Energy 233 (2021) 121123

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Energy
journal homepage: www.elsevier.com/locate/energy

Prediction of the equilibrium compositions in the combustion

products of a domestic boiler
Semih Yılmaz a, b, *, Dilek Kumlutaş a, Utku Alp Yücekaya a, Ahmet Yakup Cumbul a
a
Mechanical Engineering Department, Dokuz Eylul University, Tınaztepe, Izmir, Turkey
b
Marine Engineering Department, Dokuz Eylul University, Tınaztepe, Izmir, Turkey

a r t i c l e i n f o a b s t r a c t

Article history: In this study, two prediction models were developed to determine equilibrium compositions in the
Received 20 April 2020 combustion products of a domestic boiler. These models are based on the Gibbs energy minimization and
Received in revised form equilibrium constant methods. According to the domestic boiler standards (EN 15502e1 and EN 437),
29 May 2021
gaseous fuels (G20, G25, and NG) were selected to predict gaseous emissions. A novel investigation was
Accepted 1 June 2021
Available online 4 June 2021
realized for a domestic boiler's lean premixed burner in compliance with relevant standards. In the range
of 0.6e0.9 equivalence ratio, the equilibrium compositions of the species were obtained.
The proposed models were compared with CHEMKIN commercial software to verify the prediction of
Keywords:
Domestic boiler
the results. Adiabatic flame temperatures and combustion products (NO, CO, N2, O2, CO2, and H2O) were
Combustion estimated using prediction models. The estimated values showed good agreement with the results ob-
Emissions tained from CHEMKIN software. Under efficient boiler operating conditions (f¼0.65, 0.7, and 0.75),
Prediction models minor deviations were observed comparing with the CHEMKIN results. For gaseous fuels, CO and NO
emissions reach peak values near f¼0.9 and f¼0.85, respectively. Without using complex chemical ki-
netics mechanisms, models provide reliable estimates. The proposed models can be parametrically
applied not only for boilers but also for other applications in combustion processes.
© 2021 Elsevier Ltd. All rights reserved.

1. Introduction
Combustion of hydrocarbon fuels emerges emissions and cre-
ates concerns about public health and the environment. Emissions
such as carbon dioxide (CO2) and water (H2O) cause greenhouse
effects and local fog. Besides that, other pollutants of hydrocarbon
combustion are carbon monoxide (CO), nitric oxides (NOx), un-
burned hydrocarbons (HC), sulfur oxides (SOx), and particulate
matter (PM). These pollutants affect the health of humans and
animals negatively. Also, SOx and NOx are significant contributors to
acid rains [1]. Today, residential boilers used for hot water and
heating burn fossil fuels (primarily natural gas). They significantly
contribute to these pollutant gases, especially NOx and CO, which
are macro pollutants that emerge by natural gas combustion with
global warming potential [2]. According to European Environ-
mental Agency (EEA) report for European countries, these resi-
dential boilers that commonly burn natural gas have emission
* Corresponding author. Mechanical Engineering Department, Dokuz Eylul Uni-
versity, Tınaztepe, Izmir, Turkey.
E-mail address: semih.yilmaz@deu.edu.tr (S. Yılmaz).
factors of 57 g/GJ for NOx and 46 g/GJ for CO, respectively [3]. Thus,
various standards have been introduced to prevent these pollutant
gases' environmental effects from the boilers [4]. One of these
standards' purposes is to reduce the CO and NOx emission levels of
gas-fired heating boilers [5] following the European Union regu-
lations such as EN 15502e1:2012þA1:2015 [4]. Therefore, it is
crucial to examine the combustion parameters and effects that
create these emissions. Thus, several studies have been published
in the literature on investigating these issues. These studies have
been conducted with numerical, experimental, and theoretical
methods.
Several numerical and experimental studies were performed
focusing on pollutant emissions and environmental impacts
[5e12], effects of various gaseous fuels on combustion [13e16],
combustion stability [17,18], system optimization [19e21], com-
bustion performance and energy efficiency [22e24], emission
predictions [25e27].
Emerging emissions resulting from combustion are predicted by
kinetic/dynamic models and chemical equilibrium methods,
mainly known as equilibrium constants or minimization of Gibbs
energy [28]. In combustion applications, the estimation of

