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At least 649 records · Page 36

Voltage cycling process for the electroconversion of biomass-derived polyols

Electrification of chemical reactions is crucial to fundamentally transform our society that is still heavily dependent on fossil resources and unsustainable practices. In addition, electrochemistry-based approaches offer a unique way of catalyzing reactions by the fast and continuous alteration of applied potentials, unlike traditional thermal processes. In this work, we show how the continuous cyclic application of electrode potential allows Pt nanoparticles to electrooxidize biomass-derived polyols with turnover frequency improved by orders of magnitude compared with the usual rates at fixed potential conditions. Moreover, secondary alcohol oxidation is enhanced, with a ketoses-to-aldoses ratio increased up to sixfold. The idea has been translated into the construction of a symmetric single-compartment system in a two-electrode configuration. Its operation via voltage cycling demonstrates high-rate sorbitol electrolysis with the formation of H 2 as a desired coproduct at operating voltages below 1.4 V. The devised method presents a potential approach to using renewable electricity to drive chemical processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fast estimation of reaction rates in spherical and non-spherical porous catalysts

Here we present a methodology for modeling multi-step reaction rates in porous catalyst particles for use in CFD-DEM and two fluid models. Single-step effectiveness factors based on a Thiele modulus, while useful, cannot accurately capture the cascading reaction systems common in high temperature vapor-phase chemical reactors like fluidized catalytic cracking units and catalytic biomass fast pyrolysis systems. Instead, multi-step effectiveness vectors derived from steady-state solutions to the governing reaction-diffusion equations are needed. Solutions for various catalyst shapes are presented, including spheres, cylinders, and prisms. Computational challenges inherent in repeated evaluation of reaction rates with diffusion limitations are discussed, and an efficient implementation based on pre-computed lookup tables is proposed and demonstrated on a simulation of a fluidized bed reactor. Open-source code is provided for the compilation of reaction rate tables for use in ODE, DEM, and two-fluid models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

One-pot ethanol production under optimized pretreatment conditions using agave bagasse at high solids loading with low-cost biocompatible protic ionic liquid

Agave bagasse (AG) is a potential bioenergy feedstock due to its high biomass productivity, even in semiarid lands. In particular, ionic liquid (IL) pretreatment using aprotic ILs (AILs) has greatly reduced AG recalcitrance towards downstream processing by lowering lignin content and achieving high sugar yields. However, AIL's low biocompatibility towards enzymes and bacteria combined with the high initial cost has limited further development of this technology. In a wash-free one-pot (OP) ethanol conversion process, the evaluation of AG pretreatment with a biocompatible low-cost protic IL (PIL), 2-hydroxyethylammonium acetate ([2-HEA][OAc]) was achieved, where PIL pretreatment was followed by enzymatic saccharification, then ethanol fermentation in a single vessel. The pretreatment conditions were optimized using a central composite design to enable high sugar conversion at low PIL content. Under optimized pretreatment conditions (160 °C, 60% IL loading and 1.5 h), a yield of 132 kg of ethanol per Ton of untreated biomass was estimated using high solids loading (30% solids loading) under a PIL-OP scheme. High lignin removal (>50%), a decreased cellulose crystallinity, and high glucan conversion (>85%) were achieved with PIL-pretreated AG comparable to yields obtained in an AIL-AG pretreated sample using 1-ethyl-3-methyl-imidazolium acetate ([C 2 C 1 Im][OAc]). Here, these results using [2-HEA][OAc] demonstrate the potential of AG in an OP scheme with improved total ethanol yields paving the way towards a more feasible IL-based biorefinery.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Separation, recovery and upgrading of biomass derived 2,3-butanediol

