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On the effects of hydrogen addition in premixed


formaldehyde flames

Minye Luo, Dong Liu*


School of Energy and Power Engineering, Nanjing University of Science and Technology, Nanjing 210094,
People's Republic of China

article info abstract

Article history: The influences of hydrogen addition on laminar premixed fuel-rich formaldehyde flames
Received 20 April 2016 at the atmospheric pressure are studied by the detailed kinetic analysis. The chemical
Received in revised form effects of hydrogen addition on flame structures, mole fractions of major species and free
4 July 2016 radicals are distinguished clearly from the dilution and thermal effects. The results show
Accepted 6 July 2016 that the H2 chemical effects can promote the oxidation of formaldehyde and make the
Available online xxx mole fraction profile of formaldehyde move toward the upstream side. The increase of H
radical concentration is mainly due to the chemical effects of hydrogen addition. The re-
Keywords: action OH þ H2 ¼ H þ H2O plays a major role in the productions of H and OH radicals. The
Formaldehyde flames productions of O, HCO and HO2 radicals are enhanced by the H2 chemical effects. However,
Hydrogen addition the hydrogen dilution and thermal effects on decreasing these radicals' concentrations are
Chemical effects more dominant. The mole fractions of CO and CO2 decrease with H2 addition. The H2
Kinetic analysis chemical effects facilitate the formation of CO, but suppress the production of CO2.
© 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

previous studies, they developed a decomposition mechanism


Introduction with six reactions which was validated by numerous experi-
mental observations in literature. Vandooren et al. [10]
Formaldehyde is a significant intermediate species in the measured the mole fractions of flame species via molecular
combustion of hydrocarbon and oxygenated fuels. Better un- beam sampling coupled with mass spectrometric analysis in a
derstanding of the oxidation kinetics of formaldehyde can low pressure lean formaldehyde flame. Since formaldehyde
contribute to the hierarchical kinetic mechanisms of hydro- emissions are harmful to human health and are not negligible
carbon and oxygenated fuels. Several fundamental combus- in engines, Zhang et al. [11] intensively evaluated the formal-
tion studies on formaldehyde under different conditions have dehyde emissions of methanol-gasoline blended fuels in spark
been performed in static reactors [1], flow reactors [2e4] and ignition engines. Donkerbroek et al. [12] measured the form-
shock tubes [5e7] in recent years. Glarborg et al. [8] experi- aldehyde concentrations during n-heptane combustion in
mentally studied the oxidation of formaldehyde from fuel-lean diesel engines. The better understanding of the formation and
to fuel-rich conditions in a flow reactor, and they proposed consumption reaction pathways of formaldehyde which con-
a detailed mechanism for the oxidation of formaldehyde. tributes to minimize its emissions is required. The kinetic
Friedrichs et al. [9] investigated the thermal decomposition of model for the combustion of CO, CH2O and CH3OH modified by
formaldehyde behind shock waves. Based on the results of Li et al. [13] agreed well with the experimental measurements

* Corresponding author. Fax: þ86 25 84314960.


