flow patterns were identified by means of Probability Mass Function and time series analysis of the data acquired from Gamma and ECT devices with high speed camera used to validate the results. Measured Liquid holdups for both devices were also compared.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

DOE OSTI2023

Examining Rail Transportation Route of Crude Oil in the United States Using Crowdsourced Social Media Data

Safety issues associated with transporting crude oil by rail have been a concern since the boom of the U.S. domestic shale oil production in 2012. During the last decade, over 300 crude-oil-by-rail incidents have occurred in the United States. Some of them have caused adverse consequences including fire and hazardous materials leakage. However, only limited information on crude-on-rail routes and their associated risks is available to the public. To this end, this study proposed an unconventional way to reconstruct crude-on-rail routes using geotagged photos harvested from the Flickr website. The proposed method linked the geotagged photos of crude oil trains posted online with national railway networks to identify potential railway segments that those crude oil trains were traveling on. Here, a shortest path-based method was applied to infer the complete crude-on-rail routes, by utilizing the confirmed railway segments as well as their directional information. Validation of the inferred routes was performed using a public map and official crude oil incident data. The results suggested that the inferred routes based on geotagged photos had high coverage, with approximately 96% of the documented crude oil incidents aligned with the reconstructed crude-on-rail network. The inferred crude oil train routes were found to pass through several metropolitan areas of high population density, who were exposed to potential risk. These findings could improve situational awareness for policy makers and transportation planners. In addition, with the inferred routes, this study has established a good foundation for future crude oil train risk-analyses along the rail route.

42 ENGINEERING↗

DOE OSTI2018

A transgene design for enhancing oil content in Arabidopsis and Camelina seeds

Background: Increasing the oil yield is a major objective for oilseed crop improvement. Oil biosynthesis and accumulation are influenced by multiple genes involved in embryo and seed development. The leafy cotyledon1 (LEC1) is a master regulator of embryo development that also enhances the expression of genes involved in fatty acid biosynthesis. We speculated that seed oil could be increased by targeted overexpression of a master regulating transcription factor for oil biosynthesis, using a downstream promoter for a gene in the oil biosynthesis pathway. To verify the effect of such a combination on seed oil content, we made constructs with maize (Zea mays) ZmLEC1 driven by serine carboxypeptidase-like (SCPL17) and acyl carrier protein (ACP5) promoters, respectively, for expression in transgenic Arabidopsis thaliana and Camelina sativa. Results: Agrobacterium-mediated transformation successfully generated Arabidopsis and Camelina lines that overexpressed ZmLEC1 under the control of a seed-specific promoter. This overexpression does not appear to be detrimental to seed vigor under laboratory conditions and did not cause observable abnormal growth phenotypes throughout the life cycle of the plants. Overexpression of ZmLEC1 increased the oil content in mature seeds by more than 20% in Arabidopsis and 26% in Camelina. In conclusion: The findings suggested that the maize master regulator, ZmLEC1, driven by a downstream seed-specific promoter, can be used to increase oil production in Arabidopsis and Camelina and might be a promising target for increasing oil yield in oilseed crops.0

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2021

Evaluation of “Tight Oil” Well Performance and Completion Practices in the Powder River Basin - “Time Slice” Analysis

