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Analysis of nitrogen oxide emissions from modern vehicles using hydrogen or other natural and synthetic fuels in combustion chamber
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 1 1 5 1 e1 1 5 7
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Analysis of nitrogen oxide emissions from modern vehicles using hydrogen or other natural and synthetic fuels in combustion chamber* S.E. Shcheklein*, A.M. Dubinin Ural Federal University Named After the First President of Russia B.N. Yeltsin, 19 Mira Str., Yekaterinburg, 620002, Russia
article info
abstract
Article history:
The paper presents a calculated analysis of the equilibrium emission of nitrogen oxides on
Received 28 October 2019
the exhaust of carburetor and diesel internal combustion engines. The temperature of fuel
Accepted 29 October 2019
oxidation is assumed to be 1,400 C while the pressure for carburetor and diesel engines is
Available online 26 November 2019
assumed to be 60 atm and 80 atm respectively. The studies have been carried out for natural and synthetic fuels such as hydrogen, ethanol, methanol, petroleum, diesel fuel
Keywords:
and methane at the excess air coefficient corresponding to the fuel oxidation temperature
Nitrogen oxides
of 1,400 C. In the paper, the method for calculating the equilibrium composition based on
Hydrogen
the equilibrium constant and mass conservation equations has been applied. It is shown
Ethanol
that with an increase in pressure from 1 atm to 60 atm for carburetor engines and up to
Methanol
80 atm for diesel engines, the reaction of nitrogen dioxide formation may shift towards an
Petroleum
increase in NO2. The formation of NO may be not affected by the increase in pressure by
Methane
virtue of the fact that the reaction proceeds without changes in the amount. It has been determined that NO is the major atmospheric pollutant. However, it would be advisable to use more extensively the fuels characterized by the lowest output of nitrogen dioxide (methane and methanol), since nitrogen dioxide (NO2) related to the 2nd hazard class is appeared to be the most dangerous to humans. It has been revealed that the reduction in oxidation temperature using hydrogen as a fuel for electrochemical current generators may allow reducing nitrogen oxide emissions by more than an order of magnitude as compared to the best results for ICE. © 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
*
This paper is the English version of the paper reviewed and published in Russian in International Scientific Journal for Alternative Energy and Ecology “ISJAEE”, issue 291e293, number 07e09, date March 31, 2019. * Corresponding author. E-mail address: [email protected] (S.E. Shcheklein). https://doi.org/10.1016/j.ijhydene.2019.10.206 0360-3199/© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
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Nomenclature Acronyms ICE internal combustion engine Greek words m volume concentration of components in a gas mixture sum of mixture components after reaction, m3/ Sni m3 Svi algebraic sum of kilomoles of reaction (1e7) components before and after reaction Latin words equilibrium constant of reaction (1) Kр P pressure, atm R universal gas constant, kkal/mol К r concentration in a base mixture, g$mol/l T temperature, К admitted temperature, K ( C) to Z varying equilibrium concentration, m3/m3 Superscripts and subscripts in inert gases p equilibrium * after reaction (7) о standard parameters
Introduction In recent years, the possibility of using natural gas and different types of synthetic fuels for application in power engineering and transport has been explored [1e5]. An interest in these studies has arisen in connection with the necessity to reduce the dependence on imported fuel resources, primarily oil, which show a steady growth trend in cost as well as to use available resources of biomass, coal, domestic and industrial organic waste. On the other hand, the developed (USA, EU, Japan etc.) countries and emerging (China, India, Brazil etc.) countries are facing the issue of negative environmental impact of transport and power engineering. First and foremost, there is a problem of reducing greenhouse effect caused by fuel combustion products, the main one being carbon dioxide. In addition to fuel, combustion reaction may require an oxidizer, and the only oxidizer for power engineering and transport is atmospheric air consisting of more than 70% nitrogen. At high temperatures typical for the fuel combustion, and when the excess oxidizer volume (in relation to stoichiometric) is required, various nitrogen compounds may be formed in fuel combustion products. Most of these compounds are anthropogenic as well as strictly limited [6e8]. Nitrogen dioxide and nitrogen oxide may pose the greatest danger. The results of a study on the content of nitrogen oxides (NOx) in big cities in a number of countries show a substantial increase of such compounds exceeding the established norms by several times in some instances [9e12]. Reduction of NOx emissions from modern vehicles and power plants may be achieved by improving the design of engines
and furnaces, applying neutralization systems, and increasing quality requirements for conventional fuels [13e16]. The formation of nitrogen oxides while using modern synthetic fuels has not been sufficiently studied so far. On the other hand, new fuels may be an efficient instrument for improving environmental condition [17,18]. The paper presents the results of theoretical study on NOx formation while using conventional and new vehicle fuels.
