Low Temperature Oxidation Kinetics of Biodiesel Molecules: Rate Rules for Concerted HO2 Elimination from Alkyl Ester Peroxy Radicals.

In an attempt to construct detailed kinetic mechanisms for biodiesel fuels on the fly, high-pressure rate rules for the concerted HO2 elimination reaction class were derived using a comprehensive training reaction set of more than 60 reactions involving different alkyl methyl/ethyl ester peroxy radicals (RCOOR')-OO•. Using the composite electronic structure method CBS-QB3 in combination with classical statistical mechanics and the transition state theory (TST) rate model, high-pressure rate constants for the reactions in the training set as well as thermodynamic properties for the species involved were calculated. The corrections from Eckart tunneling and hindered internal rotation (HIR) treatments were also included in the calculations. The results reveal that the ester group (-COO-) selectively promotes the reaction when compared with the traditional hydrocarbon fuels; thus it is recommended that the seven derived rate rules for the title reaction class (including the thermodynamic data of the species involved in the NASA format) should be used for construction of detailed kinetic mechanisms for real biodiesel molecules.

Kinetics of Thermal Unimolecular Decomposition of Acetic Anhydride: An Integrated Deterministic and Stochastic Model.

An integrated deterministic and stochastic model within the master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) framework was first used to characterize temperature- and pressure-dependent behaviors of thermal decomposition of acetic anhydride in a wide range of conditions (i.e., 300-1500 K and 0.001-100 atm). Particularly, using potential energy surface and molecular properties obtained from high-level electronic structure calculations at CCSD(T)/CBS, macroscopic thermodynamic properties and rate coefficients of the title reaction were derived with corrections for hindered internal rotation and tunneling treatments. Being in excellent agreement with the scattered experimental data, the results from deterministic and stochastic frameworks confirmed and complemented each other to reveal that the main decomposition pathway proceeds via a 6-membered-ring transition state with the 0 K barrier of 35.2 kcal·mol-1. This observation was further understood and confirmed by the sensitivity analysis on the time-resolved species profiles and the derived rate coefficients with respect to the ab initio barriers. Such an agreement suggests the integrated model can be confidently used for a wide range of conditions as a powerful postfacto and predictive tool in detailed chemical kinetic modeling and simulation for the title reaction and thus can be extended to complex chemical reactions.

Numerical modeling of pulsatile blood flow through a mini-oxygenator in artificial lungs.

While previous in vitro studies showed divergent results concerning the influence of pulsatile blood flow on oxygen advection in oxygenators, no study was done to investigate the uncertainty affected by blood flow dynamics. The aim of this study is to utilize a computational fluid dynamics model to clarify the debate concerning the influence of pulsatile blood flow on the oxygen transport. The computer model is based on a validated 2D finite volume approach that predicts oxygen transfer in pulsatile blood flow passing through a 300-micron hollow-fiber membrane bundle with a length of 254 mm, a building block for an artificial lung device. In this study, the flow parameters include the steady Reynolds number (Re = 2, 5, 10 and 20), Womersley parameter (Wo = 0.29, 0.38 and 0.53) and sinusoidal amplitude (A = 0.25, 0.5 and 0.75). Specifically, the computer model is extended to verify, for the first time, the previously measured O2 transport that was observed to be hindered by pulsating flow in the Biolung, developed by Michigan Critical Care Consultants. A comprehensive analysis is carried out on computed profiles and fields of oxygen partial pressure (PO2) and oxygen saturation (SO2) as a function of Re, Wo and A. Based on the present results, we observe the positive and negative effects of pulsatile flow on PO2 at different blood flow rates. Besides, the SO2 variation is not much influenced by the pulsatile flow conditions investigated. While being consistent with a recent experimental study, the computed O2 volume flow rate is found to be increased at high blood flow rates operated with low frequency and high amplitude. Furthermore, the present study qualitatively explains that divergent outcomes reported in previous in vitro experimental studies could be owing to the different blood flow rates adopted. Finally, the contour analysis reveals how the spatial distributions of PO2 and SO2 vary over time.

A novel flameless oxidation and in-chamber melting system coupled with advanced scrubbers for a laboratory waste plant.