The invention relates to a two-way approach to isolate, recover and upgrade 2,3-Butanediol (2,3-BDO) from fermentation broth. A complete separation and recovery process for 2,3-BDO using acetalization and trans-acetalization sequence. Acetalization with butyraldehyde using heterogeneous catalysts, either Amberlyst-15® or Nafion NR50®, efficiently isolates 2,3-BDO as phase-separated protected dioxolane. The approach provides significant process advantages with easy product recovery and high recyclability of the catalyst. Trans-acetalization of dioxolane with methanol (methanolysis) followed by distillation of acetal, yielded very high purity 2,3-BDO with about 90% isolated yield. Alternatively, dioxolane is used in a process direct to methyl ethyl ketone (MEK) as a BDO synthon allowing for recovery of the aldehyde.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermophilic biocatalysts for one-step conversion of citrus waste into lactic acid

Agri-food residues offer significant potential as a raw material for the production of L-lactic acid through microbial fermentation. Weizmannia coagulans, previously known as Bacillus coagulans, is a spore-forming, lactic acid-producing, gram-positive, with known probiotic and prebiotic properties. This study aimed to evaluate the feasibility of utilizing untreated citrus waste as a sustainable feedstock for the production of L-lactic acid in a one-step process, by using the strain W. coagulans MA-13. By employing a thermophilic enzymatic cocktail (Cellic CTec2) in conjunction with the hydrolytic capabilities of MA-13, biomass degradation was enhanced by up to 62%. Moreover, batch and fed-batch fermentation experiments demonstrated the complete fermentation of glucose into L-lactic acid, achieving a concentration of up to 44.8 g/L. These results point to MA-13 as a microbial cell factory for one-step production of L-lactic acid, by combining cost-effective saccharification with MA-13 fermentative performance, on agri-food wastes. Moreover, the potential of this approach for sustainable valorization of agricultural waste streams is successfully proven.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sticky roots--implications of widespread, cryptic, viral infection of plants in natural and managed ecosystems for soil carbon processing in the rhizosphere

Plants strongly influence soil properties through rhizodeposition, in which exudates diffuse from roots, additional secretions are actively released, and root cells are sloughed into the soil. This contribution by plants of carbon compounds belowground is at the core of soil health, water holding capacity, and the soil carbon storage that pulls carbon dioxide out of the atmosphere. Once in soil, organic matter can bind with minerals such as iron hydroxides, where it can be protected from microbial attack for millenia, preserving very large terrestrial soil carbon pools. However, those same compounds contributed by roots to soil may also destabilize the long-term protective associations of SOM with minerals, making that soil organic matter (SOM) more vulnerable to microbial attack and decomposition. Plant roots thus influence both the buildup and breakdown of soil carbon pools. DOE’s E3SM Land Model (ELM) includes a representation of soil carbon storage on minerals, but the potential vulnerability of SOM–mineral associations to effects of rhizodeposition is not yet represented in ELM. To begin testing for this effect of rhizodeposition on soil carbon storage and decomposition, we worked to develop a novel approach during this TES Exploratory project DE-SC0019142 – we harnessed the power of plant viral infection. We examined whether plant virus infection can serve as a tool to intensify rhizodeposition at the root surface, and therefore possibly intensify mobilization of SOM from minerals making it visible to our analytical techniques. Viral infection is widespread in terrestrial ecosystems; 25-70% of plants have virus infection, yet the influence of such infection on root traits and terrestrial soil carbon dynamics remains largely unexplored. We used two plant hosts: the annual Avena sativa (oats) and the genetically tractable, model grass Brachypodium distachyon. These grasses were infected with the broad host range virus Barley Yellow Dwarf Virus (BYDV) via aphids (Rhopalosiphum padi). BYDV infects at least 150 grass species in agricultural and natural ecosystems, and in previous experiments, oats infected with BYDV had roots that were very sticky to the touch, strongly suggesting that infection altered rhizodeposition. We developed this new experimental approach mostly in a one virus (Barley Yellow Dwarf Virus)–one plant (Avena sativa) system. (Several effects of infection in a Brachypodium-BYDV system were similar in nature to effects on Avena sativa, but were more variable.) In the BYDV-Avena system, we developed protocols for consistently infecting target plants (and avoiding infection of control plants) using aphid caging on leaves. We measured that infected plants exhibited reduced photosynthesis, plant (including root) biomass, and root:shoot ratio, as well as simplified root system architecture. We established procedures for sampling the organic compounds carried specifically in phloem (vascular tissue) of leaves and roots, using aphid stylectomy. We used FTICR-MS, Orbitrap GC-MS, and LC-MS/MS to analyze organic compounds in phloem, liquid around roots of plants grown hydroponically, and pore water around roots in soil, and found differences in the compounds in solution bathing roots when infected and uninfected plants were grown hydroponically. Finally, we synthesized isotopically-labeled mineral–organic matter (MAOM) associations in the lab and developed assays using them in solution and in soil. Assays quantified the extent and rate of mineralization of labeled MAOM that was mobilized by functionally distinct rhizodeposits and then attacked by microbes. Two mechanisms for MAOM mobilization emerged, with distinct dynamics. During “direct” mobilization, rhizodeposits such as the strong ligand oxalic acid could drive rapid dissolution of minerals, mobilizing MAOM. During “indirect” mobilization, rhizodeposits such as the simple sugar glucose did not attack minerals directly but instead intensified microbial activity, which led to mobilization via changes in e.g. pH, Eh, and microbial metabolite production (Li et al. 2021). Mechanistic understanding derived from these data and our ongoing experiments using these techniques will inform future development of ELM. Plant roots not only contribute newly fixed organic compounds to soils, but also root activities can drive mineralization of the carbon and nutrients mobilized off minerals via “indirect” or “direct” mechanisms. Using viral infection as a new tool, ongoing combined experimentation and modeling will explore the strength and larger-scale significance of the cascade of processes from rhizodeposition to MAOM mobilization for soil carbon storage and nutrient cycling in terrestrial ecosystems. And if viral infection leads quite generally to “sticky roots”, our perception of the potential importance of prevalent virus infection in terrestrial landscapes will be transformed.

