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At least 1,009 records · Page 56

Graphene Oxide Reduces the Hydrolytic Degradation in Polyamide-11

Graphene oxide (GO) was incorporated into polyamide-11 (PA11) via in-situ polymerization. The GO-PA11 nano-composite had elevated resistance to hydrolytic degradation. At a loading of 1 mg/g, GO to PA11, the accelerated aging equilibrium molecular weight of GO-PA11 was higher (33 and 34 kg/mol at 100 and 120 °C, respectively) compared to neat PA11 (23 and 24 kg/mol at 100 and 120 °C, respectively). Neat PA11 had hydrolysis rate constants (kH) of 2.8 and 12 ( × 10(exp -2) day(exp -1)) when aged at 100 and 120 °C, respectively, and re-polymerization rate constants (kP) of 5.0 and 23 ( × 10(exp -5) day(exp -1)), respectively. The higher equilibrium molecular weight for GO-PA11 loaded at 1 mg/g was the result of a decreased kH, 1.8 and 4.5 ( × 10(exp -2) day(exp -1)), and an increased kP, 10 and 17 ( × 10(exp -5) day(exp -1)) compared with neat PA11 at 100 and 120 °C, respectively. The decreased rate of degradation and resulting 40% increased equilibrium molecular weight of GO-PA11 was attributed to the highly asymmetric planar GO nano-sheets that inhibited the molecular mobility of water and the polymer chain. The crystallinity of the polymer matrix was similarly affected by a reduction in chain mobility during annealing due to the GO nanoparticles' chemistry and highly asymmetric nano-planar sheet structure.

Samuel J A Hocker↗

Analysis of Volatile Organic Compounds in the Apollo Next Generation Sample Analysis (ANGSA) 73002 Core Sample

Understanding the organic content of lunar regolith was an early priority upon the return of Apollo samples, with amino acids being of special interest because of their importance to life on Earth and their astrobiological relevance. Many initial studies focused on the detection of amino acids in these samples and attempts to determine the origin of those compounds. Although no consensus on the origin of the amino acids was reached in those early studies, more recent work determined that the detected amino acids originated from both terrestrial contamination and meteoritic or cometary in fall to the lunar surface. A majority of the amino acids in the Apollo samples studied originated from precursor molecules, either indigenous to the lunar samples or contaminants, that reacted during the water extraction and acid hydrolysis process for analysis in the laboratory, but the identities of the amino acid precursors still remain poorly understood. Such precursors could include hydrogen cyanide (HCN) and other volatile organic compounds such as amines, carboxylic acids, or aldehydes and ketones. The identities of these compounds, as well as the effects of years of curation on their abundances in lunar regolith samples stored at ambient temperature under nitrogen gas purge, are not clear. The specially curated samples available through the Apollo Next Generation Sample Analysis (ANGSA) program provide a unique opportunity to use state-of- the-art analytical techniques to examine previously unstudied lunar materials. The ANGSA samples include three types of samples: 1) samples stored frozen since <1 month after Earth arrival; 2) samples stored under helium; and 3) a double drive tube collected by Apollo 17 astronauts, with the bottom portion of the drive tube sealed under vacuum on the Moon and never opened. In contrast to the typically curated Apollo samples that have been kept for decades at room temperature under flowing nitrogen purge that may have significantly reduced the abundance of volatiles, the vacuum-sealed and frozen samples may have enhanced preservation of these volatiles. Our initial investigation examines amino acids and their potential volatile precursors, including hydrogen cyanide (HCN), aldehydes, ketones, amines, and mono-carboxylic acids, in a sample from the top portion of the Apollo 17 double drive tube. These results will aid in understanding the lunar abundances of these molecules and will also be compared to future analyses of other drive tube and frozen ANGSA samples.