The objective of this paper is to assess how well completion practices and well performance have evolved over time (“time slices”) in the tight sands and shales of the Powder River Basin (PRB). This information can provide a foundation for helping operators define more effective well completion practices and thus optimize well performance in an emerging “tight oil” basin. To start, the authors assembled a “database” containing well completion practices, production data, and geologic information for more than 800 horizontal (Hz) wells targeting three “tight oil” formations -- Turner, Frontier, and Mowry--placed on production in the past dozen years. To control for the impact of geologic and reservoir properties on well performance, the authors defined 12 geologically distinct areas (“partitions”) for the Turner, Frontier, and Mowry Shale in the Powder River Basin (4 partitions in each formation). This paper discusses the methodology for establishing “time slices” for each partition within each of the three “tight oil” formations, including (1) taking out, to the extent practical, the effects of geology by partitioning the three “tight oil” formations based on their geologic parameters; (2) using type curves and estimated ultimate recoveries (EURs) to establish a reliable measure of well performance; and (3) rigorously inspecting the production and well completion data to assure a quality dataset. Partition #2, a high thermal maturity area of the Frontier Sandstone in the western Powder River Basin, helps illustrate the results of the study. Using a dataset of 55 Hz wells, the study found that well performance has steadily improved, with oil EURs increasing from 180 MBbl in 2012-13 to 290 MBbl in 2018-19. Much of this improvement was due to the use of longer Hz laterals, increasing notably from 3,765 ft in 2012-13 to 10,260 ft in 2018-19. More intensive completion practices contributed, as well. For example, the number of frac stages more than doubled, from 17 to 35, and proppant concentrations increased from 1,060 lbs/ft to 1,320 lbs/ft. Finally, the data show diminishing returns to longer laterals and more intensive completion practices. For example, the key performance measure of oil EUR per 1,000 ft of lateral is decreasing. For 2012-13, Hz wells recovered 50 MBbl of oil per 1,000 ft of lateral while the more recent 2018-19 Hz wells only provide 30 MBbl of oil per 1,000 ft of lateral. Considerable insight can be gained by using “time slices” and geologic partitioning to better understand the relationship between changes in well drilling and completion practices and changes in well performance in emerging “tight oil” plays. The results from this study can also serve as a foundation for subsequent, more intense efforts involving data analytics for defining more optimum well completion practices targeting specified geologic settings and formations.

02 PETROLEUM↗

DOE OSTI2014

Stabilization of Bio-Oil Fractions for Insertion into Petroleum Refineries

This project is part of a collaboration effort between Iowa State University (ISU), University of Oklahoma (OK) and Pacific Northwest National Laboratory (PNNL). The purpose of this project is to stabilize bio-oil fractions and improve their suitability for insertion into petroleum refineries. Bio-oil from fast pyrolysis of biomass is a complex mixture of unstable organic compounds. These organic compounds react under standard room conditions resulting in increases in bio-oil viscosity and water content – both detrimental for bio-oil storage and transportation. This study employed fractionation and upgrading systems to improve the stability of bio-oil. The fractionation system consists of a series of condensers, and electrostatic precipitators designed to separate bio-oil into five fractions: soluble carbohydrates (SF1&2), clean phenolic oligomers (CPO) and middle fraction (SF3&4), light oxygenates (SF5). A two-stage upgrading process was designed to process bio-oil stage fractions into stable products that can be inserted into a refinery. In the upgrading system, heavy and middle bio-oil fractions were upgraded into stable oil via cracking and subsequent hydrodeoxygenation. The light oxygenate fraction was steam reformed to provide a portion of requisite hydrogen for hydroprocessing. Hydrotreating and hydrocracking employed hydrogen from natural gas, fuel gas and light oxygenates reforming. The finished products from this study consist of gasoline- and diesel-blend stock fuels.

09 BIOMASS FUELS↗

DOE OSTI2019

Approaches for Integrating Renewable Energy Technologies in Oil and Gas Operations

Petroleum (including both oil and gas) heats our homes, drives our transportation system, generates electricity and makes modern life possible. Continued demand from developed countries along with growth from developing economies implies demand for oil and gas will likely continue to be robust. Considering the desire to maximize production efficiency and economic returns, there is increased attention to the fact that nearly 10% of oil is consumed in the process of oil production, transportation and refining (Halabi, et al., 2015), and that a quarter of a barrel of oil is used to produce a barrel of heavy oil (Wesoff, 2015). As oil and gas development shifts to secondary and other non-conventional sources, meeting future demand is anticipated to require substantial amounts of energy to produce, transport and refine petroleum. Increasing efficiency of operations and incorporating energy sources that maximize product revenue while simultaneously addressing local environmental concerns as well as reducing overall greenhouse gas emissions has prompted a growing interest in integrating renewable energy technologies in oil and gas operations. Furthermore, due to dramatic declines in the cost of energy generation from renewable sources, integrating renewable energy technology can in many cases reduce operations costs as well. This report provides an overview of where renewable energy technologies can economically be integrated into oil and gas operations.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

DOE OSTI2025

Can Charge Transfer Across C─H⋅⋅⋅O Hydrogen Bonds Stabilize Oil Droplets in Water?

