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At least 73 records · Page 4

Process development and scale-up of value added molecules (CRADA Final Report)

In this project, a genetically modified Saccharomyces cerevisiae was used to produce Histamine via fermentation of dextrose. Zymergen provided a tech transfer document based on their 1 L studies, where they observed a titer of 0.9 g/L with this strain. The ABPDU staff performed two bench scale campaigns, with four 2 L reactors in each campaign, to carry out tech transfer and process optimization studies. Optimization was pursued by varying initial glucose concentration, feed initiation conditions, feed strategies, vitamin supplementation, inoculum size, etc. We chose a 2 L process condition, with 4% inoculum volume, continuous feed initiated after complete ethanol depletion, that yielded the most promising titers (2.41 g/L) for scale up to 300 L.

60 APPLIED LIFE SCIENCES↗

Agroecosystem model simulations reveal spatial variability in relative productivity in biomass sorghum and maize in Iowa, USA

Biomass sorghum (Sorghum bicolor L. Moench) is an annual C 4 grass that has emerged as a candidate bioenergy crop but has not been widely grown in the United States. Corn (Zea mays L.), another annual C 4 grass, has been produced on a large scale in the United States for biofuels. Iowa leads the nation in both corn and ethanol production. The high productivity of corn in Iowa creates the research question: could biomass sorghum be as or more productive than corn in the state in terms of bioenergy? Efforts to use crop models to fill the gaps left by field experimentation on biomass sorghum have also been limited thus far. To address our research question, we collected biophysical data on biomass sorghum grown in Iowa for two growing seasons, used them to develop a biomass sorghum module in an agroecosystem model (Agro-IBIS), and predict the potential performance of biomass sorghum across Iowa compared to maize. Despite dry conditions in 2019 and 2020, average biomass sorghum yields were 17.20 Mg ha –1 . By comparison, average corn aboveground biomass was higher in 2020 (22.02 Mg ha –1 ). Soil cores indicated average belowground biomass of 1.46 Mg ha –1 , with roots concentrated near the surface (73% of biomass above 50 cm in a 1 m core). When biomass sorghum model parameters were calibrated with measured values, model output was in close agreement with measured biomass (slope = 0.932, R 2 = 0.91) and evapotranspiration (slope = 0.757, R 2 = 0.64). Subsequent regional simulations revealed a notable latitudinal gradient in biomass sorghum yield, with a strong linear relationship between yield and seasonal growing degree-days (R 2 = 0.89). When these yields were compared to simulated corn aboveground biomass yields, only 3.4% of the state had biomass sorghum yields that were significantly higher than corn. This number was reduced to 0.3% when comparing the crops in terms of energy ethanol yield. Thus, we conclude biomass sorghum must be improved to be competitive with corn as an annual biofuel crop in Iowa. This study provides a baseline against which to compare advancements in sorghum breeding for biomass and stress tolerance in Iowa.

Agro-IBIS↗

High temperatures and low soil moisture synergistically reduce switchgrass yields from marginal field sites and inhibit fermentation

‘Marginal lands’ are low productivity sites abandoned from agriculture for reasons such as low or high soil water content, challenging topography, or nutrient deficiency. To avoid competition with crop production, cellulosic bioenergy crops have been proposed for cultivation on marginal lands, however on these sites they may be more strongly affected by environmental stresses such as low soil water content. In this study we used rainout shelters to induce low soil moisture on marginal lands and determine the effect of soil water stress on switchgrass growth and the subsequent production of bioethanol. Five marginal land sites that span a latitudinal gradient in Michigan and Wisconsin were planted to switchgrass in 2013 and during the 2018–2021 growing seasons were exposed to reduced precipitation under rainout shelters in comparison to ambient precipitation. The effect of reduced precipitation was related to the environmental conditions at each site and biofuel production metrics (switchgrass biomass yields and composition and ethanol production). During the first year (2018), the rainout shelters were designed with 60% rain exclusion, which did not affect biomass yields compared to ambient conditions at any of the field sites, but decreased switchgrass fermentability at the Wisconsin Central–Hancock site. In subsequent years, the shelters were redesigned to fully exclude rainfall, which led to reduced biomass yields and inhibited fermentation for three sites. When switchgrass was grown in soils with large reductions in moisture and increases in temperature, the potential for biofuel production was significantly reduced, exposing some of the challenges associated with producing biofuels from lignocellulosic biomass grown under drought conditions.

