International Journal of Hydrogen Energy 32 (2007) 4059 4070 www.elsevier.

com/locate/ijhydene

Effects of addition of electrolysis products in methaneair diffusion ames

Jeong Park a , , Sang In Keel b , Jin Han Yun b , Tae Kwon Kim c
a School of Mechanical Engineering, Pukyung National University, San 100, Yongdang-dong, Nam-gu, Busan 608 739, Republic of Korea b Environment & Energy Research Division, Korea Institute of Machinery and Materials, 171 Jang-dong, Yuseong-gu, Daejeon 305 343, Republic of Korea c School of Mechanical & Automotive Engineering, Keimyung University, 1000 Singdang-dong, Dalseo-gu, Daegu 704 701, Republic of Korea

Received 30 December 2006; received in revised form 22 May 2007; accepted 22 May 2007 Available online 5 July 2007

Abstract Evaluation of steam-added methanehydrogen blends through the comparison of ame structures and pollutant emissions is numerically conducted with detailed chemistry. The composition of fuel is systematically changed from pure methane and pure hydrogen to the blending fuel of methanehydrogen-steam through the molar addition of H2 O. Flame structure is changed considerably for CH4 .H2 ames and CH4 .H2 .H2 O ames in comparison to pure methane ame. The discernible differences in major ame structure are compared among a pure methane ame, CH4 .H2 ames and CH4 .H2 .H2 O ames. Especially, emission indices of CO increase and then decrease after showing a maximum in the increase of methane mole fraction for CH4 .H2 ames and in the increase of H2 O mole fraction for CH4 .H2 .H2 O ames, while those of CO2 increase monotonously. These behaviors are mainly caused by the competition of the production through the reaction step HCO + H2 O H + CO + H2 O with the destruction of CO by the reaction step CO + OH CO2 + H. The changes of thermal NO and Fenimore NO are also analyzed for various combinations of the fuel composition. Importantly, contributing reaction steps to thermal NO and Fenimore NO are addressed in pure methane, CH4 .H2 ames and CH4 .H2 .H2 O ames. 2007 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
Keywords: Electrolysis products; Emission index; Fenimore NO; Fuel consumption layer; H2 .CO consumption layer; Thermal NO

1. Introduction Hydrocarbonhydrogen blends are receiving attention as alternative fuels for power generation applications for three main reasons. The rst reason is relevant to the opportunity of adding hydrogen to methane in order to improve performance and to reduce pollutant emissions of lean combustion and mobile combustion systems [1,2]. The second reason is due to concerns about global warming and the prospect of using hydrogen in fuel cells and combustors of next generation. However, the use of pure hydrogen may be still far distant due to stringent problems of safety and storage, and enormous investment cost for the replacement of fossil fuels by hydrogen in existing power plant system. To bypass these difculties for a moment, blending hydrogen into methane or other hydrocarbons might be a proposal as an intermediate solution towards a fully developed
Corresponding author. Tel.: +82 51 620 1601; fax: +82 51 620 1531.

E-mail address: jeongpark@pknu.ac.kr (J. Park).

hydrogen-economy society [38]. The third reason is related to the extension of ame stability limit. This technology has been especially applicable to lean-burning combustors since this lean combustion stability problem can be resolved through addition of even a small amount of hydrogen, which can sustain vigorous burning at lower temperatures compared to hydrocarbons [9]. Production of hydrogen by electrolysis of water may be preferred because of the safety and cost considerations of handling and storing hydrogen as a fuel additive. Practical applications of the addition of electrolysis products into other fuels are already available in practical combustors such as IC engines [10]. Produced hydrogen through this process also contains water vapor, and then water vapor may make combustion phenomena complicated in hydrocarbonhydrogen blended ames. Methane ame is well described by a fuel consumption layer and a H2 .CO consumption layer in the side of ame structure [11]. The addition of hydrogen to methane may result in intensifying the characteristic of H2 .CO consumption layer, and it was shown that these affected ame structure and NOx

0360-3199/$ - see front matter 2007 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.ijhydene.2007.05.024

4060

J. Park et al. / International Journal of Hydrogen Energy 32 (2007) 4059 4070

H 2 u
Flame

d dx

FG

3G 2

d dx

d dx

= 0,

(2) (3)

Oxidizer

d d Yk + ( Y k Vk ) w k W k = 0 , dx dx 1 d dT dx cp d x 1 + cp dT dx

k = 1, . . . , K , dT dx

cp

cpk Vk Yk
k

r u Stagnation Plane Fuel

qr hk wk = 0, cp

(4)

Fig. 1. Schematic of conguration of counterow diffusion ame.

