Bio-Oil Analytical Method Standardization with ASTM International
This presentation, part of the ACS Fall 2020 Virtual Meeting, discusses how standardized techniques and specifications provide a common language.
bio-oil↗
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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 currently 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.
09 BIOMASS FUELS↗
Data for Development of Vegetative Oil Sorghum: From Lab-to-Field
Biomass crops engineered to accumulate energy-dense triacylglycerols (TAG or ‘vegetable oils’) in their vegetative tissues have emerged as potential feedstocks to meet the growing demand for renewable diesel and sustainable aviation fuel (SAF). Unlike oil palm and oilseed crops, the current commercial sources of TAG, vegetative tissues, such as leaves and stems, only transiently accumulate TAG. In this report, we used grain (Texas430 or TX430) and sugar-accumulating ‘sweet’ (Ramada) genotypes of sorghum, a high-yielding, environmentally resilient biomass crop, to accumulate TAG in leaves and stems. We initially tested several gene combinations for a ‘push-pull-protect’ strategy. The top TAG-yielding constructs contained five oil transgenes for a sorghum WRINKLED1 transcription factor (‘push’), a Cuphea viscosissima diacylglycerol acyltransferase (DGAT; ‘pull’), a modified sesame oleosin (‘protect’) and two combinations of specialized Cuphea lysophosphatidic acid acyltransferases and medium-chain acyl-acyl carrier protein thioesterases. Though intended to generate oils with medium-chain fatty acids, engineered lines accumulated oleic acid-rich oil to amounts of up to 2.5% DW in leaves and 2.0% DW in stems in the greenhouse, 36-fold and 49-fold increases relative to wild-type (WT) plants, respectively. Under field conditions, the top-performing event accumulated TAG to amount to 5.5% DW in leaves and 3.5% DW in stems, 78-fold and 58-fold increases, respectively, relative to WT TX430. Transcriptomic and fluxomic analyses revealed potential bottlenecks for increased TAG accumulation. Overall, our studies highlight the utility of a lab-to-field pipeline coupled with systems biology studies to deliver high vegetative oil sorghum for SAF and renewable diesel production.
Biofuels↗
2016 U.S. Petroleum Fuels Life Cycle Baseline
The National Energy Technology Laboratory (NETL) has performed a well-to-wheels life cycle assessment (LCA) of petroleum production and refining for the United States (US), both from international and domestic oil sources. This analysis largely follows the same methods and framework established by Cooney et al., which performed a greenhouse gas (GHG) LCA of crude products for the 2014 data year (Cooney et al., 2017). Results are presented for six major petroleum products (gasoline, diesel, jet fuel, fuel oil, coke, bunker/residual fuel oil) across each of the five Petroleum Administration for Defense Districts (PADDs) and at the national US level. However, there are at least seven other refinery outputs (liquified petroleum gas, refinery fuel gas, hydrogen, petrochemical feedstocks, asphalt, sulfur) that are modeled but not shown in this report for brevity. Petroleum product amounts are compared against those reported by US Energy Information Administration (EIA) for each region.
02 PETROLEUM↗
Review of Hazards and Accidentology of an Integrated Energy Systems to Nuclear Power Plant Safety
With the interconnectivity of industrial processes in a nuclear integrated energy system (IES) the primary issue becomes the safety of the nuclear power plant (NPP). The industrial processes being supported are assumed to have been in colocation prior to the addition of an NPP. Do the hazards from each process reach beyond the perimeter of the plant to affect the NPP? This paper reviews hazards and accident statistics from processes in an IES as a first step to answer this question. Hazards and accidentology discussed cover hydrogen, ammonia, syngas, methanol, synthetic fuels, and oil refineries. They include mainly fire, explosion, and toxicity in varying degrees. Historical accident statistics are given whenever available, and accident causes are evaluated and ranked based on their frequencies. Lessons learned from previous accidents are presented. Future work will focus on utilizing the data collected for accidentology of the industrial processes to perform Failure Modes and Effects Analysis and analyze the impacts of additional hazards on the colocated existing nuclear power plant or newly built advanced nuclear reactor. The analysis will provide the frequency and consequence of external events that can affect the NPP.