Formation of nitrogen oxides There are three known mechanisms for nitrogen oxide formation, according to which they are divided into thermal, fuel and prompt nitrogen oxides. Fuel oxides may be formed from nitrogen compounds chemically bound to the fuel used, being typical for solid fuels (coal, wood etc.). Prompt oxides may arise from air nitrogen at high temperatures (more than 2,000 С). Thermal mechanism is the main one for modern internal combustion engines (ICE) running on liquid and gaseous fuels at moderate temperatures. Thermal oxides may be produced by the oxidation of air nitrogen, and their concentration cannot exceed the equilibrium [19]. It has been shown in pioneering works of Y.B. Zel’dovich [20] that the formation of nitrogen oxides during fuel combustion in the air is based on the nonbranched chain reaction wherein atoms of oxygen and nitrogen may play an active role. It has been determined that the energy barrier of NO formation reaction is sufficiently high, being composed of the energy of the oxygen atom formation (499$103kJ) and the energy of the oxygen atom interaction with nitrogen molecule (314$103kJ), and could be overcome at sufficiently high temperatures only. According to [20], the dependence of NO equilibrium concentration on temperature may be determined as follows: . pffiffiffi pffiffiffiffiffiffiffiffiffiffiffiffiffi p 3 , ro2 rN2 ,expð21400 = RTÞ rNO ¼ 8 Here, rO2 ; rN2 are concentrations of oxygen and nitrogen in a base mixture, g$mol/l; R ¼ 1.98kkal/mol$K. The analysis of NOx formation for the admitted combustion temperature range in modern ICE and in fuels of different chemical compositions is provided below.
Nitrogen oxide formation The oxidation reaction of molecular nitrogen by air oxygen may run in the following way: N2þО2 ¼ 2NO.
(1)
Logarithm of the equilibrium constant for reaction (1) [21,22] may be written as follows: lgKp ¼ 9; 581 T 0:022lgT þ 0:068,105 T2 þ 1:38:
(2)
The equilibrium constant for reaction (1) at the admitted temperature to ¼ 1,673 K (1,400 С) can be written as: Kp ¼ 40$106.
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On the other hand, the following condition is met for the equilibrium mixture [23,24]: P 2 X r P vi : Kp ¼ NO P ni rPN2 rPO2
(3)
Here, equilibrium concentrations of N2 and O2 in combustion products of the first stage may be written as follows [23,24]:
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A part of the formed NO may be spent on the formation of NO2 according to reaction (7). Logarithm of the equilibrium constant for reaction (7) [21] may be written as follows: lgK*р ¼ 6; 017:2 T 0:998lgT þ 0:302,103 T 0:237,105 T2 5:175:
¼ rN2 0; 5Z;
(4)
For the admitted temperature to ¼ 1,673 K (1,400 С) it may be written as follows:
rO2 ¼ rO2 0; 5Z;
(5)
K*p ¼ 50 106.
p rN2 p
Here, rN2 and rO2 are volume ratios of N2 and O2 in combustion products of various fuels at the excess air coefficient (a) at which the temperature of combustion products is equal to P 1,673 K (to ¼ 1,400 С); P is the pressure of mixture, atm; ni is a 3 3 sum of mixture components, m /m . In this instance, fuel oxidation may assume the form shown in Table 1 [25e27].
Concentration of N2 and O2 in oxidation products For example, concentrations for Н2 may take the following 3:196 0:35 ¼ 0:703m3/m3; rO2 ¼ 1þ3:196þ0:35 ¼ forms: rN2 ¼ 1þ3:196þ0:35 3 3 0:0769m /m . p We shall denoterNO ¼ Z. Reaction (1) proceeds without changes in volume as folP P lows: vi ¼ vNO vN2 vO2 ¼ 2e1 e 1 ¼ 0. Then, ðP= ni Þ0 ¼ 1. Here, the pressure does not affect the reaction. Taking into account equations (4) and (5), equation (3) could be written as follows: Kр ¼ z2 =ðrN2 0:5z rO2 0:5z
(6) p
Solving this equation, we find thatrNO ¼ Z, while the values p p forrN2 and rO2 (m3/m3) may be found from equations (4) and (5) respectively. The results for each fuel are given in Table 2 and Fig. 1. These results will be used further to determine equilibrium p concentrationrNO2 .
Formation of nitrogen dioxide The main reaction of NO2 formation in combustion products may correspond to oxidation of the formed nitrogen oxide by the residual oxygen as follows: 2NO þ О2 ¼ 2NO2.