Elsila, J. E.↗

Abundant Extraterrestrial Amino Acids in the Primitive CM Carbonaceous Chondrite Asuka 12236

The Asuka (A)-12236 meteorite has recently been classified as a CM carbonaceous chondrite of petrologic type 3.0/2.9 and is among the most primitive CM meteorites studied to date. Here, we report the concentrations, relative distributions, and enantiomeric ratios of amino acids in water extracts of the A-12236 meteorite and another primitive CM chondrite Elephant Moraine(EET) 96029 (CM2.7) determined by ultra-high-performance liquid chromatography time-of-flight mass spectrometry. EET 96029 was highly depleted in amino acids and dominated by glycine, while a wide diversity of two- to six-carbon aliphatic primary amino acids were identified in A-12236, which had a total amino acid abundance of 360 ± 18 nmol g-1, with most amino acids present without hydrolysis (free). The amino acid concentrations of A-12236 were double those previously measured in the CM2.7 Paris meteorite, consistent with A-12236 being a highly primitive and unheated CM chondrite. The high relative abundance of α-amino acids in A-12236 are consistent with formation by a Strecker-cyanohydrin dominated synthesis during a limited early aqueous alteration phase on the CM meteorite parent body. The presence of predominantly free glycine, a near racemic mixture of alanine (D/L ~0.93 to 0.96), and elevated abundances of several terrestrially rare non-protein amino acids including α-amino isobutyric acid (α-AIB) and racemic isovaline, indicate that these amino acids in A-12236 are extraterrestrial in origin. Given a lack of evidence for biological amino acid contamination in A-12236, it is possible that some of the L-enantiomeric excesses (Lee ~34 to 64%) of the protein amino acids aspartic and glutamic acids and serine are indigenous to the meteorite; however, isotopic measurements are needed for confirmation. In contrast to more aqueously altered CMs of petrologic types ≤ 2.5, no L-isovaline excesses were detected in A-12236. This observation strengthens the hypothesis that extensive parent body aqueous activity is required to produce or amplify the large L-isovaline excesses that cannot be explained solely by exposure to circularly polarized radiation or other chiral symmetry breaking mechanisms prior to incorporation into the asteroid parent body.

Daniel P Glavin↗

The Search for Chiral Asymmetry as a Potential Biosignature in Samples from Mars

The search for evidence of extraterrestrial life in our solar system is currently guided by our understanding of terrestrial biology and its associated biosignatures. The observed homochirality in all life on Earth, that is, the predominance of “left-handed” or L-amino acids and “right-handed” or D-sugars, is a unique property of life that is crucial for molecular recognition, enzymatic function, information storage and structure and is thought to be a prerequisite for the origin or early evolution of life. Therefore, the detection of L- or D-enantiomeric excesses of chiral amino acids and sugars could be a powerful indicator of extant or extinct life on Mars or other habitable environments in our solar system. The exploration of habitable environments on Mars, including an assessment of the preservation potential for complex organics of either abiotic or biological origin, remains a key goal of both current and future Mars missions. Now with the unambiguous detection of indigenous organic matter in sedimentary rocks on Mars [1-3], NASA’s Curiosity rover has significantly advanced our understanding of the preservation of potential chemical biosignatures in the martian near surface. Although amino acids have not yet been identified by in situ measurements on Mars, if they were present, it is expected that amino acid hydrolysis and racemization would be very slow and any chiral or isotopic signatures from an extinct martian biota could be preserved for billions of years, given the extremely cold and dry surface conditions [4]. One of ESA’s Rosalind Franklin rover payload instruments called the Mars Organic Molecule Analyzer (MOMA) includes a wet chemistry package capable of measuring the enantiomeric ratios of any chiral amino acids present at part-per-million concentrations or higher [5]. The complexity and limited duration of spaceflight operations and the known analytical challenges associated with in situ extraction and characterization of trace reduced organic compounds in ancient rocks make it challenging to determine the origins of martian organic matter found to date. Coordinated state-of-the-art laboratory measurements of returned samples from Mars that include spatially resolved chemical, mineralogical, and isotopic studies and molecule-specific isotopic and enantiomeric measurements will be required to firmly establish whether the complex organic matter detected on Mars comes from biotic or abiotic sources. Ultimately, sample return may be our best chance of identifying chemical biosignatures from a past or present martian biota, if one ever existed on Mars. NASA’s Perseverance rover will collect dozens of surface sample cores for possible future return to Earth by NASA and ESA. Here we review our current knowledge of the distributions and enantiomeric and isotopic compositions of non-biological amino acids found in meteorites compared to terrestrial biochemistry and propose a set of measurement criteria that should be used to help establish the origin of any chiral asymmetry detected in samples from Mars [6].

