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At least 235 records · Page 13

Bio-Based Polymers with Performance-Advantaged Properties

Bio-based compounds with unique chemical functionality can be obtained through selective transformations of plant and other non-fossil, biogenic feedstocks for the development of new polymers to displace those produced from fossil carbon feedstocks. Although substantial efforts have been invested to produce bio-based polymers that are chemically identical to and directly replace those from petroleum, a long-pursued goal is to synthesize new, sustainable, bio-based polymers that either functionally replace or exhibit performance advantages relative to incumbent polymers. Owing to anthropogenic climate change and the environmental consequences of global plastics pollution, the need to realize a bio-based materials economy at scale is critical. To that end, in this Review we describe the concept of performance-advantaged, bio-based polymers (PBPs), highlighting examples wherein superior performance is facilitated by the inherent chemical functionality of bio-based feedstocks. We focus on PBPs with C–O and C–N inter-unit chemical bonds, as these are often readily accessible from bio-based feedstocks, which are heteroatom-rich relative to petroleum-derived feedstocks. Finally, we outline guiding principles and challenges to aid progress in the development of PBPs.

bio-based feedstock↗

Microbial production of advanced biofuels

Concerns over climate change have necessitated a rethinking of our transportation infrastructure. One possible alternative to carbon-polluting fossil fuels is biofuels produced by engineered microorganisms that use a renewable carbon source. Two biofuels, ethanol and biodiesel, have made inroads in displacing petroleum-based fuels, but their uptake has been limited by the amounts that can be used in conventional engines and by their cost. Further, advanced biofuels that mimic petroleum-based fuels are not limited by the amounts that can be used in existing transportation infrastructure but have had limited uptake due to costs. In this Review, we discuss engineering metabolic pathways to produce advanced biofuels, challenges with substrate and product toxicity with regard to host microorganisms and methods to engineer tolerance, and the use of functional genomics and machine learning approaches to produce advanced biofuels and prospects for reducing their costs.

59 BASIC BIOLOGICAL SCIENCES↗

Progress and roadmap for electro-privileged transformations of bio-derived molecules

Biomass incorporates carbon captured from the atmosphere and can serve as a renewable feedstock for producing valuable chemicals and fuels. Here we look at how electrochemical approaches can impact biomass valorization, focusing on identifying chemical transformations that leverage renewable electricity and feedstocks to produce valorized products via electro-privileged transformations. First, we recommend that the field should explore widening the spectrum of platform chemicals derived from bio-feedstocks, thus offering pathways to molecules that have historically been derived from petroleum. Second, we identify opportunities in electrocatalytic production of energy-dense fuels from biomass that utilize water as the hydrogen source and renewable electricity as the driving force. Finally, we look at the potential in electrochemical depolymerization to preserve key functional groups in raw feedstocks that would otherwise be lost during harsh pre-treatments in traditional depolymerization routes. Finally, on the basis of these priorities, we suggest a roadmap for the integration of biomass and electrochemistry and offer milestones required to tap further into the potential of electrochemical biomass valorization.

electrocatalysis↗

Trends and 2025 Insights on the Rise of Electric Vehicles in the USA

Plug-in electric vehicles (EVs) are reshaping the transportation energy landscape, providing a practical alternative to petroleum fuels for a growing number of applications. EV sales grew 55x in the past decade (2014-2024) and 6x since 2020, driven by technological progress enabled by policies to reduce transportation emissions as well as industrial plans motivated by strategic value of EVs for global competitiveness, jobs and geopolitics. In 2024, 22% of passenger cars sold globally were EVs and opportunities for EVs beyond on-road applications are growing, including solutions to electrify off-road vehicles, maritime and aviation. This Review updates and expands our 2020 assessment of the scientific literature and describes the current status and future projections of EV markets, charging infrastructures, vehicle-grid integration and supply chains in the USA. EV is the lowest-emission motorized on-road transportation option, with life-cycle emissions decreasing as electricity emissions continue to decrease. Charging infrastructure grew in line with EV adoption but providing ubiquitous reliable and convenient charging remains a challenge. EVs are reducing electricity costs in several US markets and coordinated EV charging can improve grid resilience and reduce electricity costs for all consumers. The current trajectory of technology improvement and industrial investments points to continued acceleration of EVs.