https://doi.org/10.1016/j.energy.2021.121123
0360-5442/© 2021 Elsevier Ltd. All rights reserved.
S. Yılmaz, D. Kumlutaş, U.A. Yücekaya et al.
Nomenclature
A number of atoms of elements in species
bi number of atoms of element i in the products
G Gibbs energy [kJ]
K equilibrium constant
n number of gaseous species
R gas constant, 8.3146 [kJ kmol1 K1]
S total entropy [kJ K1]
l Lagrangian multiplier
f equivalence ratio (fuel/air)
ε convergence tolerance
as stoichiometric molar air-fuel ratio
Cp specific heat [kJ kmol1 K1]
H total enthalpy [kJ]
N total number of species
NE number of elements
NS number of species
m chemical potential [kJ kmol1]
Tin inlet temperature [K]
Tad adiabatic flame temperature [K]
y mole fraction of species
emissions depends on the correct identification of chemical re-
actions with all their components. For long decades, researchers
have developed numerical tools to predict chemical reactions.
Achieving emissions is related to finding the final chemical equi-
librium. These methods are the most renowned and robust tech-
niques in the literature and commercial codes (ASPEN, CEA of
NASA, GASEQ, HSC) [26] to supply thermochemical equilibrium.
Thus, many studies and efforts were introduced to examine these
approaches.
Liu et al. [29] reviewed the numerical tools and most renowned
techniques for minimizing Gibbs energy. Predicting the chemical
equilibrium of the reactions was discussed, including limitations
and solution methods. Existing minimization methods such as the
Lagrange Multipliers method (CEA from NASA), Morley method
(GASEQ), Rand method (ASPEN, HSC) were compared. An alterna-
tive resolution method is implemented with a home-made code
(CIRCE).
Rashidi [30] calculated the equilibrium in combustion products
with different mathematical methods. Rakopoulos et al. [31]
developed a fast model for calculating chemical equilibrium com-
positions in diesel combustion. They discussed pressure, temper-
ature, and equivalence ratio (fuel/air ratio) effects on composition
products. Thomsen et al. [32] examined NO formation in premixed
methane flames and compared two different chemical kinetic
mechanisms. Besides that, the premixed flame code with GRI
Mechanism [33] was validated against the measurements of NO
emissions. Li et al. [34] developed an equilibrium model with the
Gibbs energy minimization method to predict the performance and
gas compositions. They examined pressurized circulating fluidized
bed gasifiers for coal combustion. The kinetically modified equi-
librium model was applied to the gasifier, and good results were
obtained from the gaseous combustion products. Nabi [35] theo-
retically investigated exhaust emissions and combustion-related
parameters such as theoretical air-fuel ratio (AFR), lower calorific
value (LCV), and the ratio of LCV and theoretical AFR for different
oxygenated fuels over a diesel engine. The author applied the
equilibrium constants method to obtain combustion products of
€
the pentadecane fuel on the diesel engine. Oztürk et al. [36] studied
the combustion of three different natural gas compositions in
2
Energy 233 (2021) 121123
various operating conditions. Mole fractions of gaseous products,
NOx emissions, and outlet temperatures were obtained by chemical
reaction kinetic mechanism program for different natural gas fuels.
In another important study, Neron et al. [37] utilized the Gibbs
energy minimization method to calculate complex equilibria on
adiabatic and non-adiabatic systems. Various thermodynamic
models were presented with kinetic and energy boundary condi-
tions. The equilibrium temperature and compositions were calcu-
lated for hydrocarbon mixtures. Kayadelen and Ust [38] predicted
equilibrium products and thermodynamic properties with com-
puter code. They examined water injected CaHbOgNd type fuel
combustion with the equilibrium constant method. Composition
products were presented for two different equivalence ratios. Their
results were validated with CHEMKIN and GASEQ software.
Zajemska et al. [9] calculated the chemical composition of flue
gas of natural gas in an industrial burner. Combustion calculations
were dealt with commercial CHEMKIN software. Flue gas compo-
sitions were obtained. Sieradzka et al. [39] predicted gaseous
products of fuel pyrolysis using CHEMKIN chemical modeling
software. Mole fractions of gaseous products are presented for
various temperatures. Mlonka-Me˛ drala et al. [40] performed nu-
merical modeling of pyrolytic gas with CHEMKIN-Pro software.
Measured gas compositions showed good agreement for major
gaseous products.
Ko€kkülünk et al. [41] applied a new steam injection method to
control NOx emissions over a direct injection diesel engine. The
extended Zeldovich mechanism was utilized for calculating com-
bustion products via the equilibrium constant method. Effective
power, engine efficiency, specific fuel consumption, and NO emis-
sions were determined. Gonca [42] used the same approach to
obtain the effects of steam injection on NO emissions and perfor-
mance. Ethanol-diesel blends were employed as fuel on a diesel
engine. Temperature, pressure, NO emissions, effective power, and
efficiency were determined.
Boukhalfa [43] modeled methane combustion with the chemical
kinetic method. Emissions and combustion efficiency were calcu-
lated via computer code. Fournel et al. [44] developed a model for
predicting gaseous emissions of biomass fuels. The thermodynamic
equilibrium model was based on the Gibbs energy minimization
method. The predicted emissions were compared with measure-
ments. Good agreement was observed on the prediction of CO, CO2,
NOx, and SO2 emissions. Kayadelen [45] examined natural gas
components mixed one by one to methane gas with different
diluent gas molar ratios on methane-air engine combustion.
Thermodynamic properties and emerging emissions were investi-
gated with the equilibrium constant method for a gas-fueled en-
gine. Results were compared with the chemical equilibrium code of
NASA and GASEQ software.
There are highly non-linear equations in the Gibbs energy
minimization and equilibrium constants methods mentioned in the
literature. Apart from the literature, in this study, step-by-step
resolution techniques [46,47] were used to analyze these non-
linear equations within the developed codes, and the initial
values were optimized for emission estimates. To get more accurate
results, the thermochemical database published by NASA [48] was
integrated into the developed codes. These methods have pros and
cons compared to each other. The essential advantage of Gibbs
energy minimization is predicting emissions without kinetic and
dynamic models. Also, Gibbs free energy minimization does not
need equilibrium constant coefficients. There is no need to know
the process of the chemical reaction. However, initial values must
be defined correctly for the Newton Raphson iterations to converge.
The equilibrium constants method can be easily adapted to
different applications without using Lagrange Multipliers [29,44].
In reviewed studies, combustion performance and emission
S. Yılmaz, D. Kumlutaş, U.A. Yücekaya et al. Energy 233 (2021) 121123

