energies

Article
Combustion and Heat Release Characteristics of Biogas
under Hydrogen- and Oxygen-Enriched Condition
Jun Li 1 , Hongyu Huang 2, *, Huhetaoli 2 , Yugo Osaka 3 , Yu Bai 2 , Noriyuki Kobayashi 1, *
and Yong Chen 2
1 Department of Chemical Engineering, Nagoya University, Nagoya, Aichi 464-8603, Japan; junli@energy.gr.jp
2 Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China;
taoli@ms.giec.ac.cn (H.); baiyu@ms.giec.ac.cn (Y.B.); chenyong@ms.giec.ac.cn (Y.C.)
3 Faculty of Mechanical Engineering, Kanazawa University, Kakuma, Kanazawa, Ishikawa 920-1192, Japan;
y-osaka@se.kanazawa-u.ac.jp
* Correspondence: huanghy@ms.giec.ac.cn (H.H.); kobayashi@energy.gr.jp (N.K.);
Tel.: +86-20-870-48394 (H.H.); +81-52-789-5428 (N.K.)

Received: 10 May 2017; Accepted: 20 July 2017; Published: 13 August 2017

Abstract: Combustion and heat release characteristics of biogas non-premixed flames under
various hydrogen-enriched and oxygen-enriched conditions were investigated through chemical
kinetics simulation using detailed chemical mechanisms. The heat release rates, chemical reaction
rates, and molar fraction of all species of biogas at various methane contents (35.3–58.7%, mass
fraction), hydrogen addition ratios (10–50%), and oxygen enrichment levels (21–35%) were calculated
considering the GRI 3.0 mechanism and P1 radiation model. Results showed that the net reaction rate
of biogas increases with increasing hydrogen addition ratio and oxygen levels, leading to a higher
net heat release rate of biogas flame. Meanwhile, flame length was shortened with the increase in
hydrogen addition ratio and oxygen levels. The formation of free radicals, such as H, O, and OH,
are enhanced with increase in hydrogen addition ratio and oxygen levels. Higher reaction rates of
exothermic elementary reactions, especially those with OH free radical are increased, are beneficial to
the improvement in combustion and heat release characteristics of biogas in practical applications.

Keywords: biogas; heat release; methane content; hydrogen addition; oxygen enriched

1. Introduction
With continuous depletion of fossil fuels and worsening pollution, research and development of
renewable energy sources have attracted considerable interest [1–7]. Biogas can be produced using an
anaerobic digester of biomass or biodegradable organic wastes. Compositions of biogas vary with the
feedstock and the fermentation process [1–3]. The main compositions of biogas are methane (CH4 )
and carbon dioxide (CO2 ), as well as a small amount of water (H2 O), nitrogen (N2 ), and hydrogen
(H2 ) [3–5].
As an advantageous energy source, biogas is widely considered as a suitable fuel for heating
facilities, power generation, and vehicles [8–15]. However, biogas possesses a relatively lower heating
value (about 3000–6000 kcal·m−3 ) and lower heat release rate than conventional fuels, which limits
the application of biogas in combustion devices. Somehsaraei et al. [16] developed a steady state
thermodynamic model for biogas application in 100 kW micro gas turbines. They found that mass
flow and pressure ratio in the micro gas turbines are lower than those of the natural gas–fueled
turbines. Furthermore, the total electrical efficiency decreases with decreasing CH4 content in biogas
fuel, and the use of biogas negatively affects heat recovery. A three-dimensional computational
fluid dynamic study on biogas flameless mode was developed by Hosseini et al. [17]. Although
increasing preheated temperature positively affects the reduction of fuel consumption, a fuel with

Energies 2017, 10, 1200; doi:10.3390/en10081200 www.mdpi.com/journal/energies

Energies 2017, 10, 1200 2 of 11

high calorific value is necessary to preheat the furnace prior to the application of biogas combustion
in the combustion furnace. The flameless combustion temperature of a biogas furnace is lower than
traditional combustion throughout a combustion chamber. Several experimental and numerical
studies have explored the fuel characteristics of biogas. In such studies, high-quality fuel such as
H2 [18–22] is blended with biogas to improve the relatively poor combustion characteristics of biogas.
Zhen et al. [18] experimentally investigated the effect of H2 addition on the characteristics of a biogas
diffusion flame. They found that H2 addition significantly improved the stability of the biogas
flame. The flame temperature increased and visible flame length reduced with increasing H2 addition
ratios. Wei et al. [19] numerically investigated the effects of equivalence ratio, H2 , and CO2 on the
heat release characteristics of the premixed laminar biogas-hydrogen flames. The results showed
that OH + H2 ⇔ H + H2 O was major endothermic reaction for biogas-hydrogen premixed flames.
The total heat release was enhanced evidently with H2 addition. Non-premixed are widely applied in
the industrial process, while the heat release rate of biogas flame is low, which obstructs the application
of biogas in practical application. Therefore, the improvement of heat release characteristics of biogas
flame at various condition are necessary.
The above results show that numerous studies have investigated the combustion characteristics
of biogas premixed flame. Nevertheless, understanding the non-premixed combustion of a fuel
in practical application is necessary. To utilize biogas in internal combustion engines, the unburnt
composition CO2 or N2 is expected to be excluded from biogas. Therefore, mechanical biological
treatment is needed to upgrade raw biogas and increase CH4 content in biogas. The high cost of
such treatment process is unfavorable to the application of biogas as a fuel. Therefore, the direct
application of raw biogas is more economic for engines or heat supply. The current research proposes
biogas combustion under hydrogen-enriched and oxygen-enriched conditions as potential methods to
improve biogas combustion. The non-premixed flames of biogas under various hydrogen-enriched
and oxygen-enriched conditions are studied, and the combustion and heat release characteristics of
biogas non-premixed flames are numerically investigated. A non-premixed combustion model of
biogas is established. The GRI 3.0 mechanism with 53 species and 325 elementary chemical reactions is
employed, and the P1 radiation model is considered. All elementary chemical reaction rates and heat
release rates are programmed. To enhance the combustion and heat release characteristics, hydrogen
addition and oxygen enriched combustion are selected for biogas combustion in future practical
application. The mass contents of CH4 in biogas, hydrogen addition ratios, and oxygen enrichment
levels are ranged from 35.3% to 58.7%, 0% to 50%, and 21% to 35%, respectively.