54 ENVIRONMENTAL SCIENCES↗

Application of an Erosion Wear Model to Predict Wear of Hammer Milling Components

A workable analytical erosion model that relates critical hammermill process parameters (hammermill geometry and rotational speed) to critical material attributes of inorganic mineral species in feedstock (density, size, and aspect ratio) and substrate (hardness, toughness, and fatigue ductility) was applied to model wear (more specifically, change in the shape of hammers) in hammer milling operations. Results of the model were compared to experimental observations of the shape of hammers used in the INL Stage 1 Vermeer hammermill. Results showed good agreement between predicted and measured shape of the hammer, and that a quality-by-design (QbD) approach can be developed to predict component reliability based on scientific engineering principles in lieu of trial-and-error approaches.

36 MATERIALS SCIENCE↗

Bioenabled Platform to Access Polyamides with Built-In Target Properties

The diversification of platform chemicals is key to today’s petroleum industry. Likewise, the flourishing of tomorrow’s biorefineries will rely on molecules with next-generation properties from biomass. Herein, we explore this opportunity with a novel approach to monomers with custom property enhancements. Cyclic diacids with alkyl and aromatic decorations were synthesized from muconic acid by Diels-Alder cycloaddition and copolymerized with hexamethylenediamine and adipic acid to yield polyamides with built-in hydrophobicity and flame retardancy. Testing shows a 70% reduction in water uptake and doubling of char production while largely retaining other key properties of the parent Nylon-6,6. In conclusion, the present approach can be generalized to access a wide range of performance-advantaged polyamides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrocatalytic synthesis of heterocycles from biomass-derived furfuryl alcohols

