Prediction of NOx Emissions in Recovery Boilers  An Introduction to NOx Module

Dr. Jerry J.W. Yuan

Process Simulations Ltd. 2386 East Mall, Suite 204 Vancouver, B.C., V6T 1Z3, Canada

April, 1999

Prompt NOx 1 . particularly at near-stoichiometric conditions and in fuel-rich mixtures: k +3 N + OH ←→ H + NO The rate of formation of thermal NOx is significant only at high temperatures (greater than 1800 K) because fixation of nitrogen requires the breaking of the strong N2 triple bond. and fuel NOx is produced by oxidation of nitrogen contained in the fuel. The NOx formed by these three processes is described as thermal NOx. Thermal NOx The formation of thermal NOx is determined by a set of highly temperature-dependent chemical reactions known as the extended Zeldovich mechanism. and fuel NOx. Thermal NOx is formed by the oxidation of atmospheric nitrogen present in the combustion air. prompt NOx. and at the molecular level within turbulent flames. the formation of NOx can be attributed to three distinct chemical kinetic processes. Prompt NOx is produced by high-speed reactions at the flame front. The principal reactions governing the formation of thermal NOx from molecular nitrogen are as follows: k +1 O + N 2 ←→ N + NO k +2 N + O2 ←→ O + NO  A third reaction has been shown to contribute. Yuan Prediction of NOx Emissions in Recovery Boilers  An Introduction to NOx Module 1.Prediction of NOx Emissions in Recovery Boilers Dr. Introduction In laminar flames.W. Jerry J.

Tao et al. in the reaction zone. The relative importance of thermal NOx and prompt NOx may increase. Prompt NOx also contributes less to the total NOx emission from recovery boilers because the flame is less rich comparing with the normal gas flames. Therefore. The actual formation involved a complex series of reactions and many possible intermediate species. CN. 2. The route now accepted is as follows: CH + N 2 ← → HCN + N N + O2 ← → NO + O HCN + OH ← → CN + H 2O CN + O2 ← → NO + CO Many investigations have shown that the prompt NOx contribution to total NOx from stationary combustors is small. Fuel-bound nitrogen-containing compounds are released into the gas phase when the fuel droplets or particles are heated during the devolatilization stage. bark. N. However. the NOx emission from recovery boilers is in a lower level comparing with utility boilers fuelled by fossil fuels.Prediction of NOx Emissions in Recovery Boilers Dr. Fuel NOx It is well known that nitrogen-containing organic compounds present in liquid or solid fuel can contribute to the total NOx formed during the combustion process. fuelled by black liquor. [1] 2 . both thermal NOx and prompt NOx can be neglected in the NOx emission prediction at present.W. Yuan Prompt NOx is most prevalent in rich flames. radicals such as HCN. Jerry J. The extent of conversion of fuel nitrogen to NOx is dependent on the local combustion characteristics and the initial concentration of nitrogen-bound compounds. From the thermal decomposition of these compounds. Normally in recovery boilers. or hogfuels. thermal NOx is significant only at the temperature higher than 1800 K. and NH can be formed and converted to NOx. NOx Formation and Destruction in Recovery Boilers As mentioned above. the maximum gas temperature is lower than 1800 K.

CN and so on. HCN will be oxidized by O2 into NO. As an alternative way. such as HCN. [3]. As a normal treatment. In the gas phase.Prediction of NOx Emissions in Recovery Boilers Dr. when it is released into the gas phase. Yuan predicted the NOx emission from a Kraft recovery boiler. 3]. In the gas phase. while those released during the char burning stage as char-N. According to the investigation by Forssen et al. The char-N may be oxidized into NO if oxygen can reach the surface of the char particle. The heterogeneous reaction of NO reduction on the char particle surface has been found in our experiment [4].W. or reduced by NO into N2 . therefore. The release rate of char-N is assumed as the same as char burning rate. and also by Iisa et al. both thermal NOx and prompt NOx should be included in the NOx prediction. but it needs to make improvements on the existing black liquor combustion program. it is assumed in this model that the char-N releases out during the char burning stage in the form of HCN. In this model. The reduction rate determined by Iisa et 3 . The distribution of fuel nitrogen in volatile-N and char-N depends on the fuel properties. and found that 19 ppm is from thermal-NOx among the total NOx emission of about 48 ppm. Fuel NOx makes the greatest contribution to the total NOx emission from recovery boilers. We name the nitrogen-containing compounds released during the devolatilization stage as volatile-N. The volatile-N may appear as different forms of chemical species. it is acceptable to assume that the mass fractions of volatile-N and char-N are proportional to the mass fractions of volatile and fixed carbon respectively if no related experimental data are available. It may also release into gas phase in the form of N2 if oxygen cannot reach the surface of the char particle [2. It is possible to simulate this process. we assume the form of volatile-N to be NH3 only. NH3 will be oxidized by O2 into NO. For further study. NH3 . It is also assumed that the volatile-N evolution has the same rate as the devolatilization. Jerry J. especially when the nitrogen content in the fuel is high. and may vary from fuel to fuel. or reduced by NO into N2 . [3]. the volatile-N mainly releases into gas phase in the form of NH3 in the case of black liquor combustion in the recovery boiler. [2] and Iisa et al. The nitrogen-containing compounds in the fuel may release into gas phase at both devolatilization stage and char burning stage.

