Paper #11 Nox Prediction and Control in Oxygen Enriched Air-Natural Gas Burners C. E, Baukal, J. W. Mitchell and A. I. Dalton Air Products and Chemicals, Inc. Allentown, PA 18195 Copyright 1989, Gas Research Institute Abstract Air Products has an ongoing program to develop oxygen-based technologies for combustion processes used in heating and melting applications. These processes are typically found in the glass and metals industries. Oxygen enrichment of existing air-fuel combustion processes can _increase production, reduce fuel consumption, and reduce flue gas volume. As part of this program, a model is being developed to predict the impact of oxygen enrichment on NOx levels in the flue of industrial furnaces, The model (GRREK) incorporates gas flow and radiation with reaction equilibrium and kinetics. GRREK is being used to predict flue NOx at various oxygen enrichment levels in a furnace. It is also being used to identify the important parameters in the production and control of NOx in order to develop alternatives to the capitally intensive post combustion cleaning systems. GRREK is designed for steady-state, turbulent flow in a two- dimensional cylindrical furnace with a burner at one end and anexit flue at the other end. The full Navier-Stokes equations are solved using a finite difference, control volume technique. The model is designed to solve any level of complexity for the NOx chemical kinetics. Each control volume in the furnace is treated as a Perfectly Stirred Reactor (PSR). Radiative transport between the flame and the furnace is modeled using the method of discrete ordinates. The paper compares the model predictions of NO against data taken in the Air Products combustion furnace for a North American air-fuel burner tested at various stoichiometries and levels of oxygen enrichment. The measured values at two stoichiometries are compared against the theoretically predicted values. The model predicted the correct trend, but an order of magnitude higher than the measured values. The laboratory tests and model development are being jointly funded by the Gas Research Institute and Air Products.Introduction In this environmentally conscious age, increasingly more stringent regulations are being placed on discharges to the atmosphere from industrial processes. Nitrogen oxides have captured considerable attention in recent years because of their adverse affect on the general population via smog, acid rain, and ozone formation. Approximately 30% of acid rain is due to NOx. Other than the automobile, the largest sources of NOx are power plants and industrial processes!. There are currently three generally accepted methods for NOx formation. Thermal NOx is formed by the reaction of nitrogen with oxygen at high temperatures. Prompt NOx is formed by the relatively fast reaction between nitrogen, oxygen, and hydrocarbon radicals. Fuel NOx is formed by the direct oxidation of organo-nitrogen compounds contained in the fuel. The overall reactions are as follows: Nz + 02 --> NO, NOz Thermal NOx CHs + 02 + Nz --> NO, NOz, COz, HzO = Prompt NOx RsN + Oz --> NO, NOz, COz, H20 Fuel NOx With high-quality fuels like natural gas, which contains only trace amounts (if any) of organically bound nitrogen, fuel NOx is not a concern. Oxygen enrichment of air-natural gas combustion processes increases the flame temperature. As a result flame radiation is increased which reduces the amount of energy lost with the exhaust gases. This has several significant commercially demonstrated advantages. | Oxygen enrichment can increase production in heating and melting applications, increase energy efficiency, reduce particulates, and reduce total gaseous emissions by substantial reduction of the flue gas volume. At low to intermediate enrichment levels, the higher flame temperatures may also lead to higher NOx formation. It is important to understand how NOx is formed in natural gas combustion processes and the impact of oxygen enrichment on NOx production. With this understanding, combustion control techniques to minimize NOx formation can be identified rather than relying solely on expensive treatment systems. Toward this goal, Air Products is developing a combustion model to predict the importance of various parameters, including enrichment level, on NOx production. This research project is being sponsored by the Gas Research Institute. The main tasks are: to develop a computer model to predict the NOx concentrations in the exhaust products of an oxygen enriched air-natural gas flame,+ to. conduct an experimental program to verify the model performance, and 3. to formulate NOx reduction strategies for industrial processes using oxy-natural gas burners. Research is now focused on objectives one and two. Numerical Model Air Products is currently developing a computer model called GRREK to predict NOx levels