where G(x) = v/r , F (x) = u/2, and the radial pressure gradient, H = (1/r)jp/jr is constant and is an eigenvalue of the problem. In this formulation, the axial and radial velocity components at the nozzle exit can be independently specied and the pressure eigenvalue is computed as part of the solution. The boundary conditions for the fuel and oxidizer streams at the nozzles are uF x = 0 : F = F , G = 0 , T = TF , 2 uY k + Yk Vk = ( uY k )F , x=L:F = , G = 0 , T = TO , 2 uY k + Yk Vk = ( uY k )O ,
O uO

emission considerably [12]. Up to now, most of past research efforts have been given to study ame structure and NO emissions in blended fuels of methane and hydrogen only for the low hydrogen content side. Indeed, combustion characteristics and NO emission behavior are not yet understood so much at intermediate and high hydrogen contents. Especially, considering the extensive application of the utilization of electrolysis products in the future, some fundamental research efforts are still needed to better understand ame structure and NOx emission in steam added hydrocarbonhydrogen combustion system. The objectives of the present numerical work are, therefore: (i) to compare the difference of ame structures in methane/hydrogen/steamair ames over a wide range of mixture compositions as a fuel; (ii) to clarify the effects of added hydrogen and steam on pollutant emissions such as CO, CO2 , and NOx ; (iii) to examine the dominant reaction steps in reaction contribution to Fenimore NO at various conditions by varying the content of hydrogen and water vapor in the blend. 2. Numerical strategies and model description A laminar opposed jet diffusion ame is established between two opposed jets impinging on each other as shown in Fig. 1. The mathematical description near the stagnation point is onedimensional, and the model adopted in the study is that developed by Kee et al. [13] and extended by Lutz et al. [14]. The only difference between this work and those conducted by them is energy conservation equation, in which we retain the sink term relevant to the thermal radiation. All these conservation equations are transformed into a set of ordinary differential equations and are written as G(x) = dF (x) , dx (1)

(5)

where the velocities of both nozzle exits are maintained symmetric such as uF = uO . The main contribution to radiative heat loss is given to CO2 , H2 O, CO, and CH4 , and the radiative heat loss, based on the optically thin approximation, is as follows [15]:
4 qr = 4 Kp (T 4 T ), 4

(6) (7)

Kp =
i =1

Pi K i ,

i = CO2 , H2 O, CO, CH4 ,

where is the StefanBoltzmann constant, T and T the local and ambient temperatures, respectively, and Kp Plank mean absorption coefcient. Pi and Ki are the partial pressure and the Plank mean absorption coefcient of a species, respectively. The Plank mean absorption coefcient is approximately obtained as a polynomial function of temperature. The transport properties (viscosity , thermal conductivity , and diffusion coefcients) are given in a multicomponent formulation in which the diffusion velocities are given as Vk = 1 Xk W
K

Wj Dkj
j =k

D T 1 jT jXj k . Yk T jx jx

(8)

The governing equations are solved using a CHEMKIN-based code [16] and a transport-based code [17]. An adaptive grid redistributes a weighting function of the rst and second derivatives of the temperature, and the system of algebraic equations is solved by a damped Newton algorithm. In the strategy for a converged solution, if the Newton algorithm fails to converge, the solution estimate is conditioned by a period of time integration. This provides a new starting point for the Newton algorithm that is close to the solution.

J. Park et al. / International Journal of Hydrogen Energy 32 (2007) 4059 4070

4061

The separation distance of the two opposed jets is 2.0 cm, and the ame zone is located at the position which momentum uxes of fuel- and oxidizer-sides balance each other. The global strain rate is obtained as follows [18]:
Maximum flame temperature, K

2400
ag=157s-1

ag =

uF 2(uO ) 1+ L (uO )

2300

CH4-H2 Flames

F O

(9)

2200

Here the subscripts F and O mean the fuel and oxidizer, respectively. In the previous study [9], the GRI v-3.0 mechanism [19] was validated by comparing experimentally and numerically determined ame properties for various fuel combinations in hydrogen-enriched CH4 air premixed ames. Accordingly, the present reaction model adopts the GRI v-3.0 mechanism. Flame structure of CH4 air diffusion ame is systematically changed into those of the blending fuels (methanehydrogenH2 O) through molar additions of H2 and H2 O in the fuel stream. The ambient pressure is 1 atm, and the temperatures in the fueland oxidizer-sides are 300 K. 3. Results and discussion

2100

2000

1900 0.0 0.2 0.4 XCH4 2400

ag=157s-1 CH -H -H O Flames
4 2 2

0.6

0.8

1.0

Maximum flame temperature, K

3.1. Major ame structure Fig. 2 shows the variation of maximum ame temperature with: (a) methane mole fraction for CH4 .H2 ame and (b) H2 O mole fraction for CH4 .H2 .H2 O ame at the strain rate of 157 s1 . In Fig. 2(a) the zero with the mole fraction of methane means pure hydrogen and the unity represents pure methane. Thus the reduction of methane mole fraction implies the increase of hydrogen mole fraction. Fig. 2 shows that maximum ame temperature decreases in the increase of methane mole fraction and steam mole fraction. In general, the reaction rate of the chain branching reaction H+O2 O+OH, which is an indicator of overall reaction rate, is relatively less than those between H atoms and hydrocarbons, and both the reactions compete each other for H-atom [20]. Thus the increase of the population of hydrocarbons forces the ame strength to decrease through the relative enfeeblement of the reaction rate of the principal chain branching reaction. It is also seen in Fig. 2 that maximum ame temperature decreases with the increase of added steam mole fraction. This is so because the addition of steam reduces the population of the reactive species such as H2 and CH4 . This is also conrmed by the fact that extremely added steam produces ame extinction in the Fig. 2(b). Fig. 3 shows the typical ame structures: (a) of major species, (b) of production rates of the major species and (c) of CH3 and chain carrier radicals at the strain rate of 157 s1 in pure methane ame. Fig. 4 depicts the same information for XCH4 = 0.7 and XH2 = 0.3 in CH4 .H2 ame. Fig. 5 represents those in the case of XCH4 = 0.3, XH2 = 0.4, and XH2 O = 0.3 in CH4 .H2 .H2 O ame. In the gures the s.p. and Tmax just above the bold line represent the stagnation point and the position of maximum ame temperature, respectively. It has been known for methane ame that the following reaction steps mainly contribute to the formation of methyl as the rst step of methane