Also, the following relation holds for equilibrium conditions [28,29]: 2 P vi r*NO2 P P ¼ 2 : (8) ni r*NO r*O2 P Here, vi ¼ vNO2 vNO vO2 ¼ 2e2e1 ¼ e1. The reaction is accompanied by a decrease in volume. An increase in pressure shifts the equilibrium towards an increase in NO2 concentration. We shall introduce the following notations of the mixture components [23,24]:
K*P
r*NO2 ¼ Z* ;
(9)
r*O2 ¼ rO2 0:5Z* ;
(10)
r*NO ¼ rNO Z* ;
(11)
p
p
p p rин ¼ 1 rO2 þ rNO : Here, rin is the volume fraction of inert ingredients (H2O, CO2). Then, X
p p ni ¼ Z* þ rNO Z* þ rO2 0:5Z* þ rin ¼
¼ rNO þ rO2 0:5Z* þ 1 rO2 rNO ¼ 1 0:5Z* : p
p
p
p
p
p
The values for rNO and rO2 are given in Table 2. We shall use the previously obtained equilibrium values for NO formation (see Table 2) to write equation (8) in the following way: K*р ¼
ðZ* Þ2 2 * rNO r*O2
P 1 0:5Z*
1 ¼
ðZ* Þ2 ð1 0:5Z* Þ : * 2 * rNO rO2 P
(7)
Table 1 e Excess air coefficients and fuel combustion reactions at 1,400 C. Fuel Hydrogen Ethanol Methanol Petroleum Diesel Methane
Excess air coefficient a
Equation
1.7 1.55 1.5 1.6 1.4 1.43
H2 þ 0.85(О2 þ 3.76 N2) ¼ H2O þ 3.196N2 þ 0.35О2 C2 H5 OH þ 4.66(О2 þ3.76 N2) ¼ 2СO2 þ 3H2O þ 17.52N2 þ 1,66О2 C H3 OHþ2.25(О2 þ3.76 N2) ¼ СO2 þ 2H2O þ 8.46N2 þ 0,75О2 C7 H16 þ 17.6(О2 þ 3.76 N2) ¼ 7СO2 þ 8H2O þ 66.176N2 þ 6,6О2 C8 H18 þ 17.5(О2 þ 3.76 N2) ¼ 8СO2 þ 9H2O þ 65.8N2 þ 5О2 СH4 þ 2.86(O2 þ 3.76N2) ¼ CO2 þ 2H2O þ 10.7536N2 þ 0,86О2
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Table 2 e Equilibrium concentrations of NO, N2 and О2 (m3/m3) in combustion products of the first stage. Characteristic p
rNO p rN2 p rO 2
Notation
Hydrogen
Ethanol
Methanol
Petroleum
Diesel
Methane
m3/m3 m3/m3 m3/m3
0.0015347 0.7022683 0.0762234
0.0014707 0.72383 0.067916
0.0013602 0.692195 0.060745
0.0015702 0.753134 0.074406
0.0013615 0.74875 0.056267
0.0013717 0.735177 0.058163
Fig. 2 e Equilibrium concentrations of NO2 in combustion products (P ¼ 1 atm).
Fig. 1 e Equilibrium NO concentrations in combustion products.
The solution for determining NO2 concentration may be found from the following equation: 2 K*P , r*NO , r*O2 , P ¼ ðZ* Þ2 ,ð1 0; 5Z* Þ:
(12)
Valuesr*NO2 ¼ Z* andr*NO may be determined from equations (12) and (11) respectively. Then, their sumr*NO þ r*NO2 may be found. Calculation results at pressure of 1 atm are shown in Table 3 and Fig. 2, while those at pressure 60 atm and 80 atm for carburetor and diesel ICE respectively are shown in Fig. 3. As expected, an increase in pressure may result in the increased equilibrium concentration of NO2 by more than 10 times. Hence, the increase in thermodynamic parameters of the combustion in ICE as a means to increase their energy efficiency may simultaneously result in negative environmental consequences (Fig. 4). This phenomenon requires developing more efficient methods for neutralizing combustion products in regard to all fuels under consideration.
Results and discussion Nitrogen dioxide (NO2) related to the 2nd hazard class chemical substances may be most dangerous for humans.
Fig. 3 e Equilibrium NO2 concentrations in combustion products (P ¼ 60 atm for carburetor ICE and P ¼ 80 atm for diesel ICE).
