A Numerical Approach to Determining Flammability Limits of Hydrocarbon Process Fluids

PresentationIntrinsic to the computer modeling of explosions and fires is the concept of flammability limits. Conventionally, the term “flammability limit” is defined loosely as the concentration limits beyond which flame propagation is no longer possible. More formally, a fundamental flammability limit is defined as the mixture concentration at which a steady, laminar, one- dimensional, planar, and adiabatic flame fails to propagate. Fundamental flammability limits are reached when the heat release from chemical reactions becomes comparable to the radiative heat loss from the flame. The difficulty in predicting these fundamental limits, a priori, for a given combustible mixture is the dependence of the flammability limit on chemical kinetics. In this study we present a computational methodology for the determination of a mixture’s fuel lean and fuel rich flammability limits. Numerical calculations were performed using a modified version of the CHEMKIN PREMIX flame code. This code has been modified to allow for the capturing of the singular behavior around the turning point and allowing, thus, the accurate determination of a mixture’s flammability limits. The present methodology has been extensively validated to determine the flammability limits of single component and binary fuel mixtures. These validations are presented. Real hydrocarbon process fluids are complex mixtures that consist of hundreds of species spanning a wide range of molecular weights and chemical classes. The surrogate fuel approach, whereby the kinetics of the complex mixture is modeled using a few individual components, is now applied to determine the flammability limits of real hydrocarbons

Identifying Where REDD+ Financially Out Competes Oil Palm in Floodplain Landscapes Using a Fine-Scale Approach

Reducing Emissions from Deforestation and forest Degradation (REDD+) aims to avoid forest conversion to alternative land-uses through financial incentives. Oil-palm has high opportunity costs, which according to current literature questions the financial competitiveness of REDD+ in tropical lowlands. To understand this more, we undertook regional finescale and coarse-scale analyses (through carbon mapping and economic modelling) to assess the financial viability of REDD+ in safeguarding unprotected forest (30,173 ha) in the Lower Kinabatangan floodplain in Malaysian Borneo. Results estimate 4.7 million metric tons of carbon (MgC) in unprotected forest, with 64% allocated for oil-palm cultivations. Through fine-scale mapping and carbon accounting, we demonstrated that REDD+ can outcompete oil-palm in regions with low suitability, with low carbon prices and low carbon stock. In areas with medium oil-palm suitability, REDD+ could outcompete oil palm in areas with: very high carbon and lower carbon price; medium carbon price and average carbon stock; or, low carbon stock and high carbon price. Areas with high oil palm suitability, REDD + could only outcompete with higher carbon price and higher carbon stock. In the coarse-scale model, oil-palm outcompeted REDD+ in all cases. For the fine-scale models at the landscape level, low carbon offset prices (US $3 MgCO2e) would enable REDD+ to outcompete oil-palm in 55$27 million to secure these areas for 25 years. Higher carbon offset price (US $30 MgCO2e) would increase the competitiveness of REDD+ within the landscape but would still only capture between 69$380–416 million in carbon financing. REDD+ has been identified as a strategy to mitigate climate change by many countries (including Malaysia). Although REDD+ in certain scenarios cannot outcompete oil palm, this research contributes to the global REDD+ debate by: highlighting REDD+ competitiveness in tropical floodplain landscapes; and, providing a robust approach for identifying and targeting limited REDD+ funds

Chemical kinetic model uncertainty minimization through laminar flame speed measurements.

Laminar flame speed measurements were carried for mixture of air with eight C3-4 hydrocarbons (propene, propane, 1,3-butadiene, 1-butene, 2-butene, iso-butene, n-butane, and iso-butane) at the room temperature and ambient pressure. Along with C1-2 hydrocarbon data reported in a recent study, the entire dataset was used to demonstrate how laminar flame speed data can be utilized to explore and minimize the uncertainties in a reaction model for foundation fuels. The USC Mech II kinetic model was chosen as a case study. The method of uncertainty minimization using polynomial chaos expansions (MUM-PCE) (D.A. Sheen and H. Wang, Combust. Flame 2011, 158, 2358-2374) was employed to constrain the model uncertainty for laminar flame speed predictions. Results demonstrate that a reaction model constrained only by the laminar flame speed values of methane/air flames notably reduces the uncertainty in the predictions of the laminar flame speeds of C3 and C4 alkanes, because the key chemical pathways of all of these flames are similar to each other. The uncertainty in model predictions for flames of unsaturated C3-4 hydrocarbons remain significant without considering fuel specific laminar flames speeds in the constraining target data set, because the secondary rate controlling reaction steps are different from those in the saturated alkanes. It is shown that the constraints provided by the laminar flame speeds of the foundation fuels could reduce notably the uncertainties in the predictions of laminar flame speeds of C4 alcohol/air mixtures. Furthermore, it is demonstrated that an accurate prediction of the laminar flame speed of a particular C4 alcohol/air mixture is better achieved through measurements for key molecular intermediates formed during the pyrolysis and oxidation of the parent fuel

Chemical kinetic model uncertainty minimization through laminar flame speed measurements.