09 BIOMASS FUELS↗

Data from: High temperatures and low soil moisture synergistically reduce switchgrass yields from marginal field sites and inhibit fermentation

‘Marginal lands’ are low productivity sites abandoned from agriculture for reasons such as low or high soil water content, challenging topography, or nutrient deficiency. To avoid competition with crop production, cellulosic bio- energy crops have been proposed for cultivation on marginal lands, however on these sites they may be more strongly affected by environmental stresses such as low soil water content. In this study we used rainout shelters to in- duce low soil moisture on marginal lands and determine the effect of soil water stress on switchgrass growth and the subsequent production of bioetha- nol. Five marginal land sites that span a latitudinal gradient in Michigan and Wisconsin were planted to switchgrass in 2013 and during the 2018–2021 growing seasons were exposed to reduced precipitation under rainout shelters in comparison to ambient precipitation. The effect of reduced precipitation was related to the environmental conditions at each site and biofuel produc- tion metrics (switchgrass biomass yields and composition and ethanol pro- duction). During the first year (2018), the rainout shelters were designed with 60% rain exclusion, which did not affect biomass yields compared to ambient conditions at any of the field sites, but decreased switchgrass fermentability at the Wisconsin Central–Hancock site. In subsequent years, the shelters were redesigned to fully exclude rainfall, which led to reduced biomass yields and inhibited fermentation for three sites. When switchgrass was grown in soils with large reductions in moisture and increases in temperature, the potential for biofuel production was significantly reduced, exposing some of the chal- lenges associated with producing biofuels from lignocellulosic biomass grown under drought conditions.

bioethanol↗

Antimicrobial Properties of Corn Stover Lignin Fractions Derived from Catalytic Transfer Hydrogenolysis in Supercritical Ethanol with a Ru/C Catalyst

Converting lignin to value-added products at high yields provides an avenue for making ethanol biorefineries more profitable while reducing the carbon footprint of products generally derived from petroleum. In this study, corn stover lignin was depolymerized by catalytic transfer hydrogenolysis (CTH) in supercritical ethanol with a Ru/C catalyst. The lignin-derived bio-oil was then sequentially extracted utilizing hexane, petroleum ether, chloroform, and ethyl acetate as solvents in order of less polar to polar, and the subsequent bio-oils were characterized using GPC, GC/MS, and HSQC NMR. In this work, results show that the monomers in the bio-oil fractions contained primarily alkylated phenols, hydrogenated hydroxycinnamic acid derivatives, syringol and guaiacol-type lignins created from reductive cleavages of ether linkages, which were sequentially extracted into groups depending on the solvent polarity. The antimicrobial properties of the bio-oils were screened against Gram-positive (Bacillus subtilis, Lactobacillus amylovorus, and Staphylococcus epidermidis) and Gram-negative (Escherichia coli) bacteria and yeast (Saccharomyces cerevisiae) by examining microbial growth inhibition. Results show that CTH-derived bio-oils inhibited all tested organisms at concentrations less than 3 mg/mL. Total monomer concentration and the presence of specific monomers (i.e., syringyl propane) showed correlations to antimicrobial activity, likely due to cell death or membrane damage. This study provides insights into using sequential extraction to fractionate lignin-derived compounds and correlations between the properties of the extracted compounds and their antimicrobial activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impairment of Human Ocular Tracking with Low-Dose Alcohol