Daniel P Glavin↗

Formation of Amino Acids and Carboxylic Acids in Weakly Reducing Planetary Atmospheres by Solar Energetic Particles from the Young Sun

Life most likely started during the Hadean Eon; however, the environmental conditions which contributed to the complexity of its chemistry are poorly known. A better understanding of various environmental conditions, including global (heliospheric) and local (atmospheric, surface, and oceanic), along with the internal dynamic conditions of the early Earth, are required to understand the onset of abiogenesis. Herein, we examine the contributions of galactic cosmic rays (GCRs) and solar energetic particles (SEPs) associated with superflares from the young Sun to the formation of amino acids and carboxylic acids in weakly reduced gas mixtures representing the early Earth’s atmosphere. We also compare the products with those introduced by lightning events and solar ultraviolet light (UV). In a series of laboratory experiments, we detected and characterized the formation of amino acids and carboxylic acids via proton irradiation of a mixture of carbon dioxide, methane, nitrogen, and water in various mixing ratios. These experiments show the detection of amino acids after acid hydrolysis when 0.5% (v/v) of initial methane was introduced to the gas mixture. In the set of experiments with spark discharges (simulation of lightning flashes) performed for the same gas mixture, we found that at least 15% methane was required to detect the formation of amino acids, and no amino acids were detected in experiments via UV irradiation, even when 50% methane was used. Carboxylic acids were formed in non-reducing gas mixtures (0% methane) by proton irradiation and spark discharges. Hence, we suggest that GCRs and SEP events from the young Sun represent the most effective energy sources for the prebiotic formation of biologically important organic compounds from weakly reducing atmospheres. Since the energy flux of space weather, which generated frequent SEPs from the young Sun in the first 600 million years after the birth of the solar system, was expected to be much greater than that of GCRs, we conclude that SEP-driven energetic protons are the most promising energy sources for the prebiotic production of bioorganic compounds in the atmosphere of the Hadean Earth.

Kensei Kobayashi↗

Life Cycle Assessment and Design of LignoBlock: A Lignin Bound Block on the Path Towards a Green Transition of the Construction Industry

Lignin-based biopolymer-bound soil composites (BSCs) are a new class of sustainable construction materials that utilize a bio-based biopolymer — lignin — as a binder. Prior use of lignin suggests that lignin is a promising candidate for the development of bio-based construction materials. Inspired by these applications, lignin-based BSCs were developed using lignoboost lignin, lignoforce lignin, alkali lignin, and hydrolysis lignin. Uni-axial compressive testing of lignin-based BSC shows that the compressive strength for these BSCs range from 1.6–8.1 MPa, which makes them appropriate for low compressive strength construction applications. We performed a life cycle assessment (LCA) of lignin-based BSC, with the functional unit being a CMU-sized block ( V =6423 cm -3 ). The major advantage of BSC lies in the elimination of ordinary portland cement, which is common to many construction materials, including many forms of concrete. Furthermore, the use of lignin in lignin-based BSC results in carbon sequestration (lignin ≈ 60 wt% carbon), potentially making construction materials made from lignin-based BSC carbon negative. Additionally, a design guide for estimating the life cycle carbon footprint of lignin-based BSC for a required compressive strength was developed. By utilizing the results from material tests and the LCA, designers are now able to use lignin effectively in construction applications, as they can now design lignin-based BSC for a target compressive strength with a full understanding of the life cycle carbon footprint implications.