E-mail address: dongliu@njust.edu.cn (D. Liu).
http://dx.doi.org/10.1016/j.ijhydene.2016.07.046
0360-3199/© 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article in press as: Luo M, Liu D, On the effects of hydrogen addition in premixed formaldehyde flames, International
Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.07.046
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in the lean flat CH2O flame. In 2012, Dias et al. [14] extended a these changes are either because of the reduction of reactants'
kinetic model of formaldehyde and validated it against several concentrations, or due to H2 additions. To our best knowledge,
flames of hydrocarbon and oxygenated fuels. there is very little work on studying formaldehyde/hydrogen
Hydrogen which is generally adopted as a clean fuel or fuel flames and distinguishing the different effects of hydrogen
additive has some good characteristics such as high flame addition on major species and free radicals of formaldehyde
speed, wide flammability range, high calorific value and low flames. Therefore, the aim of this work is to analyze the in-
emissions etc [15]. Many studies have proposed that hydrogen fluences of different levels of hydrogen addition on premixed
can be added to hydrocarbon fuels to promote the combustion laminar fuel-rich formaldehyde flames at atmospheric pres-
efficiency and reduce pollutant emissions [16e25]. Verhelst sure. The chemical effects of hydrogen addition on formal-
et al. [16] proved that hydrogen which was used as a blending dehyde flames are distinguished and separated from its
fuel to other fuels could improve the engine efficiency and dilution and thermal effects.
emission performances. Akansu et al. [17] found that CO and
CO2 emissions of natural gas-hydrogen mixtures reduced with
increasing hydrogen in internal combustion engines. Ma et al.
[18,19] conducted an experimental study on the effects of Kinetic modeling and analysis method
hydrogen addition on spark ignition natural gas engine's
thermal efficiency and emissions. Park et al. [20] studied the The detailed mechanism we adopted for the CH2O oxidation
influences of hydrogen addition on soot formation and and combustion is AramcoMech 1.3 which was developed by
oxidation in premixed C2H2 flames. The results showed that Metcalfe et al. [35]. This mechanism builds on recent work
hydrogen slowed the formation of benzene. Due to the published from NUI Galways [36e39], and has been validated
promising application of hydrogen, some studies on ignition against a large array of experimental measurements including
[21], laminar flame speed [22,23], flame instability [24] and data from shock tubes, flames, jet-stirred and flow reactors.
flame structure [25] of hydrogen/methane blended fuels were The mechanism consists of 124 species and 766 reactions.
also conducted. Researchers numerically investigated the in- Moreover, the detailed H2 combustion mechanism is included.
fluences of hydrogen additions on blended fuels in recent The modified ChemkinII/Premix code [40] is adopted to
years [26e34]. Luo et al. [26] found that the addition of H2 could simulate accurately the freely propagated premixed laminar
reduce the mole fractions of C2H2 and C3H3 in premixed pri- fuel-rich CH2O/H2/Air flames. To keep the adiabatic equilib-
mary reference fuels flames. Liu [29] analyzed the chemical rium, the computing domain ranges from 2.0 cm at the up-
effects of hydrogen addition on premixed laminar low- stream to 10.0 cm at the downstream. The initial temperature
pressure dimethyl ether flames. Yan et al. [31] simulated the and pressure at the upstream are set to 300 K and 1.0 atm. For
combustion characteristics of H2 addition on catalytic micro- better comparisons, the equivalence ratios for all flames keep
combustion of CH4-air. The results showed that H2 could the same. Table 1 displays the other detailed flame conditions.
shorten the methane ignition time and lower ignition tem- The added hydrogen fraction (RH2) is set as the mole fraction
perature. Wang et al. [33] conducted the rate of production of H2 in CH2O/H2 fuel blends.
analysis and analyzed the influences of H2 addition on specific Usually, the chemical, dilution and thermal effects of an
species in methane flames. additive occur simultaneously and are intimately coupled. It is
Formaldehyde is a well-known air pollutant and immedi- impossible to completely isolate the chemical effects of the
ate species in alcohol and hydrocarbon combustion. Hydrogen additive from other effects experimentally. In order to sepa-
which can be used as a fuel additive performs well on rate and analyze these effects of hydrogen addition [41] on
improving engines efficiency and emissions performance. CH2O/H2 flames, the following numerical method developed
Since monomer formaldehyde is difficult to be obtained and by Liu et al. [29,32,42] is adopted here. The added H2 is
measured experimentally, the study on formaldehyde/ assumed as normal H2 and fictitious inert H2 (written as F-H2)
hydrogen flames has the important value on methods to to distinguish the chemical effects of H2 addition. F-H2 can be
control formaldehyde emissions in hydrocarbon and achieved by modified the original mechanism. Normal reac-
oxygenated fuel flames. Whereas, when hydrogen is added, tive H2 can participate in all relevant chemical reactions in
the mole fraction of fuel changes, and the combustion fea- flames as usual. The transport, thermochemical data and the
tures could be changed as well including the concentrations of third-body collision efficiency of fictitious H2 are same with
major and intermediate species and radicals. We don't know the normal H2, but F-H2 can't involve in any related chemical