2200

XH O=0.1
2 2 2 2

XH O=0.3 XH O=0.5 XH O=0.7

2000

1800
Flame Extinction

1600 0.0

0.2

0.4 XH2O

0.6

0.8

1.0

Fig. 2. Variation of maximum ame temperature with: (a) methane mole fraction for CH4 .H2 ame, and (b) steam mole fraction for CH4 .H2 .H2 O ame at the strain rate of 157 s1 .

oxidation reaction. CH4 + O = CH3 + OH, CH4 (+M) = H + CH3 (+M), CH4 + H = CH3 + H2 , CH4 + OH = CH3 + H2. (R11) (R52) (R53) (R98)

Here the reaction numbers are referred to those from the GRI v-3.0 mechanism. It is seen that the reaction contribution of (R53) for methyl formation is the largest in the reaction steps. As shown in Fig. 3(c), methyl is formed at the location which methane is consumed rapidly near the ame zone. Since the above reaction steps consume the chain carrier radicals considerably, mole fractions of the chain carrier radicals such as H, O, and OH are small at the region. Maximum mole fractions

4062

J. Park et al. / International Journal of Hydrogen Energy 32 (2007) 4059 4070

s.p. Tmax 1 CH4 H2 O CO2 Mole fraction 0.1 CO H2 0.01 Pure CH4 Flame ag=157 s-1 Mole production rate, mole/cm3s O2 0.006 0.004 0.002 0.000 -0.002

s.p.

Tmax

H2 H 2O CO CO2

CH4 Pure CH4 Flame ag=157 s-1

O2

-0.004 -0.006 0.75 Tmax

1E-3 0.0

0.5

1.0

1.5 s.p.

2.0

0.80

0.85

0.90

0.95

1.00

1.05

Separation distance from fuel nozzle, cm 10-2 Pure CH4 Flame ag=157 s-1

Separation distance from fuel nozzle, cm

OH H CH3 O

Mole fraction

10-3

10-4 0.75

0.80 0.85 0.90 0.95 1.00 Separation distance from fuel nozzle, cm

1.05

Fig. 3. Typical ame structures of: (a) major species, (b) mole production rates of the major species, and (c) CH3 and chain carrier radicals at the strain rate of 157 s1 in pure methane ame.

of the chain carrier radicals are located in the oxidizer side since the oxidation of the produced H2 from methane oxidation is responsible for the formation of the chain carrier radicals. As shown in Fig. 3, ame zone is located in the oxidizer-side and the maximum mole fraction of major species such as H2 , CO, CO2 , and H2 O appear at the location which methane and oxygen are consumed rapidly. The oxygen is penetrated into the fuel-side through the stagnation point while the methane is consumed rapidly near the zone of maximum ame temperature. The ame structure of methane oxidation process can be understood by a methane consumption layer and a H2 .CO consumption layer [11]. It should be, therefore, noted that the change of H2 .CO consumption layer through addition of hydrogen and water vapor could be the one of important factors to affect ame structure and pollutant emissions.

For CH4 .H2 ame in Fig. 4, the oxygen is consumed at the right-hand side of the stagnation point, and relatively less oxygen and methane are overlapped each other, compared to methane ame. But the oxygen and hydrogen are overlapped considerably as shown in Fig. 4(a). Therefore, the methane consumption rate decreases while the hydrogen consumption rate increases as shown in Fig. 4(b). Moreover, the production rate of H2 O increases. As a result the maximum mole fraction of methyl decreases but the maximum mole fractions of the chain carrier radicals of H, O, and OH increase as shown in Fig. 4(c). For CH4 .H2 .H2 O ame in Fig. 5, the oxygen is again consumed at the right-hand side of the stagnation point, and relatively less oxygen and methane are overlapped each other. Fig. 5(a) also indicates that a maximum of H2 O mole fraction

J. Park et al. / International Journal of Hydrogen Energy 32 (2007) 4059 4070

4063

1 H2

s.p. Tmax CH4 H2 O O2 CH4-H2 Flame XCH4=0.7, XH2=0.3 ag=157 s-1

b
0.006

s.p.