08 - HYDROGEN↗
Renewable Polyurethanes from Sustainable Biological Precursors
Due to the depletion of fossil fuels, higher oil prices, and greenhouse gas emissions, the scientific community has been conducting an ongoing search for viable renewable alternatives to petroleum-based products, with the anticipation of increased adaptation in the coming years. New academic and industrial developments have encouraged the utilization of renewable resources for the development of ecofriendly and sustainable materials, and here, we focus on those advances that impact polyurethane (PU) materials. Vegetable oils, algae oils, and polysaccharides are included among the major renewable resources that have supported the development of sustainable PU precursors to date. Renewable feedstocks such as algae have the benefit of requiring only sunshine, carbon dioxide, and trace minerals to generate a sustainable biomass source, offering an improved carbon footprint to lessen environmental impacts. Incorporation of renewable content into commercially viable polymer materials, particularly PUs, has increasing and realistic potential. Biobased polyols can currently be purchased, and the potential to expand into new monomers offers exciting possibilities for new product development. This Review highlights the latest developments in PU chemistry from renewable raw materials, as well as the various biological precursors being employed in the synthesis of thermoset and thermoplastic PUs. We also provide an overview of literature reports that focus on biobased polyols and isocyanates, the two major precursors to PUs.
09 BIOMASS FUELS↗
Sustainable Biofuels for Low-Carbon Maritime Transportation
The marine shipping sector heavily depends on fossil fuels and is one of the largest petroleum fuel consumers [1,2]. The annual global marine fuel consumption was estimated to be around 400 million metric tons in 2019 (2.5 billion barrels). Moreover, ocean shipping is one of the most significant contributors to sulfur oxides, nitrogen oxides, and particulate matter emissions. Global shipping contributes 13% of human-caused sulfur emissions and 2.6% of anthropogenic carbon dioxide emissions. As a major source of pollutant emissions, the marine industry faces several challenges related to emission regulations. The International Maritime Organization (IMO) has established a framework for reducing the carbon intensity of shipping: 40% reduction relative to 2008 levels by 2030 and 70% reduction by 2050. As the aviation sector, the maritime shipping sector is difficult to decarbonize through electrification. Biofuels offer the best opportunities for decarbonizing marine shipping in the near and medium-term. Advanced biofuels such as pyrolysis bio-oil offer the low-cost potential for meeting carbon reduction goals. For instance, the pyrolysis bio-oil exhibited promising marginal CO2 abatement costs at less than $100/tonne CO2-equivalent at a heavy fuel oil price greater than $1.10/gal [1]. As a potential biofuel option for low-carbon maritime shipping, this presentation focuses on a comparative techno-economic analysis (TEA) of bio-oils produced via a fast pyrolysis-based conversion pathway. The pathway converts a 50/50 blend of forest residues and clean pine to bio-oil via three process options: fast pyrolysis without vapor upgrading, and fast pyrolysis with vapor phase upgrading over ZSM-5 zeolite catalyst and Pt/TiO2 catalyst. The process configuration and operation variation led to different capital and operating costs, as well as the resulting raw bio-oil’s yield and quality, e.g., the water content, total acid number, and carboxylic acid number. The study also determined the minimum upgrading of bio-oils required to enable blending with very low sulfur fuel oil (VLSFO), with the associated costs reflected in TEA. This study shows that bio-oil could be a cost-effective fuel option for decarbonizing maritime shipping. Further research is required with respect to biofuel blending properties, such as compatibility with existing fuel system infrastructure and suitable engine performance.
BIOMASS FUELS↗
Optimum concentration of fly ash nanoparticles to stabilize CO 2 foams for aquifer and soil remediation
Contamination caused by non-aqueous phase liquids (NAPLs) in aquifers and soil is an important challenge that requires effective remediation techniques. One potential approach is through the use of CO 2 foams to displace NAPLs from permeable media. CO 2 foams generated only by surfactants are not stable enough for the efficient removal of NAPLs contamination. This shortcoming may be alleviated via the use of nanoparticles (NPs)-surfactant mixtures as a stabilizing agent. This work focuses on the evaluation of the optimum concentration of fly ash nanoparticles for stabilizing CO 2 foam with the combined action of the surfactant. The performance of this foam is evaluated in remediating a contaminated 41 mm × 36 mm surrogate permeable medium in a microfluidic device. Mixtures of fly ash, a by-product of coal-burning power plants, and alpha-olefin sulfonate (AOS) and lauramidopropyl betaine (LAPB) surfactants are used to generate stable foams. The results show that a 1000 mg/L AOS-LAPB surfactant solution along with 1000 mg/L of fly ash NPs produces the best performance. Formation of deposits in the matrix is observed. These deposits, which are more prominent at higher NP concentrations, appear to adversely affect displacement, displacement efficiency and remediation of the medium. This study demonstrates that using fly ash nanoparticles and optimizing their concentration can effectively stabilize CO 2 foams and improve the displacement efficiency for aquifer and soil remediation.