2. Numerical Simulations
A typical gaseous combustion cylindrical chamber with a diameter of 200 mm (r) and 600 mm
length (z) is employed in this research, as shown in Figure 1. The fuel inlet is located at a central nozzle
with a radius of 6.8 mm, and air inlet is surrounded with a fuel inlet with a radius of 100 mm. Three
kinds of biogas fuel are applied in this research. The H2 addition ratio to fuel (XH2 , based on low heat
value) and O2 -enriched level (ΩO2 ) are defined as following equations:

VH2 × LHVH2
X H2 = (1)
VCH4 × LHVCH4 + VH2 × LHVH
2

VO2
ΩO2 = (2)
VO2 + VN2
where VCH4 , VH2 , VO2 , and VN2 are the flow rates of CH4 , H2 , O2 , and N2 respectively; LHVH2 and
LHVCH4 are the low heat values of H2 and CH4 . The inlet fuel and oxidizer conditions at various
H2 -enriched condition and O2 -enriched condition are shown in Table 1. The inlet power is kept
constant under all calculation conditions. The mass contents of CH4 in biogas are 35.3%, 45.9%, and
Energies 2017, 10, 1200 3 of 11
Energies 2017, 10, 1200 3 of 11

namely
58.7%, BG-1,
namely BG-2,
BG-1, and and
BG-2, BG-3,BG-3,
respectively. H2 addition
respectively. ratio toratio
H2 addition biogas
toisbiogas
arranged from 10%from
is arranged to 50%,
10% to
50%,and
andOO
2 inin
2
the oxidizer
the is
oxidizer from
is 21%
from to
21% 35%.
to 35%.

Figure Geometry
1. 1.
Figure Geometryof
ofthe
the combustion chamber(not
combustion chamber (not
to to scale).
scale).

Table
Table 1. Composition
1. Composition of of biogasflames
biogas flamesat
atH
H22-enriched
-enrichedand
andOO
2-enriched conditions.
2 -enriched conditions.

Items CH4/L·min−1 CO2/L·min−1 H2/L·min−1 O2/L·min−1 Air/L·min−1 Power/kW

Items CH /L·min−1 CO2 /L·min−1 H2 /L·min−1 O2 /L·min−1 Air/L·min−1 Power/kW
BG-1 4 1.829 1.220 - - 18.340 1
BG-1 BG-2 1.8291.829 1.220
0.784 -- - - 18.34018.340 1 1
BG-2 BG-3 1.8291.829 0.784
0.457 -- - - 18.34018.340 1 1
BG-3 H2 10% 1.8291.647 0.457
1.098 -
0.602 - - 18.01418.340 1 1
H2 10% 1.647 1.098 0.602 - 18.014 1
H2 30% 1.281 0.854 1.805 - 17.361 1
H2 30% 1.281 0.854 1.805 - 17.361 1
H2 50%H 2 50%
0.9150.915 0.610
0.610 3.008
3.008 - - 16.70916.709 1 1
O2 25%O2 25% 1.8291.829 1.220
1.220 -- 0.7800.780 14.62614.626 1 1
O2 30%O2 30% 1.8291.829 1.220
1.220 -- 1.4631.463 11.37611.376 1 1
O2 35%O2 35% 1.8291.829 1.220
1.220 -- 1.9501.950 9.054 9.054 1 1