Tmax CH4-H2 Flame XCH =0.7, XH =0.3 4 2 ag=157 s-1

Mole production rate, mole/cm3s

0.004 H2 0.002 CO

H 2O

0.1 Mole fraction CO CO2

CO2

0.000

0.01

-0.002

CH4 O2

-0.004

1E-3 0.0

0.5

1.0

1.5

2.0

-0.006 0.70

0.75

Separation distance from fuel nozzle, cm s.p. 10-2 CH4-H2 Flame XCH4=0.7, XH2=0.3 ag=157 s-1 OH H O Tmax

0.80 0.85 0.90 0.95 1.00 Separation distance of fuel nozzle, cm

1.05

Mole fraction

CH3 10-3

10-4 0.70

0.80 0.85 0.90 0.95 1.00 0.75 Separation distance from fuel nozzle, cm

1.05

Fig. 4. Typical ame structures of: (a) major species, (b) mole production rates of the major species, and (c) CH3 and chain carrier radicals at the strain rate of 157 s1 , XCH4 = 0.7, and XH2 = 0.3 in CH4 .H2 ame.

disappears. This means that most of the displayed H2 O in Fig. 5(a) does not result from chemical reaction but mainly from excessively added steam, and the ame is highly diluted by added H2 O. As a result, both the methane and hydrogen consumption rates decrease globally. In Fig. 5(c) this directly gives rise to the reduction of methyl mole fraction and the relative decrease of the mole fractions of chain carrier radicals despite of the relative increase of added hydrogen. 3.2. Pollutant emission of CO and CO 2 Fig. 6 describes: (a) the variation of emission indices of CO and CO2 with methane mole fraction for CH4 .H2 ames, (b) those of CO, and (c) those of CO2 with mole fraction of added H2 O for CH4 .H2 .H2 O ames. The use of mole fraction is

not appropriate to grasp the behavior of CO, CO2 , and NOx since they include of convection and diffusion terms, and the following emission indices of CO, CO2 , and NOx , suggested by Nishioka et al. [21], are adopted: , dx where i = CO, CO2 , and NO. EI i =
L 0 W i wi d x L 0 WCH4 wCH4

(10)

Here Wi is the molecular weight of a chemical species i and wi the molar production rate of chemical species i . For CH4 .H2 ames in Fig. 6(a), the emission index of CO increases and decreases after showing a maximum at the methane mole fraction of 0.3 while those of CO2 increase monotonously in the increase of methane mole fraction. For CH4 .H2 .H2 O ames

4064

J. Park et al. / International Journal of Hydrogen Energy 32 (2007) 4059 4070

s.p. Tmax 1
H2 H2O CH4-H2-H2O Flame XCH =0.3, XH =0.4, XH O=0.3
4 2 2

s.p. 0.006 0.005 Mole productionrate, mole/cm3s 0.004 0.003 0.002 0.001 0.000 -0.001 -0.002 -0.003 -0.004 -0.005
CH4-H2-H2O Flame XCH =0.3, XH =0.4, XH O=0.3
4 2 2

Tmax

ag=157 s-1

O2

0.1 Mole fraction

CH4

H2 CO

H2O CO2

CO

CO2

CH4

0.01

O2

ag=157 s

-1

1E-3 0.0 0.5 1.0 1.5 2.0 Separation distance from fuel nozzle, cm s.p. 0.01
CH4-H2-H2O Flame XCH =0.3, XH =0.4, XH O=0.3
4 2 2

-0.006 0.70

0.75

0.80

0.85

0.90

0.95

1.00

Separation distance from fuel nozzle, cm Tmax

OH H

ag=157 s

-1

Mole fraction

CH3

1E-3

1E-4 0.70

0.75

0.80

0.85

0.90

0.95

1.00

Separation distance from fuel nozzle, cm

Fig. 5. Typical ame structures of: (a) major species, (b) mole production rates of the major species, and (c) CH3 and chain carrier radicals at the strain rate of 157 s1 , XCH4 = 0.3, XH2 = 0.4, and XH2 O = 0.3 in CH4 .H2 .H2 O ame.

in Figs. 6(b) and (c), emission indices of CO also increase and then decrease in the increase of mole fraction of added H2 O for methane mole fractions of 0.1 while those emission indices decrease for the mole fraction of 0.7. Meanwhile emission indices of CO2 increase monotonously in the increase of H2 O. These complicated behaviors may be addressed only through the inspection of important contribution reaction steps to the production and destruction of CO. The importantly contributing reaction steps to CO production in the present study are as follows: O + C2 H2 CO + CH2 , H + HCO H2 + CO, H + HCCO CH2 (s) + CO, (R23) (R55) (R79)

HCO + H2 O H + CO + H2 O, HCO + M H + CO + M, O + CH3 H + H2 + CO.