It is very attractive yet underexplored to synthesize heterocyclic moieties pertaining to biologically active molecules from biomass-based starting compounds. Herein, we report an electrocatalytic Achmatowicz reaction for the synthesis of hydropyranones from furfuryl alcohols, which can be readily produced from biomass-derived and industrially available furfural. Taking advantage of photo-induced polymerization of a bipyridyl ligand, we demonstrate the facile preparation of a heterogenized nickel electrocatalyst, which effectively drives the Achmatowicz reaction electrochemically. A suite of characterization techniques and density functional theory computations were performed to aid the understanding of the reaction mechanism. It is rationalized that the unsaturated coordination sphere of nickel sites in our electrocatalyst plays an important role at low applied potential, not only allowing the intimate interaction between the nickel center and furfuryl alcohol but also enabling the transfer of hydroxide from nickel to the bound furfuryl alcohol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Determination of Carbon, Hydrogen, Nitrogen, and Oxygen in Bio-Oils: Laboratory Analytical Procedure (LAP)

The determination of total carbon, hydrogen, and nitrogen in bio-oils is important as these values can be used to track the carbon balance of production processes as well as calculate total oxygen content by difference. Oxygen content of bio-oils is a key metric for production and upgrading strategies as these are typically aimed at reducing oxygen. Oxygenates in bio-oils contribute to poor hydrocarbon miscibility, high acidity, high viscosity, and poor stability. Upgrading of bio-oils via deoxygenation produces hydrocarbons which can be used to generate feedstocks for renewable fuels and chemicals. In this Laboratory Analytical Procedure (LAP), combustion-based ultimate analysis is used to determine the weight percent (wt%) of C, H, and N in bio-oils and upgraded products. Ultimate analysis uses high temperatures and a pure oxygen environment to completely combust organic samples to carbon dioxide (CO 2 ), water (H 2 O), and nitrogen oxides (NO x ). In this procedure the amount of C and H in the sample are quantified by measuring resultant CO 2 and H 2 O with Fourier-transform infrared spectroscopy (FTIR). For N, NO x is reduced to nitrogen (N 2 ) which is measured with a thermal conductivity detector (TCD), providing total N content.

09 BIOMASS FUELS↗

Evaluation of the energy balance of chemical looping combustion of solid fuels using CuO-based oxygen carriers

Chemical looping combustion (CLC) can inherently capture the CO2 generated during thermal energy production. When using CuO-based oxygen carriers, the reactions in both the fuel reactor (FR) and air reactor (AR) are exothermic, facilitating autothermal operation. To prevent the oxygen carrier from becoming agglomerated while ensuring a sufficient oxygen release rate, it is necessary to predict the FR temperature and remove an appropriate amount of heat from the AR when burning high-rank fuels. Here in this work, the energy balance of a CuO-based CLC system firing various solid fuels (biomass, coal, and petroleum coke) was investigated by establishing a thermodynamic model using FactSage. The energy distribution characteristics of the FR were quantified based on a virtual five-step thermodynamic sequence. The effects of fuel properties, oxygen carrier properties, and operating conditions on the energy balance were evaluated systematically. The results indicate that the temperature difference between the FR and AR is not very sensitive to the heating value of the fuel, while the CuO loading of the oxygen carrier, the heat capacity of the support material, and the flow rate of the fluidizing gas have significant impact. The insights obtained in this work will help improve the design and heat management of CLC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bridging Scales in Bioenergy and Catalysis: A Review of Mesoscale Modeling Applications, Methods, and Future Directions

Between the molecular and reactor scales, which are familiar to the chemical engineering community, lies an intermediate regime, here termed the “mesoscale,” where transport phenomena and reaction kinetics compete on similar time scales. Bioenergy and catalytic processes offer particularly important examples of mesoscale phenomena owing to their multiphase nature and the complex, highly variable porosity characteristic of biomass and many structured catalysts. In this review, we overview applications and methods central to mesoscale modeling as they apply to reaction engineering of biomass conversion and catalytic processing. A brief historical perspective is offered to put recent advances in context. Applications of mesoscale modeling are described, and several specific examples from biomass pyrolysis and catalytic upgrading of bioderived intermediates are highlighted. Methods including reduced order modeling, finite element and finite volume approaches, geometry construction and import, and visualization of simulation results are described; in each category, recent advances, current limitations, and areas for future development are presented. Owing to improved access to high-performance computational resources, advances in algorithm development, and sustained interest in reaction engineering to sustainably meet societal needs, we conclude that a significant upsurge in mesoscale modeling capabilities is on the horizon that will accelerate design, deployment, and optimization of new bioenergy and catalytic technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Biocompatible organosolv fractionation via a novel alkaline lignin-first strategy towards lignocellulose valorization