This is the first study integrate the flameless oxidation (FO) and in-chamber melting (ICM) processes in a primary chamber of a laboratory waste incinerator to improve energy and emission performances. Two liquid burners created a twin-cyclonic fluid field that achieved the FO and ICM in the same chamber. The first cyclone provided a well-mixed and lower temperature FO to reduce auxiliary diesel consumption, NOx and PM emissions by 25.8%, 30.9%, and 79.2%, respectively, from the original system. The hot gases produced by FO enhance the ICM process and transformed the bottom ashes to stabler slags, in turn meeting the regulations for nonhazardous wastes. The other cyclone enhanced the drying and water-gas shift reaction in the drying zone by recirculating the CO and enthalpy from FO and ICM. Eventually, the residual CO, hydrocarbons, and H2 were sent to the secondary chamber for further oxidation. A computational fluid dynamic simulation supported the fluid field assumption posed in this study. Moreover, advanced scrubbers were employed after thermal treatments to reduce HCl and SO2 by 81.8% and 38.8% and further retarded the corrosion rate in the baghouse supporting cage by 87.7%. The precursors of condensable particulate matter were reduced by condensation and finally removed in the baghouse. Nevertheless, the emissions of the high- and mid-molecular-weight polycyclic aromatic hydrocarbons were greatly reduced by 60.8-93.1% and 80.2-99.9%, respectively. Consequently, the new system reduced annual emissions by 40.7-87.6% and operating costs by 41.5%, allowing recovery of the remodification investment in 20.5 months.

Kinetic modeling of methyl butanoate in shock tube.

An increased necessity for energy independence and heightened concern about the effects of rising carbon dioxide levels have intensified the search for renewable fuels that could reduce our current consumption of petrol and diesel. One such fuel is biodiesel, which consists of the methyl esters of fatty acids. Methyl butanoate (MB) contains the essential chemical structure of the long-chain fatty acids and a shorter, but similar, alkyl chain. This paper reports on a detailed kinetic mechanism for MB that is assembled using theoretical approaches. Thirteen pathways that include fuel decomposition, isomerization, and propagation steps were computed using ab initio calculations [J. Org. Chem. 2008, 73, 94]. Rate constants from first principles for important reactions in CO(2) formation, namely CH(3)OCO=CH(3) + CO(2) (R1) and CH(3)OCO=CH(3)O + CO (R2) reactions, are computed at high levels of theory and implemented in the mechanism. Using the G3B3 potential energy surface together with the B3LYP/6-31G(d) gradient, Hessian and geometries, the rate constants for reactions R1 and R2 are calculated using the Rice-Ramsperger-Kassel-Marcus theory with corrections from treatments for tunneling, hindered rotation, and variational effects. The calculated rate constants of reaction R1 differ from the data present in the literature by at most 20%, while those of reaction R2 are about a factor of 4 lower than the available values. The new kinetic model derived from ab initio simulations is combined with the kinetic mechanism presented by Fisher et al. [Proc. Combust. Inst. 2000, 28, 1579] together with the addition of the newly found six-centered unimolecular elimination reaction that yields ethylene and methyl acetate, MB = C(2)H(4) + CH(3)COOCH(3). This latter pathway requires the inclusion of the CH(3)COOCH(3) decomposition model suggested by Westbrook et al. [Proc. Combust. Inst. 2008, accepted]. The newly composed kinetic mechanism for MB is used to study the CO(2) formation during the pyrolysis of MB as well as to investigate the autoignition of MB in a shock tube reactor at different temperatures and pressures. The computed results agree very well with experimental data present in the literature. Sensitivity and flux (rate-of-production) analyses are carried out for the CO(2) formation with the new MB mechanism, together with available reaction mechanisms, to assess the importance of various kinetic pathways for each regime. With the new mechanism, the flux analyses for the formation of C(2)H species, one of the most important species for ignition delay time, are also presented at different conditions. In addition to giving a better chemical insight of the pyrolysis/oxidation of MB, the results suggest ways to improve the mechanism's capability to predict CO(2) formation and ignition delay times in pyrolysis and oxidation conditions.