has been adopted in this model. When the secondary fuel is injected into the furnace to form a fuel rich zone. In this model. named reburning zone. Jerry J. as discussed above. R2 = conversion rate of NH3 (1/s) R3 = NO reduction rate by char particle (m3 /s/mBET2 ) 4 . the NO reduction by reburning mechanism will be significant. can be summarized by the reaction pathway as follows: Char-N Fuel-N Volatile-N HCN 6: CHi 4: O2 5: NO NH3 1: O2 2: NO N2 NO 3: Char N2 The reaction rates of above six reactions are as follows: a R1 = A1 x NH 3 x O2 exp( − E1 / RT ) R2 = A2 x NH 3 x NO exp( − E2 / RT ) R3 = [ A31 exp( − E31 / RT ) + A32 x CO exp( − E32 / RT )] x NO a R4 = A4 x HCN xO2 exp( − E4 / RT ) R5 = A5 x HCN x NO exp( − E5 / RT ) R6 = A6 x HC x NO exp( −E 6 / RT ) where R1. the global reaction rate between CHi and NO derived by Chen [5] is adopted. Many investigations have proved that the NO reduction rate can be as high as 60 % by using reburning technique. If the fuel staging technique is adopted in the recovery boiler. Yuan al.Prediction of NOx Emissions in Recovery Boilers Dr. HCN is mainly reduced by NO into N2 . Under the reducing atmosphere. the hydrocarbon radicals CHi will react with the formed NO from the main combustion zone to produce HCN.W. The NOx formation and reduction in recovery boilers.

12×1010 m3 /mBET 2 /s (if T > 923 K) E32 = 18.300 cal/ mol (if T > 923 K) A32 = 37.0×1012 1/s E5 = 60.000 cal/ mol A31 = 0.8×108 1/s E2 = 27.300 cal/ mol (if T > 923 K) A4 = 3.8 m3 /mBET2 /s (if T ≤ 923 K) = 7.000 cal/ mol (if T ≤ 923 K) = 57.000 cal/ mol A6 = 2.5×1010 1/s E4 = 67.72×106 1/s 5 .0×106 1/s E1 = 32.Prediction of NOx Emissions in Recovery Boilers Dr. Jerry J.000 cal/ mol A2 = 1.204 m3 /mBET2 /s (if T ≤ 923 K) = 1.000 cal/ mol A5 = 3. R5 = conversion rates of HCN (1/s) R6 = NO reduction rate by reburning (1/s) T T = instantaneous temperature (K) = mean temperature (K) = mole fractions x A1 = 4.160 cal/ mol (if T ≤ 923 K) = 57. Yuan R4 .W.26×109 m3 /mBET2 /s (if T > 923 K) E31 = 16.

9 ln x O2 . k M i Aρ ε mR k υ ' R. In the eddy breakup model. Additional effort is necessary in order to calculate the mean reaction rate correctly.k (kg/m3 /s) is given by the smallest of the two expressions below: Ri .1.03 3. The influence of turbulence on the reaction is taken into account by employing combined Arrhenius and eddy breakup model.0.03  0.1 ln x O2 . x O2 ≥ 0.W. Yuan E6 = 18.k = υ ' i.986 cal/(mol⋅K) The oxygen reaction order a is calculated from the following equation: 1.11 × 10 − 2 a= −2 − 0.k P where υ ' i .35 − 0. k M i ABρ ∑m ∑ υ' M P P P P . k = molar stoichiometric coefficient for species i in reaction k Mi = molecular weight of species i (kg/kmol) ε = dissipation rate of turbulent kinetic energy (m2 /s3 ) k = turbulent kinetic energy (m2 /s2 ) mR = the mass fraction of a particular reactant. k M R ε k Ri . giving the smallest value of Ri.Prediction of NOx Emissions in Recovery Boilers Dr.800 cal/ mol R = universal gas constant equal to 1. Turbulence-Chemistry Interaction Model The flow in recovery boiler is fully three-dimensional and turbulent.k mP = the mass fraction of any product species.1 × 10 −3  − 3.0 6 . R.k = υ ' i. xO2 ≤ 4. P A = an empirical constant equal to 4. There are interactions between turbulence and chemistry.1 × 10 −3 < x O2 ≤ 1.11× 10 < x O2 < 0. the rate of reaction Ri.95 − 0. Jerry J.4.