Previous studies have documented adverse effects of alcohol on oculomotor performance. For example, moderate-dose alcohol (yielding a Blood Alcohol Concentration or BAC of 0.04-0.1%) has been shown to decrease steady-state pursuit gain (Fransson et al., 2010, Clin Neurophysiol, 121(12): 2134; Moser et al., 1998, J Neurol, 245(8): 542; Roche & King, 2010, Psychopharmacology, 212(1): 33), to increase saccade latency (Moser et al., 1998, J Neurol, 245(8): 542; Roche & King, 2010, Psychopharmacology, 212(1): 33), to decrease peak saccadic velocity (Fransson et al., 2010, Clin Neurophysiol, 121(12): 2134; Roche & King, 2010, Psychopharmacology, 212(1): 33), and to increase the frequency of catch-up saccades (Moser et al., 1998, J Neurol, 245(8): 542). Here, we administered two doses of ethanol on different days, yielding moderate (0.06%) and low (0.02%) levels of initial BAC, to examine the effects on human ocular tracking over BACs ranging from 0.00 to 0.07%. Twelve subjects (8 females) participated in a 5-day study. Three days of at-home measurements of daily activity and sleep were monitored, followed by two laboratory days where, ~5 hours after awakening, we administered one of the two possible single doses of alcohol. Using a previously published paradigm (Liston & Stone, 2014, J Vis, 14(14): 12), we measured oculomotor performance multiple times throughout the day with three pre-dosing baseline runs and bi-hourly post-dosing test runs until the subject recorded a BAC of 0.00% for two hours. BAC was measured before each run using an Alco-Sensor IV breathalyzer (Intoximeters, Inc., St. Louis, MO). For each of the oculometric measures, for each subject, we computed the within-subject % deviation for each test run from their baseline averaged across their three pre-dosing runs. We then averaged the data across subjects in 0.01% BAC bins. Finally, we used linear regression to compute the slope and x-intercept (threshold) of the mean binned % deviation as a function of BAC. We found that pursuit initiation was impaired at very low BAC levels, with significant (p < 0.002) linear trends in latency (+1.3%/0.01%BAC) and initial acceleration (-4.6%/0.01%BAC) with extrapolated absolute thresholds at or below 0.01% BAC. We also found that steady-state tracking was impaired showing significant (p < 0.002) linear trends in gain (- 3.8%/0.01%BAC) and catch-up saccade amplitude (+9.1%/0.01%BAC), again with extrapolated absolute thresholds around 0.01% BAC. We also found a significant (p < 0.02) increase in pursuit direction noise (+9.8%/0.01%BAC) with an extrapolated absolute threshold below 0.01% BAC. Many aspects of ocular tracking are impaired in a dose-dependent manner beginning at a BAC level around 0.01%, with significant effects at levels lower than previously reported and up to 8-times lower than the legal limit for driving in most states.

human performance↗

Scale sensitivity of ethanol production via consolidated bioprocessing with consideration of feedstock cost

We examine feedstock cost and minimum selling price for ethanol production from corn stover as a function of scale, stover yield, participation rate, and price incentives for two conversion technologies: a conventional base case featuring thermochemical pretreatment with added cellulase, and an advanced case featuring consolidated bioprocessing with cotreatment (C-CBP). Delivered feedstock cost ranged from $\$85$ Mg −1 at small (10 million gallons year −1 or ~38 million L year −1 ) scale with high yield and participation rates to $\$124$ Mg −1 at large scale (60 million gallons year −1 or 227 million L year −1 ) and low yield and participation rates. The minimum ethanol selling price (MESP) was approximately twofold lower for the advanced case compared with the base case. The payback period was several times lower for the advanced case compared with the base case, with increasing disparity at smaller scales, and was highly sensitive to ethanol price supports. For both C-CBP and the conventional processing paradigm, MESP decreased with increasing scale, indicating that the cost penalty due to higher feedstock transport distances was more than outweighed by lower capital costs. However, the cost penalty for operation at small scale, expressed in $ gallon −1 ethanol, is lower for C-CBP than for the conventional paradigm by roughly twofold. Particularly for initial applications of C-CBP, we speculate that this cost penalty will likely be modest compared with the anticipated benefits of small-scale operation such as increased opportunity to use existing infrastructure, easier plant siting and supply chain establishment, and lower total investment required.

