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At least 253 records · Page 14

Combined Sugarcane Pretreatment for the Generation of Ethanol and Value-Added Products

In this work, we have tested individual and combination of applications of ozonolysis and liquid hot water (LHW) to pretreat sugarcane bagasse (SCB) for the removal of enzyme and/or microbial inhibitors and generation of potential value-added chemicals. A solid content with 80% cellulose and a liquid phase (liquor) rich in phenolic derived compounds (3 g . L −1 ) from lignin, sugars (>20 g . L −1 ), and other compounds, such as furfural and hydroxymethylfurfural (HMF), were generated. Maximal (59%) glucan conversion occurred in the presence of double-pretreated bagasse, which had 32–50% more glucan available than the samples that were individually LHW or ozone-pretreated, resulting in maximal ethanol production (92% after 42 h) from double-pretreated SCB enzyme hydrolyzate. In summary, this work showed that ozone reacts effectively with lignin without the use of any other chemical reagent, and LHW pretreatment, followed by a washing step, was effective in solubilizing and cleaning up the fiber enzyme and microbial inhibitory compounds with ozone being effective against phenolics. Moreover, the generated cellulose-rich substrate is readily fermentable. The acidic liquor fraction removed by sequential washings and containing mainly sugars and phenolic compounds may be evaluated for use in green chemistry bioconversions processes.

09 BIOMASS FUELS↗

Using Incremental Changes to Convert Lignocellulosic Feedstocks to Cellulosic Ethanol

One billion tons of biomass feedstocks have been identified for the production of renewable biofuels and biochemicals. This is one of the key carbon feedstocks to supply energy to the transportation sector for light duty, heavy duty and aviation fuels. Utilization of lignocellulosic feedstocks supports an improved energy security by reducing demand of petroleum imports, agricultural development, job creation, and reducing greenhouse gas emissions. To date, however, operational challenges have stymied the industrial production of large volumes of lignocellulosic-based fuels and chemicals. As a result, significant research investment has been led by the United States Department of Energy to understand and improve operational reliability at pioneer cellulosic biorefineries. In this perspective article lignocellulosic conversion technologies are described that have been adopted from the starch ethanol process. The developed process culminated in successful demonstration of 1,000-h integrated runs using several feedstocks, including switchgrass, energy sorghum, and two types of corn kernel fiber. This report highlights process development that solved several of the issues that plagued—and continue to plague—many in the cellulosic sugars space such as biomass feeding into equipment, high ash content, diversified co-product value, and others.

09 BIOMASS FUELS↗

Ethanol Electrooxidation at 1–2 nm AuPd Nanoparticles

We report a systematic study of the electrocatalytic properties and stability of a series of 1–2 nm Au, Pd, and AuPd alloy nanoparticles (NPs) for the ethanol oxidation reaction (EOR). Following EOR electrocatalysis, NP sizes and compositions were characterized using aberration-corrected scanning transmission electron microscopy (ac-STEM) and energy dispersive spectroscopy (EDS). Two main findings emerge from this study. First, alloyed AuPd NPs exhibit enhanced electrocatalytic EOR activity compared to either monometallic Au or Pd NPs. Specifically, NPs having a 3:1 ratio of Au:Pd exhibit an ~8-fold increase in peak current density compared to Pd NPs, with an onset potential shifted ~200 mV more to the negative compared to Au NPs. Second, the size and composition of AuPd alloy NPs do not (within experimental error) change following 1.0 or 2.0 h chronoamperometry experiments, while monometallic Au NPs increase in size from 2 to 5 nm under the same conditions. Notably, this report demonstrates the importance of post-catalytic ac-STEM/EDS characterization for fully evaluating NP activity and stability, especially for 1–2 nm NPs that may change in size or structure during electrocatalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Performance of Vehicle Fuel System Elastomers and Plastics with Test Fuels Representing Gasoline Blended with 10% Ethanol (E10) and 16% Isobutanol (iBu16)

The compatibilities of fuel system elastomers and plastics were evaluated for test fuels containing 16 vol.% isobutanol (iBu16) and 10 vol.% ethanol (E10). Elastomers included two fluorocarbons, four acrylonitrile butadiene rubbers (NBRs), and one type of fluorosilicone, neoprene, and epichlorohydrin/ethylene oxide. Plastic materials included four nylon grades, three polyamides, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), ethylene tetrafluoroethylene (ETFE), polyphenylene sulfide (PPS), high-density polyethylene (HDPE), polybutylene terephthalate (PBT), polyoxymethylene (POM), flexible polyvinylchloride (PVC), polyetherimide (PEI), polyetheretherketone (PEEK), and a phenol formaldehyde reinforced with glass fiber (GFPF). For each polymer material, the volume, mass, and hardness were measured before and after drying. Dynamic mechanical analysis (DMA) measurements were also performed on the dried specimens.For the elastomer materials the measured properties were similar for both fuels. The fluorocarbons and fluorosilicone swelled the least (~20%), while more moderate (20-45%) expansion occurred for the two NBR hose grades and (ECO). HNBR, neoprene, and silicone exhibited high swelling and softening, which likely precludes their use in many fuel systems. For the plastic materials, the observed swell was low; Nylon 11 swelled around 15%, but otherwise, their measured swell was <10%. Many of the plastics also showed sensitivity to alcohol type, as the E10 test fuel often imparted appreciably higher swell than iBu16. In general, the plastic materials showed good compatibility with the iBu16 and E10 test fuels. Here, the sole exception was the PVC material, which was structurally degraded from exposure to either fuel type. Compositional analysis showed high fuel retention in Nylon 12 and PVC. PVC also experienced a significant reduction in plasticizer compounds following exposure, which resulted in embrittlement and an increase in the glass-to-rubber transition temperature.