33 ADVANCED PROPULSION SYSTEMS↗

Lignin monomer conversion into biolubricant base oils

Despite progress in the depolymerization of lignin, only a few studies convert the obtained monomers to value-added products. Here we introduce a strategy to synthesize branched benzene lubricant (BBL) and branched cyclic lubricant (BCL) base oils from lignin-derived monomers and aldehyde. We perform carbon–carbon coupling via Brønsted acid-catalyzed hydroxyalkylation/alkylation (HAA) then hydrodeoxygenation (HDO). Optimum HAA reaction conditions achieve up to 90% guaiacol conversion and an HAA product containing 76% BBL and 24% enal condensation product over a P-SiO 2 catalyst. Subsequent HDO of HAA products over an Ir-ReO x /SiO 2 catalyst produces a lubricant-ranged mixture of BCL (C 24 ) up to yield (82%) and small fractions of dodecyl cyclohexane and C 10 and C 15 carbons alkanes. The kinematic viscosity, viscosity index, and Noack volatility of these base oils are comparable to commercial petroleum-derived poly α-olefin Group IV and refrigerant base oils. In conclusion, this approach provides a sustainable pathway for replacing petroleum-derived base oils.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Aliphatic Amines from Waste Polyolefins by Tandem Pyrolysis, Hydroformylation, and Reductive Amination

Pyrolysis of waste plastics can produce a product mixture with a high concentration of olefins (>50 wt%). The olefins, as building blocks in the petroleum industry, are potential precursors for valuable commodity chemicals with higher values (>$2000 per ton). In this work, we produce aldehydes by hydroformylation of the olefins present in pyrolysis oil from colored post-consumer recycled high-density polyethylene (PCR-HDPE). The obtained aldehydes in the oil are then converted into aliphatic amines via reductive amination with a Ru/C catalyst. The aminated oil was characterized by multiple analytical chemistry techniques including elemental analysis, nuclear magnetic resonance spectroscopy, high-resolution liquid chromatography-mass spectrometry, and gas chromatography-mass spectrometry with a Polyarc flame ionization detector. The concentration of metals in the PCR-HDPE and oil changes during the tandem processes, showing limited effects of these elements (e.g., Al, Ca, Fe, Mg, Ti, Zn) on hydroformylation and reductive amination. Additionally, we demonstrated that reductive amination of aldehydes with varied carbon numbers and branching properties can be achieved in the presence of a complex mixture, including paraffins and aromatics. The results indicate that waste plastics have the potential to serve as a renewable source for mono and di aliphatic amines, thereby diminishing reliance on fossil feedstocks as the current primary amine source.

aliphatic amines↗

Forest residue harvest optimization: spanning the bridge between plant biology and biorefinery performance

Forestry residues have immense potential as alternative feedstocks to petroleum, yet their inherent complexity remains a major challenge to widespread use. Pairing the temporal rhythms of plant biology with biorefinery performance is critical to industrial-scale biorefinery development. Here, we provide the first report of a techno-economic analysis (TEA) and life cycle assessment (LCA) for a model integrated reductive catalytic fractionation (RCF)–molten salt hydrolysis process for forestry residues varying in tree part, species, and phenophase. All forestry residues resulted in net-negative greenhouse gas (GHG) emissions vs. comparable petroleum feedstocks, with GHG emissions potentially reduced >4.0× through composition-based feedstock selection (e.g., harvesting American beech bark in spring vs. summer). Moreover, American beech twigs/branchlets and bark in leafed and emergence phenophases, respectively, had 7.9× lower predicted phenolic minimum selling prices (MSPs) vs. other feedstocks and MSPs within the current global phenolic market range. Hemicellulose content and RCF yield emerged as key parameters impacting GHG emissions and biorefinery revenue, identifying hardwood twigs/branchlets in the leafed phenophase as optimal biofeedstocks. Biorefinery expenses were dominated by purchased equipment, raw materials, and utility costs, highlighting essential areas for future study. Notably, RCF reactor pressures drove 85–90% of equipment costs, but sensitivity analysis revealed that decreasing the pressure 20% could reduce the phenol MSP 4-fold. Structural carbohydrate dynamics were also investigated using a two-step acid hydrolysis method to resolve tissue- and species-level patterns in biomass composition throughout the year to enable harvest optimization based on TEA/LCA findings. Ultimately, elucidating the impact of biofeedstock dynamics on biorefinery performance enables harvest optimization, informed engineering design, and progress towards an expanded bioeconomy.