reduction methodologies were investigated using the combustion
chemical equilibrium methods. Many of these studies provided
information on emissions for gas turbines and engines. General
hydrocarbons [30,36], diesel blends [31,35,42], coal [34], methane
[29,38,43], and natural gas [9,36,45], biomass [44] fuels were
considered separately, however, studies on test gases of domestic
heating boilers are lacking in the research field. Thus, test gases
need further investigation, including requirements of the EN
437:2018 [49] standards. In the previous studies, a comprehensive
theoretical investigation has not been performed, and there is still
insufficient research available on domestic heating boilers.
This study aims to investigate the fundamental parameters
related to combustion in domestic boilers with developed com-
puter codes. The main contribution of this investigation is to pre-
dict emissions and adiabatic flame temperatures on the domestic
boilers' premixed burners. Two prediction models based on Gibbs
energy minimization and equilibrium constant methods were
created. The fuels were selected as test gases (G20, G25) and natural
gas (NG) defined in EN 15502e1:2012þA1:2015 [4] and EN
437:2018 [49] standards. The thermodynamic states of fuels and
combustion products were calculated according to the temperature
and pressure. Adiabatic flame temperatures and equilibrium com-
positions of the species were obtained in the range of 0.6e0.9
equivalence ratio. This range is an optimal lean premixed condition
[6,17,19,22,50] for the burner of a domestic boiler. The results of two
prediction models were compared with commercial software
(CHEMKIN).
2. Methodology
Combustion equilibrium calculations are generally handled by
using chemical kinetics and chemical equilibrium approaches. Both
equivalent formulations usually describe the chemical equilibrium:
equilibrium constants or minimization of free energy [51,52]. In the
scope of the study, codes were developed within these two ap-
proaches, and a theoretical study was carried out for standard gases
as G20, G25, and NG with different equivalence ratios. Here,
equivalence ratio is defined as fuel/air ratio [1]. Properties of these
gases are given in Table 1 for standard test conditions defined in EN
437:2018 [49].
In this study, the reactants' temperature and pressure were
defined as 300 K and 1 atm. The air composition in the inlet of the
combustion chamber was specified as 21% O2 and 79% N2. Other
minor species in the air were neglected. The walls of the combus-
tion chamber were defined as adiabatic. The constant pressure-
enthalpy approach was applied to the combustion domain.
Detailed descriptions of the two methods used in the proposed
models were presented in Sections 2.1 and 2.2. The data obtained
from these two methods were compared with the commercial
software (CHEMKIN) uses the element potential method. The cur-
rent version of CHEMKIN commercial software is an evaluated
version of combustion kinetics code Chemkin II developed at
Sandia National Laboratories [53]. For the gaseous species, ther-
modynamic properties are stored in the database in terms of
polynomial fits to the specific heats. The software has the same
format that utilized in the NASA chemical equilibrium code [54].
2.1. Gibbs energy minimization method
After the combustion process, the composition of the product
should be calculated at a known temperature, pressure, and stoi-
chiometry for chemical equilibrium. Gibbs energy (G) can be
defined with thermodynamic properties of total enthalpy (H), total
entropy (S), and temperature (T) (Equation (1)) [28]:
G ¼ H  TS (1)
The Gibbs energy minimization method used for calculating the
thermodynamic state with temperature and pressure is a valuable
and practical process than the equilibrium constant method. In
chemical equilibrium, Gibbs energy function gets the minimum
value; in contrast, entropy has maximum value (Equation (2)):
ðdGÞT;P ¼ 0 (2)
NASA developed a multi-functional code [51] for calculating the
complex chemical equilibrium composition and temperature. Gibbs
energy minimization is obtained by solving equations with Newton
Raphson method iteratively. This code has advantages over other
methods that equilibrium composition is attained even without
knowledge of chemical kinetics [55]. Gordon and McBride define
Gibbs energy of gaseous mixture and chemical potential per kmole
in Equations (3) and (4) [51]:
X
NS
G¼ m j nj (3)
j¼1
!
vg
mj ¼ (4)
vnj
T;P;nisj
The chemical equilibrium condition is maintained by minimi-
zation of free energy with certain constraints. The mass balance
constraints of the minimization are expressed in Equations (5) and
(6):
X
NS
Aij nj  b0i ¼ 0 (5)
j¼1
bi  b0i ¼ 0 (6)
For considering the standard state, the chemical potential can be
described with the ideal gas assumption in Equation (7):

Table 1
!
n
Composition of the gases [49]. mj ¼ m0j þ RT ln þ RT lnðPÞ (7)
nj
Gas Type Composition by mole (%)