Lignin↗

Evaluation of Hydrolytic Degradation of Poly(lactic acid) (PLA) Matrices in Compression Molded Flax/PLA Composites

Poly(lactic acid) (PLA) is a bio-based plastic that is an attractive alternative to its petroleum-based counterparts because of its high strength and ease of thermal processing. In an effort to reduce the carbon footprint of fossil-fuel based polymer matrix composites, PLA along with naturally-occurring fibers are being explored to produce entirely bio-based replacements. Challenges in producing these composites occur due to the water affinity of the natural fibers and the susceptibility of the PLA to hydrolytic degradation. Hydrolysis of PLA occurs at elevated processing temperatures and can further be accelerated by the presence of water contained in the natural fibers. This talk will discuss the challenges and considerations associated with processing PLA in the presence of water-absorbing flax fibers to produce composites via compression molding. The thermal, physical, and mechanical properties of PLA/flax composites will be characterized at various processing times in an effort to identify optimal manufacturing conditions.

Natural Materials↗

Project Methods to Enhance Wellbore Cement Integrity with Microbially-Induced Calcite Precipitation (MICP) (Final Scientific/Technical Report)

The goal of this project was to develop improved methods for sealing compromised wellbore cement in leaking oil and gas wells, thereby reducing the risk of unwanted upward fluid migration. Novel methods for improving wellbore integrity, such as microbially induced calcite precipitation (MICP), can reduce leakage potential, improve the safety of fossil fuel extraction, improve the public perception of hydraulic fracturing, and promote environmentally-prudent unconventional oil and gas development. Microbes, with the urease enzyme, can catalyze the chemical reaction of urea hydrolysis to induce the precipitation of calcium carbonate which can be used as a cementitious material to seal leakage pathways. In this project, methods to promote robust bio-composite cementitious materials were designed and tested in the laboratory. Scale-up of those methods were tested in meso-scale reactor systems and in field applications. In this report, in Section One, we describe laboratory efforts to develop injection strategies to promote precipitation in wellbore analogs and determine the strength of the bio-composite cements as compared to fine cement. In Section Two, we describe the efforts to scale up the work and study the use of materials that can be used in field application, for example exploring the use of calcium chloride ice melt or urea fertilizer as source chemicals. In Section Three, the three field trials (methods and results) performed as part of the project are described and summarized. At the end of the report is a comprehensive summary and conclusion section which highlights the key findings of the project. The work performed during this project significantly advanced the technology readiness level (TRL) of the MICP wellbore sealing strategy.

02 PETROLEUM↗

Methods to Enhance Wellbore Cement Integrity with Microbially-Induced Calcite Precipitation (MICP) (Final Scientific/ Technical Report)

The goal of this project was to develop improved methods for sealing compromised wellbore cement in leaking oil and gas wells, thereby reducing the risk of unwanted upward fluid migration. Novel methods for improving wellbore integrity, such as microbially induced calcite precipitation (MICP), can reduce leakage potential, improve the safety of fossil fuel extraction, improve the public perception of hydraulic fracturing, and promote environmentally-prudent unconventional oil and gas development. Microbes, with the urease enzyme, can catalyze the chemical reaction of urea hydrolysis to induce the precipitation of calcium carbonate which can be used as a cementitious material to seal leakage pathways. In this project, methods to promote robust bio-composite cementitious materials were designed and tested in the laboratory. Scale-up of those methods were tested in meso-scale reactor systems and in field applications. In this report, in Section One, we describe laboratory efforts to develop injection strategies to promote precipitation in wellbore analogs and determine the strength of the bio-composite cements as compared to fine cement. In Section Two, we describe the efforts to scale up the work and study the use of materials that can be used in field application, for example exploring the use of calcium chloride ice melt or urea fertilizer as source chemicals. In Section Three, the three field trials (methods and results) performed as part of the project are described and summarized. At the end of the report is a comprehensive summary and conclusion section which highlights the key findings of the project. The work performed during this project significantly advanced the technology readiness level (TRL) of the MICP wellbore sealing strategy.