The flow mass, chemical species, momentum, and energy equation based on Navier–Stokes
The flowismass,
equations chemical
expressed species,
in Equation (3): momentum, and energy equation based on Navier–Stokes
equations is expressed in Equation (3):
+ = Γ + (3)
δ(ρY ) →
+ div(ρVY ) = div(ΓY gradY ) + SY (3)
where , , , Γ , and δtare density, general dependent variable, velocity vector, associated
transport →
coefficient of Y, and the source term. Thermal radiation is programmed to the source term
whereof ρ,the V, ΓY , and
Y, mixture enthalpy.
SY are In this research,
density, P1 radiationvariable,
general dependent developed by Grosshandler
velocity of National
vector, associated transport
Institute
coefficient ofofY,Standards
and the and Technology
source (NIST) [23]
term. Thermal was selected.
radiation The gas radiation
is programmed was
to the considered
source termbyof the
the determination of Planck mean absorption coefficient. Gas radiation contributed
mixture enthalpy. In this research, P1 radiation developed by Grosshandler of National Institute to the gases of
CH4, CO2, and
of Standards CO, and H2O. The mean
Technology (NIST)absorption
[23] wascoefficient
selected.ofThe
thesegas
gases ( ) can be
radiation wasfitted as functions
considered by the
of temperature, which are summarized as Equations (4)–(6):
determination of Planck mean absorption coefficient. Gas radiation contributed to the gases of CH4 ,
Mean absorption coefficient of CH4:
CO2 , CO, and H2 O. The mean absorption coefficient of these gases (αi ) can be fitted as functions of
temperature, which are summarized= + +
as Equations +
(4)–(6): + + (4)
Mean absorption
Mean coefficient
absorption ofofCH
coefficient CO4 :2 and H2O:

1000 1000 1000 1000 1000

= + a1 T + a2 T+2 + a3 T 3 ++a4 T 4 + a5 T 5+
+ α i = a0 + (5) (4)

Mean
Mean absorption
absorption coefficient
coefficient ofofCO
CO:
2 and H2 O:
=  + 2 +  + 3 +  (6)
1000 4 1000 5

   
1000 1000 1000
i = values
αThe a0 + aof
1 constants+ a2 to + 4a, 3CO2, CO, and
for CH + aH4 2O are shown
+ ain
5 Table 2. The (5)
T T T T T
boundary wall is treated as a gray heat sink with emissivity of 0.8, and the wall temperature is
Mean absorption coefficient of CO:

αi = a0 + T { a1 + T [ a2 + T ( a3 + a4 T )] } (6)
Energies 2017, 10, 1200 4 of 11

The values of constants a0 to a5 for CH4 , CO2 , CO, and H2 O are shown in Table 2. The boundary
wall is treated as a gray heat sink with emissivity of 0.8, and the wall temperature is maintained at 300 K
through water cooling. The total absorption coefficient of radiating gas mixture is calculated as the sum
of the absorption coefficients of CH4 , CO2 , CO, and H2 O in the flame. All transport equations with
radiation are solved by CFD software PHOENICS 2014 (Cham-Japan, Tokyo, Japan) [24]. The velocity
and pressure coupling are treated by a SIMPLE method algorithm [25]. The GRI 3.0 mechanism with
53 species and 325 reactions [26] is applied to this research. The transport and thermal properties
of all species are calculated by GRI 3.0 database and CHEMKIN codes. As a key parameter in fuel
combustion, the heat release rates of all elementary reactions are defined and programed. Taking
reaction R52 as example, we can calculate the heat release rate by following equations:

R52 : H + CH3 (+M) ⇔ CH4 (+M)

∆hi=52 = − hCH4 , J·mol−1

hH + hCH3 (7)

qi=52 = ∆hi=52 × k i=52 (8)

325
qnet = ∑ qi (9)
i =1

where h j is formation enthalpy of specie j (J·mol−1 ); ∆hi , k i , and qi are enthalpy change of reaction i
(J·mol−1 ), the reaction rate of reaction i (mol·cm−3 ·s−1 ), and heat release of reaction i (J·cm−3 ·s−1 ),
respectively. Furthermore, qnet indicates the total heat release rate of all reactions (mol·cm−3 ·s−1 ).

Table 2. Absorption coefficient of a0 to a5 for CH4 , CO, CO2 , and H2 O.

Coefficient CO2 H2 O CH4 CO (T < 750 K) CO (T > 750 K)

a0 18.741 −0.23093 6.6334 4.7869 10.09
a1 −121.31 −1.1239 −3.5686 × 10−3 −0.06953 −0.01183
a2 273.5 9.4153 1.6682 × 10−8 2.95775 × 10−4 4.7753 × 10−6
a3 −194.05 −2.9988 2.5611 × 10−10 −4.25732 × 10−7 −5.87209 × 10−10
a4 56.31 0.51382 −2.6558 × 10−14 2.02894× 10−10 −2.5334 × 10−14
a5 −5.8169 −1.884 × 10−5 0 - -

3. Discussion
Figure 2 shows several typical measured outlet temperatures of BG-2/air flames with various
H2 addition ratios and O2 -enriched levels at the same input power of 1.0 kW and equivalence ratio
of 0.95; the simulation results are shown for comparison. The outlet temperature was measured
by a K-type thermocouple on a same combustion chamber and burner size with simulation, which
was described in our previous study [27]. The error of experimental temperature at all H2 addition
ratios and O2 -eneriched levels are less than 15%. Furthermore, the deviation of simulation and
experimental results are below 11%. Therefore, the simulation results show good agreement with
experimental data at all H2 addition ratios and O2 -enriched levels, thereby confirming that the GRI 3.0
mechanism provides an acceptable and repeatable result for biogas combustion under H2 -enriched
and O2 -enriched conditions.
The effect of CH4 content in biogas fuel on the combustion temperature distribution is shown in
Figure 3. The maximum combustion temperature increases with increasing CH4 content in biogas fuel.
Furthermore, the flame length through the z-direction decreases at a higher CH4 content condition,
and flame width through the r-direction also shrinks with increasing CH4 content in biogas fuel. These
findings are attributed to the following explanations: (a) the reaction rate of elementary reactions in
biogas fuel flames increases with increasing CH4 content in biogas fuel as shown in Figure 4, and
is usually related to the flame structure; (b) the heat loss to heat up unburnt CO2 in biogas fuel gas
decreases with higher CH4 content in biogas fuel; and (c) the total volume of combustion gas (including
Energies 2017, 10, 1200 5 of 11