biorefinery scale↗

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↗

Effective utilization of quantum-cascade distributed-feedback lasers in absorption spectroscopy

A variable duty cycle quasi-cw frequency scanning technique was applied to reduce thermal effects resulting from the high heat dissipation of type I quantum-cascade lasers. This technique was combined with a 100-m path-length multipass cell and a zero-air background-subtraction technique to enhance detection sensitivity to a parts-in-10(9) (ppb) concentration level for spectroscopic trace-gas detection of CH4, N2O, H2O, and C2H5OH in ambient air at 7.9 micrometers. A new technique for analysis of dense high resolution absorption spectra was applied to detection of ethanol in ambient air, yielding a 125-ppb detection limit.

NASA Discipline Environmental Health↗

Prebiotic synthesis of imidazole-4-acetaldehyde and histidine

The prebiotic synthesis of imidazole-4-acetaldehyde and imidazole-4-glycol from erythrose and formamidine has been demonstrated as well as the prebiotic synthesis of imidazole-4-ethanol and imidazole-4-glycol from erythrose, formaldehyde, and ammonia. The maximum yields of imidazole-4-acetaldehyde, imidazole-4-ethanol, and imidazole-4-glycol obtained in these reactions are 1.6, 5.4, and 6.8 percent respectively, based on the erythrose. Imidazole-4-acetaldehyde would have been converted to histidine on the primitive earth by a Strecker synthesis, and several prebiotic reactions would convert imidazole-4-glycol and imidazole-4-ethanol to imidazole-4-acetaldehyde.

Shen, Chun↗

Gauche Ethyl Alcohol: Laboratory Assignments and Interstellar Identification

Ethyl alcohol (ethanol) is known to possess a pair of closely spaced excited torsional substates (gauche+, gauche-) at an energy of approximately 57 K above the ground (trans) torsional substate. We report an extended analysis of some gauche - gauche+ Q-branch ((Delta)J = 0) transitions with a three-substate fixed frame axis method (FFAM) Hamiltonian. Our approach accounts for complex trans-gauche interactions for the first time. In addition, we are able to obtain intensities for perturbed rotational transitions, and to determine the trans to gauche+ separation to be 1185399.1 MHz. A complete ground state rotational-torsional partition function accounting for the previously neglected gauche substates is presented. Based on our analysis, a total of 14 U lines obtained towards Orion KL can now be assigned to gauche substates of ethanol. Analysis of these lines yields a rotational temperature of 223 K and a total (trans + gauche) column density of 7.0 x 10(exp 15)/sq cm. The column density is in reasonable agreement with the recent value of 2-3 x 10(exp 15)/sq cm based on observations of trans-ethanol by Ohishi et al., although there is some disparity in the rotational temperatures. Eight additional U lines in the literature are assigned to transitions of gauche ethanol.

Pearson, J. C.↗

A combination of deep eutectic solvent and ethanol pretreatment for synergistic delignification and enhanced enzymatic hydrolysis for biorefinary process

Here, a novel pretreatment system containing deep eutectic solvents and ethanol (DES-E) for synergistic carbohydrate conversion and delignification was reported in this study. The DES-E pretreatment resulted in an enhanced glucose yield compared to individual DES and ethanol pretreatment for the three tested biomass, including Broussonetia papyrifera, corn stover and pine. To further explore the delignification mechanism, the solubilized lignin and residual lignin from Broussonetia papyrifera was recovered and extracted, then thoroughly characterized. The highest total OH content was found in the DES-E solubilized lignin, which could be used as antioxidant. The presence of ethanol in pretreatment liquor could protect the β-O-4 substructure from breakage and reduce lignin condensation, which favors the subsequent enzymatic hydrolysis. Comparable glucose yield and delignification performance was achieved by recycled DES. DES-E pretreatment offers a promising method for lignin isolation and cellulose digestibility improvement simultaneously.

