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At least 631 records · Page 35

Bioblendstocks to Optimize Mixing Controlled Compression Ignition (MCCI) Engines

In this project, a team of researchers from the University of Massachusetts Lowell, the University of Maine, and Mainstream Engineering developed an integrated process for the product of bioblendstocks to optimize mixing controlled compression ignition (MCCI) engines. The objective was to improve the energy density, sooting propensity, and cetane number of base diesel fuel while maintaining cold weather behavior. The process converts woody biomass (e.g. sawmill residues) into bio-oil through selective fast pyrolysis; the bio-oil is then selectively upgraded to form selectively oxygenated, minimally-branched hydrocarbons using non-noble metal catalysts in combination with metal-catalyzed hydrogenation. Advanced predictive models, in conjunction with existing property databases, and experimental testing are used to evaluate overall bioblendstock properties and their impact on base diesel fuel. An iterative, targeted upgrading approach was implemented to optimize the proposed bioblendstock’s properties. Assessment methodologies included techno-economic analysis, life-cycle assessment, property testing, and engine testing. Ultimately, the project team successfully produced a viable bioblendstock while identifying critical process points related to scale-up efforts. It was found that producing pyrolysis oils at 500 degrees C and with pine particle sizes of 1-2 mm led to bio-oil with a higher yield (of approximately 45 wt%) and rich amounts of aromatic alcohols. The resultant pyrolysis oil was then upgraded using a sequence of mild hydrotreating, followed by catalytic etherification and esterification, followed by another final mild hydrotreating to produce a blendstock containing saturated species with a limited, but non-zero, amount of oxygen. The aromatic alcohols produced by pyrolysis were especially helpful in this regard, as the resulting bicycloethers and derivatives exhibited high cetane numbers. While most bulk properties of the bioblendstock met or exceeded targeted thresholds, viscosity and cloud point notably fell outside the expected range; this could be addressed by blending limits and/or through the use of additives that are commonplace in current refinding practices. Identification of a bioblendstock that can be produced economically at scale while improving the performance and emissions characteristics of internal combustion engines positively affects the economy by boosting domestic fuel production and the environment by decreasing harmful emissions and increasing efficiency.

09 BIOMASS FUELS↗

Multifunctional Catalysts for the Tandem Reactions of Oxygenates

Industrially-relevant catalytic reactions rarely consist of a simple sequence of elementary steps. Moreover, kinetic coupling of multiple reactions on a catalyst surface is highly desired for process intensification and improved energy efficiency for large scale chemical transformations. The shifting landscape of hydrocarbon chemical feedstocks in the US also motivates research on the selective conversion of more complex molecules. One desirable type of catalytic reaction is the reduction of carboxylic acids that are produced from biomass feedstocks to their corresponding alcohols. The proposed research explores the fundamental importance of hydrogen spillover on a multifunctional catalyst for carboxylic acid reduction with H 2 composed of metal particles coupled to metal oxide particles. Recent work has demonstrated the excellent performance of supported tungsten oxide clusters for carboxylic acid reduction, but only after they are promoted with a late transition metal such as palladium. Elucidating the active state of the catalyst and the associated reaction mechanism for acid reduction on that active state are the overall goals of the proposed project and successful completion will enable future design of efficient multifunctional catalysts. The critically important role of the metal promoter is hypothesized to be its ability to dissociate H2 and spillover atomic H to the support. Although hydrogen spillover is a well-recognized phenomenon in catalysis, its role in both catalyst activation and catalytic turnover are still unresolved. The study combined materials synthesis, characterization, reactivity testing, and molecular simulations, to explore the effect of hydrogen chemical potential on the formation of the active catalytic sites and on the steady state catalytic reduction of carboxylic acid. Varying the hydrogen chemical potential through modification of the gas conditions, support composition, and metal loading to modulated the structure and catalytic performance of the reducible metal oxide. Dual function catalysts containing supported Pd and WO x species co-located on a non-reducible carrier (silica) and a reducible carrier (titania) were synthesized and characterized by electron microscopy, temperature-programmed reduction, and chemisorption. Spectroscopic methods such as X-ray absorption and UV-vis were also used to evaluate the catalysts, which were used in the reduction of propionic acid to aldehyde and alcohol. Quantum chemical calculations, including ab initio phase diagrams provided molecular insights into the H spillover phenomenon.