54 ENVIRONMENTAL SCIENCES↗
Techno-economic Analysis of Sustainable Biofuels for Marine Transportation
Not Available
09 BIOMASS FUELS↗
The Overlooked Potential of Sulfated Zirconia: Reexamining Solid Superacidity Toward the Controlled Depolymerization of Polyolefins
Closed-loop recycling via an efficient chemical process can help alleviate the global plastic waste crisis. However, conventional depolymerization methods for polyolefins, which compose more than 50% of plastics, demand high temperatures and pressures, employ precious noble metals, and yield complex mixtures of products limited to single-use fuels or oils. Superacidic sulfated zirconia (SZrO) with Hammet Acidity Functions (H 0 ) = -12 (i.e., stronger than 100% H 2 SO 4 ) is an industrially deployed heterogeneous catalyst capable of activating hydrocarbons under mild conditions and is shown to decompose polyolefins at ambient pressure and temperatures near 200 °C. Additionally, confinement of active sites in porous supports is known to radically increase selectivity, coking and sintering resistance, and acid site activity, presenting a possible approach to low-energy polyolefin depolymerization. However, a critical examination of the literature on SZrO led us to a surprising conclusion: despite 40 years of catalytic study, engineering, and industrial use, the surface chemistry of SZrO is poorly understood. Ostensibly spurred by SZrO's impressive catalytic activity, the application-driven study of SZrO has resulted in deleterious ambiguity in requisite synthetic conditions and insufficient characterization of acidity, porosity, and active site structure. Here, this ambiguity has produced significant knowledge gaps surrounding the synthesis, structure, and mechanisms of hydrocarbon activation for optimized SZrO, stunting the potential of this catalyst in olefin cracking and other industrially relevant reactions, such as isomerization, esterification, and alkylation. Toward mitigating these long extant issues, we herein identify and highlight these current shortcomings and knowledge gaps, propose explicit guidelines for characterization of and reporting on characterization of solid acidity, and discuss the potential of pore-confined superacids in the efficient and selective depolymerization of polyolefins.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Development of Nanocrystalline Graphite from Lignin Sources
Carbon composites are attractive to a variety of high-impact applications, such as carbon fibers, batteries, and vehicle parts, due to their multifunctional properties. The properties of carbon are highly dependent on the allotrope the carbon takes and the functionality, impurities, and defects contained within the structure. The increase in demand for sustainable carbon sources in energy storage devices motivates interest in understanding synthesis parameters of lignin value-added products. Also, as the dependence on oil for fuel decreases, alternative sources for carbon in many applications will be needed. In this work, the thermochemical conversion of lignin powders from different feedstocks was evaluated via small and wide-angle X-ray scattering techniques to resolve the amorphous, disordered, and crystalline domains present in the lignin carbons. Scattering analyses indicated an evolution of hierarchical structures along with an increase in ordered domains as a function of carbonization temperature. Qualitative and quantitative methods were used to describe isotropic scattering intensity profiles at multiple length scales. The use of power law models in the mesoscopic region served as the basis to describe morphological changes related to structural features, for example, graphene stacking, degree of roughness, and surface fractals. Kraft softwood and switchgrass produced carbon powder with the most crystalline domains and the least surface roughness. Softwoods reached the highest degree of crystallinity followed by switchgrass samples and had less variability in particle sizes. These results suggest lignin carbons extracted from softwoods and switchgrass are viable substitutes for graphite. Interpretation of X-ray scattering data from lignin carbon powders elucidates feedstock- and processing-dependent morphological features across multiple length scales providing a straightforward framework to evaluate the feasibility of leveraging lignin carbons for producing tunable application-specific materials.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Supercritical water co-liquefaction of LLDPE and PP into oil: properties and synergy
The major plastic wastes are always mixtures, which are difficult to separate to treat in practice. Because of some possible cross-reactions, the degradation behaviors of plastics could not be mathematically represented by a simple addition of each polymer according to their proportions. This work examines supercritical water (scH 2 O) to liquefy poly-ethylene and poly-propylene mixtures into an oil with special interest in the oil quality and positive effect. Additionally, linear low-density polyethylene (LLDPE) and polypropylene (PP) were chosen as parent materials because of their high proportions in plastic wastes. The results show that a high conversion rate of around 99.75% was achieved with as high as 90.7 wt% oil yield without additional catalysts or hydrogen. The scH 2 O co-liquefaction of the LLDPE/PP mixture was different from that of the single polymer along with an improvement in the oil yield. Cyclic hydrocarbon ( i.e. , cyclic) generation was promoted while the production of paraffins was hindered in scH 2 O co-liquefaction using a mixture of LLDPE/PP. TGA reveals that the scH 2 O co-liquefaction of LLDPE/PP mixtures generated more diesel and lubricant oils and less gasoline and (jet fuel + light diesel) oils, thus slightly lowering the oil quality. Overall, the supercritical fluid technology was a powerful and promising means to liquefy mixed plastic wastes into oil at a high conversion rate free of catalysts or hydrogen.