fuel gas2017,
Energies and10,air) decreases when CH4 content in biogas fuel increases, leading to higher temperature
1200
Energies 2017, 10, 1200 55 of
of 11
11
Energies
and heat 2017, 10,rate
release 1200 under higher CH content condition. The maximum heat release rate increased 5 of 11
4
maximum heat release
release rateto 432 J·cmby
increased −3 ·about
by s−1 ) with
19.3% (from 362
362CHto 432
by about 19.3% (from 362 increasing 4432 J·cm
content −3 ·s−1)) with
with increasing
increasing
from BG-1CH
−3 in−1biogas to4
maximum
maximum heat release rate increased byabout
heat rate increased 19.3%
about 19.3% (from
(from 362 toto J·cm
432 J·cm −3·s−1·s
) with increasing CH4 CH4
content
BG-3,
content in
leading biogas
in biogasto a from
stronger
from BG-1
BG-1heatto BG-3,
release
totoBG-3, leading
rate to
flame a stronger
with heat
shorter release
flame rate
lengths flame
at higherwith
CH shorter
contentflame in
content in biogas from BG-1 BG-3,leading
leading to
to aa stronger
strongerheat
heatrelease
release rate
rate flame
flame withwith shorter
4
shorter flameflame
lengths
biogas
lengths at
fuel. higher
at higher
lengths at higher
CH
CHCH 4 content in biogas fuel.
4 content
4 content ininbiogas
biogasfuel.
fuel.

Figure 2. Comparison of predication temperature (line) and measurement temperature (plot) at the
Figure 2. Comparison of predication temperature (line) and measurement temperature (plot) at the
outlet
Figure of BG-2/air flames
2.BG-2/air
Comparison with various H
of predication
predication 2 addition ratios (black line) and O2 enrichment levels (red line).
temperature (line) and(black
measurement temperature (plot)levels
at the
the
outlet
Figure of2. Comparison flames
of with various H2 addition
temperature ratios
(line) and line) and
measurement O2 enrichment
temperature (plot) at
outlet
(red ofBG-2/air
line).
outlet of BG-2/airflames
flameswith
withvarious
variousH H22addition
additionratios
ratios(black
(blackline)
line)and
andO O22enrichment
enrichmentlevels
levels(red
(redline).
line).

Figure 3. Effect of CH4 content in biogas fuel on combustion temperature distribution.

Figure
Figure 3.Effect
Figure3.
3. Effectof
Effect ofCH
of CH444content
CH contentin
content inbiogas
in biogasfuel
biogas fuelon
fuel oncombustion
on combustiontemperature
combustion temperaturedistribution.
temperature distribution.
distribution.

Figure 4. Effect of CH4 content in biogas fuel on net heat release rate distribution.

The effects of H2 addition ratios and O2 enrichment levels in BG-2/air flame on combustion
temperature distributions are shown in Figure 5. The maximum combustion temperature in flames
Figure 4. Effect of CH4 content in biogas fuel on net heat release rate distribution.
Figure 4.
Figure 4. Effect
Effect of
of CH
CH44 content
content in
in biogas
biogas fuel
fuel on
on net
net heat
heat release
release rate
rate distribution.
distribution.

The effects
The effects of
of H
H22 addition
addition ratios
ratios and
and O
O22 enrichment
enrichment levels
levels in
in BG-2/air
BG-2/air flame
flame on
on combustion
combustion
temperature distributions are shown in Figure 5. The maximum combustion temperature
temperature distributions are shown in Figure 5. The maximum combustion temperature in in flames
flames
Energies 2017, 10, 1200 6 of 11