Oil-water emulsions resist aggregation due to the presence of negative charges at their surface that leads to mutual repulsion between droplets, but the molecular origin of oil charge is currently under debate. Although much evidence has suggested that ionic species must accumulate at the interface, an alternative perspective attributes the negative charge on the oil droplet to charge transfer of electron density from water to oil molecules. Although the charge transfer mechanism is consistent with the correct sign of oil charge, it is just as important to provide good estimates of the charge magnitude to explain emulsion stability and electrophoresis experiments. Here, we show using energy decomposition analysis that the amount of net flow of charge from water to oil is negligibly small due to nearly equal forward and backward charge transfer through weak oil-water interactions, such that oil droplets would be unstable and coalesce, contrary to experiment. The lack of charge transfer also explains why vibrational sum frequency scattering reports a blue shift in the oil C-H frequency when forming emulsions with water, which arises from Pauli repulsion due to localized confinement at the interface. Finally, unlike ions, neither charge transfer nor dynamic polarization can produce a finite conductivity needed to couple to electric fields that would explain electrophoretic mobility.

Zhao, Ruoqi↗

DOE OSTI2022

Combustion dynamics of crude and upgraded Thermal DeOxygenation oils in a compression ignition engine

Thermal DeOxygenation (TDO) is a robust thermochemical conversion scheme to produce hydrocarbons from biomass feedstock. The process targets the carbohydrate fraction of biomass to yield a broad mixture of primarily aromatic hydrocarbons within a boiling point range of 348–798 K with low oxygen content (<4 wt%). The resulting materials are amenable to traditional hydrotreating and distillation processes with approximately 70% by mass in the distillate fuel range. The simple conversion scheme combined with commercially viable upgrading routes makes TDO oils a feasible alternative fuel for transportation applications. Here this paper is the first systematic treatment of fit-for-purpose testing of TDO oils in a compression ignition engine. Blends of partially upgraded TDO oils (e.g. whole oil, distilled oil, hydrotreated oil and hydrotreated-distilled oil) are prepared with certified ultra-low sulfur diesel at 5%, 10%, 15% and 20% by volume. The resulting fuels are analyzed for fuel characteristics and combustion dynamics in an instrumented single-cylinder compression ignition engine. All fuel blends at 10% blend level by volume exhibited adequate engine performance. Hydrotreating of the oils is a necessary step to meet cetane number and EPA soot emissions requirements at 20% blend volume. Combined distillation and hydrotreatment meet or exceed all fuel specification and engine performance benchmarks. Partially upgraded TDO oils are suitable fuel options for compression ignition applications.

42 ENGINEERING↗

DOE OSTI2023

Methane foam performance in oil-wet unconsolidated porous media: A systematic experimental investigation at reservoir conditions

Methane foam performance was systematically evaluated using high-pressure and high-temperature experiments performed on oil-wet proppant packs. The sensitivities of foam performance to various key factors, including surfactant concentration, foam quality, total injection rate, salinity, operating pressure, and initial oil saturation were examined. The results showed that even though the foamability and foam strength in oil-wet proppant packs were adversely affected by wettability and presence of oil, the steady-state pressure drops across the proppant packs were insensitive to the quantity of oil initially present. The presence of oil above the critical oil saturation impeded the onset of foam generation. This suggested that the foamability of surfactants depends on the synergetic effects of surfactant’s ionic nature and foam parameters, such as foam quality and total injection rate, on their ability to reduce the oil saturation to a threshold value below which favorable bubble generation sites could be created. It was observed that, for low injection rate, anionic surfactant was ineffective at low salinity conditions, while amphoteric agent performed well at all salinities. Additionally, an increase in salinity resulted in enhanced pressure drop across the proppant packs for both anionic and amphoteric surfactants. Further, the results also established that too high operating pressures are somewhat detrimental to the foam strength and stability, irrespective of the ionic nature of foaming agents and the wettability of the porous medium. For the anionic surfactant, the increase in the total flow rate was found to mitigate the adverse effects of low salt concentration and operating pressure. Results from quality-sensitivity foam tests identified two regions for the foam behavior, named low-quality and high-quality regimes, separated by the transition foam quality. Finally, we discuss the implications of the results for the design and effective implementation of enhanced oil recovery (EOR) schemes that deploy hydrocarbon-based foams.