33 ADVANCED PROPULSION SYSTEMS↗

Highly Selective Photoelectroreduction of Carbon Dioxide to Ethanol over Graphene/Silicon Carbide Composites

Using sunlight to produce valuable chemicals and fuels from carbon dioxide (CO 2 ), i.e., artificial photosynthesis (AP) is a promising strategy to achieve solar energy storage and a negative carbon cycle. However, selective synthesis of C 2 compounds with a high CO 2 conversion rate remains challenging for current AP technologies. Here, we performed CO 2 photoelectroreduction over a graphene/silicon carbide (SiC) catalyst under simulated solar irradiation with ethanol (C 2 H 5 OH) selectivity of>99 % and a CO 2 conversion rate of up to 17.1 mmol g cat -1 h -1 with sustained performance. Experimental and theoretical investigations indicated an optimal interfacial layer to facilitate the transfer of photogenerated electrons from the SiC substrate to the few-layer graphene overlayer, which also favored an efficient CO 2 to C 2 H 5 OH conversion pathway.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Furfural Acetalization with Ethanol over Hierarchical vs. Conventional Beta Zeolites

A set of hierarchical Beta zeolites was synthesized using concentrated reaction mixtures and compared to conventional materials with a similar composition. The obtained zeolite catalysts were investigated in acetalization of furfural with ethanol at room temperature yielding a commercially valuable fuel additive (furfural diethyl acetal). The highest yield of the desired product (91 %) was achieved over a zeolite catalyst possessing developed mesoporosity (V meso 0.75 cm 3 /g) and a high external surface area (280 m 2 /g). Here, the concentration of accessible acid sites was found to be responsible for high catalytic performance of the tested zeolitic catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical and Morphological Structure of Transgenic Switchgrass Organosolv Lignin Extracted by Ethanol, Tetrahydrofuran, and $\mathcal{γ}$-Valerolactone Pretreatments

We report the recalcitrance of lignocellulosic biomass is a challenge in biological-based biorefinery systems due to the complex physicochemical structure of plant cell walls. Pretreatment and genetic modification are two approaches in biomass conversion that have succeeded in modifying the structure of lignocellulose to enable better enzymatic deconstruction. However, the structural differences among pretreatment-solubilized lignin isolated from switchgrass genotypes have not been extensively investigated. Here, three organosolv pretreatment systems-ethanol (EtOH), tetrahydrofuran (THF), and γ-valerolactone (GVL)-were used on wild-type (WT) and two transgenic switchgrasses. All organosolv pretreatments caused a significant reduction in the molecular mass of lignins; particularly, up to ~90% decrease was observed in EtOH-pretreated lignin compared to untreated lignin. The WT EtOH lignin also presented the smallest particle size among all WT lignins. THF pretreated transgenic lignins showed a higher molecular mass, β-O-4 linkages, and aliphatic hydroxyl content compared to EtOH and GVL pretreated lignin. The number of hydrogen bonds between lignin and the organic solvents calculated from the molecular dynamics simulations followed the same trend as the experimentally determined reduction in lignin molecular mass. The results revealed the structural changes of solubilized lignin isolated from wild-type and transgenic switchgrass after different organosolv pretreatments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Integrating catalytic fractionation and microbial funneling to produce 2-pyrone-4,6-dicarboxylic acid and ethanol

Replacing biorefinery designs that use stepwise fractionation, depolymerization, and conversion processes with designed tandem process steps can greatly reduce a biorefinery's operating costs and environmental impact. Reductive Catalytic Fractionation (RCF) is a highly efficient lignin-first approach that combines biomass fractionation and lignin depolymerization to generate a hydrogenolysis oil and pulp. The oil is composed of a complex mixture of phenolic monomers, dimers, and oligomers. Intergrating this chemical deconstruction process with microbial funneling of phenolics can simplify the product mixture and make high-value products. We applied RCF to poplar biomass in a biomass-to-bioproduct processing chain in which the phenolics were funneled to 2-pyrone-4,6-dicarboxylic acid (PDC) by an engineered strain of Novosphingobium aromaticivorans DSM12444. The pulp was enzymatically digested and the glucose and xylose was funneled to ethanol by an engineered strain of Saccharomyces cerevisiae GLBRCY945. By combining biomass fractionation and lignin depolymerization we removed a costly processing step that directly translated into a 29% reduction in the minimum selling price of PDC. This work combines experimentation with process modeling of an integrated biorefinery design to show how utilizing tandem process steps can significantly reduce operating expenses and environmental impact of upgrading lignocellulosic biomass to a portfolio of high value products.