(R166) (R167) (R284)

Most of the produced CO2 result from the following reaction step: CO + OH CO2 + H. (R99)

Fig. 7(a) displays importantly contributing reaction steps to the production and destruction of CO for XCH4 = 0.2 and XH2 = 0.8 as a representative case of CH4 .H2 ame. As shown in Fig. 7(a) most of CO are produced through the reaction steps of (R166) and (R167) and are consumed through the reaction step of (R99). The reaction rates of the reaction steps (R99),

J. Park et al. / International Journal of Hydrogen Energy 32 (2007) 4059 4070

4065

25 100
CH4-H2 flames

Emission indices of CO and CO2, kg/kg

ag=157 s-1 EICO EICO

2

Emission indices of CO, kg/kg

20

15
CH4-H2-H2O flames

10

10

ag=157 s

-1

XCH =0.1, H2O addition

4 4

XCH =0.7, H2O addition

1 0.0 0.2 0.4 XCH4 100

CH4-H2-H2O flames ag=157 s
-1

0.6

0.8

1.0

0 0.0

0.2

0.4 XH2O

0.6

0.8

1.0

80 Emission indices of CO2, kg/kg

XCH =0.1, H2O addition

4 4

XCH =0.7, H2O addition

60

40

20

0 0.0 0.2 0.4 XH O

2

0.6

0.8

1.0

Fig. 6. Variation of emission indices of: (a) CO and CO2 with methane mole fraction for CH4 .H2 ames, (b) emission indices of CO, and (c) that of CO2 with steam mole fraction at XCH4 = 0.1 and the strain rate of 157 s1 of CH4 .H2 .H2 O ames.

(R166), and (R167), which are dominantly contributing to production and destruction of CO, are displayed in the increase of methane mole fraction in Fig. 7(b). Both the CO production rates though the reaction steps (R166) and (R167) increase in the increase of methane mole fraction. But the CO consumption rate though the reaction step (R99) increases much more steeply with increasing methane mole fraction. This implies that the produced CO is immediately converted to CO2 through the reaction step (R99). This is the direct reason why the CO emission index in Fig. 6(a) increases and then decreases. The reaction rates of the reaction steps (R99), (R166), and (R167), which are dominantly contributing to production and destruction of CO, are displayed in the increase of H2 O mole fraction for: (a) XCH4 = 0.1 and (b) XCH4 = 0.7 of CH4 .H2 .H2 O ame

in Fig. 8. Even if we do not provide all the data, the abovementioned reaction steps of CO production increase and then decrease in the increase of H2 O mole fraction except of the reaction step of (R166). The reason why the tendency is opposite to those of the reaction steps is relevant to the fact that the reaction rate of the reaction step (R166) is directly increased by the increase of H2 O mole fraction. Figs. 8(a) and (b) also show for XCH4 = 0.1 and 0.7 that in both the cases the CO consumption rates though the reaction step (R99) are much larger than the CO production rates though the reaction step (R166) and (R167) and the CO consumption rate, moreover, increases much more steeply in comparison to the CO production rates. These cause CO2 emission indices increase according to H2 O mole fraction for both the cases of

4066

J. Park et al. / International Journal of Hydrogen Energy 32 (2007) 4059 4070

8.0x10-6 6.0x10-6 4.0x10-6

CH4-H2 flames ag=157s-1 XCH =0.2, XH =0.8

4 2

R23

R55

R79

R166

R167

-2.0x10-6 -4.0x10-6 -6.0x10-6

2.0x10-5 Production and destruction rates of CO, mole/cm3s 1.0x10-5 0.0 -1.0x10-5 -2.0x10-5 -3.0x10-5 -4.0x10-5 0.0
CH4-H2 flames

ag=157s-1
R166 R167 R99

0.2

0.4 XCH
4

0.6

0.8

R284

0.0

R99

2.0x10-6

1.0

and thermal mechanisms is due to Fenimore mechanism since the contributions by N2 O mechanism and NO2 mechanism are negligible in the present study. This tendency is consistent with the results in methane ame of the previous study [21]. The difference between the full and thermal mechanisms in the pure hydrogen ame (XCH4 = 0) is due to the contribution of NH-, NNH-, and HNO-related reactions. Fig. 9(a) clearly shows that Fenimore NO is larger than thermal NO and this tendency is consistent with the results in diffusion ames of the previous study [21], and also claries that the full NO is mainly a direct outcome from Fenimore NO at large methane mole fractions for CH4 .H2 ame. For CH4 .H2 .H2 O ame in Fig. 9(b) thermal NO decreases in the increase of H2 O mole fraction while Fenimore NO increases and then decreases at XCH4 = 0.1.For large H2 O mole fractions Fenimore NO approaches to full NO, and this also implies that Fenimore NO becomes predominated as H2 O mole fraction increases. Fig. 9(b) also shows that chemical effects of added H2 O reduce emission index of NO mainly through Fenimore NO. Fig. 9(c) shows for XCH4 = 0.7 of CH4 .H2 .H2 O ame that both Fenimore NO and thermal NO decrease in the increase of H2 O mole fraction and the role of Fenimore NO in full NO is much more important in comparison to that at XCH4 = 0.1 in Fig. 9(b). Meanwhile the behavior of thermal NO can be understood based on the relevance to ame temperature, but the tendencies of Fenimore NO in Figs. 9(b) and (c) are not clearly addressed. More cautious examination may be required to understand the NO behavior through the comparison to pure methane ame for CH4 .H2 ames and CH4 .H2 .H2 O ames to clarify those behaviors. The Zeldovich mechanism relevant to thermal NO production is generally as follows: N + NO N2 + O, N + O2 NO + O, N + OH NO + H. (R178) (R179) (R180)

Fig. 7. (a) Importantly contributing reaction steps to production and destruction of CO in the case of XCH4 = 0.2,XH2 = 0.8, and (b) the variation of maximum production and destruction rates of CO with methane mole fraction at the strain rate of 157 s1 of CH4 .H2 ame.