The2017,
Energies effects of H2 addition ratios and O2 enrichment levels in BG-2/air flame on combustion
10, 1200
1200
Energies 2017, 10, 66 of
of 11
11
temperature distributions are shown in Figure 5. The maximum combustion temperature in flames
increased
increasedby byapproximately
approximately 10.8% 10.8% from
from 18031803 toto 1998
1998 K K asas H addition ratio
H222 addition ratio varied
variedfromfrom0% 0%toto50%,
50%,
and
andwas
wasslightly
slightlyhigherhigherby byabout
about11.2%
11.2%from from1803
1803to to2005
2005 K K asas O enrichment levels
O222 enrichment levels increased
increased from from
21%
21%toto35%.35%.Conversely,
Conversely,the themaximum
maximumheat heatrelease
releaserate
rateininflames
flamesincreased
increasedbyby 3.69
3.69times
times from
from 362362 to
J·cmJ·cm− 3 − 1
·s−3·s−1atatHH J·cm − 3 − 1
1336
to 1336 −3 −1
2 addition
22 addition conditions
conditionsand andonly
only2.29
2.29times
timesfromfrom362362toto829829 J·cm−3·s·s−1 under
−3 −1 under O O222
additionconditions,
addition conditions,as as shown
shown in Figure
Figure 6. 6. This
Thisdifference
differenceisisalso alsorelated
relatedtoto
thetheshape
shape and and structure
structure of
biogas flames, which is important in the direct application of biogas
of biogas flames, which is important in the direct application of biogas for heating. Specifically, the for heating. Specifically, the
position
positionof ofmaximum
maximum heat heat release
release rate
rate varying
varyingwithwithHH 2 addition
22 addition and and
O22 O 2 enrichment
enrichment is different.
is different. At
Atthe
theH22Haddition
2 addition condition,
condition, the fuel
the composition
fuel composition at fuel
at inlet
fuel varies
inlet with
varies H
with2
2 addition
H 2 additionrate, the
rate, fuel
the
combustion
fuel combustion velocity
velocityenhances
enhances because
because of of
high
highreactivity
reactivity (more
(moreOH OHand andHHradicals
radicalswith with higher
higher
formationrate
formation ratebecause
becauseofofhigh highburning
burningvelocity
velocity[28–30]
[28–30] and combustion temperature of H222))and
and combustion andhighhigh
mobilityofofHH2 22[28–30].
mobility [28–30]. Therefore,
Therefore, the the maximum
maximum heat heat release
release rate at the H H222 addition
addition conditions
conditions isis
locatedatatcenter
located centerofofthe theflame.
flame.At Atthe
theOO222enrichment
enrichment condition,
condition, the the fuel
fuel composition
composition keeps keeps constant,
constant,
andthe
and the airair composition
composition at outside
at outside of fuelof inlet
fuel inlet
variesvaries
with Owith 2 O 2 enrichment.
enrichment.
2 The The
fuel fuel
combustion combustion
velocity
velocity also improves because of the higher collision rate of oxidizer
also improves because of the higher collision rate of oxidizer with fuel near flame edges. Therefore, with fuel near flame edges.
Therefore, the maximum heat release rate locates near the
the maximum heat release rate locates near the flame edges at O2 enriched condition. flame edges at O 2
2 enriched condition.

Figure5.5.Effects
Figure EffectsofofHH222 addition
addition ratio
ratio (a)
(a) and
and OO222 enrichment
enrichment levels
levels (b)
(b) in
in BG-2/air flame on
BG-2/air flame on the
the
distribution
distributionofofcombustion
combustiontemperature.
temperature.

Figure6.6. Effects
Figure Effects of
of HH222 addition
addition ratio
ratio (a)
(a) and
and O
O222 enrichment
enrichment levels
levels (b)
(b) in
in BG-2/air flame on
BG-2/air flame on the
the
distribution of the heat release rate.
distribution of the heat release rate.

To
Toobtain
obtain an in-depth understanding
an in-depth understandingofofheat heatrelease
release characteristics
characteristics of biogas
of biogas flamesflames
under under
H22-
enriched and O -enriched conditions, the net heat release rate distribution
H2 -enriched and2 O2 -enriched conditions, the net heat release rate distribution at centerline along
2 at centerline along the z-
the z-direction
direction is shown
is shown in Figure
in Figure 7. The
7. The maximum
maximum net heat
net heat release
release rate rate at centerline
at centerline is enhanced
is enhanced by
approximately
by approximately two twoorders
ordersofofmagnitude
magnitude(from
(from 0.155
0.155 to to 120.0 cm−−3
120.0 J·J·cm −3
·s−1−1−)1 )when
3·s whenHH22 2addition
additionratio
ratio
increasesfrom
increases from0%0%toto50%;50%;and
andthe
themaximum
maximumnet netheat
heat release
release rate
rate at
at centerline
centerline is is enhanced
enhanced by by about
about
oneorder
one orderofofmagnitude
magnitude (from 0.155 to
(from 0.155 to 3.66
3.66J·cm −
−3 3−1 − 1
J·cm ·s ·s) when
−3 −1 the the
) when O22 addition
O2 addition ratioratio
increases from from
increases 21%
to 35%.
21% The The
to 35%. enhancement
enhancement of theofheat release
the heat rate can
release ratelead to a change
can lead to a changein flame structure
in flame and heat
structure and
release characteristics in the flame reaction zone. Therefore, average
heat release characteristics in the flame reaction zone. Therefore, average temperature temperature T was defined
a Ta was defined
a to
explore the effect of H22-enriched and O22-enriched conditions on flame kernel. Taa is based on the
barycenter of heat release rate as follows:
Energies 2017, 10, 1200 7 of 11

to explore the effect of H2 -enriched and O2 -enriched conditions on flame kernel. Ta is based on the
Energies
barycenter of 2017,
heat10,release
1200 rate as follows: 7 of 11