03 NATURAL GAS↗

BETO 2021 Peer Review - Biochemical Process Modeling and Simulation (BPMS)

The Biochemical Process Modeling and Simulation project aims to reduce the cost and time of research by applying theory, modeling, and simulation to the most relevant bottlenecks in the biochemical process. We use molecular modeling, quantum mechanics, metabolic modeling, fluid dynamics, and reaction-diffusion methods in close collaboration with pretreatment, hydrolysis, upgrading, and TEA. The project's outcomes are increased yields and efficiency of the biochemical process, added value to products, and reduced price of fuels by specifically targeting catalytic efficiency, reactor design, enzyme efficiency, and microbial design.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Atomic Layer Deposition for Materials-Based H2 Storage: Opportunities and Limitations

The transportation demands in our growing hydrogen (H2) economy requires robust storage systems. The current commercially implemented technology in fuel cell cars relies on the well-established technology of hydrogen gas compressed to 350-700 bar, depending on the application. The compressed gas tanks in use today are bulky and cost intensive. To address this challenge, material-based storage is one of the long-term alternatives considered and constitutes the focus of this talk. Material-based storage is broadly defined as hydrogen bound to solid materials, with its binding strength varying from physisorption to porous materials, such as zeolites and metal organic frameworks, to chemisorption in (complex) metal hydrides. The ultimate targets set by the U.S. Department of Energy for this technology include a system gravimetric capacity of 6.5 wt% and volumetric capacity of 40 g/L at 100 bar, operating temperatures ranging between -40 C and +40 C and adsorption/desorption timescales of < 5 min. Storage in the form of physisorbed or chemisorbed hydrogen has guided the materials research, which metal- organic framework and (complex) metal hydrides being the most promising materials classes. A variety of these materials have met one or more of the targets, but it has remained elusive for a single material system to meet all these stringent requirements. Nano-encapsulation and low-concentration chemical additives have previously been employed separately to overcome such challenges. Functionalization via atomic layer deposition (ALD), however, offers unique characteristics that make it suitable for both, nano-encapsulation and "doping" with low-concentration additives. This deposition technique has sub-monolayer thickness control, is highly conformal in high-surface area materials and is self-limiting, i.e., once the gas-phase precursor reacts with the available surface sites, the surface reactions stop. In this presentation, we will showcase examples where ALD, more generally vapor-phase functionalization, on (complex) metal hydrides and organic frameworks has improved the material properties for H2 storage. In our first study, Al2O3 was deposited on magnesium borohydride, Mg(BH4)2, at room temperature using trimethylaluminum (TMA) and water. From our findings, encouraging initial results were obtained: the H2 desorption temperature was lowered by 60-120 degrees C, the desorbed gravimetric H2 capacity at temperatures < 250 degrees C was doubled, and the desorption kinetics increased by a factor of ~6 compared to uncoated Mg(BH4)2. However, hydrolysis reactions caused by residual surface -OH groups from the ALD water-pulse degraded the sample substantially. Through this study, the use of TMA was observed to be highly reactive with the Mg(BH4)2 surface species, leading to the strategy of exposing the sample only to TMA. The relative mole fraction of the vapor-phase additive can be precisely controlled with the number of TMA pulses and pulse duration. By tuning these parameters, we show in our second study that 10 pulses of TMA at ambient conditions were able to decrease the H2 desorption temperature by ~100 degrees C while retaining <95 % of its H2 capacity. We applied this approach with other additives such as BBr3, TiCl4 and tetrahydrofuran, and demonstrate that this unique approach opens the door to a new class of molecular additives and catalysts which cannot easily be introduced with conventional mechano-chemical or solvent-based techniques for (complex) metal-hydrides. In the case of metal organic frameworks, ALD is a promising technique to functionalize the pores with metal atoms or functional groups able to tune the gas selectivity and binding energy, for which ~15 kJ/mol has been established as the optimal value for H2 storage in sorbent materials. Vapor-phase techniques such as ALD have numerous benefits over other functionalization tools for H2 storage materials opening innumerable opportunities to the field. To exploit these opportunities, the current limitations on room temperature and water-less ALD processes needs to be overcome which will greatly expand the possibilities of encapsulation and incorporation of additives for organic frameworks and (complex) metal hydrides.