09 BIOMASS FUELS↗

Techno Economic Analysis for Production of Renewable Natural Gas and Value-Added Chemicals from Forest Biomass Residues (CRADA Final Report)

West Biofuels - in collaboration with the University of California San Diego, the University of California Davis, the National Laboratory of the Rockies (NLR), the Colorado School of Mines’ Center for Hydrate Research, Placer County Air Pollution Control District, the Sierra Business Council, and the Southern California Gas Company (SoCalGas)-will demonstrate an innovative pathway to convert forest biomass to renewable gas (RG). The project, Production of Pipeline Grade Renewable Natural Gas and Value-Added Chemicals from Forest Biomass Residues, will utilize an existing pilot-scale gasification system and data and lessons learned from a lab-scale catalytic reactor design, develop, and demonstrate an integrated pilot-scale RG process with a scaled-up catalytic reactor and hydrate-based gas separation process. This robust and simple process uses a commercial proven gasifier, a commercially available catalyst that can tolerate gas contaminants, and a gas separation process that simplifies the downstream processing. Current testing has shown that the process can yield a large amount of methane rich renewable gas in addition to a mixture of propanol, ethanol and other higher alcohols and the relative amounts can be controlled by shifting the process conditions. This process is novel and groundbreaking because the product mixture of RG and valuable alcohols byproducts makes RG production economically feasible at $\$$12 per million British thermal units (MMBtu) or less using forest biomass from high hazard zones.

09 BIOMASS FUELS↗

Solvent-Induced Selectivity of Isoprene From Bio-Derived Prenol

In this work we demonstrate the selective catalytic conversion of prenol, which is an allylic alcohol that can be prepared from renewable resources to isoprene. The catalyst is an inexpensive molybdenum complex (Molyvan L) designed and used as an additive for lubricants. Isoprene is generated under relatively mild reaction parameters at 130–150°C, for 2 h, under vapor pressure conditions that do not exceed 50 psi. Two cases were studied: one in which Molyvan L was dissolved in a base oil at 1% concentration (weight/weight) and then mixed with a solvent and prenol and the other in which neat Molyvan L was introduced in the reaction and the base oil was replaced with the solvent and prenol. We investigated the selectivity of the reaction using the following solvents in both cases: dodecane, dodecanol, isododecane, octane, blendstock for oxygenate blending (BOB3), a fuel surrogate, a polyalphaolefin (PAO4), and methoxy polyethylene glycol (methoxy PEG350). Although conversion of prenol was above 94% in all experiments, isoprene was formed with various degrees of efficiency alongside a prenol isomeric alcohol, diprenyl ether and mixed ether via intramolecular and intermolecular dehydration reactions. Dodecane appeared to have the highest level of selectivity initially in base oil so we studied the effect of various dodecane-like solvents on isoprene yield and product profile. Surprisingly, octane (similar to dodecane) and isododecane (branched alkane) generated insignificant amounts of byproducts, essentially providing the highly desired isoprene with a very high selectivity. Branching of the solvent does not appear to have an effect on selectivity. Another advantage of this catalyst is the low loadings required to effect the transformation; that is, 0.25% (weight/volume) in the cases using neat Molyvan L and 0.5% (weight/volume) in the cases using Molyvan L dissolved in the base oil. Provided that prenol can be produced in large scale from bioresources, this work would enable the sustainable production of isoprene, in good yield, and with very high selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Epicuticular wax accumulation and regulation of wax pathway gene expression during bioenergy Sorghum stem development