02 PETROLEUM↗

DOE OSTI2023

Economic and operational investigation of CO 2 sequestration through enhanced oil recovery in unconventional reservoirs in Colorado, USA

The ongoing CCUS commercial projects are highly relied on the support of government incentives due to massive capital investment. Here, this study analyzes the economics of carbon capture utilization and sequestration (CCUS) projects, shows a state-wide CCUS deployment exercise, followed by simulation results of enhanced oil recovery (EOR) based CO 2 storage in unconventional reservoirs. The comprehensive economic analysis of capture, transportation, sequestration costs, enhanced 45Q tax credits, and EOR revenue implies the practicality of CO 2 -EOR to offset the high CCUS costs. With the economics understanding, we study the top CO 2 sources, existing CO 2 pipelines, and sequestration sinks in the state of Colorado, USA. This paper next presents results from EOR simulation in one section of the unconventional Denver-Julesburg (DJ) Basin Niobrara and Codell reservoirs. The simulation model is based on a geological static model, incorporated with hydraulic fracture stimulation, history matched to production, and calibrated to the microseismic and time-lapse surface seismic data. The CO 2 -EOR simulation results show that oil production can be increased and more CO 2 stored with: a longer primary production period; the presence of a shut-in period; higher injection rates; and multi-well injectors. The modeling results show that about 7–10 Mscf of CO 2 will be stored when recovering 1 stb of EOR oil. By adding the enhanced oil revenue and the carbon credits together, it is estimated that the most economic case can generate $\$13$ MM when oil price is assumed to be $\$80$/stb, and the EOR oil revenue is 3.4 times greater than that generated from 45Q incentives. It corresponds to the scenario that a five-year primary production is followed by CO 2 injection into four wells with the sequence of injection (4 MMscf/day for 6 months), shut-in (6 months) and production (12 months). The best practices in this study will provide valuable insights for similar CCUS projects in other unconventional fields. Furthermore, this study defines a term named “Carbon Neutrality Index (CNI)” by comparing the amount of CO 2 stored with that burned by EOR oil. The CNI value of 0 indicates the enhanced oil is carbon neutral; a negative CNI value implies there is a net reduction in carbon emission. The 4-year huff-n-puff (HnP) simulation leads to a positive CNI value, indicating that the EOR oil generated in this process is not carbon neutral yet.

03 NATURAL GAS↗

DOE OSTI2017

pH Neutralization of Aqueous Bio-Oil from Switchgrass Intermediate Pyrolysis Using Process Intensification Devices

Despite the potential carbon-neutrality of switchgrass bio-oil, its high acidity and diverse chemical composition limit its utilization. The objectives of this research are to investigate pH neutralization of bio-oil by adding various alkali solutions in a batch system and then perform neutralization using process intensification devices, including a static mixer and a centrifugal contactor. The results indicate that sodium hydroxide and potassium hydroxide are more appropriate bases for pH neutralization of bio-oil than calcium hydroxide due to the limited solubility of calcium hydroxide in aqueous bio-oil. Mass and total acid number (TAN) balances were performed for both batch and continuous-flow systems. Upon pH neutralization of bio-oil, the TAN values of the system increased after accounting the addition of alkali solution. A bio-oil heating experiment showed that the heat generated during pH neutralization did not cause a significant increase in the acidity of bio-oil. The formation of phenolic compounds during neutralization was initially suspected of increasing the system’s overall TAN value because some of these compounds (e.g., vanillic acid) act as polyprotic acids and have a stronger influence on the TAN value than monoprotic acids (e.g., acetic acid). The amount of phenolics in separated bio-oil phases, however, did not change significantly after pH neutralization. In conclusion, process intensification devices provided sufficient mixing and separation of the organic and aqueous phases, suggesting a scale-up route for the bio-oil pH neutralization process.

