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. Prompt NOx 1 . Introduction In laminar flames. The NOx formed by these three processes is described as thermal NOx. and fuel 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. 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. the formation of NOx can be attributed to three distinct chemical kinetic processes. 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. and at the molecular level within turbulent flames. Prompt NOx is produced by high-speed reactions at the flame front. and fuel NOx is produced by oxidation of nitrogen contained in the fuel. Jerry J. Yuan Prediction of NOx Emissions in Recovery Boilers  An Introduction to NOx Module 1.Prediction of NOx Emissions in Recovery Boilers Dr. Thermal NOx is formed by the oxidation of atmospheric nitrogen present in the combustion air.W.

bark. both thermal NOx and prompt NOx can be neglected in the NOx emission prediction at present.Prediction of NOx Emissions in Recovery Boilers Dr.W. However. Fuel-bound nitrogen-containing compounds are released into the gas phase when the fuel droplets or particles are heated during the devolatilization stage. Jerry J. 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. the NOx emission from recovery boilers is in a lower level comparing with utility boilers fuelled by fossil fuels. 2. From the thermal decomposition of these compounds. The extent of conversion of fuel nitrogen to NOx is dependent on the local combustion characteristics and the initial concentration of nitrogen-bound compounds. N. in the reaction zone. 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. and NH can be formed and converted to NOx. CN. or hogfuels. 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. fuelled by black liquor. The actual formation involved a complex series of reactions and many possible intermediate species. radicals such as HCN. Normally in recovery boilers. [1] 2 . The relative importance of thermal NOx and prompt NOx may increase. Tao et al. Therefore. the maximum gas temperature is lower than 1800 K. Yuan Prompt NOx is most prevalent in rich flames. thermal NOx is significant only at the temperature higher than 1800 K. NOx Formation and Destruction in Recovery Boilers As mentioned above.

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

the NO reduction by reburning mechanism will be significant. The NOx formation and reduction in recovery boilers. HCN is mainly reduced by NO into N2 . Under the reducing atmosphere. Yuan al. as discussed above. has been adopted in this model. the global reaction rate between CHi and NO derived by Chen [5] is adopted. R2 = conversion rate of NH3 (1/s) R3 = NO reduction rate by char particle (m3 /s/mBET2 ) 4 . Jerry J. When the secondary fuel is injected into the furnace to form a fuel rich zone.Prediction of NOx Emissions in Recovery Boilers Dr.W. the hydrocarbon radicals CHi will react with the formed NO from the main combustion zone to produce HCN. 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. If the fuel staging technique is adopted in the recovery boiler. Many investigations have proved that the NO reduction rate can be as high as 60 % by using reburning technique. named reburning zone. In this model.

000 cal/ mol A31 = 0.W.8 m3 /mBET2 /s (if T ≤ 923 K) = 7. Jerry J.0×1012 1/s E5 = 60.000 cal/ mol A5 = 3.8×108 1/s E2 = 27.000 cal/ mol A2 = 1.000 cal/ mol (if T ≤ 923 K) = 57.72×106 1/s 5 . 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. Yuan R4 .000 cal/ mol A6 = 2.26×109 m3 /mBET2 /s (if T > 923 K) E31 = 16.160 cal/ mol (if T ≤ 923 K) = 57.300 cal/ mol (if T > 923 K) A4 = 3.5×1010 1/s E4 = 67.0×106 1/s E1 = 32.Prediction of NOx Emissions in Recovery Boilers Dr.12×1010 m3 /mBET 2 /s (if T > 923 K) E32 = 18.300 cal/ mol (if T > 923 K) A32 = 37.204 m3 /mBET2 /s (if T ≤ 923 K) = 1.

There are interactions between turbulence and chemistry.4.1 × 10 −3 < x O2 ≤ 1.k = υ ' i. k M i Aρ ε mR k υ ' R. In the eddy breakup model.800 cal/ mol R = universal gas constant equal to 1. The influence of turbulence on the reaction is taken into account by employing combined Arrhenius and eddy breakup model.k = υ ' i.11× 10 < x O2 < 0. xO2 ≤ 4. R.986 cal/(mol⋅K) The oxygen reaction order a is calculated from the following equation: 1.k (kg/m3 /s) is given by the smallest of the two expressions below: Ri .11 × 10 − 2 a= −2 − 0. 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.03 3. P A = an empirical constant equal to 4. Yuan E6 = 18. k M i ABρ ∑m ∑ υ' M P P P P .Prediction of NOx Emissions in Recovery Boilers Dr. Additional effort is necessary in order to calculate the mean reaction rate correctly. giving the smallest value of Ri.03  0.0 6 .k P where υ ' i .0. k M R ε k Ri .1.W.9 ln x O2 .1 × 10 −3  − 3. x O2 ≥ 0.k mP = the mass fraction of any product species. Turbulence-Chemistry Interaction Model The flow in recovery boiler is fully three-dimensional and turbulent.1 ln x O2 .95 − 0.35 − 0. Jerry J. the rate of reaction Ri.

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

temperature. NOx chemistry has negligible influence on the predicted flow field. As a result. NOx Module NOx concentrations generated in the combustion process in recovery boilers are generally low.Prediction of NOx Emissions in Recovery Boilers Dr. Jerry J. 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 . Yuan S NO −2 = − min{ R2 M N2 M NO P ε P ε P . M NO x NO A . It follows that the 8 .206×10-2 m3 ⋅atm/(kmol⋅K) ABET = BET surface area of char particle (m2 /kg) cs = concentration of particles (kg/m3 ) 4. and major combustion product concentrations. 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 HCO k RT M NO P ε P M HCN ε P . M NO x HCN A .W. M NO x HCN A . M NO x NH 3 A .

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

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

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

[O] is formulated as [O ] = 36.986 × 10 −3 kcal ⋅ mol −1 ⋅ K −1 = 8. 12 . [Fuel] in the above equation can be replaced by the concentration of 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 = 1.8 ×10 3 T exp( −20820 / T ) All concentrations are in unit of mol m-3. k 1 = 1.8 ×10 4 T exp( −4680 / T ) k −2 = 3.Prediction of NOx Emissions in Recovery Boilers Dr. 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.8 × 108 exp( −38370 / T ) k −1 = 3. If the main combustible species released from bark or wood chip is CH4 .W.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).8 × 107 exp( −425 / T ) k 2 = 1.2 × 10 7 ( RT / P) a+1 Ea = 60 kcal ⋅ mol −1 ( m3 ⋅ mol ) a +1 ⋅ s −1 R = 1.206 × 10 −5 m 3 ⋅ atm ⋅ mol −1 ⋅ K −1 P is pressure in unit of atm. Jerry J.

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