Search NASA⌕ Search

SEARCH · Search NASA

Results for “PETROLEUM”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 415 records · Page 23
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Elucidating the differences in oxidation of high-performance α- and β- diisobutylene biofuels via Synchrotron photoionization mass spectrometry

Abstract Biofuels are a promising ecologically viable and renewable alternative to petroleum fuels, with the potential to reduce net greenhouse gas emissions. However, biomass sourced fuels are often produced as blends of hydrocarbons and their oxygenates. Such blending complicates the implementation of these fuels in combustion applications. Variations in a biofuel’s composition will dictate combustion properties such as auto ignition temperature, reaction delay time, and reaction pathways. A handful of novel drop-in replacement biofuels for conventional transportation fuels have recently been down selected from a list of over 10,000 potential candidates as part of the U.S. Department of Energy’s (DOE) Co-Optimization of Fuels and Engines (Co-Optima) initiative. Diisobutylene (DIB) is one such high-performing hydrocarbon which can readily be produced from the dehydration and dimerization of isobutanol, produced from the fermentation of biomass-derived sugars. The two most common isomers realized, from this process, are 2,4,4-trimethyl-1-pentene (α-DIB) and 2,4,4-trimethyl-2-pentene (β-DIB). Due to a difference in olefinic bond location, the α- and β- isomer exhibit dramatically different ignition temperatures at constant pressure and equivalence ratio. This may be attributed to different fragmentation pathways enabled by allylic versus vinylic carbons. For optimal implementation of these biofuel candidates, explicit identification of the intermediates formed during the combustion of each of the isomers is needed. To investigate the combustion pathways of these molecules, tunable vacuum ultraviolet (VUV) light (in the range 8.1–11.0 eV) available at the Lawrence Berkeley National Laboratory’s Advanced Light Source (ALS) has been used in conjunction with a jet stirred reactor (JSR) and time-of-flight mass spectrometry to probe intermediates formed. Relative intensity curves for intermediate mass fragments produced during this process were obtained. Several important unique intermediates were identified at the lowest observable combustion temperature with static pressure of 93,325 Pa and for 1.5 s residence time. As this relatively short residence time is just after ignition, this study is targeted at the fuels’ ignition events. Ignition characteristics for both isomers were found to be strongly dependent on the kinetics of C 4 and C 7 fragment production and decomposition, with the tert-butyl radical as a key intermediate species. However, the ignition of α-DIB exhibited larger concentrations of C 4 compounds over C 7 , while the reverse was true for β-DIB. These identified species will allow for enhanced engineering modeling of fuel blending and engine design.

09 BIOMASS FUELS↗
DOE OSTI2021

Design new epoxy nanocomposite coatings based on metal vanadium oxy-phosphate M 0.5 VOPO 4 for anti-corrosion applications

Epoxy nanocomposite coatings are an essential way to protect petroleum storage tanks from corrosion. For this purpose, the new nanocomposite epoxy coatings (P-M/epoxy composites) have been successfully designed. The P-M/epoxy composites are based on the metal vanadium oxy-phosphate M 0.5 VOPO 4 (where M = Mg, Ni, and Zn). The function of P-M/epoxy composites as anti-corrosion coatings was explored using electrochemical and mechanical tests. Using electrochemical impedance spectroscopy (EIS), it has been noticed that the pore resistance and polarization resistance of the P-M/epoxy composites remain higher as compared to the neat epoxy. The P-M/epoxy composites have the greatest impact on the cathodic dis-bonded area and water absorption. Besides, P-M/epoxy composites exhibit a very high order of mechanical properties. Further, Mg 0.5 VOPO 4 has the greatest effect on the anti-corrosion properties of epoxy coating followed by Zn 0.5 VOPO 4 and Ni 0.5 VOPO 4 . All these properties lead to developing effective anti-corrosion coatings. Thus, the net result from this research work is highly promising and provides a potential for future works on the anti-corrosion coating.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Importance of incorporating spatial and temporal variability of biomass yield and quality in bioenergy supply chain

Abstract Biofuels made from biomass and waste residues will largely contribute to United States’ 2050 decarbonization goal in the aviation sector. While cellulosic biofuels have the potential fuel performance equivalent to petroleum-based jet fuel, the biofuel industry needs to overcome the supply chain barrier caused by temporal and spatial variability of biomass yield and quality. This study highlights the importance of incorporating spatial and temporal variability during biomass supply chain planning via optimization modeling that incorporates 10 years of drought index data, a primary factor contributing to yield and quality variability. The results imply that the cost of delivering biomass to biorefinery may be significantly underestimated if the multi-year temporal and spatial variation in biomass yield and quality is not captured. For long term sustainable biorefinery operations, the industry should optimize supply chain strategy by studying the variability of yield and quality of biomass in their supply sheds.