09 BIOMASS FUELS↗

Partial oxidation of methane to methanol on boron nitride at near critical acetonitrile

Abstract Direct catalytic conversion of methane to methanol with O 2 has been a fundamental challenge in unlocking abundant natural gas supplies. Metal-free methane conversion with 17% methanol yield based on the limiting reagent O 2 at 275 °C was achieved with near supercritical acetonitrile in the presence of boron nitride. Reaction temperature, catalyst loading, dwell time, methane–oxygen molar ratio, and solvent-oxygen molar ratios were identified as critical factors controlling methane activation and the methanol yield. Extension of the study to ethane (C2) showed moderate yields of methanol (3.6%) and ethanol (4.5%).

03 NATURAL GAS↗

One-step transformation of biomass to fuel precursors using a bi-functional combination of Pd/C and water tolerant Lewis acid

Direct one-pot transformation of lignocellulosic biomass has been developed as an effective and sustainable strategy to produce fuel blend stocks and high value chemical building blocks. In this wok, a bi-functional catalyst system consisting of palladium supported on carbon (Pd/C) and metal triflates (i.e., Sm(OTf) 3 , La(OTf) 3 , and Cu(OTf) 2 ) were shown to promote the biomass liquefaction in both hot-compressed water and supercritical ethanol medium, converting fir wood into oxygenated compounds. We report the highest bio-oil yield from hydrothermal liquefaction (HTL) was 10.47 wt% over Pd/C whereas the highest bio-oil yield of 49.71 wt% was achieved from supercritical ethanol liquefaction (SCEL) over the bi-functional catalyst system of Pd/C and La(OTf) 3 . Higher heating values, carbon recovered values and boiling point distributions were further determined for elucidating the physical properties of the bio-oils. Gas chromatography mass spectrometry (GC–MS) analysis of the bio-oils revealed the chemical composition of the bio-oils. Substituted phenols and cyclopentenone/cyclopentanone type compounds consisted of more than 60 area% of the total products from HTL, whereas phenol and esters represented the major products from SCEL. The major reaction pathways are proposed based on the GC–MS results, which include depolymerizaton, isomerization, dehydration, condensation, and hydrogenation.

09 BIOMASS FUELS↗

Techno‐economic feasibility analysis of engineered energycane‐based biorefinery co‐producing biodiesel and ethanol

Abstract High feedstock cost and low oil yields per unit of land from temperate oilseed crops limit the growth of commercial‐scale biodiesel production. Recently, highly productive crops, such as sugarcane and energycane, have been engineered to accumulate triacylglycerides (TAGs) that allow the production of far more industrial vegetable oil than previously possible. A proof‐of‐concept suggests that biodiesel production from engineered energycane will be possible. However, before making efforts for scale‐up, it is critical to understand the commercial feasibility and economic competitiveness of this process. This study performs techno‐economic analysis of a unique biorefinery processing energycane to co‐produce biodiesel and ethanol. Comprehensive process simulation models were developed for two scenarios: (i) biodiesel from TAGs and ethanol from fermentation of sugars in juice and (ii) biodiesel from TAGs and ethanol from fermentation of sugars in juice and hydrolysis of carbohydrates in bagasse. Based on the target levels, the analysis was performed for energycane containing 0%, 5%, and 7.7% TAGs (d.b.). The biodiesel from engineered energycane was found economically viable and competitive to soybean biodiesel. Although the capital investment is higher compared to the soybean biodiesel plant, the biodiesel production costs ($0.66–$0.9/L) were lower than soybean biodiesel ($0.91/L). Biorefinery‐scenario‐1 processing energycane containing 7.7% TAG produces biodiesel with profitability (IRR 7.84) slightly lower than soybean biodiesel (IRR 8.3), but yields five times of biodiesel per unit land and is self‐sustainable for energy requirements. The surplus electricity can displace fossil electricity and provide environmental benefits. Monte Carlo simulation indicated that biorefinery is profitable with a 29%–65% probability (NPV > 0) which is largely controlled by feedstock composition and biodiesel market price. It is important to note that energycane can be grown on the marginal rainfed lands in S.E. USA, where soybean would not be viable. Biodiesel from engineered energycane would therefore be complementary to soydiesel in the United States.