Methane (G20) CH4 ¼ 100 A G’ term can be defined as in Equation (8) with Lagrangian
Test gas (G25) CH4 ¼ 86 multipliers, and the equilibrium equation emerges as indicated in
N2 ¼ 14 Equation (9):
CH4 ¼ 95.72
C2H6 ¼ 2.45 X
NE  
Natural Gas (NG) C3H8 ¼ 0.84
G0 ¼ G þ li bi  b0i (8)
N2 ¼ 0.78 i¼1
CO2 ¼ 0.17

3
S. Yılmaz, D. Kumlutaş, U.A. Yücekaya et al. Energy 233 (2021) 121123

!
X
NS X
NE NE 
X 
0
dG ¼ mj þ li Aij dnj þ bi  b0i dli (9)
j¼1 i¼1 i¼1

Along with independent variables dnj and dli, the equation

transforms to Equations (10) and (11):

X
NE
mj þ li Aij ¼ 0 (10)
i¼1

bi  b0i ¼ 0 (11)
All defined equations are not linear with composition variables
for obtaining gaseous combustion products. Therefore, the Newton
Raphson method is utilized iteratively for predicting moles of
gaseous species (n), compositions (nj), Lagrangian multipliers (lj),
and if the necessary temperature (T). This method contains a Taylor
series expansion of suitable equations [56].
In the light of these explanations, an in-house prediction model
(Model 1) was developed with Java programming language. The
proposed model was generated based on NASA's complex chemical
equilibrium procedure [51] with the Gibbs energy minimization
method.
Model 1 has several advantages over commercial CHEMKIN
software using the element potential method and Model 2 using
the equilibrium constant method. Along with higher numerical
convenience for the computation of components, this model re-
quires fewer property data and can perform calculations without
equilibrium constants and chemical kinetic mechanisms defined
separately for each type of fuel. The algorithm of Model 1 is easily
adapted to use with boilers, engines, gas turbines, and other com-
bustion systems for various fuels or fuel mixtures. The flow algo- Fig. 1. Flow algorithm of Model 1.
rithm of Model 1 is shown in Fig. 1.
In the flow algorithm of Model 1, type of fuel, equivalence ratio,
an initial guess of adiabatic flame temperature, inlet temperature, complex computer programs. This method has more convenience
and reactants' pressure are given as input parameters at the first than the Gibbs energy minimization method using the Lagrange
step. After that, the properties of reactants and products are Multiplier Approach and element potential method (CHEMKIN)
calculated using the thermodynamic properties database. For a using complex chemical kinetic mechanisms.
given temperature and pressure, it is crucial to use the appropriate In the equilibrium constant method, thermophysical properties
curve fitting method. In this step, the least-squares curve fitting were calculated by the coefficients specified in the NASA report
method is used to determine the curve fitting coefficients of [48]. While using equilibrium constants, all the products and re-
properties. Otherwise, there may be deviations in the predicted actants were assumed as ideal gas. Therefore, thermophysical
values of the products formed. properties change depending on the temperature only. Emission
Gibbs energy minimization function handles input parameters values were determined by applying the combustion process for
and thermodynamic properties to solve minimization equations three different gas compositions in Model 2.
with the Newton Raphson iteration method. The main function and In the calculation method, specific heats are computed with
five different sub-functions are employed in the minimization NASA coefficients according to Equation (12):
process. The converge criteria are determined as ε < 10e7 in the
calculations. It is vital to correctly define the Newton Raphson Cp+ ðTÞ
¼ a1 T 2 þ a2 T 1 þ a3 þ a4 T þ a5 T 2 þ a6 T 3 þ a7 T 4
method's first estimation values to achieve convergence in the R
Gibbs energy minimization function. Appropriate selection of (12)
initial predictive values provides faster convergence. If convergence
is not achieved, the initial guess of the adiabatic flame temperature Enthalpy and entropy are calculated from integration of the
is adjusted, and the steps are restarted. After the function Cp (T) and Cp (T)/T with respect to T, as shown in Equations (13)
converged, adiabatic flame temperature and compositions of and (14):
combustion products are obtained as outputs.
h ðTÞ lnðTÞ T T2 T3 T4
¼ a1 T 2 þ a2 þ a3 þ a4 þ a5 þ a6 þ a7
RT T 2 3 4 5
2.2. Equilibrium constants method
b1
þ (13)
In this method, chemical equilibrium is calculated using the T
equilibrium of the reactants and products for the hydrocarbon
fuels. The equilibrium constant method has advantages over other s ðTÞ T 2 T2 T3
methods with its simple adaptation. Besides that, satisfactory re- ¼ a1  a2 T 1 þ a3 ln T þ a4 T þ a5 þ a6
R 2 2 3
sults can be obtained for combustion problems without using
4
S. Yılmaz, D. Kumlutaş, U.A. Yücekaya et al. Energy 233 (2021) 121123