According to International norms (CAS 10102-44-02) and Russian National norms (GN 2.1.6.695e8), NO2 maximum single concentration should not exceed the value of 0.085 mg/ m3 while its mean daily concentration should not be more than 0.04 mg/m3 [6,7,12,13]. However, numerous experiments carried out in recent years around the world demonstrate a
Table 3 e Equilibrium concentrations of NO2, NO, and NOx in combustion products, m3/m.3. Characteristic r*NO2
r*NO r*NOx
Pressure, atm
Hydrogen
Ethanol
Methanol
Petroleum
Diesel
Methane
1 60 80 1 60 80
2.99E-06 2.32E-05 e 0.00156 0.001563 e
2.71E-06 2.1E-05 e 0.00147 0.00149 e
2.37E-06 1.836E-05 e 0.00136 0.00138 e
3,023E-06 2.346E-05 e 0.00157 0.00159 e
2.28E-06 e 2.01E-05 0.00136 e 0.00138
2.33E-06 1.812E-05 e 0.00137 0.00139 e
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Fig. 4 e Equilibrium concentrations of NOx in combustion products (P ¼ 60 atm for carburetor ICE and P ¼ 80 atm for diesel ICE).
significant excess of these levels [30e34] owing mainly to the expansive growth of the vehicle fleet. The situation is especially alarming in megacities and countries having rapid economic growth [35]. To reduce NOx concentration, the catalytic and non-catalytic neutralization methods are being developed. Thus, the Exon Research Engineering Company has developed and patented the method for deoxidizing NO to molecular nitrogen by adding ammonia or urea to exhaust gases [36e41]. The way out of this situation may also lie through increasing the development of electric transport, lowtemperature technologies for using fuel as well as measures and administrative regulations to improve the use of vehicles and industrial enterprises in centers of population [42,43]. The experience of Canada wherein NO2 concentration in cities has been reduced by more than twice due to a number of administrative measures taken over the period from 1998 to 2013 [44] may be required of great interest in this regard. It may be advisable to compare nitrogen oxide emissions from different natural and synthetic fuels with allowance for their different energy values and hence different amount of the required oxidizer (air) in order to obtain an equal energy efficiency (fuel consumption per 100 km). Specific values for NO2 and NOx emissions calculated with allowance for actual combustion values are given in Figs. 5 and 6.
Fig. 5 e Specific NO2 concentration in combustion products (P ¼ 60 atm for carburetor ICE and P ¼ 80 atm for diesel ICE).
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Fig. 6 e Specific NOx concentration in combustion products (P ¼ 60 atm for carburetor ICE and P ¼ 80 atm for diesel ICE).
It can be seen from the data provided in Figs. 5 and 6 that methanol and methane may have the lowest emission level of the most dangerous gas (NO2). These results could be used in complex optimization of the energy and ecological efficiency of modern and advanced ICE in combination with other factors characterizing the effect of thermodynamic parameters on the specific fuel consumption and the formation of other anthropogenic combustion products [46]. However, lowering the fuel oxidation temperature may become an efficient method for reducing nitrogen oxide emissions. For example, using hydrogen as a fuel for electrochemical current generators may allow abandoning ICE in vehicles as well as reducing nitrogen oxide emissions by more than an order of magnitude. Thus, calculations carried out on the basis of this method for a power plant with a hightemperature electrochemical generator (to ¼ 1,058 K) using hydrogen as a fuel and atmospheric air as an oxidizer [45] have shown that total NOx concentration in combustion products may be reduced by 32 times, as compared to ICE.
Conclusion Modern high-temperature methods for using natural and synthetic fuels as an oxidizer of atmospheric air inevitably result in formation of substantial amount of various nitrogen oxides. The higher the concentration of N2 and O2 in fuel oxidation products, the higher is that of NO and NO2 in exhaust gases. For example, the concentration of nitrogen is 8.8% higher and oxygen is 22% higher during petroleum oxidation as compared to methanol oxidation, so the output of nitrogen oxide is 14% higher and nitrogen dioxide is 21% higher than during methanol oxidation. An increase in pressure from 1 atm to 80 atm during diesel fuel oxidation may increase NO2 concentration by 8.8 times while the concentration of other fuels under consideration has demonstrated 7.8 times increase with an increase in pressure from 1 atm to 60 atm.
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NO is considered the major atmospheric pollutant. However, since nitrogen dioxide (NO2) related to the 2nd hazard class is appeared to be the most dangerous to humans, it would be advisable to use extensively the fuels characterized by the lowest output of nitrogen dioxide (methane and methanol). The reduction in oxidation temperatures using hydrogen as a fuel for electrochemical current generators may become an efficient method for reducing nitrogen oxide emissions by more than an order of magnitude as compared to the best results for ICE.
Acknowledgements The article was prepared with the financial support of the Government of the Russian Federation (Contract N02.А03.21.0006).