Simultaneous valorization of both carbohydrate and lignin fractions in lignocellulose remains a great challenge. Herein, a novel lignin-first strategy using triethylene glycol (TEG) under alkaline conditions for effective biomass fractionation producing highly digestible carbohydrates and reactive lignin was developed. Delignification was over 80% and fermentable sugar yields were close to 90% after pretreatment at 90°C. The biocompatibility of TEG allowed direct enzymatic hydrolysis of the solid residue without washing, thus minimizing wastewater generation. Furthermore, the obtained lignin (TEGL) had an uncondensed structure with well-preserved β-O-4 linkage, leading to near-equal aromatic monomer yields compared to cellulolytic enzyme lignin after catalytic-free pyrolysis, demonstrating high valorization potential. Finally, the proposed TEG solvent system is promising for a green and sustainable biorefinery process to achieve the complete utilization of lignocellulose.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Novel Approach to Modeling Biomass Pyrolysis in a Fluidized Bed Reactor

A novel approach to simulating biomass pyrolysis in a fluidized bed of mostly inert material is presented. The bed is assumed to be externally heated, although simulation of autothermal operation with partial oxidation of the products is a future objective. Combining pyrolysis reaction kinetics developed by the CRECK Modeling Group and a previously published component properties model, material and energy balances are closed by tracking the residence time of biomass particles without regard for their exact spatial distribution. The model is used to simulate a pilot-scale fluidized bed pyrolysis process being developed at Iowa State University, and model predictions are compared with experimental results for red oak and corn stover feedstocks. The results are in general agreement, with the model typically predicting more noncondensable gas and less low-boiling liquid products. The differences are ascribed to the limitations of the kinetics model. This model provides a rigorous energy balance for fluidized bed pyrolysis processes that can be incorporated into commercial flowsheet models with the capacity for future addition of partial oxidation reactions and implementation of improved kinetics models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Neutron scattering maps the higher-order assembly of NADPH-dependent assimilatory sulfite reductase

Precursor molecules for biomass incorporation must be imported into cells and made available to the molecular machines that build the cell. Sulfur-containing macromolecules require that sulfur be in its S2- oxidation state before assimilation into amino acids, cofactors, and vitamins that are essential to organisms throughout the biosphere. In α-proteobacteria, NADPH-dependent assimilatory sulfite reductase (SiR) performs the final six-electron reduction of sulfur. SiR is a dodecameric oxidoreductase composed of an octameric flavoprotein reductase (SiRFP) and four hemoprotein metalloenzyme oxidases (SiRHPs). SiR performs the electron transfer reduction reaction to produce sulfide from sulfite through coordinated domain movements and subunit interactions without release of partially reduced intermediates. Efforts to understand the electron transfer mechanism responsible for SiR’s efficiency are confounded by structural heterogeneity arising from intrinsically disordered regions throughout its complex, including the flexible linker joining SiRFP’s flavin-binding domains. As a result, high-resolution structures of SiR dodecamer and its subcomplexes are unknown, leaving a gap in the fundamental understanding of how SiR performs this uniquely large-volume electron transfer reaction. In this work, we use deuterium labeling, in vitro reconstitution, analytical ultracentrifugation (AUC), small-angle neutron scattering (SANS), and neutron contrast variation (NCV) to observe the relative subunit positions within SiR’s higher-order assembly. AUC and SANS reveal SiR to be a flexible dodecamer and confirm the mismatched SiRFP and SiRHP subunit stoichiometry. NCV shows that the complex is asymmetric, with SiRHP on the periphery of the complex and the centers of mass between SiRFP and SiRHP components over 100 Å apart. SiRFP undergoes compaction upon assembly into SiR’s dodecamer and SiRHP adopts multiple positions in the complex. The resulting map of SiR’s higher-order structure supports a cis/trans mechanism for electron transfer between domains of reductase subunits as well as between tightly bound or transiently interacting reductase and oxidase subunits.