Bioenergy sorghum is a drought-tolerant high-biomass C4 grass targeted for production on annual cropland marginal for food crops due primarily to abiotic constraints. To better understand the overall contribution of stem wax to bioenergy sorghum’s resilience, the current study characterized sorghum stem cuticular wax loads, composition, morphometrics, wax pathway gene expression and regulation using vegetative phase Wray, R07020, and TX08001 genotypes. Wax loads on sorghum stems (~103-215 µg/cm 2 ) were much higher than Arabidopsis stem and leaf wax loads. Wax on developing sorghum stem internodes was enriched in C28/30 primary alcohols (~65%) while stem wax on fully developed stems was enriched in C28/30 aldehydes (~80%). Scanning Electron Microscopy showed minimal wax on internodes prior to the onset of elongation and that wax tubules first appear associated with cork-silica cell complexes when internode cell elongation is complete. Sorghum homologs of genes involved in wax biosynthesis/transport were differentially expressed in the stem epidermis. Expression of many wax pathway genes (i.e., SbKCS6, SbCER3-1, SbWSD1, SbABCG12, SbABCG11 ) is low in immature apical internodes then increases at the onset of stem wax accumulation. SbCER4 is expressed relatively early in stem development consistent with accumulation of C28/30 primary alcohols on developing apical internodes. High expression of two SbCER3 homologs in fully elongated internodes is consistent with a role in production of C28/30 aldehydes. Gene regulatory network analysis aided the identification of sorghum homologs of transcription factors that regulate wax biosynthesis (i.e., SbSHN1, SbWRI1/3, SbMYB94/96/30/60, MYS1 ) and other transcription factors that could regulate and specify expression of the wax pathway in epidermal cells during cuticle development.

09 BIOMASS FUELS↗

Visualization of lignification in flax stem cell walls with novel click-compatible monolignol analogs

As an essential part of plant cell walls, lignin provides mechanical support for plant growth, enhances water transport, and helps to defend against pathogens. As the most abundant natural aromatic-based renewable resource on earth, its biosynthesis has always been a research focus, and it is still currently under study. In this study, the p-coumaryl alcohol analog (H ALK ) and the coniferyl alcohol analog (G ALK ) containing an alkyne group at the ortho position were synthesized and applied to lignification in vivo and in vitro. The incorporation of these novel lignin monomers was observed via fluorescence imaging. It was found that the two monolignol analogs could be incorporated in dehydrogenated polymers (DHPs) in vitro and in flax cell walls in vivo. The results showed that as the cultivation time and precursor concentration varied, the deposition of H and G-type lignin exhibited differences in deposition mode. At the subcellular scale, the deposited lignin first appears in the cell corner and the middle lamella, and then gradually appears on the cell walls. Furthermore, lignin was also found in bast fiber. It was demonstrated that these new molecules could provide high-resolution localization of lignin during polymerization.

59 BASIC BIOLOGICAL SCIENCES↗

Dimethyl Carbonate: Review of Synthesis Routes and Catalysts Used

This review summarizes the performance of potential catalysts for the synthesis of dimethyl carbonate (DMC) using CO2 as a feedstock by two major processes—the direct route of carbonylation of alcohols and the indirect route of alcoholysis of urea. The reaction mechanisms and corresponding catalysts that were previously investigated are discussed. The major challenges associated with the conversion of CO2 to DMC are the low yields, low DMC selectivity, and thermodynamic limitations (alcohol carbonylation) of reversible reactions with low equilibrium constants. This occurs mainly due to the highly stable carbon dioxide molecules. The development of novel catalysts with high yields and high selectivity needs to be studied to overcome these technical challenges. In addition, to enhance the DMC yield, the use of dehydrating agents for water removal from the reaction mixture is recommended and discussed in detail in this article. This review critically examines the different catalysts used by investigators, along with their respective operating conditions and suitability in applications for the commercial synthesis of CO2-based DMC.

10 SYNTHETIC FUELS↗

Crystallographic Fragment Screening of a Bifunctional Proline Catabolic Enzyme Reveals New Inhibitor Templates for Proline Dehydrogenase and L-Glutamate-γ-semialdehyde Dehydrogenase

The proline catabolic pathway consisting of proline dehydrogenase (PRODH) and L-glutamate-γ-semialdehyde (GSAL) dehydrogenase (GSALDH) catalyzes the four-electron oxidation of L-proline to L-glutamate. Chemical probes to these enzymes are of interest for their role in cancer and inherited metabolic disease. Here, we report the results of a crystallographic fragment-screening campaign targeting both enzymes. A unique aspect of our approach is the screening of both enzymes simultaneously using crystals of the bifunctional PRODH-GSALDH enzyme, proline utilization A (PutA). A 288-fragment library from Zenobia was screened in crystallo in cocktails of six fragments. Validation X-ray crystallography with individual fragments identified seven crystal hits distributed in the PRODH active site, GSALDH aldehyde substrate-binding site, and GSALDH NAD+ adenine-binding site. The fragment bound in the PRODH active site, 4-methoxybenzyl alcohol, is structurally distinct from all known PRODH inhibitors as it lacks an anionic anchor and stabilizes open conformations of the active site, motivating the study of eighteen analogs. In total, thirteen crystal structures with resolutions ranging from 1.32 Å to 1.80 Å were determined, resolving the poses and interactions of seven fragments from the Zenobia library and five analogs of 4-methoxybenzyl alcohol. These results expand the chemical space of probes targeting proline catabolic enzymes and provide new structural information for further inhibitor development.