42 ENGINEERING↗
Leverage demand-side policies for energy security
Energy security is a top priority for governments, companies, and households because energy systems and the critical functions that they support are threatened by disruptions from wars, pandemics, climate change, and other shocks (1). More often than not, governments rely on policies focused on energy supply to enhance energy security while generally ignoring demand-side possibilities. Further, the indicators traditionally used to measure energy security are also tilted toward the supply side; this fails to capture the full spectrum of vulnerability to energy crises. Energy security assessments need to reflect the wider benefits of security related interventions more accurately. To that end, we develop a systematic approach to measuring the energy security impacts of policy interventions that explicitly considers energy demand (buildings, transport, and industry). Here, we determine that demand-side actions outperform conventional supply-side approaches at making countries more resilient. Energy demand links more directly than supply to the satisfaction of critical social functions and human well-being that are at the core of energy security. Yet, demand-side perspectives tend to be neglected or underrepresented in analysis and policy debates on energy security. Factors that contribute to this supply-side bias include the traditional sectoral organization of industries and policy institutions along fuels (coal, oil, and gas) and energy forms (electric utilities) as well as the decentralized and multivaried activities characteristic of energy demand (from vehicles to household appliances to manufacturing and more), which leads to a multitude of actors and institutional fragmentation. The basic fundamentals of energy systems and markets, where demand and supply are intricately linked, have also not yet risen from vague awareness to a central organizing principle among policy-makers for structuring the energy security discourse.
29 ENERGY PLANNING, POLICY, AND ECONOMY↗
Projected Operational Energy Life Cycle Data Development: 2025 Update
This report documents the data sources and methods used to develop the energy life cycle data for use by the National Institute of Standards and Technology (NIST) Engineering Laboratory (EL) to be used for the development of measurement science and incorporation into decision-support tools for evaluating building and facility capital investments. The data are posted separately under DOI 10.18141/2575194.
29 ENERGY PLANNING, POLICY, AND ECONOMY↗
PURIFICATION OF BROWN GREASE FOR FUEL PRODUCTION
Explore the source record for details and available documents.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Bioprocessing, Recovery, and Mass Balance of Vegetative Lipids from Metabolically Engineered “Oilcane” Demonstrates Its Potential as an Alternative Feedstock for Drop-In Fuel Production
Plant oils are increasingly in demand as renewable feedstocks for biodiesel and biochemicals. Currently, oilseeds are the primary source of plant oils. Although the vegetative tissues of plants express lipid metabolism pathways, they do not hyper- accumulate lipids. Elevated synthesis, storage, and accumulation of lipids in vegetative tissues have been achieved by metabolic engineering of sugarcane to produce “oilcane”. This study evaluates the potential of oilcane as a renewable feedstock for the co- production of lipids and fermentable sugars. Oilcane was grown under favorable climatic and field conditions in Florida (FLOC) as well as during an abbreviated growing season, outside its typical growing region, in Illinois (ILOC). The potential lipid yield of 0.35 tons/ha was projected from the hyperaccumulation of fatty acids in the stored vegetative biomass of FLOC, which is approaching the lipid yield of soybean (0.44 tons/ha). Processing of the vegetative tissues of oilcane recovered 0.20 tons/ha, which represents the recovery of 55% of the total lipids from FLOC. Chemical-free hydrothermal bioprocessing of ILOC and FLOC bagasse and leaves at 180 °C for 10 min prevented the degeneration of in situ plant lipids. Here, this allowed the recovery of lipids at the end of the bioprocess with a major fraction of lipids remaining in the biomass residues after pretreatment and saccharification. Improvements through refined biomass processing, crop management, and metabolic engineering are expected to boost lipid yields and make oilcane a prime feedstock for the production of biodiesel.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Data for Bioprocessing, Recovery, and Mass Balance of Vegetative Lipids from Metabolically Engineered ‘Oilcane’ Demonstrates Its Potential as an Alternative Feedstock for Drop-In Fuel Production