59 BASIC BIOLOGICAL SCIENCES↗

Self-Assembling Metabolon Enables the Cell Free Conversion of Glycerol to 1,3-Propanediol

Cell free biocatalysis is showing promise as a replacement or complement to conventional microbial biocatalysts due to the potential for achieving high yields, titers, and productivities. However, there exist several challenges that need to be addressed before its broader industrial adoption is achieved. New paradigms and innovative solutions are needed to overcome these challenges. In this study we demonstrate high levels of glycerol conversion to 1,3-propanediol using a self-assembling metabolic pathway leveraging the arraying strategy (protein scaffolds) used by thermophilic cellulolytic bacteria to assemble their biomass degrading enzymes. These synthetic metabolons were capable of producing 1,3-PDO at a yield more than 95% at lower glycerol concentration and close to 70% at higher concentrations at a higher productivity rate than the equivalent microbial strain. One of the benefits of our approach is the fact that no enzyme purification is required, and that the assembly of the complex is accomplished in vivo before immobilization, while product formation is conducted in vitro. We also report the recovery of enzymatic activity upon fusion enzymes binding to these protein scaffolds, which could have broader applications when assembling arrayed protein complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding the influence of solvents on the Pt-catalyzed hydrodeoxygenation of guaiacol

Bio-oil derived from fast pyrolysis of lignocellulosic biomass needs to be deoxygenated to become a substitute for petroleum fuels. Here, we study the hydrodeoxygenation mechanism of guaiacol, a bio-oil model compound derived from the lignin fraction of biomass, on Pt(1 1 1) terrace sites in the presence of water, diethyl ether, 1-butanol, and n-hexane as solvent. Using first-principles periodic density functional theory (DFT) calculations and mean-field microkinetic reactor modeling, a detailed reaction mechanism is investigated targeting various products such as catechol, phenol, anisole, benzene, cyclohexanone, and cyclohexanol. Solvent phase DFT outcomes are mostly similar to that of the vapor phase; however, microkinetic modeling results suggest that rate controlling species and transition states differ somewhat in the various reaction environments. Catechol was found to be the major aromatic product across all reaction environments. Over Pt(1 1 1), unsaturated monooxygenate production from catechol is unlikely.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Terrestrial Organism and Biogeochemistry Spatial Sampling Design for the National Ecological Observatory Network

The National Ecological Observatory Network (NEON) seeks to facilitate ecological prediction at a continental scale by measuring processes that drive change and responses at sites across the United States for thirty years. The spatial distribution of observations of terrestrial organisms and soil within NEON sites is determined according to a “design‐based” sample design that relies on the randomization of sampling locations. Development of the sample design was guided by high‐level NEON objectives and the multitude of data products that will be subjected to numerous analytical approaches to address the causes and consequences of ecological change. A requirement framework permeates the NEON design, ensuring traceability from each facet of the design to the high‐level requirements that make the NEON mission statement actionable. Requirements were developed for the terrestrial sample design to guide the key components of the design: Randomizing the sample locations ensures the unbiased collection of data, is appropriate for organisms and soil, and provides data suitable for a variety of analyses. Stratification increases efficiency and allows sampling to focus on those parts of the landscape measured by other NEON observation platforms. Attention to the sample size and spatial plot allocation ensures that data products will be sufficient to inform questions asked of the data and the NEON objectives. Establishing a framework with the capacity for re‐evaluate and design iteration allows for adaption to unexpected challenges and optimization of the sample design based on early data returns. The utility of the NEON sampling design is highlighted by its application across terrestrial systems. The data generated from this unique design will be used to quantify patterns in: the abundance and diversity of small mammals, breeding birds, insects, and soil microbes; vegetation structure, biomass, productivity, and diversity; and soil biogeochemistry.

National Ecological Observatory Network↗