Production and destruction rates of CO, mole/cm3s

XCH4 = 0.1 and 0.7 in Fig. 5(c). But the CO2 emission index for XCH4 = 0.1 increases more sensitively with increasing H2 O mole fraction in comparison to that for XCH4 = 0.7. This implies that CO2 is produced much more for the blended fuels, in which hydrogen is more populous relatively to methane. As a result the CO emission index increases steeply and decreases rapidly for the case of XCH4 = 0.1, while that decreases mildly for XCH4 = 0.7. 3.3. Behavior of NO x emission Fig. 9 describes the variation of emission indices of NO through the full and thermal mechanisms with methane mole fraction for CH4 .H2 ame and with methane mole fraction and/or fraction of added steam for CH4 .H2 .H2 O ame at the strain rate of 157 s1 . Both the emission indices of NOx by the thermal and full mechanisms decrease in the increase of methane mole fraction for CH4 .H2 ame and in the increase of H2 O mole fraction. In Fig. 9 the difference between the full

Fig. 10 displays the reaction contribution to the production and destruction of thermal NO for: (a) pure methane ame and CH4 .H2 ames, and (b) CH4 .H2 .H2 O ames. The main source of thermal NO is the reaction step (R180), and thermal NO is consumed through the reaction step (R178) for CH4 .H2 ame and CH4 .H2 .H2 O ames as shown in Fig. 10. These global features are very similar to those in the previous study on CO2 added methane ames except the point that the reaction step (R178) contributes to the production of thermal NO in CH4 .H2 ames with large hydrogen mole fraction such as the condition of XCH4 = 0.1 and XH2 = 0.9. Fig. 11 also displays the production and destruction rates of the importantly contributing reaction steps to Fenimore NO for pure methane ame, CH4 .H2 ames, and CH4 .H2 .H2 O ames. The NO production through Fenimore mechanism in methane ame is mainly relevant to the following reaction steps [22]: NH + O NO + H, NNH + O NH + NO, (R190) (R208)

J. Park et al. / International Journal of Hydrogen Energy 32 (2007) 4059 4070

4067

Production and destrcution rates of CO, mole/cm3s

Production and destruction rates of CO, mole/cm3s

2.0x10-5 1.0x10-5 0.0 -1.0x10-5 -2.0x10-5 -3.0x10-5 -4.0x10-5

CH4-H2-H2O flames ag=157s-1 XCH4=0.7, XH2=0.05, XH O=0.25 2 H2O adiition

1.0x10-5

R99

5.0x10-6

R23

R55

R79

R166

R167

R284

0.0
CH4-H2-H2O flames XCH =0.1, ag=157s-1
4

-5.0x10

-6

R166 R167 R99

-1.0x10-5

-1.5x10-5 0.0

0.2

0.4 0.6 XH O or XX
2

0.8

1.0

Productionand destruction rates of CO, mole/cm3s

2.0x10-5
CH4-H2-H2O flames XCH =0.7, ag=157s
4 -1

R166

0.0

R167 R99

-2.0x10-5

-4.0x10-5 0.0

0.2

0.4 XH

0.6 or X O X

0.8

1.0

Fig. 8. (a) Importantly contributing reaction steps to production and destruction of CO in the case of XCH4 = 0.7, XH2 = 0.05, and XH2 O = 0.25 and (b) the variation of maximum production and destruction rates of CO with methane mole fraction at the strain rate of 157 s1 of CH4 .H2 .H2 O ame.

HNO + H H2 + NO, HNO + OH NO + H2 O, NCO + O NO + CO.

(R214) (R215) (R222)

CH2 + NO H + HNCO, CH2 + NO H + HCNO, CH3 + NO HCN + H2 O, HCCO + NO HCNO + CO.

(R249) (R251) (R255) (R274)

The major NO destruction through Fenimore mechanism [22] is contributed by H + NO + M HNO + M, C + NO CN + O, C + NO CO + N, CH + NO HCN + O, CH + NO H + NCO, CH + NO N + HCO, (R212) (R244) (R245) (R246) (R247) (R248)

For CH4 .H2 ame and CH4 .H2 .H2 O ame the HNO-related reaction steps such as (R214) and (R215) importantly contribute to the NO formation while the HNO-related reaction step (R212) consumes NO remarkably according to the increase of H2 mole fraction. These characteristics according to the addition of H2 are much more remarkable. The importance of the NH-related reaction steps such as (R190) in NO production is diminished according to the addition of H2 . It is also noted that the reaction step (R222), which is one of the major sources for NO production, becomes less important in NO formation according to the addition of H2 . The