Shapiro, Alison J. [University of Delaware, Newark↗

The shape of electrified transportation

Transportation is currently the least-diversified energy demand sector, with over 90% of global transportation energy use coming from petroleum products [1]. For more than a century, petroleum fuels have been relied upon to move people and goods within and between towns and cities, and on roads, railways, farms, waterways, and in the air. These energy-dense fuels have unquestionably provided reliable and convenient mobility options to power the modern global economy. However, these benefits have also created challenges associated with geopolitics, energy security, price volatility, and environmental impacts.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Overexpression of RuBisCO form I and II genes in Rhodopseudomonas palustris TIE-1 augments polyhydroxyalkanoate production heterotrophically and autotrophically

ABSTRACT With the rising demand for sustainable renewable resources, microorganisms capable of producing bioproducts such as bioplastics are attractive. While many bioproduction systems are well-studied in model organisms, investigating non-model organisms is essential to expand the field and utilize metabolically versatile strains. This investigation centers on Rhodopseudomonas palustris TIE-1, a purple non-sulfur bacterium capable of producing bioplastics. To increase bioplastic production, genes encoding the putative regulatory protein PhaR and the depolymerase PhaZ of the polyhydroxyalkanoate (PHA) biosynthesis pathway were deleted. Genes associated with pathways that might compete with PHA production, specifically those linked to glycogen production and nitrogen fixation, were deleted. Additionally, RuBisCO form I and II genes were integrated into TIE-1’s genome by a phage integration system, developed in this study. Our results show that deletion of phaR increases PHA production when TIE-1 is grown photoheterotrophically with butyrate and ammonium chloride (NH 4 Cl). Mutants unable to produce glycogen or fix nitrogen show increased PHA production under photoautotrophic growth with hydrogen and NH 4 Cl. The most significant increase in PHA production was observed when RuBisCO form I and form I & II genes were overexpressed, five times under photoheterotrophy with butyrate, two times with hydrogen and NH 4 Cl, and two times under photoelectrotrophic growth with N 2 . In summary, inserting copies of RuBisCO genes into the TIE-1 genome is a more effective strategy than deleting competing pathways to increase PHA production in TIE-1. The successful use of the phage integration system opens numerous opportunities for synthetic biology in TIE-1. IMPORTANCE Our planet has been burdened by pollution resulting from the extensive use of petroleum-derived plastics for the last few decades. Since the discovery of biodegradable plastic alternatives, concerted efforts have been made to enhance their bioproduction. The versatile microorganism Rhodopseudomonas palustris TIE-1 (TIE-1) stands out as a promising candidate for bioplastic synthesis, owing to its ability to use multiple electron sources, fix the greenhouse gas CO 2 , and use light as an energy source. Two categories of strains were meticulously designed from the TIE-1 wild-type to augment the production of polyhydroxyalkanoate (PHA), one such bioplastic produced. The first group includes mutants carrying a deletion of the phaR or phaZ genes in the PHA pathway, and those lacking potential competitive carbon and energy sinks to the PHA pathway (namely, glycogen biosynthesis and nitrogen fixation). The second group comprises TIE-1 strains that overexpress RuBisCO form I or form I & II genes inserted via a phage integration system. By studying numerous metabolic mutants and overexpression strains, we conclude that genetic modifications in the environmental microbe TIE-1 can improve PHA production. When combined with other approaches (such as reactor design, use of microbial consortia, and different feedstocks), genetic and metabolic manipulations of purple nonsulfur bacteria like TIE-1 are essential for replacing petroleum-derived plastics with biodegradable plastics like PHA.