in flue gas. GRREK is an acronym for Gas flow and Radiation with Reaction Equilibrium and Kinetics. GRREK incorporates submodels for calculating fluid flow, radiation heat transfer, and chemical kinetics. The specific objectives of the model development are: 1. to generate a model to predict flue NOx at various 02 enrichment levels in a furnace with a natural gas fired burner at one end and a flue at the other end, and 2. to identify the significant parameters in NOx production. GRREK is constructed with interconnected modules. This approach has several advantages. Parallel development of modules decreases the development and debugging time. GRREK can be easily modified by substituting more efficient routines or improved kinetics when they become available. Unneeded modules can be made inactive while solving a particular problem to reduces computation time. The fluid flow module has its source in the combustion model (COMO) developed by Babcock and Wilcox for the U.S. Department of Energy?. COMO is a numerical model for predicting furnace performance in axisymmetric geometries. The model was originally written to study pulverized coal combustion in utility boilers. COMO also consists of relatively independent modules that represent the major processes in pulverized coal combustion: flow, heterogeneous and homogeneous chemical reaction, and heat transfer. This modularity makes COMO readily adaptable to other types of chemical processes. The fluid flow module is designed to solve the full Navier- Stokes equations for steady-state, turbulent, two-dimensional axisymmetric (cylindrical) flows. The furnace is divided into control volumes. The governing equations are integrated over each control volume, assuming some distribution for the dependent variables. The assumed distribution is iteratively corrected until a converged solution is obtained. The partial differential equations are discretized using finite difference techniques’. The module solves the resulting algebraic equations to predict the pressure and velocity fields. The k-e approximation is used to model turbulence and the overall macromixing in the furnace.The chemistry module quantifies the effect of homogeneous gas phase chemical reactions within the furnace. A common assumption in combustion modeling is that the chemical reaction rates are controlled by the rate of turbulent mixing. This "fast kinetics" assumption, valid when the reaction time scales are much less than the mixing time scales, greatly simplifies the model equations and provides reasonably accurate predictions for the major chemical components. Temperature and velocity field calculations are also predicted adequately. For the NOx chemistry, where reaction time scales are similar in magnitude to the time scales for mixing, the "fast kinetics" hypothesis is not valid. A full kinetic description is used in the present effort. To meet the objectives of this work, the reaction set employed must contain detailed descriptions of the hydrocarbon combustion, thermal NOx, and prompt NOx kinetic mechanisms. Westbrook and Dryer have reported a large number of potential reactions in a typical combustion process!. A kinetic sensitivity analysis was performed to determine a realistic but manageable reaction set to describe the combustion/NOx chemistry'. The analysis was performed by simulating a premixed gas-oxidant flame under adiabatic conditions. Table 1 displays the resulting set of 115 reactions chosen to represent the complex chemistry. Thermodynamic properties for the reacting species are evaluated based on the JANF databank. The control volumes are treated as perfectly stirred reactors (PSR) in the solution procedure. For initialization purposes only, each control volume is assumed to be at chemical equilibrium. During subsequent iterations, the steady state solutions to the fully kinetic component material balance equations are determined via a Newton-Raphson convergence. If the Newton-Raphson method fails, which is possible for near-equilibrium control volumes, the transient PSR equations are integrated to their steady state solution via a stiff ODE solver’. The heat transfer module calculates the radiative transport in the furnace using the method of discrete ordinates*. The resulting equations with the appropriate radiative boundary conditions are integrated over each control volume and solved by a point-by-point iterative scheme. The model geometry represents a cylindrical furnace with a burner at one end and an exit flue at the other end. The grid can be adjusted to provide more nodes at a given location to increase accuracy without severely penalizing computational time Typically there should be more node points in the vicinity of the flame and fewer node points near the flue end of the furnace. . GRREK currently operates on a VAX 11-780 minicomputer. Solution