Biochemistry & Molecular Biology↗

Maize Terpene Synthase 8 (ZmTPS8) Contributes to a Complex Blend of Fungal-Elicited Antibiotics

In maize (Zea mays), fungal-elicited immune responses include the accumulation of terpene synthase (TPS) and cytochrome P450 monooxygenases (CYP) enzymes resulting in complex antibiotic arrays of sesquiterpenoids and diterpenoids, including α/β-selinene derivatives, zealexins, kauralexins and dolabralexins. To uncover additional antibiotic families, we conducted metabolic profiling of elicited stem tissues in mapping populations, which included B73 × M162W recombinant inbred lines and the Goodman diversity panel. Five candidate sesquiterpenoids associated with a chromosome 1 locus spanning the location of ZmTPS27 and ZmTPS8. Heterologous enzyme co-expression studies of ZmTPS27 in Nicotiana benthamiana resulted in geraniol production while ZmTPS8 yielded α-copaene, δ-cadinene and sesquiterpene alcohols consistent with epi-cubebol, cubebol, copan-3-ol and copaborneol matching the association mapping efforts. ZmTPS8 is an established multiproduct α-copaene synthase; however, ZmTPS8-derived sesquiterpene alcohols are rarely encountered in maize tissues. A genome wide association study further linked an unknown sesquiterpene acid to ZmTPS8 and combined ZmTPS8-ZmCYP71Z19 heterologous enzyme co-expression studies yielded the same product. To consider defensive roles for ZmTPS8, in vitro bioassays with cubebol demonstrated significant antifungal activity against both Fusarium graminearum and Aspergillus parasiticus. As a genetically variable biochemical trait, ZmTPS8 contributes to the cocktail of terpenoid antibiotics present following complex interactions between wounding and fungal elicitation.

59 BASIC BIOLOGICAL SCIENCES↗

Soot Formation and Ignition Characteristics of Ethanol/Gasoline Blends in a Rapid Compression Machine

With the ever-increasing demand for sustainable energy, alcohol fuels have garnered interest for use in heavy duty engines. The significant infrastructure for ethanol production and blending of ethanol with gasoline make these fuels/fuel blends desirable candidates. However, development of heavy duty engine technology that is capable of burning alcohol fuels while retaining the advantages of traditional diesel combustion requires an improved understanding of the soot formation for these fuels under conditions relevant to mixing-controlled combustion. This work uses an extinction diagnostic to study the sooting tendency of ethanol and gasoline/ethanol blends ranging from E10 to E98 during ignition in a homogeneous environment. Experiments were conducted in a rapid compression machine (RCM) for compressed conditions of 20 ± 1 bar and an approximately constant temperature (± 10K) which was unique for each fuel. For a given soot volume fraction, a linear relationship was observed between ethanol content and the equivalence ratio in which that soot volume fraction was formed. Accounting for the oxygenated nature of ethanol, E85 and E98 fuels produced similar amounts of soot at a given Φ ox, , suggesting other factors outside of fuel oxygen content, such as fuel morphology, impact soot formation. Ignition delay data is reported for compressed pressures of 20 ± 1 bar and compressed temperatures ranging from 633 – 670 K for E10 and 771 – 789 K for E98. Varying pressures for E10 and E98 at conditions producing similar soot volume fractions demonstrated a linear dependence of soot formation on pressure, regardless of if the pressure considered was at top dead center or peak combustion pressure. Furthermore, the data gleaned from this work will be used to select soot models and chemical kinetic mechanisms for RCM simulations to ultimately model heavy duty engine technology with the studied fuels.

