Validation of the ASVDADD Constraint Selection Algorithm for Effective RCCE Modeling of Natural Gas Ignition in Air

The rate-controlled constrained-equilibrium (RCCE) model reduction scheme for chemical kinetics provides acceptable accuracies in predicting hydrocarbon ignition delays by solving a smaller number of differential equations than the number of species in the underlying detailed kinetic model (DKM). To yield good approximations, the method requires accurate identification of the rate controlling constraints. Until recently, a drawback of the RCCE scheme has been the absence of a systematic procedure capable of identifying optimal constraints for a given range of thermodynamic conditions and a required level of approximation. A recent methodology has proposed for such identification an algorithm based on a simple algebraic analysis of the results of a preliminary simulation of the underlying DKM, focused on the degrees of disequilibrium (DoD) of the individual chemical reactions. It is based on computing an approximate singular value decomposition of the actual degrees of disequilibrium (ASVDADD) obtained from the DKM simulation. The effectiveness and robustness of the method have been demonstrated for methane/oxygen ignition by considering a C1/H/O (29 species/133 reactions) submechanism of the GRI-Mech 3.0 scheme and comparing the results of a DKM simulation with those of RCCE simulations based on increasing numbers of ASVDADD constraints. Here, we demonstrate the new method for shock-tube ignition of a natural gas/air mixture, with higher hydrocarbons approximately represented by propane according to the full (53 species/325 reactions) GRI-Mech 3.0 scheme including NOx formation.

Experimental and Modeling Study of C1–C3 Hydrocarbon Ignition in the Presence of Nitric Oxide

Nitric oxide (NO) produced during combustion will be present in vitiated air used in many devices. An experimental and modeling investigation of the effect of NO on the ignition of C1–C3 hydrocarbon fuels, namely, CH4, C2H4, C2H6, and C3H6, is presented. These molecules are important intermediate species generated during the decomposition of long-chain hydrocarbon fuel components typically present in jet fuels. Moreover, CH4 and C2H6 are major components of natural gas fuels. Although the interaction between NOx and CH4 has been studied extensively, limited experimental work is reported on C2H4, C2H6, and C3H6. As a continuation of previous work with C3H8, ignition delay time (IDT) measurements were obtained using a flow reactor facility with the alkanes (CH4 and C2H6) and olefins (C2H4 and C3H6) at 900 K and 950 K temperatures with 15 mole% and 21 mole% O2. Based on the experimental data, the overall effectiveness of NO in promoting ignition is found to be: CH4 > C3H6 > C3H8 > C2H6 > C2H4. A detailed kinetic mechanism is used for model predictions as well as for reaction path analysis. The reaction between HO2 and NO plays a critical role in promoting the ignition by generating the OH radical. In addition, various important fuel-dependent reaction pathways also promote the ignition. H-atom abstraction by NO2 has significant contribution to the ignition of C2H4 and C2H6, whereas the reaction between NO2 and allyl radical (aC3H5) is an important route for the ignition of C3H6.

Experimental and Modeling Study of C1 to C3 Hydrocarbon Ignition in the Presence of Nitric Oxide

Nitric oxide produced during combustion will be present in vitiated air used in many devices with exhaust gas recirculation. An experimental and modeling investigation of the effect of nitric oxide on the ignition of C1 to C3 hydrocarbon fuels, namely, CH4, C2H4, C2H6 and C3H6, is presented. These molecules are important intermediate species generated during the decomposition of long-chain hydrocarbon fuel components typically present in jet fuels. Moreover, CH4 and C2H6 are major components of natural gas fuels. Although the interaction between NOx and CH4 has been studied extensively, limited experimental work is reported on C2H4, C2H6 and C3H6. NOx, even in very low concentrations, has previously been shown to effectively enhance the ignition of CH4. As a continuation of previous work with C3H8, ignition delay time measurements were obtained using a flow reactor facility with the alkanes (CH4 and C2H6) and olefins (C2H4 and C3H6) at 900 K and 950 K temperatures with 15 mole% and 21 mole% O2. Based on the experimental data, the overall effectiveness of NO in promoting ignition is found to be: CH4 > C3H6 > C3H8 > C2H6 > C2H4. CSE’s detailed kinetic mechanism, developed for natural gas fuel components, is used for model predictions as well as for sensitivity and species flux analyses. As expected, the reaction between HO2 and NO plays a critical role in promoting the ignition by generating the OH radical while converting NO into NO2. In addition, various important fuel-dependent reaction pathways that promote the ignition of these fuels are identified. H-atom abstraction by NO2 has significant contribution to the ignition of C2H4, and C2H6 whereas the reaction between NO2 and allyl radical (aC3H5) is an important route for the ignition of C3H6.

Validation of the ASVDADD Constraint Selection Algorithm for Effective RCCE Modeling of Natural Gas Ignition in Air

The Rate-Controlled Constrained-Equilibrium (RCCE) model reduction scheme for chemical kinetics provides acceptable accuracies in predicting hydrocarbon ignition delays by solving a smaller number of differential equations than the number of species in the underlying Detailed Kinetic Model (DKM). To yield good approximations, the method requires accurate identification of the rate controlling constraints. Until recently, a drawback of the RCCE scheme has been the absence of a fully automatable and systematic procedure capable of identifying the best constraints for a given range of thermodynamic conditions and a required level of approximation. A recent paper [1] has proposed a new methodology for such identification based on a simple algebraic analysis of the results of a preliminary simulation of the underlying DKM, focused on the behaviour of the degrees of disequilibrium (DoD) of the individual chemical reactions. The new methodology is based on computing an Approximate Singular Value Decomposition of the Actual Degrees of Disequilibrium (ASVDADD) obtained from the DKM simulation. The effectiveness and robustness of the method has been demonstrated in [1] for some cases of methane/oxygen ignition by considering a C1/H/O (29 species/133 reactions) sub-mechanism of the GRI-Mech 3.0 scheme and comparing the results of a DKM simulation with those of RCCE simulations based on increasing numbers of ASVDADD constraints. The RCCE results are in excellent agreement with DKM predictions for relatively small numbers of RCCE constraints. Here we provide a demonstration of the new method for some cases of shock-tube ignition of a natural gas/air mixture, with higher hydrocarbons approximately represented by propane according to the full (53 species/325 reactions) GRI-Mech 3.0 scheme.