time varies greatly depending on the nature of the problem, but is on the order of several minutes to severalhours. The input to the program consists of: 1) geometry data; 2) gas transport, thermodynamic and chemical properties; 3) reaction chemistry information; 4) radiation parameters; and 5) program control variables (iterations, relaxation, etc.). Model Results A standard North American 4425-8A nozzle mix, air-fuel burner (Figure 1) was fired in the Air Products combustion lab furnace (Figure 2). The parameter ranges tested were as follows 21 - 28% oxygen levels in the air stream 1.5 - 2.5 MMBtu/hr firing rates 1.8 - 2.5 stoichiometric ratios The furnace was fired at each set of conditions until steady state was achieved (one half hour minimum in a warmed up furnace). A positive furnace pressure was maintained to exclude air infiltration in order to isolate the effect of the burner on NOx formation. The model is currently being used to predict the NOx produced by this burner in the Air Products combustion lab furnace. Since GRREK is designed for 2 dimensional cylindrical coordinates, the rectangular furnace is approximated by a cylinder of equal cross-sectional area. A plot of the grid is shown in Figure 3. The grid consists of. 36 nodes in the axial direction and 31 nodes in the radial direction. The furnace is 17.7’ long and has an equivalent radius of 4.2’. The exhaust flue is 2’ in diameter. Although GRREK is designed to handle any number of reactions, only the prompt NOx and thermal NOx reactions are being considered since fuel NOx is insignificant in natural gas combustion processes. The test cases being modeled are shown in Table 2. Case 1 is the base case with the furnace wall temperature at 2000°F with the full set of prompt and thermal NOx reactions. For case 2, the wall temperature was lowered to 1000°F to see the effect on NOx. The flue NO is lowered because the increased radiation from the flame to the walls lowers the overall flame temperature which reduces the thermal NOx. Because the wall is some distance from the flame, the effect is not very significant. Case 3 is the same as case 1 except that the prompt NOx reactions are removed so that their relative importance can be assessed. Table 3 shows the reduced set of reactions suggested by Pratt and Wormeck?. The flue NO is reduced, but not significantl: Therefore prompt NOx does not eppear to be important in this particular combustion system.Case 4 is the same as case 1 except for the increased stoichiometry. The flue NO increases for the lean stoichiometry because there is more available Oz for the thermal NOx reactions. Cases 5 and 6 are the same as case 1 except with increased amounts of oxygen enrichment in the air stream. These cases were not completed at the time of this writing. It is expected that they will show increasing levels of NOx due to the increased flame temperatures. Figures 4 and 5 show the predicted surface contour plots for CHa and 02 respectively. Both of these species are quickly expended near the burner outlet. Figures 6 and 7 show the predicted temperatures for the base case on profile and surface contour plots respectively. As expected, the highest temperatures are along the centerline in the vicinity of the flame. Figures 8 and 9 show the predicted NO on profile and surface contour plots respectively. It is interesting to note the saddle point in Figure li which would seem to suggest that there are some reactions at that point which convert NO to some other species. Figure 10 shows a graph of flue NO as a function of burner stoichiometry for the model predictions and the experimental data measured in the lab furnace. The graph shows that the trends are the same, but the predicted values are about an order of magnitude higher than the measured values. Figure 11 shows a plot of flue NO as a function of percent oxygen in the oxidant. At the time of this writing, the model results for cases 5 and 6 were not available. Conclusions GRREK appears to predict the correct trend for flue NO as a function of burner stoichiometry, but the predicted values are about an order of magnitude higher than the measured data. According to GRREK, the furnace wall temperature and prompt NOx are not important in flue NO production for the combustion system analyzed. Future Work In order to improve the accuracy of the model, micromixing effects will be included by adding a first order closure model, involving a single parameter, to the turbulent concentration equations. The closure model chosen, derived from a mechanistic model of turbulent mixing is that developed by Tarbell!