09 BIOMASS FUELS↗
DOE OSTI2024

Rapid biodegradation of microplastics generated from bio-based thermoplastic polyurethane

The accumulation of microplastics in various ecosystems has now been well documented and recent evidence suggests detrimental effects on various biological processes due to this pollution. Accumulation of microplastics in the natural environment is ultimately due to the chemical nature of widely used petroleum-based plastic polymers, which typically are inaccessible to biological processing. One way to mitigate this crisis is adoption of plastics that biodegrade if released into natural environments. In this work, we generated microplastic particles from a bio-based, biodegradable thermoplastic polyurethane (TPU-FC1) and demonstrated their rapid biodegradation via direct visualization and respirometry. Furthermore, we isolated multiple bacterial strains capable of using TPU-FC1 as a sole carbon source and characterized their depolymerization products. Finally, to visualize biodegradation of TPU materials as real-world products, we generated TPU-coated cotton fabric and an injection molded phone case and documented biodegradation by direct visualization and scanning electron microscopy (SEM), both of which indicated clear structural degradation of these materials and significant biofilm formation.

09 BIOMASS FUELS↗
DOE OSTI2022

Bioplastic design using multitask deep neural networks

Abstract Non-degradable plastic waste jeopardizes our environment, yet our modern lifestyle and current technologies are impossible to sustain without plastics. Bio-synthesized and biodegradable alternatives such as polyhydroxyalkanoates (PHAs) have the potential to replace large portions of the world’s plastic supply with cradle-to-cradle materials, but their chemical complexity and diversity limit traditional resource-intensive experimentation. Here, we develop multitask deep neural network property predictors using available experimental data for a diverse set of nearly 23,000 homo- and copolymer chemistries. Using the predictors, we identify 14 PHA-based bioplastics from a search space of almost 1.4 million candidates which could serve as potential replacements for seven petroleum-based commodity plastics that account for 75% of the world’s yearly plastic production. We also discuss possible synthesis routes for the identified promising materials.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Molecular dynamics simulations for glass transition temperature predictions of polyhydroxyalkanoate biopolymers

Polyhydroxyalkanoates (PHAs) represent an emerging class of biosynthetic and biodegradable polyesters that exhibit considerable potential to replace petroleum-based plastics towards a sustainable future. Despite the promise, general structure–property mappings within this class of polymers remain largely unexplored. An efficient exploration of this vast chemical space calls for the development and validation of predictive methods for accurate estimation of a diverse range of properties for PHA-based polymers. Towards this aim, we present and validate in this work the results of our molecular dynamics (MD) simulation based approach aimed at predicting glass transition temperatures (T g ) of PHA-based polymers. Since generally available and widely used polymer forcefields exhibit a relatively poor performance for T g predictions, we have developed a new forcefield by modifying the polymer consistent force field (PCFF) via refining a selected set of torsion potentials of the polymer backbone using accurate density functional theory (DFT) computations. After carefully assessing the dependence of critical simulation parameters, such as, polymer chain length, number of polymer chains, supercell size, and thermal quenching rate used in the simulation, the applicability and transferability of the modified PCFF (mPCFF) is demonstrated by directly comparing the computed T g predictions of various polymers with different chemistries, polymer side chain lengths and functional groups forming the polymer side chains against the respective experimentally measured values. Furthermore, the transport properties such as self-diffusion coefficient and viscosity are computationally determined and their well-known correlation with the target properties is demonstrated. Lastly, we have employed the developed approach to predict T g values for a number of yet-to-be-synthesized PHA-based polymers with a diverse set of functional groups in the polymer side chains. The results are further rationalized by correlating the predicted T g values with the inter-chain H-bond formation tendencies of the different side chain functional groups. This work represents an important first step towards computationally guided design of PHA-based functional polymers and opens up new directions for a systematic investigation of composition- and configuration-dependent structure–property relationships in more complex binary and ternary copolymer systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Materials for the biorefinery: high bio-content, shape memory Kraft lignin-derived non-isocyanate polyurethane foams using a non-toxic protocol