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Available online at www.sciencedirect.com
ScienceDirect journal homepage: www.elsevier.com/locate/he
Analysis of nitrogen oxide emissions from modern vehicles using hydrogen or other natural and synthetic fuels in combustion chamber* S.E. Shcheklein*, A.M. Dubinin Ural Federal University Named After the First President of Russia B.N. Yeltsin, 19 Mira Str., Yekaterinburg, 620002, Russia
article info
abstract
Article history:
The paper presents a calculated analysis of the equilibrium emission of nitrogen oxides on
Received 28 October 2019
the exhaust of carburetor and diesel internal combustion engines. The temperature of fuel
Accepted 29 October 2019
oxidation is assumed to be 1,400 C while the pressure for carburetor and diesel engines is
Available online 26 November 2019
assumed to be 60 atm and 80 atm respectively. The studies have been carried out for natural and synthetic fuels such as hydrogen, ethanol, methanol, petroleum, diesel fuel
Keywords:
and methane at the excess air coefficient corresponding to the fuel oxidation temperature
Nitrogen oxides
of 1,400 C. In the paper, the method for calculating the equilibrium composition based on
Hydrogen
the equilibrium constant and mass conservation equations has been applied. It is shown
Ethanol
that with an increase in pressure from 1 atm to 60 atm for carburetor engines and up to
Methanol
80 atm for diesel engines, the reaction of nitrogen dioxide formation may shift towards an
Petroleum
increase in NO2. The formation of NO may be not affected by the increase in pressure by
Methane
virtue of the fact that the reaction proceeds without changes in the amount. It has been determined that NO is the major atmospheric pollutant. However, it would be advisable to use more extensively the fuels characterized by the lowest output of nitrogen dioxide (methane and methanol), since nitrogen dioxide (NO2) related to the 2nd hazard class is appeared to be the most dangerous to humans. It has been revealed that the reduction in oxidation temperature using hydrogen as a fuel for electrochemical current generators may allow reducing nitrogen oxide emissions by more than an order of magnitude as compared to the best results for ICE. © 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
*
This paper is the English version of the paper reviewed and published in Russian in International Scientific Journal for Alternative Energy and Ecology “ISJAEE”, issue 291e293, number 07e09, date March 31, 2019. * Corresponding author. E-mail address: [email protected] (S.E. Shcheklein). https://doi.org/10.1016/j.ijhydene.2019.10.206 0360-3199/© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
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Nomenclature Acronyms ICE internal combustion engine Greek words m volume concentration of components in a gas mixture sum of mixture components after reaction, m3/ Sni m3 Svi algebraic sum of kilomoles of reaction (1e7) components before and after reaction Latin words equilibrium constant of reaction (1) Kр P pressure, atm R universal gas constant, kkal/mol К r concentration in a base mixture, g$mol/l T temperature, К admitted temperature, K ( C) to Z varying equilibrium concentration, m3/m3 Superscripts and subscripts in inert gases p equilibrium * after reaction (7) о standard parameters
Introduction In recent years, the possibility of using natural gas and different types of synthetic fuels for application in power engineering and transport has been explored [1e5]. An interest in these studies has arisen in connection with the necessity to reduce the dependence on imported fuel resources, primarily oil, which show a steady growth trend in cost as well as to use available resources of biomass, coal, domestic and industrial organic waste. On the other hand, the developed (USA, EU, Japan etc.) countries and emerging (China, India, Brazil etc.) countries are facing the issue of negative environmental impact of transport and power engineering. First and foremost, there is a problem of reducing greenhouse effect caused by fuel combustion products, the main one being carbon dioxide. In addition to fuel, combustion reaction may require an oxidizer, and the only oxidizer for power engineering and transport is atmospheric air consisting of more than 70% nitrogen. At high temperatures typical for the fuel combustion, and when the excess oxidizer volume (in relation to stoichiometric) is required, various nitrogen compounds may be formed in fuel combustion products. Most of these compounds are anthropogenic as well as strictly limited [6e8]. Nitrogen dioxide and nitrogen oxide may pose the greatest danger. The results of a study on the content of nitrogen oxides (NOx) in big cities in a number of countries show a substantial increase of such compounds exceeding the established norms by several times in some instances [9e12]. Reduction of NOx emissions from modern vehicles and power plants may be achieved by improving the design of engines
and furnaces, applying neutralization systems, and increasing quality requirements for conventional fuels [13e16]. The formation of nitrogen oxides while using modern synthetic fuels has not been sufficiently studied so far. On the other hand, new fuels may be an efficient instrument for improving environmental condition [17,18]. The paper presents the results of theoretical study on NOx formation while using conventional and new vehicle fuels.