4068

J. Park et al. / International Journal of Hydrogen Energy 32 (2007) 4059 4070

500
ag=157s-1

300
CH4-H2-H2O flames ag=157s-1

Emission index of NO, kg/kg

400

CH4-H2 flames Full NO Thermal NO

Emission index of NO, kg/kg

XCH =0.1, Full NO

4 4 4

300

Fenimore NO

200

XCH =0.1, Thermal NO XCH =0.1, Fenimore NO

200

100

100

0 0.0 0.2 0.4 XCH

4

0.6

0.8

1.0

0 0.0

0.2

0.4 XH O or XX
2

0.6

0.8

100
CH4-H2-H2O flames ag=157s-1

Emission Index of NO, kg/kg

80

XCH =0.7, Full NO

4 4 4

XCH =0.7, Thermal NO

60

XCH =0.7, Fenimore NO

40

20

0 0.0 0.1 0.2 0.3 XH O or XX

2

0.4

0.5

Fig. 9. Variation of emission indices of NO through thermal and Fenimore mechanisms (a) with methane mole fraction for CH4 .H2 ames, and with steam mole fraction for the cases of (b) XCH4 = 0.1 and (c) XCH4 = 0.7 of CH4 .H2 .H2 O ames.

importantly contributing reaction steps to NO destruction are (R244), (R245), (R246), (R249), (R255), and (R274). The role of the reaction steps, (R246) and (R255), as a reburning mechanism was addressed in the previous study [21]. The importance of the reaction step (R247), known as a HCN recycle route, leading to the consumption of NO has been well described [21,22]. As can be denitely seen in Fig. 10(b), the contribution of NO consumption is through the reburning process and the HCN recycle route for the cases of small H2 mole fraction and through the HNO-related reaction (R212) for the cases of large mole fraction. It is also found for CH4 .H2 .H2 O ame that the reaction contribution of all the major reaction steps to the production and destruction of NO are suppressed according to the addition of H2 O. Chemical effects of added H2 O

repress both the production and destruction of NO as shown in Fig. 10(b). 4. Concluding remarks Numerical study was conducted to investigate the effects of the addition of hydrogen and steam in methaneair diffusion ame. The following conclusion can be obtained. Maximum ame temperature increases in the increase of hydrogen mole fraction and in the decrease of H2 O mole fraction. For CH4 .H2 ames, the emission index of CO increases and then decreases after showing a maximum while that of CO2 increases monotonically in the increase of methane mole fraction. For CH4 .H2 .H2 O ames, the emission index of CO increases

J. Park et al. / International Journal of Hydrogen Energy 32 (2007) 4059 4070

4069

Reacrion contribution to Fenimore NO, mole/cm3s

Reaction contribution to thermal NO, mole/cm3s

1.5x10-7
CH4-H2O flame ag=157s-1 XCH =1.0
4 4

1.5x10-7

CH4-H2 flames ag=157s-1 XCH 1.0

4 4 4

1.0x10-7

1.0x10-7

XCH =0.1, XH =0.9

2 2

XCH =0.1, XH =0.9

2 2

XCH4=0.7, XH =0.3

XCH =0.7, XH =0.3

R212

R246

R248

R249

R255
2 2 2

5.0x10-8

0.0 R190 R214 R215 R222

R178

R179

R180

0.0

-5.0x10-8

-5.0x10-8

-1.0x10-7

Reaction contribution to thermal NO, mole/cm3s

5.0x10-8 4.0x10-8 3.0x10-8 2.0x10-8 1.0x10-8

CH4-H2 flame -1 ag=157s XCH4=0.7, XH =0.1, XH O=0.2

2 2

Reaction contribution to Fenimore NO, mole/cm3s

6.0x10-8

1.0x10-7

CH4-H2-H2O flames ag=157s

-1

XCH =0.7, XH =0.1, XH O=0.2

4 4 4 2 2 2

XCH =0.1, XH =0.2, XH O=0.7

4 2 2

XCH =0.1, XH =0.2, XH O=0.7

XCH =0.1, XH =0.8, XH O=0.1

4 2 2

5.0x10-8 R212

XCH =0.1, XH =0.8, XH O=0.1

R246

R248

R249

R255

R190

R214

R215

R178

R179

-1.0x10-8

R180

0.0

-5.0x10-8

-1.0x10-7

Fig. 10. (a) Importantly contributing reaction steps to thermal NO production for pure methane ame and CH4 .H2 ames, and (b) at various blending conditions of CH4 .H2 .H2 O ames.

Fig. 11. (a) Importantly contributing reaction steps to Fenimore NO production for pure methane and CH4 .H2 ames, and (b) at various blending conditions of CH4 .H2 .H2 O ames.

and then decreases after showing a maximum while that of CO2 increases monotonically in the increase of fraction of added H2 O. These complicated behaviors are mainly caused by the competition of the production of CO through the reaction step (R166) with the destruction of CO by the reaction step (R99). For CH4 .H2 ame and CH4 .H2 .H2 O ame Fenimore NO is larger than thermal NO, and the full NO is mainly originated from Fenimore NO at large methane mole fractions. The main source of thermal NO is the reaction N + OH NO + H. The reaction step (R178) contributes to the consumption of NO for pure methane ame but the production of NO for large hydrogen mole fractions of CH4 .H2 ame and CH4 .H2 .H2 O ame. The HNO-related reaction steps such as (R212) and (R214) importantly contribute to the destruction and production of NO remarkably, respectively. These characteristics according to the addition of H2 are much more remarkable. The reaction step NCO + O NO + CO, which is one of the major sources for NO production, becomes less important in NO formation according to the addition of H2 and H2 O. The contribution of