Polyurethanes are among the top six polymers produced in the world and are widely used in the automotive, furniture, construction and appliance industry for their light weight, impact resistance, and insulating properties. However, the use of hazardous diisocyanates used in polyurethane formulations has led many to search for more sustainable alternatives. The lignin component of biomass has been targeted to replace the often toxic and petroleum-derived precursors to polymer synthesis in support of the biorefinery concept where natural materials are used as the feedstock for commodity plastics. The use of lignin is often hampered due to its low reactivity, heterogeneity and the necessity of employing extensive purification and/or functionalization measures to ensure materials are of comparable quality. In this report, a unique method is presented for the synthesis and processing of a non-toxic, non-isocyanate polyurethane foam utilizing unmodified Kraft lignin and a biobased curing agent. Here, raw Kraft lignin is functionalized with green organic carbonates and a non-toxic approach is taken to solubilize the precursors with a curing agent from renewable fatty acids enabling rapid gel-times. For the first time, a NIPU foam from lignin is synthesized while the structure–property relationship of different reaction mixtures is studied demonstrating shape memory capacity and 100% biobased carbon content.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Thiol-promoted catalytic synthesis of high-performance furan-containing lubricant base oils from biomass derived 2-alkylfurans and ketones

About 97% of lubricant base oils are currently sourced from petroleum and the majority of the rest is produced from vegetable oils. We demonstrate a promising catalytic route to produce base oils from lignocellulosic biomass-derived 2-alkylfurans and ketones via carbon–carbon coupling in neat conditions. Among several homogeneous and heterogeneous acid catalysts tested, a perfluorinated sulfonic acid (Aquivion PW79S) exhibits the best catalytic performance and yields up to 90% renewable furan-containing base oils with the use of a thiol promotor. The effects of the acid strength of the catalysts, molecular size and structure of thiols and ketones, and fraction of thiols are studied. Electronic structure calculations elucidate the reaction pathway and indicate that the thiol reduces the barrier of the rate-determining dehydration step. The structure and properties of base oils can be tuned by using different synthons. Here, these base oils have excellent properties and can be competitive with or surpass the commercial synthetic alkylnaphthalene and furan-containing bio-ester base oils.

09 BIOMASS FUELS↗
DOE OSTI2021

Synthesis of (hemi)cellulosic lubricant base oils via catalytic coupling and deoxygenation pathways

The past decade has witnessed a significant growth in bioproduct development due to the strong interest in creating a more diverse energy supply, environmental sustainability, and a carbon neutral bioeconomy. The initial biorefinery strategy, which focused mainly on the production of low carbon number drop-in bioproducts, has recently shifted its focus on the production of high carbon number and high performance bioproducts with unique properties and value propositions. One such product is lubricant base oil (LBO), which represents over $150 billion global lubricant market and is used for various industrial, automotive, marine, metal-working, consumer, and specialized applications. The application landscape of lubricants has changed significantly over the past decade because of environmental regulations and the growing demand for sustainable lubricants to mitigate regulatory challenges and improve carbon footprint. Currently, only 3% LBOs are produced from bio-based triglycerides/fatty acids. Because of low oxidation stability and high hydrolytic susceptibility, these bio-based LBOs have limited applications. Thus, research and development and commercialization efforts for (hemi)cellulosic LBOs to meet the market demand have received momentum over the past few years. This review describes strategies to produce (hemi)cellulosic LBOs via carbon–carbon coupling and hydrodeoxygenation chemistries. We emphasize the coupling strategies to create LBOs with a branched architecture to surrogate petroleum-based poly-α-olefins. Here, a structure–property relationship for tuning the key specifications of LBOs as a function of molecular architecture is illustrated. Mechanistic understanding and molecular interactions of multi-furan substrates with the active sites of complex multifunctional catalysts are described. Furthermore, techno-economic and life-cycle analysis is summarized along with standing challenges and future opportunities.

09 BIOMASS FUELS↗
DOE OSTI2021

A critical review on the progress and challenges to a more sustainable, cost competitive synthesis of adipic acid

Adipic acid is a key organic diacid intermediate used in nylon manufacturing. It is primarily produced by an industrial process that can form nitrous oxide as a byproduct. Nitrous oxide has a 300-fold higher global warming potential than carbon dioxide, and an estimated 10% of its annual global emissions are a result of adipic acid production. These concerns have led to significant efforts for the development of nitrous oxide mitigation technologies as well as more environmentally friendly routes for adipic acid production. New processes include both advanced chemical and biotechnological routes. Here in this review, we discuss key recent developments in mitigation as well as new technologies. We also provide a critical look at the potential of new technologies to compete with the incumbent process and highlight key remaining technical challenges to the development of greener (environmentally sustainable) and cost competitive (commercially sustainable) processes for adipic acid manufacture.