atomic layer deposition↗

Single-Use Destructive Assay for Uranium Hexafluoride Sampling

Sampling uranium hexafluoride (UF6) for the determination of enrichments by destructive analysis (DA) is a critical component in the International Atomic Energy Agency’s layered safeguards approach for uranium processing facilities. Typically, gram-quantity UF6 samples are collected during inspections and stored under tag-and-seal until transportation to an off-site analytical laboratory. The shipping times can be long, and evolving restrictions on radioactive/corrosive materials shipments may increasingly limit the IAEA’s ability to transport UF6 samples easily. Pacific Northwest National Laboratory has developed a low-cost UF6 sampling technology called Single-Use Destructive Assay (SUDA) that addresses these challenges, as well as provides DA sample geometries that can be tailored for different analytical methods, including potential on-site analyses. The SUDA samplers, along with a unique holder, are designed for direct attachment to existing taps at uranium processing facilities, allowing gaseous UF6 to come into direct contact with a zeolite film. The SUDA technology features the ability to capture uranium in a more easily shipped and handled form as the solid, more stable, and relatively less hazardous hydrated uranyl fluoride (UO2F2•nH2O), which is formed through the controlled hydrolysis of UF6. We have recently simulated uranium collection under enrichment plant sampling conditions to further improve our understanding of SUDA sampling. Presented here is our recent work on measuring the relationship between sampling conditions and uranium collection, which includes control of the uranium-mass-to-zeolite ratio and assessing variable UF6 gas and sampling parameters that can affect collection using the SUDA sampler.

Pope, Timothy R.↗

Polybenzimidazole (PBI) membranes for redox flow batteries

Disclosed are redox flow battery membranes, redox flow batteries incorporating the membranes, and methods of forming the membranes. The membranes include a polybenzimidazole gel membrane that is capable of incorporating a high liquid content without loss of structure that is formed according to a process that includes in situ hydrolysis of a polyphosphoric acid solvent. The membranes are imbibed with a redox flow battery supporting electrolyte such as sulfuric acid and can operate at very high ionic conductivities of about 100 mS/cm or greater. Redox flow batteries incorporating the PBI-based membranes can operate at high current densities of about 100 mA/cm2 or greater.

Benicewicz, Brian C.↗

Alkaline Oxidation of Lignin Using Reversibly-Soluble Bases

Production of oxidized aromatic monomers from lignin has been an intriguing process for decades, but widespread implementation has been inhibited by the high hydroxide:lignin ratios required for significant aldehyde yields. The high hydroxide loading in most scenarios renders the process uneconomical even for high-value products such as vanillin. In this work, we explore alkaline oxidation of a lignin-rich enzymatic hydrolysis residue isolated from corn stover, using alkaline earth metal hydroxides, such as Sr(OH)2 and Ba(OH)2 as base promoters. These materials are soluble at reaction temperature, but mostly insoluble at room temperature, allowing recovery and reuse by simple filtration. We show that monomer yields and profiles using these bases is similar to that obtained using NaOH as base, and that Sr(OH)2 can be recovered in yields above 90%. Preliminary TEA and LCA suggest that replacing NaOH with Sr(OH)2 can decrease monomer production costs by 40% and decrease global warming potential in lignin depolymerization by 30%, enabling a more economical and sustainable process.

BIOMASS FUELS↗

Alkaline Oxidation of Lignin Using Reversibly-Soluble Bases

Production of oxidized aromatic monomers from lignin has been an intriguing process for decades, but widespread implementation has been inhibited by the high hydroxide:lignin ratios required for significant aldehyde yields. The high hydroxide loading in most scenarios renders the process uneconomical even for high-value products such as vanillin. In this work, we explore alkaline oxidation of a lignin-rich enzymatic hydrolysis residue isolated from corn stover, using alkaline earth metal hydroxides, such as Sr(OH)2 and Ba(OH)2 as base promoters. These materials are soluble at reaction temperature, but mostly insoluble at room temperature, allowing recovery and reuse by simple filtration. We show that monomer yields and profiles using these bases is similar to that obtained using NaOH as base, and that Sr(OH)2 can be recovered in yields above 90%. Preliminary TEA and LCA suggest that replacing NaOH with Sr(OH)2 can decrease monomer production costs by 40% and decrease global warming potential in lignin depolymerization by 30%, enabling a more economical and sustainable process.