the source terms of species NH3 . Source terms for NH3 (kg/s/m3 ) S NH3 −V = SV M NV M NH 3 / M N / V S NH3 −1 = − min{ R1 M NH 3 P RT M NH 3 P RT . M HCN x NO A . the reaction rates are calculated from the Arrhenius expression (the chemical reaction rate shown above) and the eddy breakup model. Jerry J.Prediction of NOx Emissions in Recovery Boilers Dr.W. M NO x NO AB } RT k RT M NO + M H 2O k RT 7 . The limiting (slowest) rate is used as the reaction rate.5 In the combined Arrhenius and eddy breakup model. M HCN x HCN AB } RT k RT M HCN + M H 2O k RT Source terms for NO (kg/s/m3 ) S NO −1 = min{ R1 M NO P ε P M NO ε P . M HCN x NO AB } RT k RT M NO + M HCO k RT S HCN − 2 = − min{ R5 M N2 M HCN P ε P ε P . M HCN x N2 AB } RT k RT M N 2 + M HCO k RT S HCN − 3 = min{ R6 M HCN P ε P M HCN ε P . M NO x NH3 A . M NH 3 x NH 3 A Source terms for HCN (kg/s/m3 ) S HCN − C = SC M NC M HCN / M N / V S HCN −1 = − min{ R4 M HCN P ε P M NO ε P . Yuan B = an empirical constant equal to 0. According to the above models. M HCN x HCN A . M NH 3 x NH3 A ε P M NO ε P . M NH 3 x NO AB } k RT M NO + M H2 O k RT M N2 ε P ε P . and the contribution to the source terms in the species conservation equations are calculated from this reaction rate. M NH 3 x N 2 AB } k RT M N 2 + M H2 O k RT S NH3 −2 = − min{ R2 . M HCN x HCN A . HCN and NO conservation equations can be arranged as follows.

As a result. Yuan S NO −2 = − min{ R2 M N2 M NO P ε P ε P . M NO x NO A . Jerry J. M NO x N 2 AB } RT k RT M N 2 + M HCO k RT M NO P ε P M HCN ε P . M NO x HCN AB } RT k RT M HCN + M H 2O k RT S NO −6 = − min{ R6 where SNH3-V = source of NH3 from volatiles (kg/s/m3 ) SHCN-C = source of HCN from char (kg/s/m3 ) SV = source of volatiles originating from fuel droplets into the gas phase (kg/s) MNV = mass fraction of nitrogen in the volatiles SC = char burnout rate (kg/s) MNC = mass fraction of nitrogen in char V = cell volume (m3 ) P = the pressure of combustion system (atm) R = universal gas constant equal to 8. M NO x N 2 AB } RT k RT M N 2 + M H3O k RT M NO P RT S NO −3 = − ABET c s R3 S NO −4 = min{ R4 M NO P ε P M NO ε P . M NO x NO AB } RT k RT M NO + M HCO k RT S NO −5 = − min{ R5 M N2 M NO P ε P ε P . NOx Module NOx concentrations generated in the combustion process in recovery boilers are generally low. M NO x HCN A . NOx chemistry has negligible influence on the predicted flow field.W. It follows that the 8 . and major combustion product concentrations. M NO x HCN A .Prediction of NOx Emissions in Recovery Boilers Dr.206×10-2 m3 ⋅atm/(kmol⋅K) ABET = BET surface area of char particle (m2 /kg) cs = concentration of particles (kg/m3 ) 4. M NO x NH 3 A . temperature.

In the NOx module. such as volatile releasing rate. calculated from droplet combustion program SC – consumption rate of fixed carbon at each cell (kg/s). and 1. density. it can be calculated as M NV = f N2 fVM + f FC 9 . MNV – mass fraction of nitrogen in volatile. turbulent kinetics. Also the calculated values of fuel droplet combustion process.1 Input Data The necessary input data for NOx module are listed as follows: f N2 – mass fraction of nitrogen in fuel f VM – mass fraction of volatile in fuel f FC – mass fraction of fixed carbon in fuel SV – mass rate of volatile released into gas phase at each cell (kg/s). calculated from droplet combustion program cs – concentration of particles at each cell (kg/m3 ). Jerry J. the BET area has a value of 14. HCN and NO will be solved in iteration. are very important for the NOx simulation. Yuan most efficient way to use the NOx module is as a postprocessor to the main combustion calculation. According to the assumption in this model. The procedure to calculate these three equations will be the same as to other scalar equations except the diffusion coefficient and the source terms as discussed above.000 m2 /kg at the temperature of 1023 K. the species conservation equations of NH3 . [3]. char burnout rate. and so on.000 m2 /kg at the temperature of 1173 K. calculated from droplet combustion program ABET – BET surface area of char particle (m2 /kg).W. According to the measurement by Iisa et al. such as velocities. 4. and particle concentration. The calculated data from the main combustion simulation will be used in the module.Prediction of NOx Emissions in Recovery Boilers Dr. temperature.

