Comparative Investigation of the High Pressure Autoignition of the Butanol Isomers

Investigation of the autoignition delay of the butanol isomers has been performed at elevated pressures of 15 bar and 30 bar and low to intermediate temperatures of 680-860 K. The reactivity of the stoichiometric isomers of butanol, in terms of inverse ignition delay, was ranked as n-butanol > sec-butanol ~ iso-butanol > tert-butanol at a compressed pressure of 15 bar but changed to n-butanol > tert-butanol > sec-butanol > iso-butanol at 30 bar. For the temperature and pressure conditions in this study, no NTC or two-stage ignition behavior were observed. However, for both of the compressed pressures studied in this work, tert-butanol exhibited unique pre-ignition heat release characteristics. As such, tert-butanol was further studied at two additional equivalence ratios ($\phi$ = 0.5 and 2.0) to help determine the cause of the heat release.Comment: 4 pages, 4 figures, presented at the 2011 Meeting of the Eastern States Sections of the Combustion Institut

Charged Higgs production with a WW boson or a top quark

I present theoretical results for charged Higgs production in association with a $W$ boson or a top quark at the LHC. I calculate higher-order threshold corrections and show that they are very significant. I present detailed results for total cross sections as well as transverse-momentum and rapidity distributions for various LHC energies.Comment: 5 pages, 4 figures; presented at the EPS Conference on High Energy Physics (EPS-HEP2017), Venice, Italy, July 5-12, 201

Low-energy electron scattering from C_4H_9OH isomers

We present differential, integral, and momentum-transfer cross sections for elastic scattering of low-energy electrons by three butanol isomers, isobutanol, t-butanol, and 2-butanol. Our results were calculated with the Schwinger multichannel method in the static-exchange plus polarization approximation for collision energies from 1 to 50 eV. The present results are compared with previous calculations and measurements for the remaining C_4H_9OH isomer, n-butanol [Khakoo et al., Phys. Rev. A 78, 062714 (2008)]. Distinctive behavior is observed in the differential cross sections at collision energies between 5 and 10 eV. In particular, whereas n-butanol exhibits an f-wave scattering pattern, the other isomers exhibit d-wave behavior. A similar pattern is found in the related alkanes when comparing straight-chain versus branched isomers. We discuss the possible connection of this behavior to shape resonances that influence the scattering

Reduced chemistry for butanol isomers at engine-relevant conditions

Butanol has received significant research attention as a second-generation biofuel in the past few years. In the present study, skeletal mechanisms for four butanol isomers were generated from two widely accepted, well-validated detailed chemical kinetic models for the butanol isomers. The detailed models were reduced using a two-stage approach consisting of the directed relation graph with error propagation and sensitivity analysis. During the reduction process, issues were encountered with pressure-dependent reactions formulated using the logarithmic pressure interpolation approach; these issues are discussed and recommendations made to avoid ambiguity in its future implementation in mechanism development. The performance of the skeletal mechanisms generated here was compared with that of detailed mechanisms in simulations of autoignition delay times, laminar flame speeds, and perfectly stirred reactor temperature response curves and extinction residence times, over a wide range of pressures, temperatures, and equivalence ratios. The detailed and skeletal mechanisms agreed well, demonstrating the adequacy of the resulting reduced chemistry for all the butanol isomers in predicting global combustion phenomena. In addition, the skeletal mechanisms closely predicted the time-histories of fuel mass fractions in homogeneous compression-ignition engine simulations. The performance of each butanol isomer was additionally compared with that of a gasoline surrogate with an antiknock index of 87 in a homogeneous compression-ignition engine simulation. The gasoline surrogate was consumed faster than any of the butanol isomers, with tert-butanol exhibiting the slowest fuel consumption rate. While n-butanol and isobutanol displayed the most similar consumption profiles relative to the gasoline surrogate, the two literature chemical kinetic models predicted different orderings.Comment: 39 pages, 16 figures. Supporting information available via https://doi.org/10.1021/acs.energyfuels.6b0185

Production of butanol by fermentation in the presence of cocultures of clostridium

Sugars are converted to a mixture of solvents including butanol by a fermentation process employing a coculture of microorganisms of the Clostridium genus, one of said microorganisms favoring the production of butyric acid and the other of which converts the butyric acid so produced to butanol. The use of a coculture substantially increases the yield of butanol over that obtained using a culture employing only one microorganism

Adding Salt to an Aqueous Solution of t-Butanol: Is Hydrophobic Association Enhanced or Reduced?