Equilibrium constant coefficients were obtained from Olikara

T4 and Borman [58] that were curve fitted with data taken from the
þa7 þ b2 (14)
4 JANAF table for the temperature range 600<T<4000 K. Curve fitting
For hydrocarbon combustion, ten significant product species are expressions can be described as in Equation (28):
determined according to f<3 conditions that O, H, OH, and NO  
T B
dissociations are crucial [57]. The chemical equation is shown as in log10 Ki ðTÞ ¼ Ai ln þ i þ Ci þ Di T þ Ei T 2 (28)
Eq. (15): 1000 T

as When the equations are rearranged by atomic balance according

Ca Hb Oc Nd þ ðO þ 3:7N2 Þ/ to the mole fractions, the sum of the six reaction equations can be
f 2
simplified in four variables as y3, y4, y5, and y6. These variables can
be solved by the Newton Raphson iteration and Gauss-Seidel
n1 CO2 þ n2 H2 O þ n3 N2 þ n4 O2 þ n5 CO method to determine all product gas compositions [58].
Thermophysical properties such as enthalpy, specific volume,
(15)
internal energy, and entropy can be calculated for the mixture's
þn6 H2 þ n7 H þ n8 O þ n9 OH þ n10 NO known compositions. The enthalpy of the reacting mixtures de-
pends on the temperature and the pressure. To calculate the spe-
Balance in the atomic level is specified with the four equations cific heat Cp for the relevant temperature can be required to change
between Equations (16)e(19): in the mole fraction according to partial derivatives such as vyi/vP
and vyi/vT [57]. Given calculations were applied to the developed
C : a ¼ ðy1 þ y5 ÞN (16) model (Model 2). The flow algorithm of Model 2 is demonstrated in
Fig. 2.
H : b ¼ ð2y2 þ 2y6 þ y7 þ y9 ÞN (17) In the flow algorithm of Model 2, different input parameters
such as the fuel type previously defined in the model with the
composition, equivalence ratio, an initial guess of adiabatic flame
2as
O:cþ ¼ ð2y1 þ y2 þ 2y4 þ y5 þ y8 þ y9 þ y10 ÞN (18) temperature, inlet temperature, and pressure are given in the first
f
step. After that, the adiabatic flame temperature is numerically
calculated in a class function that operates according to the fuel
7:52as type and equivalence ratio with the thermodynamic properties
N :dþ ¼ ð2y3 þ y10 ÞN (19)
f taken from the calculation package. With the assumption that there
Mole fractions are shown as yi for ten different species and is no heat transfer to the environment, the enthalpy of reactants
represent the number of moles of each species divided by the total and the products are equalized for finding the adiabatic flame
number of species, hence the total mole fraction of the species is temperature with the desired tolerance (ε < 107). If there is no
equal to one. Equations (20) and (21) are shown below: convergence, the initial guess of the adiabatic flame temperature
should be updated. Thermodynamic properties of reactants and
ni products obtained from thermodynamic properties calculation
yi ¼ (20)
N package by curve fitting coefficients of species are used in the
equilibrium combustion product's calculation step. After that,
X
10 equilibrium constant equations are formed according to atomic
yi ¼ 1 (21) level balance and total mole fraction of the species. Obtained non-
i¼1 linear equations are linearized and solved by the Newton-Raphson
The K coefficients' calculations are given in Equations (22)e(27) method iteratively. In this process, initial guesses of species frac-
with pressure units of atmospheres in the gas phase reactions tions are crucial; otherwise, false estimation leads to divergence in
below. These coefficients are used to separate the products and the numerical calculations. Besides that, combining NewtoneRaphson
NO and OH formation [57]. and Gauss-Seidel methods allow convergence in a shorter time. The
convergence criteria of equilibrium constant equations are deter-
pffiffiffi
1 y7 P mined as ε < 107 in the calculations. In the final step, adiabatic
H #H K1 ¼ pffiffiffiffiffi (22) flame temperature and the composition of products are obtained as
2 2 y6
outputs. This model was generated in the MATLAB environment
pffiffiffi [59], including four different class functions and the main function
1 y8 P
O #O K2 ¼ pffiffiffiffiffi (23) for calculating equilibrium combustion products.
2 2 y4