alkaline oxidation↗

Virtual Engineering of Low-Temperature Conversion

In this work, we present the development of an overarching software framework and supporting multiphysics models to simulate the end-to-end process of biomass conversion. This virtual engineering (VE) software is designed with the goal of accelerating research and development and reducing risk for market-relevant biomass conversion processes. We currently support multiple models, computing paradigms, and fidelities representing the steps of feedstock pretreatment, enzymatic hydrolysis, and bioconversion. Although this VE approach was developed to support a biomass workflow, we have designed each component in a way that allows us to easily support new domains, unit models, and feedstocks. We begin by presenting the user-facing aspects of the VE software and highlight how simulated elements are defined and linked by VE functions. We then present an overview of the high-fidelity computational fluid dynamics (CFD) models developed to support our target domain before segueing into our efforts to develop accurate and fast surrogate models, capturing the salient outcomes from the CFD simulations in a significantly less computationally demanding manner. We then present how VE calculations interface with a commercial techno-economic analysis software, Aspen Plus. We conclude by presenting VE case studies that leverage these methods and discuss how our methods can be extended to support a wide variety of accelerated biofuel commercialization pathways in the future.

biofuel↗

2.3.4.104 - Lignin Conversion to Sustainable Aviation Fuel Blendstocks

The Lignin Conversion to Sustainable Aviation Fuel Blendstocks (LigSAF) project focuses on the conversion of lignin-rich streams to deoxygenated aromatic and cycloalkane blendstocks in the jet fuel range. This work is done in close collaboration with the BETO-funded Lignin-First Biorefinery Development project and industrial scale-up partners, and the work is closely guided by analysis to develop cost-effective and sustainable routes to produce lignin-based SAF blendstocks. To date, we have demonstrated the continuous catalytic conversion of a lignin oil from poplar to deoxygenated aromatic products at -85% C-mol yield. This hydrodeoxygenation process uses a stable, earth-abundant catalyst and requires no solvent. We have also established a baseline process model and associated techno-economic analysis and life cycle assessment that together demonstrate the potential to achieve cost parity with fossil carbon-based jet fuel at -70% reduction in greenhouse gas emissions. Current work is focused on expanding the slate of feedstocks for hydrodeoxygenation to include lignin oils from softwoods, agricultural residues, and grasses as well as from hydrolysis lignin substrates from biochemical conversion and pulp-and-paper processes. We are also undertaking catalyst development efforts to tune the reaction selectivity from aromatic compounds to cycloalkanes. Lastly, we are investigating reaction engineering strategies to slurry solids for hydrodeoxygenation reactions.

aromatics↗

Improving Volatile Fatty Acid Productivity of Anaerobic Digestion

Typical anaerobic digestion (AD) focusses on complete conversion of waste to biogas (primarily carbon dioxide and methane). However, the intermediate metabolites of the AD process, which includes short- and long-chain volatile fatty acids (VFAs), that could serve as the precursors for useful industrial applications are typically ignored. The goal of this project is to eliminate production of biogas while enhancing the production of the intermediate VFAs. Using a mixed microbial consortium (from rumen sources and waste-water sludge), we have determined the optimal carbon loading (chemical oxygen demand, "COD") and optimal pH, that results in high VFA concentrations from food waste. The best VFA yields were obtained using 15 g COD/L and a pH of 9.0 for this substrate. pH 9 produced over 200% higher VFA titers than the controlled conditions (i.e., ph 7.0) after 35 d of digestion, in comparison to pH 5 that showed - 88% higher titers than the control digestion. As expected, the cumulative biogas production was highest in the pH 7.0 condition, in comparison to pH 5.0 or pH 9.0. We further observed that removal of VFAs using solid-liquid separation technique reduce the inhibitory effects of VFAs, thereby leading to overall improvement in conversion efficiency. 16s rRNA analysis is being carried out to explain and identify the biocatalysts that enable VFA production in these AD cultures. Additional efforts to improve VFA yields via increasing the total solid content, temperature optimizations, VFA removal via electrodialysis, and improving hydrolysis via microaeration will be presented.

anaerobic digestion↗