Ranaivoarisoa, Tahina Onina↗

Exploring novel alkane-degradation pathways in uncultured bacteria from the North Atlantic Ocean

Microbes play a significant role in the degradation of petroleum hydrocarbons in the oceans, yet little is known about the native bacteria that metabolize hydrocarbons before an oil spill. The Faroe-Shetland Channel (FSC) is a deepwater subarctic region of the North Atlantic with prominent oil production and a diverse microbial community associated with the degradation of petroleum. Here, we combine DNA-based stable-isotope probing (DNA-SIP) with metagenomics to elucidate the metabolic underpinnings of native alkane-degrading bacteria from the FSC. From two 13C n-hexadecane SIP experiments using seawater from 5 and 700 m depths in the FSC, we obtained 42 metagenome-assembled genomes (MAGs) belonging to 19 genera, including two previously overlooked hydrocarbon-degrading bacteria, Lentibacter (Alphaproteobacteria) and Dokdonia (Bacteroidetes). Diversity surveys indicated Lentibacter were dominant members of the FSC, constituting up to 17% of these communities. Many of the SIP-enriched MAGs (20/42) encoded a complete alkane oxidation pathway, including alkane monooxygenase (AlkB), rubredoxin reductase (AlkT), and rubredoxin-2 (AlkG). Fourteen Aphaproteobacteria MAGs lacked AlkG for electron transfer. Instead, they encoded novel disulfide isomerases with iron-binding cysteine motifs conserved across rubredoxins. Dokdonia lacked AlkT and AlkG, however, their central alkane-degradation catabolic pathways were complete. We describe previously unrecognized bacteria capable of hydrocarbon degradation, including the dominant genera Lentibacter, which may continuously purge hydrocarbons released from oil exploration activities in the FSC. This advances the understanding of the diversity and physiologies of alkane degradation in the North Atlantic and provides evidence of new mechanisms used to metabolize alkanes.

59 BASIC BIOLOGICAL SCIENCES↗

Performance of direct injected propane and gasoline in a high stroke-to-bore ratio SI engine: Pathways to diesel efficiency parity with ultra low soot

This work explores pathways to achieve diesel-like, high-efficiency combustion with stoichiometric 3-way catalyst compatible combustion in a single-cylinder spark ignition (SI) research engine. A unique high stroke-to-bore engine design (1.5:1) with cooled exhaust gas recirculation (EGR) and high compression ratio ( r c ) was used to improve engine efficiency by up to 30% compared with a production turbocharged gasoline direct injection spark ignition engine. Engine experiments were conducted with both 91 RON E10 gasoline and liquified petroleum gas (LPG) (i.e. autogas) and were compared to legacy gasoline data on the production engine. Geometric compression ratio ( r c ) of 13.3:1 was used for both fuels with additional experiments at 16.8:1 for LPG only. Measurements of exhaust soot particle size and number concentrations were made with both fuels. Significant reduction in soot particles across the whole particle size range were achieved with LPG due to the elimination of in-cylinder liquid films. The effects of EGR, late intake valve closing (IVC) and fuel characteristics were investigated through their effects on efficiency, combustion stability and soot production. Results of 47% gross thermal efficiency, and 45% net thermal efficiency at stoichiometric engine operation, at up to 17 bar IMEP and 2000 r/min with 16.8:1 r c were achieved with LPG. Estimated brake efficiency values were compared to a contemporary medium duty diesel engine illustrating the benefits of the chosen path for achieving diesel efficiency parity.