Formation of nitrogen oxides There are three known mechanisms for nitrogen oxide formation, according to which they are divided into thermal, fuel and prompt nitrogen oxides. Fuel oxides may be formed from nitrogen compounds chemically bound to the fuel used, being typical for solid fuels (coal, wood etc.). Prompt oxides may arise from air nitrogen at high temperatures (more than 2,000 С). Thermal mechanism is the main one for modern internal combustion engines (ICE) running on liquid and gaseous fuels at moderate temperatures. Thermal oxides may be produced by the oxidation of air nitrogen, and their concentration cannot exceed the equilibrium [19]. It has been shown in pioneering works of Y.B. Zel’dovich [20] that the formation of nitrogen oxides during fuel combustion in the air is based on the nonbranched chain reaction wherein atoms of oxygen and nitrogen may play an active role. It has been determined that the energy barrier of NO formation reaction is sufficiently high, being composed of the energy of the oxygen atom formation (499$103kJ) and the energy of the oxygen atom interaction with nitrogen molecule (314$103kJ), and could be overcome at sufficiently high temperatures only. According to [20], the dependence of NO equilibrium concentration on temperature may be determined as follows: . pffiffiffi pffiffiffiffiffiffiffiffiffiffiffiffiffi p 3 , ro2 rN2 ,expð21400 = RTÞ rNO ¼ 8 Here, rO2 ; rN2 are concentrations of oxygen and nitrogen in a base mixture, g$mol/l; R ¼ 1.98kkal/mol$K. The analysis of NOx formation for the admitted combustion temperature range in modern ICE and in fuels of different chemical compositions is provided below.
Nitrogen oxide formation The oxidation reaction of molecular nitrogen by air oxygen may run in the following way: N2þО2 ¼ 2NO.
(1)
Logarithm of the equilibrium constant for reaction (1) [21,22] may be written as follows: lgKp ¼ 9; 581 T 0:022lgT þ 0:068,105 T2 þ 1:38:
(2)
The equilibrium constant for reaction (1) at the admitted temperature to ¼ 1,673 K (1,400 С) can be written as: Kp ¼ 40$106.
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 1 1 5 1 e1 1 5 7
On the other hand, the following condition is met for the equilibrium mixture [23,24]: P 2 X r P vi : Kp ¼ NO P ni rPN2 rPO2
(3)
Here, equilibrium concentrations of N2 and O2 in combustion products of the first stage may be written as follows [23,24]:
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A part of the formed NO may be spent on the formation of NO2 according to reaction (7). Logarithm of the equilibrium constant for reaction (7) [21] may be written as follows: lgK*р ¼ 6; 017:2 T 0:998lgT þ 0:302,103 T 0:237,105 T2 5:175:
¼ rN2 0; 5Z;
(4)
For the admitted temperature to ¼ 1,673 K (1,400 С) it may be written as follows:
rO2 ¼ rO2 0; 5Z;
(5)
K*p ¼ 50 106.
p rN2 p
Here, rN2 and rO2 are volume ratios of N2 and O2 in combustion products of various fuels at the excess air coefficient (a) at which the temperature of combustion products is equal to P 1,673 K (to ¼ 1,400 С); P is the pressure of mixture, atm; ni is a 3 3 sum of mixture components, m /m . In this instance, fuel oxidation may assume the form shown in Table 1 [25e27].
Concentration of N2 and O2 in oxidation products For example, concentrations for Н2 may take the following 3:196 0:35 ¼ 0:703m3/m3; rO2 ¼ 1þ3:196þ0:35 ¼ forms: rN2 ¼ 1þ3:196þ0:35 3 3 0:0769m /m . p We shall denoterNO ¼ Z. Reaction (1) proceeds without changes in volume as folP P lows: vi ¼ vNO vN2 vO2 ¼ 2e1 e 1 ¼ 0. Then, ðP= ni Þ0 ¼ 1. Here, the pressure does not affect the reaction. Taking into account equations (4) and (5), equation (3) could be written as follows: Kр ¼ z2 =ðrN2 0:5z rO2 0:5z
(6) p
Solving this equation, we find thatrNO ¼ Z, while the values p p forrN2 and rO2 (m3/m3) may be found from equations (4) and (5) respectively. The results for each fuel are given in Table 2 and Fig. 1. These results will be used further to determine equilibrium p concentrationrNO2 .
Formation of nitrogen dioxide The main reaction of NO2 formation in combustion products may correspond to oxidation of the formed nitrogen oxide by the residual oxygen as follows: 2NO þ О2 ¼ 2NO2.