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2021

Enhanced medium chain length-polyhydroxyalkanoate production by co-fermentation of lignin and holocellulose hydrolysates

Biological lignin conversion to medium chain length-polyhydroxyalkanoates (mcl-PHA) has recently emerged as an attractive alternative to petroleum-based plastics due to the renewable nature of lignin and the value-added applications of mcl-PHA. Previous reports suggested that addition of limited glucose can improve mcl-PHA accumulation in Pseudomonas putida KT2440 grown in lignin substrates. Herein, we propose a biorefinery process to systematically release lignin and sugars from lignocellulosic biomass and evaluate the potential of co-utilization of all biomass components for conversion to mcl-PHA. Our results indicate that a sequential treatment composed of acid pretreatment, enzymatic hydrolysis and alkaline treatment produces a suitable lignin stream for mcl-PHA production in engineered P. putida. In addition, the PHA titer could be increased by 71% when the lignin stream (AH) was combined with the enzymatic hydrolysate (EH) at a ratio of 75 : 25. Higher ratios of EH : AH negatively affect mcl-PHA accumulation as well as mixtures with sugars from the acid hydrolysate. The optimization of the fermentation conditions, including the inoculum (OD 600 ) and substrate (soluble solid content (SSC)), was carried out by a central composite design. The optimal conditions were achieved at OD 600 = 2.17 and SSC = 68.28 g L –1 . Under these conditions, the titer increased 4.3 fold, achieving a mcl-PHA production of 1.38 g L –1 . Lignin characterization before and after fermentation by nuclear magnetic resonance and gas chromatography showed that p-coumarates were mainly consumed during the fermentation for mcl-PHA production. Overall, this biorefinery strategy allowed us to increase mcl-PHA production by utilizing the different lignocellulosic fractions. Unlike previous studies, no model substrates were utilized at any stage of the fermentation process, representing a step forward towards process feasibility.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Phosphorus speciation analysis of fatty-acid-based feedstocks and fast pyrolysis biocrudes via gel permeation chromatography inductively coupled plasma high-resolution mass spectrometry

Renewable feedstocks, such as lignocelulosic fast pyrolysis oils and both vegetable oil and animal fats, are becoming a viable alternative to petroleum for producing high-quality renewable transportation fuels. However, the presence of phosphorus-containing compounds, mainly from phospholipids, in these renewable feedstocks is known to poison and deactivate hydrotreating catalysts during fuel production. In this work, gel permeation chromatography (GPC) combined with inductively coupled plasma high-resolution mass spectrometry (ICP-HRMS) was used to analyze feedstocks including unprocessed soybean oil, animal fat, and pyrolysis oils from red oak and milorganite to identify phosphorus species. The results have shown the presence of a wide range of different phosphorous compounds among all the samples analysed in this work. The GPC-ICP-HRMS analyses of a vegetable oil and two animal fats have shown different fingerprints based on the molecular weight of each of the samples, highlighting the structural differences among their corresponding phosphorus-containing compounds. While the presence of low-molecular-weight species, such as phospholipids, was expected, several high-molecular-weight species (MW > 10 000 Da) have been found, suggesting that high-molecular-weight micelles or liposomes might have been formed due to the high concentration of phospholipids in these samples. Results obtained through the hydroxylation of a mix of phospholipids (asolectin) and its posterior GPC-ICP-HRMS agree with this hypothesis. With respect to the lignocellulosic catalytic fast pyrolysis oil samples, the GPC-ICP-HRMS results obtained suggest that either aggregation or polymerization reactions might have occurred during the pyrolysis process, yielding phosphorus-containing compounds with an approximate molecular weight above 91 000 kDa. In addition, an aggregation phenomenom has been observed for those phosphorus species present within the fast pyrolysis oils after being stored for 3 months, especially for those pyrolysis oils contaning pre-processed feedstocks, such as milorganite.

09 BIOMASS FUELS↗
DOE OSTI2021

Pilot-scale hydrotreating of catalytic fast pyrolysis biocrudes: process performance and product analysis