09 BIOMASS FUELS↗

DOE OSTI2017

Evolution of Functional Groups during Pyrolysis Oil Upgrading

In this paper, we examine the evolution of functional groups (carbonyl, carboxyl, phenol, and hydroxyl) during stabilization at 100–200 °C of two typical wood derived pyrolysis oils from BTG and Amaron in a batch reactor over Ru/C catalyst for 4h. An aqueous and an oily phase were obtained. The content of functional groups in both phases were analyzed by GC/MS, 31P-NMR, 1H-NMR, elemental analysis, KF titration, carbonyl groups by Faix, Folin – Ciocalteu method and UV-Fluorescence. The consumption of hydrogen was between 0.007 and 0.016 g/g oil, and 0.001-0.020 g of CH4/g of oil, 0.005-0.016 g of CO2/g oil and 0.03-0.10 g H2O/g oil were formed. The content of carbonyl, hydroxyl, and carboxyl groups in the volatile GC-MS detectable fraction decreased (80, 65, and ~70% respectively), while their behavior in the total oil and hence in the non-volatile fraction was more complex. The carbonyl groups initially decreased having minimum at ~125-150°C and then increased, while the hydroxyl groups had reversed trend. This might be explained by initial hydrogenation of the carbonyl groups to form hydroxyls, followed by continued dehydration reactions at higher temperatures that may increase their content. The 31P-NMR was on the limit of its sensitivity for the carboxylic groups to precisely detect changes in the non-volatile fraction, however the more precise titration method showed that the concentration of carboxylic groups in the non-volatile fraction remains constant with increased stabilization temperature. The UV-Fluorescence results show that repolymerization increases with temperature. ATR-FTIR method coupled with deconvolution of the region between 1490 and 1850 cm-1 showed to be a good tool for following the changes in carbonyl groups and phenols of the stabilized pyrolysis oils. The deconvolution of the IR bands around 1050 and 1260 cm-1 correlated very well with the changes in the 31P-NMR silent O groups (likely ethers). Most of the H2O formation could be explained from the significant reduction of these silent O groups (from 12% in the fresh oils, to 6 to 2% in the stabilized oils) most probably belonging to ethers.

Stankovikj, Filip↗

DOE OSTI2024

Integration of plant and microbial oil processing at oilcane biorefineries for more sustainable biofuel production

Oilcane—an oil-accumulating crop engineered from sugarcane—and microbial oil have the potential to improve renewable oil production and help meet the expected demand for bioderived oleochemicals and fuels. To assess the potential synergies of processing both plant and microbial oils, the economic and environmental implications of integrating microbial oil production at oilcane and sugarcane biorefineries were characterized. Due to decreased crop yields that lead to higher simulated feedstock prices and lower biorefinery capacities, current oilcane prototypes result in higher costs and carbon intensities than microbial oil from sugarcane. To inform oilcane feedstock development, we calculated the required biomass yields (as a function of oil content) for oilcane to achieve financial parity with sugarcane. At 10 dw% oil, oilcane can sustain up to 30% less yield than sugarcane and still be more profitable in all simulated scenarios. Assuming continued improvements in microbial oil production from cane juice, achieving this target results in a minimum biodiesel selling price of 1.34 [0.90, 1.85] USD∙L –1 (presented as median [5th, 95th] percentiles), a carbon intensity of 0.51 [0.47, 0.55] kg CO 2 e L –1 , and a total biodiesel yield of 2140 [1870, 2410] L ha –1 year –1 . Compared to biofuel production from soybean, this outcome is equivalent to 3.0–3.9 as much biofuel per hectare of land and a 57%–63% reduction in carbon intensity. While only 20% of simulated scenarios fell within the market price range of biodiesel (0.45–1.11 USD∙L –1 ), if the oilcane biomass yield would improve to 25.6 DMT∙ha –1 ∙y –1 (an equivalent yield to sugarcane) 87% of evaluated scenarios would have a minimum biodiesel selling price within or below the market price range.

09 BIOMASS FUELS↗