Prediction of NOx Emissions in Recovery Boilers Dr. Use of A Computer Model for Evaluation of Combustion and NOx Control Alternatives in A Kraft Recovery Boiler. Forssen.299-312 [2] M.W. Kilpinen and M. pp. NOx Reduction in Black Liquor Combustion – Understanding Reaction Mechanisms Reveal Novel Operation Strategy Options. 10 . HCN and NO are as follows: SC − NH 3 = S NH3 −V S P− NH 3 = ( S NH3 −1 + S NH3 − 2 ) / x NH 3 SC − HCN = S HCN − C + S HCN −3 S P− HCN = ( S HCN −1 + S HCN −2 ) / x HCN SC − NO = S NO −1 + S NO −4 S P− NO = ( S NO − 2 + S NO −3 + S NO− 5 + S NO −6 ) / x NO Reference [1] L. Hupa. It is the same as MNV because of the assumption in this model. M NC = f N2 f VM + f FC 4. P. HCN and NO should be linearized as S = S C + S Pφ P Here. the source terms of NH3 . The linearized source terms of NH3 . Jerry J. Fakhrai. Blasiak.2 Linearization of Source Terms To ensure the convergence of the iteration. SP can not be positive. W. Yuan MNC – mass fraction of nitrogen in char. Tao. and R. Proceedings of 1998 International Chemical Recovery Conference.

pp. and K. Kim. N. 763-776 [4] I.747-762 [3] K. H. Aug. Yuan. and R. PhD thesis of Brigham Young University. pp. Presented at the 27th Symposium (International) on Combustion. 1994 [6] Fluent Inc. Study on Characteristics of Self-desulfurization and Self. Pianpucktr. Yuan Proceedings of 1998 International Chemical Recovery Conference. Naruse. G. Iisa. Colorado. A Global Reaction Rate for Nitric Oxide Reburning. Jing. Tangpanyapinit. Q..W. Model for NO Formation in Recovery Boilers.denitrification in Biobriquette Combustion. 1998 [5] W. Rompho. Lu. Ohtake (now deceased). Chen. J. J. 1994 11 . Proceedings of 1998 International Chemical Recovery Conference. V. Conn. User’s Guide Index. Jerry J.Prediction of NOx Emissions in Recovery Boilers Dr.

8 ×10 3 T exp( −20820 / T ) All concentrations are in unit of mol m-3. [O] is formulated as [O ] = 36.W. Yuan Appendix: Calculation of Thermal NOx and Prompt NOx Thermal NOx The NO source term due to thermal NOx mechanisms is S thermal− NOx = M NO d [ NO ] dt Here d[NO]/dt can be calculated as d [ NO] 2[O ]( k1k 2 [O2 ][ N 2 ] − k −1k − 2 [ NO]2 ) = dt k 2 [O2 ] + k −1[ NO] Using partial equilibrium [O] approach. [Fuel] in the above equation can be replaced by the concentration of CH4 .8 ×10 4 T exp( −4680 / T ) k −2 = 3.206 × 10 −5 m 3 ⋅ atm ⋅ mol −1 ⋅ K −1 P is pressure in unit of atm. 12 .986 × 10 −3 kcal ⋅ mol −1 ⋅ K −1 = 8.8 × 108 exp( −38370 / T ) k −1 = 3.8 × 107 exp( −425 / T ) k 2 = 1. If the main combustible species released from bark or wood chip is CH4 . Prompt NOx The NO source term due to prompt NOx mechanisms is S prompt− NOx = M NO d [ NO ] dt Here d[NO]/dt can be calculated as E d [ NO] = k pr [O2 ] a [ N 2 ][ Fuel ] exp( − a ) dt RT where k pr = 1.Prediction of NOx Emissions in Recovery Boilers Dr. Jerry J.64T 2 [ O2 ] 2 exp( −27123 / T ) 1 1 The rate coefficients in above formulates are as follows (in unit of m3 mol-1 s-1). k 1 = 1.2 × 10 7 ( RT / P) a+1 Ea = 60 kcal ⋅ mol −1 ( m3 ⋅ mol ) a +1 ⋅ s −1 R = 1.

Jerry J. 13 .W. Yuan Here all concentrations are also in unit of mol m-3.Prediction of NOx Emissions in Recovery Boilers Dr.