NO consumption is mainly through the reburning process and the HCN recycle route for the cases of small H2 mole fraction while it is almost through the HNO-related reaction (R212) for the cases of large mole fraction. Acknowledgment Financial support of our work by the funds with fundamental business of Korea Institute of Machine and Materials is gratefully acknowledged. References
[1] Schefer RW, Wicksall M, Agrawal AK. Combustion of hydrogenenriched methane in a premixed swirl-stabilized burner. Proc Combust Inst 2002;29:84352. [2] Bauer CG, Forest TW. Effect of hydrogen addition on the performance of methane-fueled vehicles Part I: effect on SI engine performance. Int J Hydrogen Energy 2001;26:5570.

R222

0.0

R274

R274

5.0x10-8

4070

J. Park et al. / International Journal of Hydrogen Energy 32 (2007) 4059 4070 [13] Kee RJ, Miller JA, Evans GH, Dixon-Lewis G. A computational model of the structure and extinction of strained, opposed ow, premixed methane-are ame. Proc Combust Inst 1988;22:147994. [14] Lutz AE, Kee RJ, Grcar JF, Rupley FM. A fortran program for computing opposed-ow diffusion ames. Sandia National Laboratories report, SAND 96-8243, 1997. [15] Ju Y, Guo H, Maruta K, Liu F. On the extinction limit and ammability limit non-adiabatic stretched methaneair premixed ames. J Fluid Mech 1997;342:31534. [16] Kee RJ, Rupley FM, Miller JA. Chemkin II: a fortran chemical kinetics package for analysis of gas phase chemical kinetics. Sandia National Laboratories report, SAND 89-8009B, 1989. [17] Kee RJ, Dixon-Lewis G, Warnatz J, Coltrin ME, Miller JA. A fortran computer code package for the evaluation of gas-phase multi-component transport. Sandia National Laboratories report, SAND86-8246, 1994. [18] Chellian HK, Law CK, Ueda T, Smooke MD, Williams FA. An experimental and theoretical investigation of the dilution, pressure and ow-eld effects on the extinction condition of methaneairnitrogen diffusion ames. Proc Combust Inst 1990;23:503. [19] Smith GP, Golden DM, Frenklach NW, Eiteneer MB, Goldenberg M, Bowman CT, et al. http://www.me. berkeley.edu/gri_mech/ , 2007. [20] Westbrook CK, Dryer FL. Chemical kinetic modeling of hydrocarbon combustion. Prog Energy Combust Sci 1984;10:157. [21] Nishioka M, Nakagawa S, Ishikawa Y, Takeno T. NO emission characteristics of methaneair double ame. Combust Flame 1994;98: 12736. [22] Miller JA, Bowman CT. Mechanism and modeling of nitrogen chemistry in combustion. Prog Energy Combust Sci 1989;15:287.

[3] Law CK, Kwon OC. Effects of hydrogen substitution on atmospheric hydrogenair ame propagation. Int J Hydrogen Energy 2001;29: 86779. [4] Ilbas M, Crayford AP, Yilmaz I, Bowen PJ, Syred N. Laminar-burning velocities of hydrogenair and hydrogenmethaneair mixtures: an experimental study. Int J Hydrogen Energy 2006;31:176879. [5] Halter F, Chauveau C, Djebaili-Chaumeix N, Gokalp I. Characterization of the effects of pressure and hydrogen concentration on laminar burning velocities of methanehydrogenair mixtures. Proc Combust Inst 2005;30:2018. [6] Dagaut P, Nicolle A. Experimental and detailed kinetic modeling of hydrogen-enriched natural gas blend oxidation over extended temperature and equivalence ratio ranges. Proc Combust Inst 2005;30:26318. [7] Di Sarli V, Di Benedetto A. Laminar burning velocity of hydrogen methane/air premixed ames. Int J Hydrogen Energy 2007;32:63746. [8] Ren J-Y, Qin W, Egolfopoulos FN, Tsotsis TT. Methane reforming and its potential effect on the efciency and pollutant emissions of lean methaneair combustion. Chem Eng Sci 2001;56:15419. [9] Ren J-Y, Qin W, Egolfopoulos FN, Tsotsis TT. Strain-rate effects on hydrogen-enriched lean premixed lean premixed combustion. Combust Flame 2001;124:71720. [10] Bade Shresha SO, Karim GA. Hydrogen as an additive to methane for spark ignition engine applications. Int J Hydrogen Energy 1999;24: 57786. [11] Seshadri K, Peters N. Asymptotic structure and extinction of methaneair diffusion ames. Combust Flame 1988;73:2344. [12] Park J, Hwang DJ, Park JS, Kim JS, Keel SI, Cho HC. et al. Hydrogen utilization as a fuel: hydrogen-blending effects in ame structure and NO emission behavior of CH4 air counterow diffusion ame. Int J Energy Res 2007;31:47185.