®. The micromixing parameter is thecharacteristic time scale which is determined directly from the flow field calculation of the turbulent kinetic energy, the turbulent dissipation rate, and the Schmidt number. The test cases for oxygen enrichment will be completed. The effects of firing rate and other’ stoichiometries will also be modeled. The NOx reactions in the vicinity of the flame will be further studied to determine the reason for the saddle point in the NO contour plot in Figure 11. Finally, GRREK will be used to formulate strategies for reducing NOx in industrial processes using oxy-natural gas burners. Acknowledgments This material is based on work supported by the Gas Research Institute (contracted to Air Products and Chemicals, Incorporated).References Sa 10. Lukasiewicz, M. A. et al, "NOx Control Using Oxy-Natural Gas Burners," presented at the Ninth Members Conference for the International Flame Research Foundation in the Netherlands, May 1989. Fiveland, W.A. et al, "COMO: A Numerical Model for Predicting Furnace Performance in Axisymmetric Geometries," Volume 1 - Technical Summary and Volume 2 - Users Guide, DOE Report No. DOE/PC/40265-9, 1985. Patankar, S.V., "Numerical Heat Transfer and Fluid Flow," Hemisphere Publishing, New York, 1980. Westbrook, C. K. and F. L. Dryer, “Chemical Kinetic Modeling of Hydrocarbon Combustion," Prog. Energy Combust. Sci, 1984, Vol. 10, pp. 1-57. Cernansky, N. P., Personal Communication, February 1988. Stull, D. R. and H. Prophet, eds., JANAF Thermochemical Tables, Second Edition, NBS-37, June 1971. Hindmarsh, A. C., "LSODE - Livermore Solver for Ordinary Differential Equations," Mathematics and Statistics Division, Lawrence Livermore Laboratory, Livermore, CA. Fiveland, W, A., "A Discrete Ordinates Method for Predicting Radiative Heat Transfer in Axisymmetric Enclosures," ASME Paper No. 82-HT-20, 1982. Pratt, D. T. and J. J. Wormeck, "CREK: A Computer Program for Calculation of Combustion Reaction Equilibrium and Kinetics in Laminar or Turbulent Flow," Washington State University Report No.: WSU-ME-TEL-76- 1, March 1976. Tarbell, J. M., "A Closure Model for Turbulent Reacting Flows," AIChE J., in press.Cora ReNe CHs CHe CHa CHs CHa CHs CHs CHs CHs CHs CHs CHS CHs CHs CHs CH30 CH30 CH3O CH30 CH20 CH20 CH20 CH20 cH20 CHO cHO CHO CHO CHO CHO CHa CHa CH2 CHz CHz CH2 CH2 CH2 CHe cH CH cH CH co co C02 He O2 H202 H2 02 Hz 02 HO2 HO2 HO2 Hoz HO2 RARE EEE EE EET EEE EEE EE EERE EEE EEE EERE EER EEE EEE HERE EEE Table 1: CHa CHs CHa CHs CHs 2CHs CH2 CH2 CHO CHz CHz cH20 CHO CHsO CH30 CH20 cH20 cH20 CHO 2HO2 2HO Oz O2 ERE EE TEETH EA EE EEE EEE EEE EEE EEE EEE EE EEE EEE RHEE ++ H+M He HO #20 H2 02 H+ M He H HO #20 Ha HO Full Set of NOx Reactions O2 H ° HO #20 #20 Oz HO He HNO HNO HNO NH2 NH2 NH2 NH2 NHz NH3 NH3 NHS NH N20 N20 N20 N20 + + + + + . + + + + + + + + + + + + + + + + + + + + + + + + + + + + + ie + + + + + + + + + + + + + + + + + + + + + Ha 2 He Ha +4e REET EEE EE EEE EEE E EERE TEETH EEE AE EEE EEE EEE EE EEE ET oxm mmo + = + = Hg gmOzMOOOnE 6Table 2: Test Cases Being Modeled Parameter Case aL a a ‘+ so Firing Rate (MMBtu/hr ) A it) = ao) aK) 2.0 Stoichiometry Bo) =) = os 2.0 Oz in oxidant (%) a1 21 a1 21 24 28 Furnace Wall Temp. (°F) 2000 1000 2000 2000 2000 2000 No. of Reactions nS eee 1151 3300 «11500115 115 No. of Species 30 30 19 30 30 30 Predicted NO (1b/MMBtu) 1.72 1.66 1.70 2,60 N/A N/A N/A = Not available at time of writing. e CHa CHs CHe CHa CHs CHs CHa CHs cH20 CH20 cHO CHO CHO CHO cHO CHa co C02 HOz HO2 HO2 EERE EEE EA EEE EEE E EEE EEE EE EEE ET Reduced Set of Reactions M CH» +H +M H CH: + He ° CHs + HO HO = CHs + H20 H CH2 + Hz ° CH20 + H HO = CHz + H20 02 CH20 + HO ° CHO + HO HO = CHO + #20 M co +H+M a cO + He ° co + HO HO = CO + #20 O2 CO + HOz Oz cH20 + 0 HO = COz +H M =sCO +0+4 HO = 02 + #20 H = 2HO M +H+M O2 +0 He +H He +H ° M +HHM M +O+M HO. +H 02 +0 No +0 M +O+™M H + HO °rigre 1: NORTH AMERICAN 4425 Figure 2: sumer Test Facility + elle= 1.00 Zz 2 i peers et ee or aie ae . 8 8 oe a oO a oso peers ee et : Byes ceectet ar a x eth ele a + + . + os a <= a2 3.0 407 POSITION, m Figure 3: Grid Spacing for Furnace Simulation 3. 9-007 14 CONCENTRATION, 1 9metcte Figure ¢#: Predicted CH4 SurfaceRADIAL POSITION, m Lm, HT AE oy UE . TLS is z SON) Sa eine SSS ge es IES MN Ne i NSS SI RES ENNN i WHR SR MER ESOS SSN NSS SHINN KKK MSS AN SSN . ESS SANT RSAN NS g SHIN SCRA ATA IEORX Ss ' Hs t op | HAN AN ys Figure & Predicted O2 Surfece 3 E = 7 uET OY 3 : oo E $ 2 gS - J 2eeeons— 2.08e+003 ‘003 2 2.131003 5003 ES 20 28 AXIAL POSITION, mm Figure 6: Predicted Temperature Contours (2) 213.Figure 8: Predicted NOx Contours (kg-rele/kesr Ss LIKI LESS KW nonin x 65 Noe CONCENTRATION. tome cr9 Figure 9: Predicted NOx Surface rige 10: NO in the Flue Effect of Stoichiometry Ibs NO/MMBtu 10 NA4426-8A, 2.0 MMBTUH a —— © Experimental + GRREK Model rpeaat s Seo NON 21 e222 a) 2s ae ee 2: STOICHIOMETRYFigure: NO in the Flue Effect of Oxygen Enrichment Ibs NO/MMBtu 10 NA4425-BA AIR-FUEL (UNMODIFIED) 2.0 MMBtuH Ot es © GRREK Model + Experimental oO 21 «2282S GT 2B BDO 2 IN OXIDIZER (%) -16-