1 1 y9 3. Results and discussion

H þ O #OH K3 ¼ pffiffiffiffiffiffiffiffiffiffi (24)
2 2 2 2 y4 y6
The gas compositions formed due to combustion and adiabatic
flame temperatures were investigated depending on the equiva-
1 1 y10 lence ratio for the three different gases (G20, G25, and NG). These
O þ N #NO K4 ¼ pffiffiffiffiffiffiffiffiffiffi (25)
2 2 2 2 y4 y3 gases are defined in the relevant domestic boiler standards [4,49].
The range of equivalence ratios (f¼0.6e0.9) was chosen based on
1 y2 the operating conditions where domestic heating boilers are more
H2 þ O2 #H2 O K5 ¼ pffiffiffiffiffipffiffiffi (26)
efficient and have lower emissions [6,17,19,22,50].
2 y6 y4 P
According to the selected equivalence ratio range, the Gibbs
energy minimization method was applied in Java programming
1 y1
CO2 þ O2 #CO2 K6 ¼ pffiffiffiffiffipffiffiffi (27) language as Model 1. The Equilibrium constant method was applied
2 y5 y4 P in the MATLAB environment as Model 2 for theoretical
5
S. Yılmaz, D. Kumlutaş, U.A. Yücekaya et al.
Fig. 2. Flow algorithm of the Model 2.
investigation of the specified gases combustion. The obtained re-
sults were compared with CHEMKIN commercial software that uses
the element potential method. The reliability of Models 1 and 2 was
tested with the CHEMKIN which includes 325 equations for 53
species and offers precise results via GRI-Mechanism [60].
Fig. 3 shows the effect of equivalence ratio on the adiabatic
flame temperatures for G20, G25, and NG fuels. When the adiabatic
flame temperature results are evaluated, Model 1 and 2 show good
agreement with the CHEMKIN results. It is inferred that the adia-
batic flame temperatures of G20, G25, and NG tend to increase with
the equivalence ratios. Maximum adiabatic flame temperatures
were observed at f¼0.9 because this ratio was the closest value to
the stoichiometric ratio, as expected. Model 1 overestimated
adiabatic flame temperature around f¼0.9 while comparing Model
2 and CHEMKIN results.
Investigation of CO emissions is necessary for flame presence
and stability in domestic boilers. Fig. 4 depicts mole fractions of CO
emissions varying with equivalence ratios for G20, G25, and NG
fuels. By evaluation of Fig. 4, it can be observed that the mole
6
Energy 233 (2021) 121123
)
Fig. 3. The adiabatic flame temperature and equivalence ratio changes for G20, G25,
and NG fuels.
fractions of CO were coherent with CHEMKIN results in investi-
gated equivalence ratio range. CO emissions tend to increase with
an equivalence ratio as expected in domestic boilers. The peak
values of CO emissions are observed at f¼0.9 for all models and fuel
types. The main reason for this is the CO quenching effect due to
higher flame temperatures. G25 fuel gave lower CO emissions in
the investigated equivalence ratio range.
NO emissions, which have harmful effects on the environment,
are limited by standards. Therefore, it is crucial to determine and
reduce the amount of NO emissions [4]. Fig. 5 shows the variation of
NO emissions with equivalence ratio for G20, G25, and NG fuels. It is
apparent from Fig. 5 that NO emissions increased with the
S. Yılmaz, D. Kumlutaş, U.A. Yücekaya et al.
) )
) )
)
Fig. 4. Mole fraction of CO for G20, G25, and NG fuels.
equivalence ratio due to the thermal and prompt NO mechanisms
[1] in the premixed combustion of domestic boiler burners. NO
emissions reach peak values at f¼0.85 for all models and fuel types.
G25 fuel has lower NO emissions in the investigated equivalence
ratio range.
Other major combustion equilibrium products are N2, O2, CO2,
and H2O. Mole fraction changes of these products with equivalence
ratio for G20, G25, and NG fuels are shown in Figs. 6e9. It is clearly
seen that Model 1 and Model 2 results matched with CHEMKIN
results for all equivalence ratio ranges.
The reliability of the proposed models is demonstrated with
provided comparisons in Tables 2e4, showing deviations according
to reference values taken from CHEMKIN results. Suitable three
7
Energy 233 (2021) 121123
)
Fig. 5. Mole fraction of NO for G20, G25, and NG fuels.
different operating conditions (f¼0.65, 0.7, and 0.75) [6] for the
domestic boiler were selected as comparing mole fractions and
adiabatic flame temperatures. In Tables 2e4, minor deviations were
observed in mole fractions of O2, N2, CO2, H2O, CO, and NO
comparing with the CHEMKIN results. When the results were
compared, deviations of Model 2 are lower than Model 1.
When the results of Model 1, Model 2, and CHEMKIN were
evaluated comparatively, it was seen that the results from f¼0.65
to 0.75 were in good agreement with each other. The deviations of
Model 1 and 2 results comparing with CHEMKIN were found well
below 1%. The only exceptions are mole fractions of NO. These re-
sults show us that Model 1 and 2 can be utilized practically in
combustion calculations in various devices.
S. Yılmaz, D. Kumlutaş, U.A. Yücekaya et al. Energy 233 (2021) 121123

) )

)
)

)
)

Fig. 7. Mole fraction of O2 for G20, G25, and NG fuels.

Fig. 6. Mole fraction of N2 for G20, G25, and NG fuels.

The prediction results of Model 1 and 2 were obtained to find 4. Conclusion

equilibrium compositions of combustion products. With these
compositions, the boiler's emission values can be checked whether
they exceed or not the limit values of the EN 15502-1 standard [4].
When the NO and CO emission results are examined, optimum
emissions levels were achieved for the equivalence ratio range
(f¼0.65 to 0.8). Adiabatic flame temperatures tend to increase as
the equivalence ratios rise. Higher NO and CO emissions were
observed for increased flame temperatures. Thus, emission reduc-
tion measures should be taken for premixed burner of the boiler.
A novel study was conducted with selected G20, G25, and NG
fuels specified in test gases and gas-fired heating boilers standards
[4,49] for domestic heating boilers. The findings of this study are
summarised as follows:
 Practical and efficient models using the Gibbs energy minimi-
zation and equilibrium constant methods were proposed to
predict gaseous emissions and adiabatic flame temperatures for
G20, G25, and NG combustion on domestic heating boilers.
 Prediction reliability of the proposed models was evaluated
with commercial CHEMKIN software that computes with GRI

8
S. Yılmaz, D. Kumlutaş, U.A. Yücekaya et al. Energy 233 (2021) 121123

) )

) )

) )

Fig. 8. Mole fraction of CO2 for G20, G25, and NG fuels. Fig. 9. Mole fraction of H2O for G20, G25, and NG fuels.