09 BIOMASS FUELS↗

Towards cost-competitive middle distillate fuels from ethanol within a market-flexible C2 platform-based biorefinery concept

Ethanol to middle distillates (ETMD) is a promising pathway to produce sustainable liquid fuels to decarbonize the hard-to-electrify transportation sectors due to (1) the abundant sugar/starch and lignocellulosic biomass, (2) the existing deployment scale of fuel ethanol production (similar to 29 billion gallons per year globally), and (3) emerging opportunities in C2+ alcohol synthesis from CO2. Here we report a conceptual market-responsive biorefinery centered around a new ETMD pathway based on one-step ethanol to butene-rich olefins (ETO) over a Cu-Zn-Y/Beta catalyst. Specifically, this ethanol conversion pathway comprises one-step ETO, oligomerization, and hydrotreating. This ETO is distinct from that in the conventional ethanol-to-jet process which is based on two-step ethanol to ethylene and ethylene oligomerization to butenes. Butene-rich olefins can be shifted to butadiene-rich products by simply changing the reaction atmosphere from hydrogen to inert gas over the same ETO catalyst. Leveraging the experimental results, baseline techno-economic analysis (TEA) and sensitivity analysis indicate that the ethanol conversion cost is $0.60 per gallon gasoline equivalent (GGE), with opportunities for further cost reduction via improving the liquid hydrocarbon yield and space velocities, and process optimization on balancing dewatering of ethanol feed prior to the ETO step. The minimum fuel selling price (MFSP) of liquid hydrocarbons derived from corn starch ethanol with butadiene as coproduct is $1.64 per GGE, in the range that is cost competitive with petroleum kerosene-type jet fuel. Projected MFSP for cellulosic ethanol (corn stover) derived hydrocarbons is below $3.00 per GGE and co-production of butadiene further reduces the MFSP to $1.70 per GGE. The Well-to-Wake life-cycle analysis indicates that 85% greenhouse gas emission reduction can be achieved when using corn stover compared to petroleum reference and the associated carbon credits will provide significant economic incentives to favor the cellulosic ethanol-derived hydrocarbon fuels. This study demonstrates a low-cost pathway to middle distillate fuels leveraging existing ethanol infrastructure, where catalysis innovation drives the reduction of process complexity and flexible coproduction of a value-added chemical product.

Zhang, Junyan↗

Effects_of_heterologous_expression_of_glycolysis_enzymes_on_product_formation_in_Clostridium_thermocellum

Glycolysis is central toClostridium thermocellummetabolism; however, engineered strains for high ethanol titer exhibit a decrease in yield, suggesting the presence of glycolytic bottlenecks. We expressed heterologoustpi,fba, andgapDHgenes fromThermoanaerobacterium saccharolyticumandZymomonas mobilis, along with 26 non-phosphorylatinggapNvariants, to identify limiting reactions. We demonstrated functional expression and increased activity for several Fba and Tpi enzymes in the engineered strain LL1711. DespiteC. thermocellum'slow native FBA activity compared to other industrial strains, increasing Fba or Tpi activity via heterologous expression had no significant effect on cellobiose uptake or ethanol titers in high-substrate fermentations. Furthermore, 25 of 26 tested gapN genes proved highly toxic toC. thermocellumupon transformation. In conclusion, none of the tested glycolytic enzyme modifications improved fermentation profiles. These results suggest that the primary metabolic limitation is not at the FBA or TPI reactions, supporting a shift in future engineering efforts toward downstream fermentation pathways.

6-bisphosphate aldolase; glyceraldehyde-3-phosphat↗