Table 1 e Flame conditions for CH2O/H2 flames at 1.0 atm with equivalence ratios of 1.5(Unit for reactions is mole fractions).
No. RH2 ð%Þ CH2O H2 F-H2 O2 F-O2 Ar
1 0 0.18 / / 0.12 / 0.7
2 5 0.17272729 0.00909091 / 0.11818180 / 0.7
3 5 0.17272729 / 0.00909091 0.11515153 0.00303027 0.7
4 10 0.16530615 0.01836735 / 0.1163265 / 0.7
5 10 0.16530615 / 0.01836735 0.1102041 0.0061224 0.7
6 20 0.15 0.0375 / 0.1125 / 0.7
7 20 0.15 / 0.0375 0.1 0.0125 0.7

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Fig. 1 e Temperature profiles of CH2O/H2 flames with Fig. 2 e Mole fractions of CH2O with different levels of
different hydrogen additions. hydrogen addition.

reactions. Additionally, in order to bring equivalence ratios of


F-H2 additions into correspondence with those of normal H2 of H2 addition on the CH2O oxidation are weaker than the
additions, some part of O2 should be separated from the total hydrogen chemical effects.
O2 that is defined as the fictitious O2 (written as F-O2). F-O2 has The main consumption reaction pathway analyses of
exactly the same transport, thermochemical data and third- CH2O with 0% H2, 20% H2 and 20% F-H2 additives are shown in
body collision efficiency as normal O2, and can't take part in Fig. 3. The sufficient fuel conversion is required to insure that
related chemical reactions. the major pathways for the consumption of primary prod-
ucts can be observed. The pathways for flames of CH2O with
0% H2, 20% H2 and 20% F-H2 additives are set at the distance
of 0.403 mm corresponding to a temperature of 1402 K and
Results and discussion
76.7% conversion of CH2O, the distance of 0.4 mm corre-
sponding to a temperature of 1431 K and 74.5% conversion of
Flame temperatures

Fig. 1 depicts the temperature profiles of CH2O/H2 flames with


5%, 10%, 20% H2 and 5%, 10%, 20% F-H2 additions. It is found
that the flame temperatures decrease slightly with the normal
H2 addition. Meanwhile, with the addition of fictitious
hydrogen, the flame temperatures drop largely. The discrep-
ancy between the profiles of 20% H2 and 20% F-H2 additions
reveals that the chemical effects of hydrogen addition pro-
mote the increase of flame temperatures. Additionally, the
dilution and thermal effects of hydrogen addition make the
temperatures descend significantly from the discrepancy be-
tween profiles of 0% H2 and 20% F-H2 additive. The difference
between temperatures of 0% H2 and 20% H2 additions is due to
the combined effects of H2. It can be seen that the H2 dilution
and thermal effects play the dominant role in the variations of
flame temperatures.

Major species and radicals

The mole fraction profiles of CH2O with different levels of H2


addition are given in Fig. 2. As the fuel component changes,
the initial mole fractions of CH2O decrease with the increase
of H2 addition. It is obviously that the oxidation of CH2O is Fig. 3 e CH2O consumption pathway analyses with 0% H2,
promoted and the profiles of CH2O move toward the upstream 20% H2 and 20% F-H2 additions. Percentages given in
side due to the chemical effects of hydrogen addition. How- parentheses are corresponding to the results of 20% H2,
ever, the replacement of formaldehyde by fictitious H2 delays and percentages given in angle brackets are corresponding
the consumption of CH2O and makes the profiles shift to the to the results of 40% F-H2. Dashed arrows show the main
downstream side. Moreover, the dilution and thermal effects participating species.

Please cite this article in press as: Luo M, Liu D, On the effects of hydrogen addition in premixed formaldehyde flames, International
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CH2O, and the distance of 0.448 mm corresponding to a