Plant oils are increasingly in demand as renewable feedstocks for biodiesel and biochemicals. Currently, oilseeds are the primary source of plant oils. Although the vegetative tissues of plants express lipid metabolism pathways, they do not hyper-accumulate lipids. Elevated synthesis, storage, and accumulation of lipids in vegetative tissues have been achieved by metabolic engineering of sugarcane to produce “oilcane.” This study evaluates the potential of oilcane as a renewable feedstock for the co-production of lipids and fermentable sugars. Oilcane was grown under favorable climatic and field conditions in Florida (FLOC) as well as during an abbreviated growing season, outside its typical growing region, in Illinois (ILOC). The potential lipid yield of 0.35 tons/ha was projected from the hyperaccumulation of fatty acids in the stored vegetative biomass of FLOC, which is approaching the lipid yield of soybean (0.44 tons/ha). Processing of the vegetative tissues of oilcane recovered 0.20 tons/ha, which represents the recovery of 55% of the total lipids from FLOC. Chemical-free hydrothermal bioprocessing of ILOC and FLOC bagasse and leaves at 180 °C for 10 min prevented the degeneration of in situ plant lipids. This allowed the recovery of lipids at the end of the bioprocess with a major fraction of lipids remaining in the biomass residues after pretreatment and saccharification. Improvements through refined biomass processing, crop management, and metabolic engineering are expected to boost lipid yields and make oilcane a prime feedstock for the production of biodiesel.
Conversion↗
Biofuel Options for Marine Applications: Technoeconomic and Life-Cycle Analyses
This study performed technoeconomic and life-cycle analyses to assess the economic feasibility and emission benefits and tradeoffs of various biofuel production pathways as an alternative to conventional marine fuels. We analyzed production pathways for (1) Fischer-Tropsch diesel from biomass and cofeeding biomass with natural gas or coal, (2) renewable diesel via hydroprocessed esters and fatty acids from yellow grease and cofeeding yellow grease with heavy oil, and (3) bio-oil via fast pyrolysis of low-ash woody feedstock. We also developed a new version of the Greenhouse gases, Regulated Emissions, and Energy use in Transportation (GREET) marine fuel module for the estimation of life-cycle greenhouse gas (GHG) and criteria air pollutant (CAP) emissions of conventional and biobased marine fuels. The alternative fuels considered have a minimum fuel selling price between 2.36 and 4.58 $/heavy fuel oil gallon equivalent (HFOGE), and all exhibit improved life-cycle GHG emissions compared to heavy fuel oil (HFO), with reductions ranging from 40 to 93%. The alternative fuels also exhibit reductions in sulfur oxides and particulate matter emissions. Additionally, when compared with marine gas oil and liquified natural gas, they perform favorably across most emission categories except for cases where carbon and sulfur emissions are increased by the cofed fossil feedstocks. The pyrolysis bio-oil offers the most promising marginal CO2 abatement cost at less than $100/tonne CO2e for HFO prices >$1.09/HFOGE followed by Fischer-Tropsch diesel from biomass and natural gas pathways, which fall below $100/tonne CO2e for HFO prices >$2.25/HFOGE. Pathways that cofeed fossil feedstocks with biomass do not perform as well for marginal CO2 abatement cost, particularly at low HFO prices. This study indicates that biofuels could be a cost-effective means of reducing GHG, sulfur oxide, and particulate matter emissions from the maritime shipping industry and that cofeeding biomass with natural gas could be a practical approach to smooth a transition to biofuels by reducing alternative fuel costs while still lowering GHG emissions, although marginal CO2 abatement costs are less favorable for the fossil cofeed pathways.
Greenhouse gas, life cycle assessment, techno-econ↗