Sener, Canan [Great Lakes Bioenergy Research Cente↗

Varied farm-level carbon intensities of corn feedstock help reduce corn ethanol greenhouse gas emissions

Abstract A reduction in the overall carbon intensity (CI) of a crop-based biofuel can be achieved by cutting down the CI of the biofuel’s feedstock, which in turn correlates significantly to agricultural management practices. Proposals are being made to incentivize low-carbon biofuel feedstocks under U.S. fuel regulatory programs to promote sustainable farming practices by individual farms. For such an incentive scheme to function properly, robust data collection and verification are needed at the farm level. This study presents our collaboration with U.S. private sector companies to collect and verify the corn production data necessary for feedstock-specific CI calculation at the farm level, through a carefully designed questionnaire, to demonstrate the practicality and feasibility of data collection at scale. We surveyed 71 farms that produced 0.2 million metric tons of corn grain in 2018 in a Midwestern U.S. state to obtain information on key parameters affecting corn ethanol feedstock CI, such as grain yields, fertilizer/chemical application rates, and agronomic practices. Feedstock-specific CI was calculated in the unit of grams (g) CO 2 equivalent (CO 2 e) of greenhouse gases per kilogram (kg) of corn produced. Results showed large CI variations—from 119 to 407 g CO 2 e kg −1 of corn—due to the farm-level inventory, while the production-weighted average CI for all surveyed farms was 210 g CO 2 e kg −1 , comparable to the national average CI of 204 g CO 2 e kg −1 . The nitrogen fertilizer type applied and rate were identified as key factors contributing most to CI variations at the farm level. The estimated N 2 O emissions from fertilizer and biomass nitrogen inputs to soil accounted for 51% of the overall farm-level CI and therefore need to be better monitored at farm level with high resolution. We concluded that this feedstock-specific, farm-level CI evaluation has the potential to be used to incentivize low-carbon feedstock for biofuel production.

54 ENVIRONMENTAL SCIENCES↗

The adjunctive effect for left pulmonary vein isolation of vein of Marshall ethanol infusion in persistent atrial fibrillation

Abstract Objective This study sought to assess the effect of ethanol infusion into the vein of Marshall (EIVOM) on the acute success of left pulmonary vein (LPV) isolation in persistent atrial fibrillation (PeAF). Methods and results A total of 313 patients with drug-resistant PeAF were enrolled (135 in Group 1 and 178 in Group 2). In Group 1, EIVOM was firstly performed, followed by radiofrequency ablation (RFA) including bilateral pulmonary vein isolation (PVI) and linear ablation at roofline, cavotricuspid isthmus, and mitral isthmus (MI). In Group 2, PVI and linear ablations were completed with RFA. First-pass isolation of the LPV was achieved in 119 (88.1%) and 132 (74.2%) patients in Groups 1 and 2, respectively (P = 0.002). The rate of acute pulmonary vein reconnection (PVR) was significantly lower in Group 1 (9.6% vs. 22.5%, P = 0.003). About half of acute PVR occurred in the carina with or without EIVOM. Conclusion EIVOM is effective in achieving a higher first-pass isolation and a lower acute PVR of LPV in PeAF.

Huang, Lihong (ORCID:000000027261316X)↗

Dynamics of resonant low-energy electron attachment to ethanol-producing hydroxide anions

Here, the dynamics of dissociative electron attachment to ethanol is experimentally investigated at the Feshbach resonance formed with incident electron energies near 9.5 eV. Highly differential laboratory-frame momentum distributions of OH – fragments are measured for a series of energies spanning the resonance width, using the velocity-map-imaging technique. The OH – kinetic-energy distribution indicates that the C-O breaking dissociation process could either be a three-body dissociation or a two-body dissociation with significant rovibrational excited fragments. The small, but significant, anisotropy in the OH – angular distribution provides signatures of the molecular symmetry of the associated resonant state under the axial recoil approximation, which assumes the dissociation is much faster than any rotation of the dissociation axis. Within these assumptions, the 9.5-eV Feshbach resonance can be assigned to the electronic transition from the ($10a'$) orbital with its ground-state C s symmetry to the empty ($4a''$) level, involving the simultaneous electron attachment. This dynamics could be a model for C-O dissociation in larger alcohols and ethers.

74 ATOMIC AND MOLECULAR PHYSICS↗

Metagenomes and Metagenome-Assembled Genomes from Microbiomes Metabolizing Thin Stillage from an Ethanol Biorefinery

Here, we report the metagenomes from five anaerobic bioreactors, operated under different conditions, that were fed carbohydrate-rich thin stillage from a corn starch ethanol plant. The putative functions of the abundant taxa identified here will inform future studies of microbial communities involved in valorizing this and other low-value agroindustrial residues.

Fortney, Nathaniel W.↗