Laminar flame speed measurements were carried for mixture of air with eight C3-4 hydrocarbons (propene, propane, 1,3-butadiene, 1-butene, 2-butene, iso-butene, n-butane, and iso-butane) at the room temperature and ambient pressure. Along with C1-2 hydrocarbon data reported in a recent study, the entire dataset was used to demonstrate how laminar flame speed data can be utilized to explore and minimize the uncertainties in a reaction model for foundation fuels. The USC Mech II kinetic model was chosen as a case study. The method of uncertainty minimization using polynomial chaos expansions (MUM-PCE) (D.A. Sheen and H. Wang, Combust. Flame 2011, 158, 2358-2374) was employed to constrain the model uncertainty for laminar flame speed predictions. Results demonstrate that a reaction model constrained only by the laminar flame speed values of methane/air flames notably reduces the uncertainty in the predictions of the laminar flame speeds of C3 and C4 alkanes, because the key chemical pathways of all of these flames are similar to each other. The uncertainty in model predictions for flames of unsaturated C3-4 hydrocarbons remain significant without considering fuel specific laminar flames speeds in the constraining target data set, because the secondary rate controlling reaction steps are different from those in the saturated alkanes. It is shown that the constraints provided by the laminar flame speeds of the foundation fuels could reduce notably the uncertainties in the predictions of laminar flame speeds of C4 alcohol/air mixtures. Furthermore, it is demonstrated that an accurate prediction of the laminar flame speed of a particular C4 alcohol/air mixture is better achieved through measurements for key molecular intermediates formed during the pyrolysis and oxidation of the parent fuel

Chemical kinetic model uncertainty minimization through laminar flame speed measurements.

Laminar flame speed measurements were carried for mixture of air with eight C3-4 hydrocarbons (propene, propane, 1,3-butadiene, 1-butene, 2-butene, iso-butene, n-butane, and iso-butane) at the room temperature and ambient pressure. Along with C1-2 hydrocarbon data reported in a recent study, the entire dataset was used to demonstrate how laminar flame speed data can be utilized to explore and minimize the uncertainties in a reaction model for foundation fuels. The USC Mech II kinetic model was chosen as a case study. The method of uncertainty minimization using polynomial chaos expansions (MUM-PCE) (D.A. Sheen and H. Wang, Combust. Flame 2011, 158, 2358-2374) was employed to constrain the model uncertainty for laminar flame speed predictions. Results demonstrate that a reaction model constrained only by the laminar flame speed values of methane/air flames notably reduces the uncertainty in the predictions of the laminar flame speeds of C3 and C4 alkanes, because the key chemical pathways of all of these flames are similar to each other. The uncertainty in model predictions for flames of unsaturated C3-4 hydrocarbons remain significant without considering fuel specific laminar flames speeds in the constraining target data set, because the secondary rate controlling reaction steps are different from those in the saturated alkanes. It is shown that the constraints provided by the laminar flame speeds of the foundation fuels could reduce notably the uncertainties in the predictions of laminar flame speeds of C4 alcohol/air mixtures. Furthermore, it is demonstrated that an accurate prediction of the laminar flame speed of a particular C4 alcohol/air mixture is better achieved through measurements for key molecular intermediates formed during the pyrolysis and oxidation of the parent fuel

Experimental and modeling study of the oxidation of n- and iso-butanal

Veloo PS, Dagaut P, Togbé C, et al. Experimental and modeling study of the oxidation of n- and iso-butanal. Combustion And Flame. 2013;160(9):1609-1626.Understanding the kinetics of large molecular weight aldehydes is essential in the context of both conventional and alternative fuels. For example, they are key intermediates formed during the low-temperature oxidation of hydrocarbons as well as during the high-temperature oxidation of oxygenated fuels such as alcohols. In this study, an experimental and kinetic modeling investigation of n-butanal (n-butyraldehyde) and iso-butanal (iso-butyraldehyde or 2-methylpropanal) oxidation kinetics was performed. Experiments were performed in a jet stirred reactor and in counterflow flames over a wide range of equivalence ratios, temperatures, and pressures. The jet stirred reactor was utilized to observe the evolution of stable intermediates and products for the oxidation of n- and iso-butanal at elevated pressures and low to intermediate temperatures. The counterflow configuration was utilized for the determination of laminar flame speeds. A detailed chemical kinetic interpretative model was developed and validated consisting of 244 species and 1198 reactions derived from a previous study of the oxidation of propanal (propionaldehyde). Extensive reaction pathway and sensitivity analysis was performed to provide detailed insight into the mechanisms governing low-, intermediate-, and high-temperature reactivity. The simulation results using the present model are in good agreement with the experimental laminar flame speeds and well within a factor of two of the speciation data obtained in the jet stirred reactor. (c) 2013 The Combustion Institute. Published by Elsevier Inc. All rights reserved