temperature of 1338 K and 78.8% conversion of CH2O. Under
these conditions, it can be noted clearly that CH2O oxidation
proceeds mainly via H-abstraction to form HCO. The
remnant of formaldehyde is consumed by reacting with OH
radical to produce HCO. Subsequently, the great majority of
HCO converts to CO and a fringe of HCO is oxidized to CO2
directly. Ultimately, CO converts to CO2 mainly by reacting
with OH radical. However, the chemical effects of hydrogen
addition which can be seen from Fig. 2 are not obvious from
reaction pathway analyses in Fig. 3.
The rate of consumption of CH2O with 0%, 20% H2 and 20%
F-H2 additions are shown in Fig. 4. The main reactions
responsible for the consumptions of CH2O include
CH2O þ H ¼ HCO þ H2, CH2O þ OH ¼ HCO þ H2O and
CH2O þ O ¼ HCO þ OH. Obviously, the consumption rates of
formaldehyde are mainly limited by the concentrations of H
and OH radicals. The rates of these reactions with normal
hydrogen addition decrease less than those with F-H2 addi-
tion. The hydrogen chemical effects promote all reaction
rates. Moreover, the profiles of these reactions move toward
the downstream side when CH2O is substituted by fictitious H2
due to the dilution and thermal effects of H2 addition.
From the consumption reactions of CH2O in Fig. 4, it can be
found that H, OH and O radicals play an important role in the
oxidation of CH2O. The mole fraction profiles of free radicals
(H, O, OH, HCO and HO2) with different levels of hydrogen
addition are plotted in the following pictures.
The mole fraction profiles and rate of production of H
radical with different levels of hydrogen addition are dis-
played in Fig. 5. It can be seen in Fig. 5(a) that the H radical
mole fractions increase when real H2 is added, as the
hydrogen chemical effects promote the formation of H
radical. However, the reduction of H concentrations is
observed with the fictitious hydrogen addition due to the
hydrogen dilution and thermal effects. Fig. 5(b) presents the
rate of production of H radical with 0%, 20% H2 and 20% F-H2 Fig. 5 e (a) Mole fractions of H free radical with different
additive. The dominant reactions responsible for formations levels of hydrogen addition, (b) Rate of production of H free
of H radical are HCO þ M ¼ H þ CO þ M, OH þ H2 ¼ H þ H2O radical with 0%, 20% H2 and 20% F-H2 additions.
and O þ H2 ¼ H þ OH. The primary reactions for H radical

consumptions are CH2O þ H ¼ HCO þ H2, HO2 þ H ¼ OH þ


OH and H þ O2 ¼ O þ OH. Special attention is paid to
OH þ H2 ¼ H þ H2O. The rate of it increases when other
reactions’ rates decrease with 20% normal H2 addition. This
characteristic of OH þ H2 ¼ H þ H2O may explain the vari-
ations of H radical mole fractions in Fig. 5(a). The H2 chem-
ical effects accelerate the H radical production rate. The
rates of formation and consumption of H radical decrease
and the reaction profiles shift to the downstream side with
20% F-H2 addition due to the hydrogen dilution and thermal
effects.
Fig. 6(a) exhibits the mole fractions of O radical in CH2O/H2
flames with different levels of hydrogen addition. The peak
mole fractions of O radical decrease slightly with the addition
of H2. Similarly, the addition of fictitious H2 makes the O
radical mole fractions descend larger due to the dilution and
thermal effects of H2 addition. The chemical effects of
Fig. 4 e Rate of production of CH2O with 0%, 20% H2 and hydrogen addition facilitate the formation of O radical, but are
20% F-H2 additions. not dominant.

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Fig. 6 e (a) Mole fractions of O radical with different levels


of hydrogen addition, (b) Rate of production of O radical Fig. 7 e (a) Mole fractions of OH radical with different levels
with 0%, 20% H2 and 20% F-H2 additions. of hydrogen addition, (b) Rate of production of OH radical
with 0%, 20% H2 and 20% F-H2 additions.