33 ADVANCED PROPULSION SYSTEMS↗

Data for Harnessing the Potential of Oilcane Waste Mud for Recovering Biobased Waxes

Oilcane is an engineered sugarcane with the ability to hyper-accumulate vegetative lipids. It is processed to obtain juice and bagasse as a potential substrate for the production of biofuels and biochemicals. The juice comprises solid particles that are separated as waste mud before the fermentation of the juice. In this study, the oilcane waste mud (OWM) generated from 1000 liters of oilcane juice was quantified and evaluated as a potential resource for recovering biobased waxes. Hexane and ethyl acetate were evaluated as two different solvents for extracting waxes from OWM followed by its purification using acetone. The extracted biobased wax samples were characterized for their chemical and thermal profiles which were then compared with commercial natural waxes. Detailed mass balance shows that 53.6 ± 2.6 kg (dry basis) of solid OWM gets generated upon processing 1000 L (~1068 kg) of oilcane juice. Hexane and ethyl acetate led to a crude wax yield of 25.6 ± 0.2% and 16.6 ± 0.4% (wt/wt, dry basis) respectively from OWM at the end of 8 h. The relative purification of the wax samples was reported in the range of 58%–65% (wt/wt). The purified OWM wax has a melting point of 74.7°C. The waste mud was valorized as a source of biobased waxes with characteristic chemical and thermal profiles comparable to commercial natural waxes (carnauba and beeswax). Considering the decline in the supply of petroleum wax in the future coupled with the switch to “greener” alternative products by consumers, OWM could be a valuable source of natural wax in the industrial sector reducing the dependence on petroleum waxes. Eventually, recovering biobased wax as a co-product from OWM would bring in an additional stream of revenue leading to the development of a zero-waste biorefinery based on bioenergy crops.

Biomass Analytics↗

Data for A Consolidated Bioprocess Design to Produce Multiple High-Value Platform Chemicals from Lignocellulosic Biomass and Its Technoeconomic Feasibility

5-hydroxymethyl furfural (HMF) and furfurals are DOE-listed platform chemicals that can be derived from the renewable carbon in the lignocellulosic biomasses and have the potential to replace petroleum-derived alternatives. High substrate cost and use of expensive solvents limit the economic feasibility of bio-based HMF production on an industrially relevant scale. The study presents an experimental optimized condition that maximizes the chemical-free production of HMF and furfurals without lowering the yield of total fermentable sugars from Saccharum bagasse. Hydrothermal pretreatment at 210 °C for 15 min yielded approximately 10%, 12%, and 46% of HMF, furfurals, and fermentable sugars per gram of dry biomass, respectively. Additionally, the study proposes a consolidated bioprocess model to produce and recover four high-value bioproducts i.e., HMF, furfurals, ethanol, and acetic acid based on the experimental results and evaluates its technoeconomic feasibility considering HMF as the main product. The minimum selling price (MSP) of HMF was estimated to be 930.6 USD/t which is competitive with its petroleum-derived precursor alternative p-xylene (1,113 USD/t). The sensitivity analysis performed for the process parameters suggests that pretreatment cost and revenues from coproducts immensely influence the MSP of HMF. The preliminary technoeconomic analysis performed on the consolidated bioprocess design indicates that additional revenue streams from diversified coproducts in biorefineries aid in lowering the MSP of high-value bioproducts.

Conversion↗

Basin Management of Geologic CO2 Storage: Effect of Well Spacing on CO2 Plume and Pressure Interference

This is the conference paper accompanying an oral presentation made at the Society of Petroleum Engineers (SPE) Western Regional Meeting (WRM) held in Bakersfield, California, April 26–28, 2022. The paper provides the results of a basin-scale CO2 storage modeling project investigating subsurface pressure interference among CO2 injection wells located in proximity to each other.

Wijaya, Nur↗

Corrosion Studies of Pine-Derived Bio-Oil and Heavy Fuel Oil Blends

To reduce the amount of greenhouse gas produced from the combustion of petroleum fuels, renewable liquid fuels are needed. Pyrolysis of biomass provides a means to produce liquid fuels to displace current petroleum products. However, common ferrous alloys are susceptible to high corrosion rates when exposed to bio-oil. This study analyzes the effects of blending bio-oil derived from loblolly pine with heavy fuel oil added to reduce corrosion of common structural alloys. Laboratory corrosion studies of six different blends of bio-oil/heavy fuel oil were performed for 1,000 hours at 50°C. Chemical characterization was also performed to determine the total acid content of each blend. Post-exposure characterizations such as changes in weight, X-ray diffraction, dye penetrant testing, and metallography were performed to provide more insight into the corrosion mechanism of bio-oil/heavy fuel oil blends. We hypothesized that the corrosion rates of ferrous alloys would increase with an increase in bio-oil concentration. The results of these characterization and corrosion studies confirmed this hypothesis and will be reported.

