The need for renewable and cleaner sources of energy has made biofuels an interesting alternative to fossil fuels, especially in the case of butanol isomers, with their favorable blend properties and low hygroscopicity. Although C4 alcohols are prospective fuels, some key reactions governing their pyrolysis and combustion have not been adequately studied, leading to incomplete kinetic models. Butanol reactions kinetics is poorly understood. Specifically, the unimolecular and H-assisted tautomerism of propen-2-ol to acetone, which are included in butanol combustion kinetic models, are assigned rate parameters based on the analogous unimolecular tautomerism vinyl alcohol ↔ acetaldehyde and H addition to the double bound of iso-butene, respectively. In an attempt to update current kinetic models for tert- and 2-butanol, a theoretical kinetic study of the unimolecular and H-assisted tautomerism, i-C3H5OH⟺CH3COCH3 and i-C3H5OH+Ḣ⟺CH3COCH3+Ḣ, was carried out by means of CCSD(T,FULL)/aug-cc-pVTZ//CCSD(T)/6-31+G(d,p) and CCSD(T)/aug-cc-pVTZ//M062X/cc-pVTZ ab initio calculations, respectively. For H-assisted tautomerism, the reaction takes place in two consecutive steps: i-C3H5OH+Ḣ⟺CH3ĊOHCH3 and CH3ĊOHCH3⟺CH3COCH3+Ḣ. Multistructural torsional anharmonicity and variational transition state theory were considered in a wide temperature and pressure range (200 K – 3000 K, 0.1 kPa – 108 kPa). It was observed that decreasing pressure leads to a decrease in rate constants, describing the expected falloff behavior for both isomerizations. Results for unimolecular tautomerism differ from vinyl alcohol ↔ acetaldehyde analogue reactions, which shows lower rate constant values. Tunneling turned out to be important, especially at low temperatures. Accordingly, pyrolysis simulations in a batch reactor for tert- and 2-butanol with computed unimolecular rate constants showed important differences in comparison with previous results, such as larger acetone yield and quicker propen-2-ol consumption. In the combustion and pyrolysis batch reactor simulations, using all the rate constants computed in this work, H-assisted reactions are limited because H radicals become abundant once the propen-2-ol has been consumed by other reactions, such as the non-catalyzed tautomerism i-C3H5OH⟺CH3COCH3, which becomes one of the main source of acetone. The intermediate radical (CH3ĊOHCH3) is formed exclusively from tert-butanol, with its concentration in 2-butanol oxidation being smaller because the secondary alcohol is unable to produce the radical directly. In all cases, the intermediate is converted effectively to acetone.

abstract: Buildings in the United States, account for over 68 percent of electricity consumed, 39 percent of total energy use, and 38 percent of the carbon dioxide emissions. By the year 2035, about 75% of the U.S. building sector will be either new or renovated. The energy efficiency requirements of current building codes would have a significant impact on future energy use, hence, one of the most widely accepted solutions to slowing the growth rate of GHG emissions and then reversing it involves a stringent adoption of building energy codes. A large number of building energy codes exist and a large number of studies which state the energy savings possible through code compliance. However, most codes are difficult to comprehend and require an extensive understanding of the code, the compliance paths, all mandatory and prescriptive requirements as well as the strategy to convert the same to energy model inputs. This paper provides a simplified solution for the entire process by providing an easy to use interface for code compliance and energy simulation through a spreadsheet based tool, the ECCO or the Energy Code COmpliance Tool. This tool provides a platform for a more detailed analysis of building codes as applicable to each and every individual building in each climate zone. It also facilitates quick building energy simulation to determine energy savings achieved through code compliance. This process is highly beneficial not only for code compliance, but also for identifying parameters which can be improved for energy efficiency. Code compliance is simplified through a series of parametric runs which generates the minimally compliant baseline building and 30% beyond code building. This tool is seen as an effective solution for architects and engineers for an initial level analysis as well as for jurisdictions as a front-end diagnostic check for code compliance.   / Dissertation/Thesis / Rocky Mountain Institute- Model Manager Tool / ECCO Spreadsheet Tool / M.S. Built Environment 2011