The rate of production of O radical with 0%, 20% H2 and 20% the OH mole fractions. On the contrary, the H2 chemical
F-H2 additions are illustrated in Fig. 6(b). The main reaction effects promote the formation of OH. The combined effects
responsible for O radical formation is H þ O2 ¼ O þ OH. The make the OH radical mole fractions reduced.
dominant reactions for O radical consumptions are Fig. 7(b) illustrates the rate of production of OH radical with
O þ H2 ¼ H þ OH and CH2O þ O ¼ HCO þ OH. When 20% 0%, 20% H2 and 20% F-H2 additive. The primary reactions
normal H2 is added, a slightly rise of the reaction rate of responsible for OH radical formations are HO2 þ H ¼ OH þ OH,
O þ H2 ¼ H þ OH is observed. While other reaction rates of O H þ O2 ¼ O þ OH and O þ H2 ¼ H þ OH. The main reactions for
radical decrease with 20% H2 addition. This phenomenon may OH radical consumptions are CH2O þ OH ¼ HCO þ H2O,
account for O radical mole fractions decrease in Fig. 6(a). OH þ H2 ¼ H þ H2O and CO þ OH ¼ CO2 þ H. Especially, there is
When formaldehyde is substituted by F-H2, the hydrogen an evident increase of rate of OH þ H2 ¼ H þ H2O with 20% H2
dilution and thermal effects decrease the formation and addition. That accelerates the consumption of OH radical.
consumption rates of O radical and make the reaction profiles Meanwhile, the 20% H2 additive makes other reactions rates of
shift to the downstream side. OH radical dropped slightly. It may explain the decline of mole
The mole fraction profiles and the rate of production of OH fractions of OH radical with 20% H2 addition. The rates of all
radical in CH2O/H2 flames with different levels of hydrogen reactions decrease and the profiles shift to the downstream
addition are shown in Fig. 7. It is noted that the mole fractions side with 20% F-H2 addition due to the dilution and thermal
of OH radical decrease as H2 or F-H2 is incrementally blended. effects of H2.
This behavior is more distinct in the F-H2 doped flames. The Fig. 8(a) gives the mole fraction profiles of HCO radical with
dilution and thermal effects of hydrogen addition decrease 0%, 5%, 10%, 20% H2 and 5%, 10%, 20% F-H2 additions. It is

Please cite this article in press as: Luo M, Liu D, On the effects of hydrogen addition in premixed formaldehyde flames, International
Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.07.046
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Fig. 8 e (a) Mole fractions of HCO radical with different Fig. 9 e (a) Mole fractions of HO2 radical with different
levels of hydrogen addition, (b) Rate of production of HCO levels of hydrogen addition, (b) Rate of production of HO2
radical with 0%, 20% H2 and 20% F-H2 additions. radical with 0%, 20% H2 and 20% F-H2 additions.

noted that the addition of normal hydrogen makes the mole rate of HCO þ H ¼ CO þ H2 increases slightly and impels the
fractions of HCO diminish and the profiles move toward the decomposition of HCO.
upstream side. When F-H2 substitutes normal H2 correspond- The mole fraction profiles of HO2 with different levels of
ingly, the peak value of HCO mole fraction reduces sharply and hydrogen addition are plotted in Fig. 9(a). HO2 concentrations
the profiles shift to the downstream side due to the dilution and decrease with the replacement of formaldehyde by hydrogen.
thermal effects of hydrogen addition. The difference between The influences of fictitious H2 on HO2 are similar with those of
the HCO mole fraction profiles of 20% H2 and 20% F-H2 addi- H2 addition. The chemical effects of H2 addition promote the
tions reveals that the H2 chemical effects facilitate the forma- formation of HO2 radical. The hydrogen dilution and thermal
tion of HCO. Furthermore, the dilution and thermal effects of effects which reduce the concentrations of HO2 are more
hydrogen addition are more significant than the chemical dominant than the H2 chemical effects. Fig. 9(b) presents the
effects of H2 addition. The overall mole fractions of HCO rate of production of HO2 with 0%, 20% H2 and 20% F-H2 ad-
decrease. Fig. 8(b) presents the rate of production of HCO ditions. The primary reaction responsible for HO2 formation is
radical with 0%, 20% H2 and 20% F-H2 additions. The main re- HCO þ O2 ¼ CO þ HO2. The major reactions for HO2 con-
actions responsible for HCO formations are sumptions are HO2 þ HO2 ¼ H2O2 þ O2, HO2 þ H ¼ OH þ OH and
CH2O þ H ¼ HCO þ H2, CH2O þ OH ¼ HCO þ H2O. The dominant H2 þ O2 ¼ H þ HO2. It can be seen clearly that the rate of
reactions for HCO consumptions are HCO þ O2 ¼ CO þ HO2, HO2 þ H ¼ OH þ OH increases with 20% H2 addition. It accel-
HCO þ M ¼ H þ CO þ M and HCO þ H ¼ CO þ H2. With the erates the consumption of HO2 while other reaction rates of
addition of 20% H2, the profiles of HCO þ O2 ¼ CO þ HO2 and HO2 decrease. Moreover, the profiles of these reaction rates of
CH2O þ OH ¼ HCO þ H2O shift to the upstream side, and the HO2 descend largely and move toward the downstream side