09 BIOMASS FUELS↗

Site 200 - Building 225 Construction Project: Steel Pipe Abandonment Work Plan (October 2020)

In December 2019, a capped, 4-inch diameter pipe located inside a square concrete collar was discovered on the north side of a driveway leading into a construction project located at the northeast corner of First Street and Avenue and petroleum like odors were reported to Lawrence Livermore National Laboratory's (LLNL) Environment, Safety and Health (ES&H) staff. The pipe was also found to contain liquid, which was sampled. Analysis of the liquid showed the presence of refined petroleum hydrocarbons - primarily benzene, toluene, ethylbenzene and total xylenes, and lead. Based on various historical documents and maps, the pipe is assumed to be associated with one, or more of four 25,000-gallon, single-wall, concrete-construction, underground storage tanks (USTs) installed by the U.S. Department of Navy in approximately 1943. The USTs were reported to have been closed - abandoned in place and filled with sand in 1950.

54 ENVIRONMENTAL SCIENCES↗

U.S. Airport Infrastructure and Sustainable Aviation Fuel

Worldwide, aviation accounts for 2% of all manmade carbon dioxide emissions and 12% of all transportation CO 2 emissions In 2018, the U.S. accounted for 25% of the world jet fuel consumption and 21% of global enplanements. Airports and airlines are considering alternative fuel to meet environmental and sustainability goals and mandates. Sustainable aviation fuel (SAF), made from non-petroleum feedstocks, has the potential to significantly reduce emissions from air transportation. SAF must be blended with petroleum based jet fuel prior to its use in aircraft. This report explores background information on jet fuel use, quality standards and best practices, airport infrastructure, and options for delivering SAF to airports.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

History of Ethanol Fuel Adoption in the United States: Policy, Economics, and Logistics

Ethanol has the achieved the greatest market share of all the alternative transportation fuels that have been researched, developed, and deployed in the US. There are multiple lessons to be learned from the history of ethanol adoption that can be applied to future fuels and products. Ethanol has replaced portions of gasoline in three main blend levels, with corresponding vehicles, equipment, benefits, and policies. The first is E10, which has replaced nearly all pure gasoline (E0) sold in the United States today (U.S. Energy Information Administration 2015). This was brought about through generations of policies that were motivated by multiple factors related to engine performance, energy security, health, air quality, and climate protection. Ethanol's high octane has been a consistent driver of the fuel because this enables higher performance engines. Early policies (1973-1979) were largely motivated by the desire to reduce dependence on petroleum sourced from members of the Organization of the Petroleum Exporting Countries, or OPEC. Fuel policy in the 1980s was largely in pursuit of promoting octane number enhancers that could replace lead. Criteria pollutant reduction was the overarching goal of actions taken from 1990 to 2005. From 2005 to the present, fuel policy has been largely motivated by energy security and climate protection goals. These policies were usually technology-agnostic and promoted multiple fuels and additives during each period. However, ethanol is the only fuel identified that is cost effective with qualities that enabled it to prosper in the policy environments of all four of these periods.The second market for ethanol is via 85% ethanol (E85). This fuel has the advantage of a greater concentration of ethanol but the disadvantage of not being compatible with regular gasoline vehicles. Instead, it can only be used in flexible-fuel vehicle (FFVs), which can use every blend level from E0 to E85. Therefore, much of the effort to increase E85 consumption has been aimed at incentivizing automakers to manufacture FFVs, drivers to purchase FFVs, and fueling stations to equip themselves to sell E85.The third, and newest, market through which ethanol is consumed is 15% ethanol (E15), which builds upon the E10 market to increase ethanol consumption by common gasoline vehicles. Efforts to create the E15 market consisted largely of testing vehicles and refueling equipment for compatibility, creating waivers to allow the use of E15, placing requirements on E15 retailers, and incentivizing retailers to equip themselves to purchase E15.

09 BIOMASS FUELS↗