Rz
d
qTdz
Ta == R0 z (10) (10)
d
0 qdz

(a) (b)
Figure 7. Heat release rate of biogas flames under H2-enriched (a) and O2-enriched (b) conditions
Figure 7. Heat release rate of biogas flames under H2 -enriched (a) and O2 -enriched (b) conditions
along the centerline.
along the centerline.
Figure 8 shows the average temperature Ta together with flame height of peak heat release rate
at various
Figure H2 addition
8 shows ratios andtemperature
the average O2 enrichmentT levels. As shown in Figure 8, the average temperature
a together with flame height of peak heat release
Ta shows a gradual decrease with the increasing H2 addition ratio and O2 enrichment levels. For the
rate at various H2 addition ratios and O2 enrichment levels. As shown in Figure 8, the average
biogas flame at same input power of 1 kW and equivalence ratio of 0.95, the value of average
temperature Ta shows
temperature a gradual
Ta increases fromdecrease
1215 to 1864with K, the increasing
nearly yielding an H2enhancement
addition ratio and O
of 53.4%, 2 enrichment
when H2
levels. For the biogas flame at same input power of 1 kW and equivalence
addition ratio varied from 0% to 50%. In contrast, the flame height of peak heat release rate decreases ratio of 0.95, the value
of average temperature54.5%
by approximately Ta increases
from 19.8fromto 9.01215 to 1864
cm when the HK,2 addition
nearly yielding an enhancement
ratio increases from 0% to 50%. of 53.4%,
when HThe2
enhancement
addition ratio of average
varied temperature
from 0% to T
50%.a and
In reduction
contrast, of flame
the height
flame of maximum
height of peak heat
heat release
release rate
rate resulted from the high mobility and high reactivity of H2, leading to a higher reaction rate of
decreases by approximately 54.5% from 19.8 to 9.0 cm when the H2 addition ratio increases from 0% to
biogas flame under H2-enriched condition as shown in Figure 9a. By contrast, the value of average
50%. The enhancement of average temperature Ta and reduction of flame height of maximum heat
temperature Ta increased from 1215 to 1428 K (~17.5% increase) and the flame height of peak heat
release rate resulted
release from the
rate decreases high
from 19.8mobility
to 10.9 cmand high decrease)
(~44.9% reactivitywhen of HO 2 ,2 leading
enrichment to alevels
higher reaction rate
increased
of biogas flame
from 21%under
to 35%.HWith2 -enriched condition
the enrichment of Oas
2 inshown in Figure
combustion air, the9a. By contrast,
reaction rate can be theimproved
value ofasaverage
shownTin
temperature Figure 9b. from
a increased Furthermore,
1215 tounnecessary
1428 K (~17.5% sensibleincrease)
heat to heat andupthe theflame
unburnt N2 gas
height ofalso
peak heat
decreases
release rate with increasing
decreases from 19.8 O2 to
enrichment
10.9 cm levels.
(~44.9% As shown in Figure
decrease) when 9, the
O2net reaction ratelevels
enrichment of biogas
increased
flames under the H2-enriched condition markedly increases as H2 addition ratio increases from 0% to
from 21% to 35%. With the enrichment of O2 in combustion air, the reaction rate can be improved
50% and lower increase is observed under O2-enriched condition when O2 levels increases from 21%
as shown in Figure
to 35%. To clarify9b.theFurthermore,
main elementary unnecessary sensible
reaction in biogas flame, heat
we to heat up
compared thethe unburnt
typical N2 gas also
elementary
decreases with increasing
exothermic reaction rateO2 of
enrichment
biogas flame levels.
along As the shown
centerline inatFigure 9, theratio
H2 addition net of
reaction
0% and rate50% ofin biogas
flames under
Figure the H2 -enriched
10. The formation of condition markedly
free radicals, such as increases
H, O, and as OH, Hare
2 addition
enhancedratio withincreases
the increase from
in 0% to
50% andhydrogen addition is
lower increase ratios; in particular,
observed underR83: OH + H2 ⇔condition
O2 -enriched H + H2O markedlywhen Oincreases
2 levels as H 2 is added
increases from 21%
to biogas flame, similar results have been reported for the heat release
to 35%. To clarify the main elementary reaction in biogas flame, we compared the typical elementary rate of premixed laminar
biogas-H2 flame by Wei et al. [19] and CH4/air premixed flames with H2 addition by Hu et al. [31].
exothermic reaction rate of biogas flame along the centerline at H2 addition ratio of 0% and 50% in
Furthermore, the typical elementary exothermic reaction rates of R83: OH + H2 ⇔ H + H2O;
Figure 10.
R37:TheH+O formation of free radicals, such as H, O, and OH, are enhanced with the increase
2 ⇔ O + OH are important to enhance biogas combustion. The elementary reaction of R83
in hydrogen
(H2 as addition
reactant) isratios; in particular,
higher than R83: OH
R37 (O2 as reactant). + H2 ⇔HH
Therefore, + H2 Ohas
2 addition markedly increases
a drastic effect on heatas H2 is
added torelease
biogas flame,
rate similar rate)
(and reaction results have beenthan
enhancement reported for the heat
O2 enrichment release
as shown rate of 6premixed
in Figures and 7. Thelaminar
biogas-H enhancement reaction rate can lead to structure and shape changes in biogas flame. The flame
2 flame by Wei et al. [19] and CH4 /air premixed flames with H2 addition by Hu et al. [31].
thickness along centerline under H2-enriched conditions and O2-enriched conditions are shown in
Furthermore, the typical elementary exothermic reaction rates of R83: OH + H2 ⇔ H + H2 O; R37:
Figure 11. The definition of flame thickness can be expressed as follows:
H + O2 ⇔ O + OH are important to enhance biogas combustion. The elementary reaction of R83
(H2 as reactant) is higher than R37 (O2 as reactant). Therefore, H2 addition has a drastic effect on
heat release rate (and reaction rate) enhancement than O2 enrichment as shown in Figures 6 and 7.
The enhancement reaction rate can lead to structure and shape changes in biogas flame. The flame
thickness along centerline under H2 -enriched conditions and O2 -enriched conditions are shown in
Figure 11. The definition of flame thickness can be expressed as follows:
Energies 2017, 10, 1200 8 of 11