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Fig. 11 e Mole fractions of CO2 with different levels of


hydrogen addition.

responsible for the descents of peak value of CO mole fractions


in Fig. 10(a). The rate of HCO þ H ¼ CO þ H2 increases slightly
with 20% H2 addition while other reaction rates reduce more
significantly. It may explain the discrepancy of mole fraction
profiles of CO between 0% H2 and 20% H2 additions in Fig. 10(a).
Fig. 11 gives the mole fraction profiles of CO2 with 0%, 5%,
10%, 20% H2 and 5%, 10%, 20% F-H2 additions. It can be seen
that the addition of real hydrogen can reduce the concentra-
tions of CO2, and the influences of F-H2 addition on CO2 are
similar with those of H2 addition. Comparison of the differ-
ences among CO2 mole fraction profiles with 0%, 20% H2 and
20% F-H2 additions reveals that the dilution and thermal ef-
fects of hydrogen addition can reduce the CO2 mole fractions,
Fig. 10 e (a) Mole fractions of CO with different levels of whereas the chemical effects which have the same influence
hydrogen addition, (b) Rate of production of CO with 0%, on CO2 are dominant.
20% H2 and 20% F-H2 additions.

Conclusion

with 20% F-H2 addition due to the dilution and thermal effects The influences of hydrogen addition on laminar premixed
of hydrogen addition. fuel-rich formaldehyde flames at atmospheric pressure are
CO and CO2 are the major species of formaldehyde flames studied by the detailed kinetic analysis. The chemical effects
which can be seen from Fig. 3. The mole fraction profiles and the of hydrogen addition on flame structures, mole fraction pro-
rate production of CO with different levels of hydrogen addition files of major species and free radicals are distinguished
are demonstrated in Fig. 10. When the real hydrogen is added, clearly from the dilution and thermal effects. The main con-
the peak mole fractions of CO diminish due to the combined sequences are listed as follows:
effects. Meanwhile, with the replacement of formaldehyde by F-
H2, the CO mole fractions decrease sharply and the profiles shift (a) The chemical effects of hydrogen promote the oxidation
to the downstream side due to the hydrogen dilution and ther- of formaldehyde and make the mole fraction profiles of
mal effects. The chemical effects of hydrogen promote the for- formaldehyde move toward the upstream side.
mation of CO but are not dominant. Fig. 10(b) exhibits the rate of (b) The mole fractions of H radical increase due to the
production of CO with 0%, 20% H2 and 20% F-H2 additions. chemical effects of hydrogen addition. Whereas, the OH
Obviously, the main reactions for CO formations are mole fractions reduce with the normal hydrogen addi-
HCO þ M ¼ H þ CO þ M, HCO þ O2 ¼ CO þ HO2, HCO þ H ¼ CO þ H2 tion. It is possible that the reaction OH þ H2¼H þ H2O
and HCO þ OH ¼ CO þ H2O. The dominant reaction responsible account for the variations of H and OH radicals.
for consumption of CO is CO þ OH ¼ CO2 þ H. The consumption (c) The chemical effects of hydrogen addition facilitate the
reaction rate of CO lags behind its production rate, which is production of O, OH, HCO and HO2 radicals.

Please cite this article in press as: Luo M, Liu D, On the effects of hydrogen addition in premixed formaldehyde flames, International
Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.07.046
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Nevertheless, the hydrogen dilution and thermal effects [13] Li J, Zhao ZW, Kazakov A, Chaos M, Dryer FL, Scire Jr JJ. A
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This work was supported by the Jiangsu Provincial Natural Energy 2008;33:823e31.
Science Foundation of China (BK20140034, BK20130758), the [19] Ma FH, Wang Y, Liu HQ, Li Y, Wang JJ, Zhao SL. Experimental
National Natural Science Foundation of China (51576100, study on thermal efficiency and emission characteristics of a
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Please cite this article in press as: Luo M, Liu D, On the effects of hydrogen addition in premixed formaldehyde flames, International
Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.07.046