Catalytic fast pyrolysis (CFP) is a technology option for producing advanced biofuels from hydrocarbon-rich biocrude intermediates. The relatively high oxygen content of biocrudes compared to petroleum intermediates increases hydrogen consumption and the lower thermal stability accelerates catalyst deactivation and reactor fouling hindering the adaptation of hydrotreating technology for biocrude upgrading into biofuels. In this study, four chemically different biocrude feeds were upgraded in a pilot scale hydroprocessing unit at similar process conditions using a commercial hydrodeoxygenation (HDO) catalyst. The biocrude feeds and hydrotreated products were characterized using standard ASTM procedures and advanced analytical techniques (GCxGC-FID and GCxGC-MS). HDO catalyst activity was monitored by changes in physical properties and chemical composition of the upgraded products as a function of time on stream. Aliphatic acids, ketones, aldehydes, and furan derivatives were completely converted during the hydrotreating tests while the concentration of aromatics, aliphatic hydrocarbons and phenolics increased during the hydrotreating tests. The oxygen content, nitrogen content, specific gravity, viscosity and the heavy end of the boiling point range (determined by simulated distillation) of the upgraded products increased with increasing time on stream during hydrotreating. The deactivation rate was the lowest for the biocrude feed that contained the most aliphatic and aromatic hydrocarbons and was the highest for the biocrude feed that had the most anhydrosugars. Overall, the HDO deactivation rate correlates with the total amount of oxygen in the feed (17 wt% to 29 wt%, on a wet basis).

09 BIOMASS FUELS↗
DOE OSTI2022

One-step production of renewable adipic acid esters from mucic acid over an Ir–ReO x /C catalyst with low Ir loading

The production of adipic acid, a large-volume platform chemical, from biomass represents a petroleum-free route to manufacturing nylon and other polymers more sustainably. In this study, a one-step conversion of bioderived mucic acid to adipates is reported over a heterogeneous, bifunctional Ir–ReO x /C catalyst via deoxydehydration (DODH) and catalytic transfer hydrogenation (CTH) using isopropanol as a green solvent and reductant. With very low Ir content (0.05 wt%), the catalyst provides a low-cost option for the tandem DODH–CTH process, while still enabling reuse and regeneration for at least five cycles. The reported catalytic system generates adipates in good yield (63%) without the need for additives (acids or halogens) or high pressure H 2 . Through model reactions and spectroscopic analyses, a bifunctional DODH–CTH mechanism was supported, with the Re VI/IV redox pair as the active DODH species and Ir0 saturating the dialkene intermediate via CTH. Thermal treatment in catalyst preparation and regeneration was optimized to limit metal leaching while maintaining good activity. Further, the present work outlines a one-step deoxygenation of an aldaric acid substrate from biomass using a bimetallic catalyst of low noble metal content to an important monomer for the polymer industry. This system facilitates use in future syntheses of sustainable chemicals from renewable oxygenates where the catalyst is reusable and affordable.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Conversion of plastic waste into high-value lubricants: techno-economic analysis and life cycle assessment

Given the low recycling rate of plastic waste in the United States due to low economic incentives, it is of great interest to develop a technology to upgrade plastic waste with favorable economics. Plastic upcycling to valuable chemicals could ensure a circular economy for plastics and reduce the environmental burden caused by their end use cycle and disposal. A conceptual facility to convert 250 metric ton (MT) per day of plastic waste was modeled; the main product was a high-quality liquid (HQL) with a similar performance to polyalphaolefin (PAO) lubricants. The modeled process had a lubricant yield of up to 90% based on the experimental results at the laboratory scale. Techno-economic analysis (TEA) and life cycle assessment (LCA) were also performed to evaluate the process economics and its environmental impact. By using a mixture of colored and natural high-density polyethylene (HDPE), the production cost was in the range of 0.6–1.98 dollars per kg of lubricant, depending on the operating conditions. The life cycle emissions were in the range of 0.48–1.2 kg CO 2e kg Lub -1 showing, for the best case scenario, a 52% reduction relative to the emissions for petroleum lubricants, and a 74% reduction relative to the emissions for PAO lubricants. Finally, the impacts of the lubricant yield, the catalyst amount, and reaction time were evaluated, and their effect on the final production cost was discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Highly selective cross ketonization of renewable acids over magnesium oxide

The rising demand for linear alkylbenzene surfactants (LAS) poses an environmental threat as LAS are industrially produced from petroleum using corrosive acid catalysts. Cross ketonization is a promising route of converting furans and fatty acids to oleo-furansulfonates, precursors for renewable, performance-enhanced LAS replacements. Here, we explore various alkaline earth metals and mixed metal oxides for the cross-ketonization reaction and find that MgO achieves ~90% yield by minimizing the decarboxylation side reaction. Here, we illustrate the role of molecular structure on the cross-ketonization reaction and the role of complex formation over alkaline-earth metal oxides in minimizing side reactions. We overcome catalyst deactivation by regeneration over multiple runs. This research demonstrates the effectiveness of heterogeneous catalysts for cross ketonization toward developing renewable surfactants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