Also, the following relation holds for equilibrium conditions [28,29]: 2 P vi r*NO2 P P ¼ 2 : (8) ni r*NO r*O2 P Here, vi ¼ vNO2 vNO vO2 ¼ 2e2e1 ¼ e1. The reaction is accompanied by a decrease in volume. An increase in pressure shifts the equilibrium towards an increase in NO2 concentration. We shall introduce the following notations of the mixture components [23,24]:
K*P
r*NO2 ¼ Z* ;
(9)
r*O2 ¼ rO2 0:5Z* ;
(10)
r*NO ¼ rNO Z* ;
(11)
p
p
p p rин ¼ 1 rO2 þ rNO : Here, rin is the volume fraction of inert ingredients (H2O, CO2). Then, X
p p ni ¼ Z* þ rNO Z* þ rO2 0:5Z* þ rin ¼
¼ rNO þ rO2 0:5Z* þ 1 rO2 rNO ¼ 1 0:5Z* : p
p
p
p
p
p
The values for rNO and rO2 are given in Table 2. We shall use the previously obtained equilibrium values for NO formation (see Table 2) to write equation (8) in the following way: K*р ¼
ðZ* Þ2 2 * rNO r*O2
P 1 0:5Z*
1 ¼
ðZ* Þ2 ð1 0:5Z* Þ : * 2 * rNO rO2 P
(7)
Table 1 e Excess air coefficients and fuel combustion reactions at 1,400 C. Fuel Hydrogen Ethanol Methanol Petroleum Diesel Methane
Excess air coefficient a
Equation
1.7 1.55 1.5 1.6 1.4 1.43
H2 þ 0.85(О2 þ 3.76 N2) ¼ H2O þ 3.196N2 þ 0.35О2 C2 H5 OH þ 4.66(О2 þ3.76 N2) ¼ 2СO2 þ 3H2O þ 17.52N2 þ 1,66О2 C H3 OHþ2.25(О2 þ3.76 N2) ¼ СO2 þ 2H2O þ 8.46N2 þ 0,75О2 C7 H16 þ 17.6(О2 þ 3.76 N2) ¼ 7СO2 þ 8H2O þ 66.176N2 þ 6,6О2 C8 H18 þ 17.5(О2 þ 3.76 N2) ¼ 8СO2 þ 9H2O þ 65.8N2 þ 5О2 СH4 þ 2.86(O2 þ 3.76N2) ¼ CO2 þ 2H2O þ 10.7536N2 þ 0,86О2
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Table 2 e Equilibrium concentrations of NO, N2 and О2 (m3/m3) in combustion products of the first stage. Characteristic p
rNO p rN2 p rO 2
Notation
Hydrogen
Ethanol
Methanol
Petroleum
Diesel
Methane
m3/m3 m3/m3 m3/m3
0.0015347 0.7022683 0.0762234
0.0014707 0.72383 0.067916
0.0013602 0.692195 0.060745
0.0015702 0.753134 0.074406
0.0013615 0.74875 0.056267
0.0013717 0.735177 0.058163
Fig. 2 e Equilibrium concentrations of NO2 in combustion products (P ¼ 1 atm).
Fig. 1 e Equilibrium NO concentrations in combustion products.
The solution for determining NO2 concentration may be found from the following equation: 2 K*P , r*NO , r*O2 , P ¼ ðZ* Þ2 ,ð1 0; 5Z* Þ:
(12)
Valuesr*NO2 ¼ Z* andr*NO may be determined from equations (12) and (11) respectively. Then, their sumr*NO þ r*NO2 may be found. Calculation results at pressure of 1 atm are shown in Table 3 and Fig. 2, while those at pressure 60 atm and 80 atm for carburetor and diesel ICE respectively are shown in Fig. 3. As expected, an increase in pressure may result in the increased equilibrium concentration of NO2 by more than 10 times. Hence, the increase in thermodynamic parameters of the combustion in ICE as a means to increase their energy efficiency may simultaneously result in negative environmental consequences (Fig. 4). This phenomenon requires developing more efficient methods for neutralizing combustion products in regard to all fuels under consideration.
Results and discussion Nitrogen dioxide (NO2) related to the 2nd hazard class chemical substances may be most dangerous for humans.
Fig. 3 e Equilibrium NO2 concentrations in combustion products (P ¼ 60 atm for carburetor ICE and P ¼ 80 atm for diesel ICE).