Energies 2017, 10, 1200 8 of 11

Tmax − T0
Energies 2017, 10, 1200 DF = 8 of 11 (11)
(dT/dz)max
Energies 2017, 10, 1200 − 8 of 11
= (11)
where Tmax and T0 are the maximum temperature ⁄ −
= and unburned temperature respectively, (dT/dz (11)
)max
is thewhere
peak gradient and in temperature profile temperature
along ⁄ −
the centerline. As shown in Figure 11, the
are the maximum = and unburned temperature (11) flame
respectively,
thickness ⁄ decreases
where isand
the peak
with thegradient
are in temperature
increasing
the maximum H2 addition ⁄ along
profile
ratio
temperature and the
and O centerline.
enrichment
unburned As shown
levels.
temperature in
ThisFigure 11, can
decrease
respectively,
2
the ⁄ tothickness
flame
where
be attributed isand
the decreases
the peak
burning are thewith
gradient
velocity in the
maximum increasing
temperature
enhancement Hbiogas
2 addition
profile
temperature
of along
and ratio
the
unburned
flames and OH
centerline.
under 2 enrichment
2 As shown
temperature
-enriched levels.
in
andFigure
O This
2 11,
respectively,
-enriched
the ⁄
decrease
flamecan be
is attributed
thickness
the peak to the
decreases
gradient burning
within the velocityprofile
increasing
temperature enhancement
H 2 addition
along of centerline.
ratio
the
conditions. Therefore, a flame with enhanced heat release rate is formed under H2 -enrichedbiogas
and Oflames under H
2 enrichment
As shown 2-enriched
levels.
in FigureThis
11, and
and
the O 2-enriched
decrease
flame can conditions.
be attributed
thickness toTherefore,
decreases the burning
with theaincreasing
flame with
velocity enhanced
2 additionheat
enhancement
H release
of biogas
ratio and O rate
flames is under
formedHlevels.
2 enrichment under H2-
2-enriched
This
O2 -enriched conditions, which are beneficial to the practical application of biogas as a fuel.
enriched
and
decrease and
canObe
O2-enriched2-enriched conditions,
conditions.
attributed which
toTherefore, are beneficial
a flame
the burning with
velocity to the practical
enhanced
enhancement heat application
release
of biogas of biogas
rate is under
flames formed as a fuel.
Hunder H2-
2-enriched

enriched and O2-enriched

and O2-enriched conditions,
conditions. which
Therefore, are beneficial
a flame to the practical
with enhanced application
heat release of biogasunder
rate is formed as a fuel.
H2-
enriched and O2-enriched conditions, which are beneficial to the practical application of biogas as a fuel.

(a) (b)
Figure 8. Effects of H2 (a) (b) flame on the peak
addition ratio (a) and O2 enrichment levels (b) in BG-2/air
Figure 8. Effects of H2 addition
(a) ratio (a) and O2 enrichment levels (b) in BG-2/air
(b) flame on the peak
heat release
Figure heightofand
8. Effects H2 average
additiontemperature
ratio (a) andTO
a. 2 enrichment levels (b) in BG-2/air flame on the peak
heat release height and average temperature Ta .
heat release
Figure height
8. Effects ofand average temperature
H2 addition ratio (a) andTOa.2 enrichment levels (b) in BG-2/air flame on the peak
heat release height and average temperature Ta.

(a) (b)
Figure 9. Net reaction(a) (b) ratios (a) and O2
rate of biogas flame along centerline at various H2 addition
enrichment levels (a) (b)
(b). rate of biogas flame along centerline at various H2 addition
Figure 9. Net reaction ratios (a) and O2
Figure 9. Net reaction rate of biogas flame along centerline at various H2 addition ratios (a) and O2
enrichment levels
Figure 9. Net (b). rate of biogas flame along centerline at various H2 addition ratios (a) and O2
reaction
enrichment levels (b).
enrichment levels (b).

