Hierarchical and comparative kinetic modeling of laminar flame speeds of hydrocarbon and oxygenated fuels

This paper focuses on the potential use of ammonia as a carbon-free fuel, and covers recent advances in the development of ammonia combustion technology and its underlying chemistry. Fulfilling the COP21 Paris Agreement requires the de-carbonization of energy generation, through utilization of carbon-neutral and overall carbon-free fuels produced from renewable sources. Hydrogen is one of such fuels, which is a potential energy carrier for reducing greenhouse-gas emissions. However, its shipment for long distances and storage for long times present challenges. Ammonia on the other hand, comprises 17.8% of hydrogen by mass and can be produced from renewable hydrogen and nitrogen separated from air. Furthermore, thermal properties of ammonia are similar to those of propane in terms of boiling temperature and condensation pressure, making it attractive as a hydrogen and energy carrier. Ammonia has been produced and utilized for the past 100 years as a fertilizer, chemical raw material, and refrigerant. Ammonia can be used as a fuel but there are several challenges in ammonia combustion, such as low flammability, high NOx emission, and low radiation intensity. Overcoming these challenges requires further research into ammonia flame dynamics and chemistry. This paper discusses recent successful applications of ammonia fuel, in gas turbines, co-fired with pulverize coal, and in industrial furnaces. These applications have been implemented under the Japanese ‘Cross-ministerial Strategic Innovation Promotion Program (SIP): Energy Carriers’. In addition, fundamental aspects of ammonia combustion are discussed including characteristics of laminar premixed flames, counterflow twin-flames, and turbulent premixed flames stabilized by a nozzle burner at high pressure. Furthermore, this paper discusses details of the chemistry of ammonia combustion related to NOx production, processes for reducing NOx, and validation of several ammonia oxidation kinetics models. Finally, LES results for a gas-turbine-like swirl-burner are presented, for the purpose of developing low-NOx single-fuelled ammonia gas turbine combustors.

Science and technology of ammonia combustion

An updated H2/O2 kinetic model based on that of Li et al. (Int J Chem Kinet 36, 2004, 566–575) is presented and tested against a wide range of combustion targets. The primary motivations of the model revision are to incorporate recent improvements in rate constant treatment and resolve discrepancies between experimental data and predictions using recently published kinetic models in dilute, high-pressure flames.

Attempts are made to identify major remaining sources of uncertainties, in both the reaction rate parameters and the assumptions of the kinetic model, affecting predictions of relevant combustion behavior. With regard to model parameters, present uncertainties in the temperature and pressure dependence of rate constants for HO2 formation and consumption reactions are demonstrated to substantially affect predictive capabilities at high-pressure, low-temperature conditions. With regard to model assumptions, calculations are performed to investigate several reactions/processes that have not received much attention previously. Results from ab initio calculations and modeling studies imply that inclusion of H + HO2 = H2O + O in the kinetic model might be warranted, though further studies are necessary to ascertain its role in combustion modeling. In addition, it appears that characterization of nonlinear bath-gas mixture rule behavior for H + O2(+ M) = HO2(+ M) in multicomponent bath gases might be necessary to predict high-pressure flame speeds within ∼15%.

The updated model is tested against all of the previous validation targets considered by Li et al. as well as new targets from a number of recent studies. Special attention is devoted to establishing a context for evaluating model performance against experimental data by careful consideration of uncertainties in measurements, initial conditions, and physical model assumptions. For example, ignition delay times in shock tubes are shown to be sensitive to potential impurity effects, which have been suggested to accelerate early radical pool growth in shock tube speciation studies. In addition, speciation predictions in burner-stabilized flames are found to be more sensitive to uncertainties in experimental boundary conditions than to uncertainties in kinetics and transport. Predictions using the present model adequately reproduce previous validation targets and show substantially improved agreement against recent high-pressure flame speed and shock tube speciation measurements. Comparisons of predictions of several other kinetic models with the experimental data for nearly the entire validation set used here are also provided in the Supporting Information. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 44: 444–474, 2012

Comprehensive H2/O2 kinetic model for high-pressure combustion

Alcohol combustion chemistry

Natural-gas fueled spark-ignition (SI) and compression-ignition (CI) engine performance and emissions

Experimental and numerical study on laminar burning characteristics of premixed methane–hydrogen–air flames

Experimental study on combustion characteristics of a spark-ignition engine fueled with natural gas–hydrogen blends combining with EGR

Experimental investigation on performance and emissions of a spark-ignition engine fuelled with natural gas–hydrogen blends combined with EGR

Laminar flame speeds and ignition delay times of methane–air mixtures at elevated temperatures and pressures

Cycle-by-cycle variations in a spark ignition engine fueled with natural gas–hydrogen blends combined with EGR

Erjiang Hu

Papers

Experimental and numerical study on laminar burning characteristics of premixed methane–hydrogen–air flames

Experimental study on combustion characteristics of a spark-ignition engine fueled with natural gas–hydrogen blends combining with EGR

Experimental investigation on performance and emissions of a spark-ignition engine fuelled with natural gas–hydrogen blends combined with EGR

Laminar flame speeds and ignition delay times of methane–air mixtures at elevated temperatures and pressures

Cycle-by-cycle variations in a spark ignition engine fueled with natural gas–hydrogen blends combined with EGR