According to International norms (CAS 10102-44-02) and Russian National norms (GN 2.1.6.695e8), NO2 maximum single concentration should not exceed the value of 0.085 mg/ m3 while its mean daily concentration should not be more than 0.04 mg/m3 [6,7,12,13]. However, numerous experiments carried out in recent years around the world demonstrate a
Table 3 e Equilibrium concentrations of NO2, NO, and NOx in combustion products, m3/m.3. Characteristic r*NO2
r*NO r*NOx
Pressure, atm
Hydrogen
Ethanol
Methanol
Petroleum
Diesel
Methane
1 60 80 1 60 80
2.99E-06 2.32E-05 e 0.00156 0.001563 e
2.71E-06 2.1E-05 e 0.00147 0.00149 e
2.37E-06 1.836E-05 e 0.00136 0.00138 e
3,023E-06 2.346E-05 e 0.00157 0.00159 e
2.28E-06 e 2.01E-05 0.00136 e 0.00138
2.33E-06 1.812E-05 e 0.00137 0.00139 e
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 1 1 5 1 e1 1 5 7
Fig. 4 e Equilibrium concentrations of NOx in combustion products (P ¼ 60 atm for carburetor ICE and P ¼ 80 atm for diesel ICE).
significant excess of these levels [30e34] owing mainly to the expansive growth of the vehicle fleet. The situation is especially alarming in megacities and countries having rapid economic growth [35]. To reduce NOx concentration, the catalytic and non-catalytic neutralization methods are being developed. Thus, the Exon Research Engineering Company has developed and patented the method for deoxidizing NO to molecular nitrogen by adding ammonia or urea to exhaust gases [36e41]. The way out of this situation may also lie through increasing the development of electric transport, lowtemperature technologies for using fuel as well as measures and administrative regulations to improve the use of vehicles and industrial enterprises in centers of population [42,43]. The experience of Canada wherein NO2 concentration in cities has been reduced by more than twice due to a number of administrative measures taken over the period from 1998 to 2013 [44] may be required of great interest in this regard. It may be advisable to compare nitrogen oxide emissions from different natural and synthetic fuels with allowance for their different energy values and hence different amount of the required oxidizer (air) in order to obtain an equal energy efficiency (fuel consumption per 100 km). Specific values for NO2 and NOx emissions calculated with allowance for actual combustion values are given in Figs. 5 and 6.
Fig. 5 e Specific NO2 concentration in combustion products (P ¼ 60 atm for carburetor ICE and P ¼ 80 atm for diesel ICE).
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Fig. 6 e Specific NOx concentration in combustion products (P ¼ 60 atm for carburetor ICE and P ¼ 80 atm for diesel ICE).
It can be seen from the data provided in Figs. 5 and 6 that methanol and methane may have the lowest emission level of the most dangerous gas (NO2). These results could be used in complex optimization of the energy and ecological efficiency of modern and advanced ICE in combination with other factors characterizing the effect of thermodynamic parameters on the specific fuel consumption and the formation of other anthropogenic combustion products [46]. However, lowering the fuel oxidation temperature may become an efficient method for reducing nitrogen oxide emissions. For example, using hydrogen as a fuel for electrochemical current generators may allow abandoning ICE in vehicles as well as reducing nitrogen oxide emissions by more than an order of magnitude. Thus, calculations carried out on the basis of this method for a power plant with a hightemperature electrochemical generator (to ¼ 1,058 K) using hydrogen as a fuel and atmospheric air as an oxidizer [45] have shown that total NOx concentration in combustion products may be reduced by 32 times, as compared to ICE.
Conclusion Modern high-temperature methods for using natural and synthetic fuels as an oxidizer of atmospheric air inevitably result in formation of substantial amount of various nitrogen oxides. The higher the concentration of N2 and O2 in fuel oxidation products, the higher is that of NO and NO2 in exhaust gases. For example, the concentration of nitrogen is 8.8% higher and oxygen is 22% higher during petroleum oxidation as compared to methanol oxidation, so the output of nitrogen oxide is 14% higher and nitrogen dioxide is 21% higher than during methanol oxidation. An increase in pressure from 1 atm to 80 atm during diesel fuel oxidation may increase NO2 concentration by 8.8 times while the concentration of other fuels under consideration has demonstrated 7.8 times increase with an increase in pressure from 1 atm to 60 atm.
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NO is considered the major atmospheric pollutant. However, since nitrogen dioxide (NO2) related to the 2nd hazard class is appeared to be the most dangerous to humans, it would be advisable to use extensively the fuels characterized by the lowest output of nitrogen dioxide (methane and methanol). The reduction in oxidation temperatures using hydrogen as a fuel for electrochemical current generators may become an efficient method for reducing nitrogen oxide emissions by more than an order of magnitude as compared to the best results for ICE.
Acknowledgements The article was prepared with the financial support of the Government of the Russian Federation (Contract N02.А03.21.0006).
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