(a) (b)
Figure 10. Comparison of (a)typical elementary reaction exothermic reaction rates
(b) of biogas flame along
the centerline at H (a) ratio of 0% (a) and 50% (b).
addition (b)
Figure 10. Comparison of typical elementary reaction exothermic reaction rates of biogas flame along
2

the centerline
Figure at H2 addition
10. Comparison ratio elementary
of typical of 0% (a) and 50% (b).
reaction exothermic reaction rates of biogas flame along
Figure 10. Comparison of typical elementary reaction exothermic reaction rates of biogas flame along
the centerline at H2 addition ratio of 0% (a) and 50% (b).
the centerline at H2 addition ratio of 0% (a) and 50% (b).
Energies 2017, 10, 1200 9 of 11
Energies 2017, 10, 1200 9 of 11

Figure
Figure 11.
11. Flame
Flame thickness
thickness along
along the
the centerline
centerline at
at various
various H
H22 addition
addition ratios
ratios (black
(black line) and O
line) and O2
2
enrichment levels (red line).
enrichment levels (red line).

4. Conclusions
4. Conclusions
The combustion and heat release characteristics of biogas non-premixed flames under various
The combustion and heat release characteristics of biogas non-premixed flames under various
hydrogen-enriched and oxygen-enriched conditions were investigated utilizing chemical kinetics
hydrogen-enriched and oxygen-enriched conditions were investigated utilizing chemical kinetics
simulation and the detailed chemical mechanism. The results are summarized as follows.
simulation and the detailed chemical mechanism. The results are summarized as follows.
(1) The net reaction rate of biogas increases with increasing hydrogen addition ratio and oxygen
(1) levels,
The net reaction
leading to arate of biogas
higher increases
net heat release with increasing
rate of hydrogen addition ratio and oxygen
biogas flame;
levels, leading to a higher net heat release rate of biogas flame;
(2) The formation of free radicals, such as H, O, and particularly OH, are enhanced with the increase
(2) in
The formation
hydrogen of free ratio
addition radicals,
andsuch
oxygenas H, O, and particularly OH, are enhanced with the increase
levels;
in hydrogen addition ratio and oxygen levels;
(3) Flames with enhanced heat release rates are formed under H2-enriched and O2-enriched
(3) conditions.
Flames with enhanced
Therefore, heat release
H2-enriched and rates are formed
O2-enriched under isHbeneficial
combustion 2 -enriched andimprovement
to the O2 -enriched
conditions. Therefore, H
of combustion and heat release
2 -enriched and O
characteristics
2 -enriched combustion is beneficial to
of biogas in practical application. the improvement
of combustion and heat release characteristics of biogas in practical application.
Acknowledgments: This research is partially supported by the “Knowledge Hub Aichi” Priority Research
Project from Aichi Prefectural Government, Japan.
Acknowledgments: This research is partially supported by the “Knowledge Hub Aichi” Priority Research Project
from Aichi
Author Prefectural Government,
Contributions: Japan. to the experiment and simulation, data analysis and paper writing;
Jun Li contributed
Hongyu Huang, Huhetaoli,
Author Contributions: Yucontributed
Jun Li Bai, and Yong Chen
to the contributed
experiment andtosimulation,
experimental design,
data and
analysis Yugo
and Osaka
paper and
writing;
Hongyu Huang,
Noriyuki Huhetaoli,
Kobayashi Yu Bai,
contributed and Yongselection
to modeling Chen contributed to experimental
and programing design, and Yugo Osaka and
instruction.
Noriyuki Kobayashi contributed to modeling selection and programing instruction.
Conflicts of Interest: The authors declare no conflict of interest.
Conflicts of Interest: The authors declare no conflict of interest.

Nomenclature
Nomenclature
H2 addition ratio to fuel (based on low heat value)
XH2 H2 addition ratio to fuel (based on low heat value)
Flow rate of H2 (m·s−1)
VH2 Flow rate of H2 (m·s−1−1 )
Flow rate of CH4 (m·s ) −1
VCH4 Flow rate of CH (m·s )
Low heat value of4H2 (kJ·mol−1) −1
LHVH2 Low heat value of H (kJ·mol )
Low heat value of CH42(kJ·mol−1)
LHVCH4 Low heat value
O2-enriched level (-)of CH4 (kJ·mol−1 )
Ω O2 O2 -enriched
Flow rate of O2level
(m·s−1 (-))
VO2 Flow rate of O
Flow rate of N2 (m·s2 (m ·s) −1 )
−1

VN2 Flow rate

Density of −3N) 2 (m·s−1 )
(kg·m
ρ Density
General (kg·m−3 ) variable (-)
dependent
Y Generalvector
Velocity dependent
(m·s−1)variable (-)
YΓ Velocity vector
associated transport s−1 )
(m·coefficient of Y (-)
ΓY associated
The transport
source term (-) coefficient of Y (-)
SY The absorption
Mean source termcoefficient
(-) of species i (-)
αℎi Formation enthalpycoefficient
Mean absorption of specie jof(J·mol −1) i (-)
species
∆ℎ Enthalpy change of reaction i (J·mol−1)
Energies 2017, 10, 1200 10 of 11

hj Formation enthalpy of specie j (J·mol−1 )

∆hi Enthalpy change of reaction i (J·mol−1 )
ki The reaction rate of reaction i (mol·cm−3 ·s−1 )
qi Heat release rate of reaction i (J·cm−3 ·s−1 )
qnet Total heat release rate of all reaction (J·cm−3 ·s−1 )
DF Flame thickness (cm)
Tmax The maximum temperature (K)
T0 The unburned temperature (K)
(dT/dz)max The peak gradient in temperature (K·cm−1 )

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