Mechanism considering 53 species and 325 elementary
reactions.
 After adiabatic flame temperature and gaseous emission results
were analyzed, the Model 1 and Model 2 results are in good
agreement with the CHEMKIN results.
 Major combustion equilibrium products such as NO, CO, N2, O2,
CO2, and H2O were studied. Specially, NO and CO emissions
defined as crucial combustion products in standards were
investigated in detail.
 In the range of equivalence ratios (f¼0.6e0.9), the deviations of
Model 1 and Model 2 were found well below 1%. The only ex-
ceptions are mole fractions of NO.
 For gaseous fuels, CO and NO emissions reach peak values near
f¼0.9 and f¼0.85, respectively.
The data obtained from this study provides crucial information
that will contribute to the research and development process of
domestic boilers that utilize conventional combustion design pro-
cedures. Domestic boilers are obliged to work in accordance with
the limits of their emissions in the standards. Thus, emission esti-
mates and adiabatic flame temperatures obtained in the study will
help determine domestic boilers' optimum working ranges. For
these ranges, combustion system design takes less time and
number of experiments can be reduced considerably through
modeling. Instead of time-consuming emission measurements

9
S. Yılmaz, D. Kumlutaş, U.A. Yücekaya et al. Energy 233 (2021) 121123

Table 2
Mole fraction deviations of equilibrium products and adiabatic flame temperatures for G20, G25, and NG fuels (f ¼ 0.65).

f¼0.65 Model 1 Results Model 2 Results CHEMKIN Model 1 Deviations (%) Model 2 Deviations (%)
Results

G20

Tin [K] 300.00 300.00 300.00

Tad [K] 1755.21 1754.50 1753.50 0.0976 0.0573
O2 6.78E-02 6.77E-02 6.77E-02 0.0770 0.0952
N2 7.38E-01 7.38E-01 7.38E-01 0.0034 0.0092
CO2 6.39E-02 6.38E-02 6.38E-02 0.0141 0.0004
H2O 1.28E-01 1.28E-01 1.28E-01 0.1990 0.0002
CO 3.00E-05 3.09E-05 3.08E-05 2.4895 0.5047
NO 2.09E-03 2.09E-03 1.95E-03 7.2764 6.9667

G25

Tin [K] 300.00 300.00 300.00

Tad [K] 1742.87 1742.30 1741.34 0.0880 0.0551
O2 6.71E-02 6.70E-02 6.71E-02 0.0678 0.0924
N2 7.41E-01 7.41E-01 7.41E-01 0.0028 0.0088
CO2 6.32E-02 6.32E-02 6.32E-02 0.0129 0.0004
H2O 1.26E-01 1.26E-01 1.26E-01 0.1838 0.0002
CO 2.60E-05 2.69E-05 2.68E-05 2.8815 0.5041
NO 2.00E-03 1.99E-03 1.86E-03 7.2591 7.0177

NG

Tin [K] 300.00 300.00 300.00

Tad [K] 1757.04 1755.80 1754.86 0.1237 0.0533
O2 6.78E-02 6.77E-02 6.77E-02 0.0855 0.0956
N2 7.39E-01 7.39E-01 7.39E-01 0.0138 0.0092
CO2 6.45E-02 6.46E-02 6.46E-02 0.1399 0.0004
H2O 1.26E-01 1.26E-01 1.26E-01 0.2123 0.0002
CO 3.09E-05 3.18E-05 3.16E-05 2.2164 0.4879
NO 2.11E-03 2.10E-03 1.96E-03 7.4547 6.9552

Table 3
Mole fraction deviations of equilibrium products and adiabatic flame temperatures for G20, G25, and NG fuels (f ¼ 0.7).

f¼0.7 Model 1 Results Model 2 Results CHEMKIN Model 1 Deviations (%) Model 2 Deviations (%)
Results

G20

Tin [K] 300.00 300.00 300.00

Tad [K] 1841.43 1839.20 1838.16 0.1775 0.0564
O2 5.74E-02 5.73E-02 5.73E-02 0.1868 0.1321
N2 7.35E-01 7.34E-01 7.35E-01 0.0107 0.0108
CO2 6.84E-02 6.84E-02 6.84E-02 0.0243 0.0010
H2O 1.37E-01 1.36E-01 1.36E-01 0.3233 0.0007
CO 8.53E-05 8.69E-05 8.64E-05 1.2923 0.5505
NO 2.57E-03 2.55E-03 2.39E-03 7.5011 6.6329