Recent neutron scattering experiments on aqueous salt solutions of amphiphilic t-butanol by Bowron and Finney [Phys. Rev. Lett. {\bf 89}, 215508 (2002); J. Chem. Phys. {\bf 118}, 8357 (2003)] suggest the formation of t-butanol pairs, bridged by a chloride ion via ${O}-{H}...{Cl}^-$ hydrogen-bonds, and leading to a reduced number of intermolecular hydrophobic butanol-butanol contacts. Here we present a joint experimental/theoretical study on the same system, using a combination of molecular dynamics simulations and nuclear magnetic relaxation measurements. Both theory and experiment clearly support the more intuitive scenario of an enhanced number of hydrophobic contacts in the presence of the salt, as it would be expected for purely hydrophobic solutes [J. Phys. Chem. B {\bf 107}, 612 (2003)]. Although our conclusions arrive at a structurally completely distinct scenario, the molecular dynamics simulation results are within the experimental errorbars of the Bowron and Finney work.Comment: 15 pages twocolumn revtex, 11 figure

Coupled oxidation–reduction of butanol–hexanal by resting Rhodococcus erythropolis NCIMB 13064 cells in liquid and gas phases

Rhodococcus erythropolis is a promising Gram-positive bacterium capable of numerous bioconversions including those involving alcohol dehydrogenases (ADHs). In this work, we compared and optimized the redox biocatalytic performances of 1-butanol-grown R. erythropolis NCIMB 13064 cells in aqueous and in non-conventional gas phase using the 1-butanol–hexanal oxidation–reduction as model reaction. Oxidation of 1-butanol to butanal is tightly coupled to the reduction of hexanal to 1-hexanol at the level of a nicotinoprotein–ADH-like enzyme. Cell viability is dispensable for reaction. In aqueous batch conditions, fresh and lyophilized cells are efficient redox catalysts (oxidation–reduction rate = 76 micromol min−1 g cell dry mass−1) being also reactive towards benzyl alcohol, (S)-2-pentanol, and geraniol as reductants. However, butanol hexanal oxidation–reduction is strongly limited by product accumulation and by hexanal toxicity that is amajor factor influencing cell behavior and performance. Reaction rate is maximal at 40 ◦C pH 7.0 in aqueous phase and at 60 ◦C- pH 7.0–9.0 in gas phase. Importantly, lyophilized cells also showed to be promising redox catalysts in the gas phase (at least 65 micromol min−1 g cell dry mass−1). The system is notably stable for several days at moderate thermodynamic activities of hexanal (0.06–0.12), 1-butanol (0.12) and water (0.7)

Structural and spectroscopic characterisation of C4 oxygenates relevant to structure/activity relationships of the hydrogenation of α,β-unsaturated carbonyls

In the present work, we have investigated the conformational isomerism and calculated the vibrational spectra of the C4 oxygenates: 3-butyne-2-one, 3-butene-2-one, 2-butanone and 2-butanol using density functional theory. The calculations are validated by comparison to structural data where available and new, experimental inelastic neutron scattering and infrared spectra of the compounds. We find that for 3-butene-2-one and 2-butanol the spectra show clear evidence for the presence of conformational isomerism and this is supported by the calculations. Complete vibrational assignments for all four molecules are provided and this provides the essential information needed to generate structure/activity relationships for the sequential catalytic hydrogenation of 3-butyne-2-one to 2-butanol

Heterogeneous photocatalytic oxidation of atmospheric trace contaminants

The following subject areas are covered: (1) design and construction of continuous flow photoreactor for study of oxidation of trace atmospheric contaminants; (2) establishment of kinetics of acetone oxidation including adsorption equilibration, variation of oxidation rate with acetone concentration and water (inhibitor), and variation of rate and apparent quantum yield with light intensity; (3) exploration of kinetics of butanol oxidation, including rate variation with concentration of butanol, and lack of inhibition by water; and (4) exploration of kinetics of catalyst deactivation during oxidation of butanol, including deactivation rate, influence of dark conditions, and establishment of photocatalytic regeneration of activity in alcohol-free air