33 ADVANCED PROPULSION SYSTEMS↗

Improved preparation of 9-octadecenes

Organic synthesis of cis-9 and trans-9 octadecenes from oleyl alcohol and elaidyl alcohol, respectively, by conversion to tosylates followed by lithium aluminum hydride reduction

ALKENE↗

Friction behavior of 304 stainless steel of varying hardness lubricated with benzene and some benzyl structures

The lubricating properties of some benzyl and benzene structures were determined by using 304 stainless steel surfaces strained to various hardness. Friction coefficients and wear track widths were measured with a Bowden-Leben type friction apparatus by using a pin-on-disk specimen configuration. Results obtained indicate that benzyl monosulfide, dibenzyl disulfide, and benzyl alcohol resulted in the lowest friction coefficients for 304 stainless steel, while benzyl ether provided the least surface protection and gave the highest friction. Strainhardening of the 304 stainless steel prior to sliding resulted in reduced friction in dry sliding. With benzyl monosulfide, dibenzyl disulfide, and benzyl alcohol changes in 304 stainless steel hardness had no effect upon friction behavior.

Buckley, D. H.↗

Dichromated-gelatin hologram process for improved optical quality

Optical distortions are eliminated by use of wetting agency followed by sequential immersion in several alcohol-water baths of increasing alcohol concentration. Dehydration proceeds uniformly over surface of gelatin. Dried plate is free of optically-distorting thickness variations.

Stewart, W. C.↗

Organic matter in eolian dusts over the Atlantic Ocean

The elemental and mineralogical composition and the microfossil and detritus content of particulate fallout from the lower troposphere over the Atlantic Ocean have been extensively documented in earlier work, and it was possible to ascribe terrigenous source areas to such fallout. A brief review of the organic geochemistry of eolian dusts is also presented here. The lipids of eolian dusts sampled from the air mass over the eastern Atlantic from about 35 deg N to 30 deg S were analyzed here. These lipids consisted mainly of normal alkanes, carboxylic acids and alcohols. The n-alkanes were found to range from n-C23 to n-C35 with high CPI values and maximizing at n-C27 in the North Atlantic, at n-C29 in the equatorial Atlantic and at n-C31 in the South Atlantic. The n-fatty acids had mostly bimodal distributions, ranging from n-C12 to n-C30 (high CPI), with maxima at n-C16 and in the northern samples at n-C24 and in the southern samples at n-C26. The n-alcohols ranged from n-C12 to n-C32, with high CPI values and maxima mainly at n-C28. The compositions of these lipids indicated that their terrigenous sources were comprised mainly of higher plant vegetation and desiccated lacustrine mud flats on the African continent.

Simoneit, B. R. T.↗

Measurements at 13.9 GHz of the radar backscattering cross section of the North Sea covered with an artificial surface film

The reduction of the Ku-band (13.9 GHz) normalized radar cross section (NRCS) by an artificial monomolecular surface film (oleyl alcohol) on the sea surface was measured in the North Sea during the 1975 Joint North Sea Wave Project, JONSWAP 75 experiment. The aim of the surface film experiment was to simulate natural surface films which often occur on the ocean surface and are produced by plankton or fish. NRCS measurements were obtained from an aircraft at incidence angles of 41 deg and 47 deg at vertical and horizontal polarizations. For winds between 3.5 and 4.4 m/sec the maximum measured reduction was 7.3 plus or minus 3.5 dB relative to the mean. In-situ measurements showed that the oleyl alcohol film reduced the surface tension from 74 to 43 dyne/cm.

Huehnerfuss, H.↗

Neutralizing Amine-Cured Epoxy Surfaces

New surface treatment is a rapid, convenient, and effective method for converting unused amines and amine functional groups into neutral, noncorrosive substituted urea. Reaction proceeds at room temperature, takes only a few minutes, and leaves no corrosive residue. Surface should first be washed with alcohol to remove as much as possible of unreacted amine. Then it should be dried, since residual moisture or alcohol may consume some of treatment reagent and neutralization may then be incomplete.

Lee, S. Y.↗

Method of neutralizing the corrosive surface of amine-cured epoxy resins

The corrosive alkaline surface layer of an epoxy resin product formed by the curing of the epoxy with an aliphatic amine is eliminated by first applying a non-solvent to remove most or all of the free unreacted amine and then applying a layer of a chemical reagent to neutralize the unused amine or amine functional groups by forming a substituted urea. The surface then may be rinsed with acetone and then with alcohol. The non-solvent may be an alcohol. The neutralizing chemical reagent is a mono-isocyanate or a mono-isothiocyanate. Preferred is an aromatic mono-isocyanate such as phenyl isocyanate, nitrophenyl isocyanate and naplthyl isocyanate.

Lee, S. Y.↗