G25

Tin [K] 300.00 300.00 300.00

Tad [K] 1827.59 1825.70 1824.65 0.1613 0.0576
O2 5.68E-02 5.67E-02 5.68E-02 0.1682 0.1282
N2 7.38E-01 7.37E-01 7.38E-01 0.0093 0.0104
CO2 6.76E-02 6.76E-02 6.76E-02 0.0224 0.0009
H2O 1.35E-01 1.35E-01 1.35E-01 0.2980 0.0005
CO 7.39E-05 7.55E-05 7.51E-05 1.5438 0.5483
NO 2.45E-03 2.43E-03 2.28E-03 7.4437 6.6846

NG

Tin [K] 300.00 300.00 300.00

Tad [K] 1843.37 1840.70 1839.60 0.2047 0.0598
O2 5.74E-02 5.73E-02 5.73E-02 0.1956 0.1325
N2 7.35E-01 7.35E-01 7.35E-01 0.0218 0.0109
CO2 6.91E-02 6.92E-02 6.92E-02 0.1293 0.0009
H2O 1.36E-01 1.35E-01 1.35E-01 0.3388 0.0007
CO 8.78E-05 8.92E-05 8.87E-05 1.0147 0.5330
NO 2.59E-03 2.56E-03 2.40E-03 7.6790 6.6214

with gas sampling, proposed models can be utilized as an effective programming language. Proposed models can be a reference guide
emission prediction tool with their accuracy and speed. Thanks to for engineers and researchers working on the design and optimi-
its useful and easy features, models can be coded in any zation of domestic boilers.

10
S. Yılmaz, D. Kumlutaş, U.A. Yücekaya et al. Energy 233 (2021) 121123

Table 4
Mole fraction deviations of equilibrium products and adiabatic flame temperatures for G20, G25, and NG fuels (f ¼ 0.75).

f¼0.75 Model 1 Results Model 2 Results CHEMKIN Model 1 Deviations (%) Model 2 Deviations (%)
Results

G20

Tin [K] 300.00 300.00 300.00

Tad [K] 1924.85 1920.50 1919.30 0.2888 0.0623
O2 4.73E-02 4.70E-02 4.71E-02 0.3755 0.1790
N2 7.31E-01 7.30E-01 7.31E-01 0.0227 0.0123
CO2 7.28E-02 7.27E-02 7.27E-02 0.0365 0.0022
H2O 1.46E-01 1.45E-01 1.45E-01 0.4986 0.0018
CO 2.20E-04 2.21E-04 2.19E-04 0.3530 0.6096
NO 3.00E-03 2.96E-03 2.78E-03 7.9616 6.3376

G25

Tin [K] 300.00 300.00 300.00

Tad [K] 1909.53 1905.70 1904.51 0.2634 0.0625
O2 4.68E-02 4.65E-02 4.66E-02 0.3421 0.1740
N2 7.34E-01 7.34E-01 7.34E-01 0.0201 0.0117
CO2 7.19E-02 7.19E-02 7.19E-02 0.0342 0.0020
H2O 1.44E-01 1.44E-01 1.44E-01 0.4584 0.0016
CO 1.90E-04 1.91E-04 1.90E-04 0.1502 0.6064
NO 2.86E-03 2.82E-03 2.65E-03 7.8490 6.3899

NG

Tin [K] 300.00 300.00 300.00

Tad [K] 1926.89 1922.00 1920.80 0.3171 0.0627
O2 4.73E-02 4.70E-02 4.71E-02 0.3850 0.1795
N2 7.31E-01 7.31E-01 7.31E-01 0.0345 0.0123
CO2 7.35E-02 7.36E-02 7.36E-02 0.1172 0.0022
H2O 1.45E-01 1.44E-01 1.44E-01 0.5169 0.0018
CO 2.26E-04 2.26E-04 2.25E-04 0.5083 0.5914
NO 3.02E-03 2.97E-03 2.80E-03 8.1391 6.3260

These models can also estimate equilibrium products of com-
bustion and thermodynamic properties without challenging
chemical kinetics calculations. Furthermore, proposed models can
be used to achieve optimum emissions levels defined in relevant
standards on the development of boilers, engines, gas turbines, and
other combustion systems. Parametrical analyses can be applied to
these combustion systems independent of the device and fuel type.
Promising fuels such as hydrogen, biomass-based fuels with
various fuel blends can be implemented in the prediction models.
The proposed models adjusted to investigate domestic heating
boilers in this study could be modified to predict the data outputs
for biomass thermochemical conversion processes such as gasifi-
cation, pyrolysis, forest fires, or environmental applications of
ocean acidification, the global carbonic cycle of carbonic acid.
CRediT authorship contribution statement
Semih Yılmaz: Conceptualization, Data curation, Formal anal-
ysis, Methodology, Software, Writing - original draft. Dilek
Kumlutaş: Conceptualization, Supervision, Writing - review &
editing. Utku Alp Yücekaya: Methodology, Data curation, Valida-
tion, Visualization, Writing - original draft. Ahmet Yakup Cumbul:
Data curation, Formal analysis, Methodology, Software, Writing -
original draft.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgments
This work was supported by the Scientific and Technological
Research Council of Turkey (as the project grant no: TUBITAK -
TEYDEB 5180092). We gratefully acknowledge this support.
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