Subscriber access provided by UNIVERSITY OF TOLEDO LIBRARIES
Article
Laminar flame characteristics and kinetic modeling study of ETBE compared with MTBE, ethanol, iso-octane and gasoline Jinfeng Ku, Erjiang Hu, Geyuan Yin, Chanchan Li, Xin Lu, and Zuohua Huang Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.7b03636 • Publication Date (Web): 06 Feb 2018 Downloaded from http://pubs.acs.org on February 12, 2018
Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
Energy & Fuels is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.
Page 1 of 40 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
1
Laminar flame characteristics and kinetic modeling study of ETBE
2
compared with MTBE, ethanol, iso-octane and gasoline
3
Jinfeng Ku1, Erjiang Hu*1, Geyuan Yin1, Chanchan Li2, Xin Lu1, Zuohua Huang1
4
1
5
University, Xi’an, People’s Republic of China
6
2
7
Republic of China
State key Laboratory of Muliphase Flow in Power Engineering, Xi’an Jiaotong Chinesisch-Deutsches Hochschulkolleg, Tongji University, Shanghai, People’s
8 9
ABSTRACT
10
Laminar flame speeds of ethyl tertiary butyl ether (ETBE) were measured in a
11
constant volume bomb at different initial temperatures (298 K, 373 K, 453 K) and
12
pressures (1 atm, 3 atm, 5 atm). The laminar flame experiments were also conducted
13
for methyl tertiary butyl ether (MTBE), ethanol, iso-octane and gasoline for the
14
comparison of laminar flame speeds and Markstein lengths. Experimental results
15
show that laminar flame speeds peak at the equivalence ratio of 1.1 for all tested fuels.
16
Ethanol has the fastest laminar flame speed and the other fuels have similar flame
17
speeds, indicating replacing MTBE with ETBE in gasoline will not influence the
18
laminar flame speed of present gasoline. CRECK mechanism and Curran mechanism
19
were validated by experimental results of ETBE and neither could predict laminar
20
flame speeds well. Curran mechanism was optimized by updating the underlying
21
mechanism, and the Modified Curran mechanism has better prediction performance
22
on the laminar flame speed. Sensitivity analyses were also provided to interpret the
23
differences of laminar flame speeds and the major reason of better prediction
24
performance for Modified Curran mechanism. The result of Markstein length shows
25
that gasoline has the smallest Markstein lengths and its flame front is the most
26
unstable. The Markstein lengths of ETBE and iso-octane differ little and are the
27
largest under 1.2.
28 29
1. INTRODUCTION
30
Nowadays,alternative fuels have attracted increasingly considerable attention due
31
to their importance in reducing the reliance on fossil fuels,achieving lower emission
32
and limiting the greenhouse gases in the atmosphere. Many types of oxygenated
33
alternative fuels, such as alcohols, acyclic ethers, cyclic ethers and esters, can be
34
obtained through a wide range of processes involving fermentation or catalytic
ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
35
reactions.1 To achieve higher thermal efficiency in spark ignition engines, the engine
36
downsizing with a turbocharger is getting common, which causes high pressure
37
combustion. Under such conditions, the addition of a good octane number enhancer is
38
required in order to avoid the occurrence of engine knock. Before 1970, teraethyllead
39
was added into gasoline to improve the octane number, thereby allowing higher
40
compression ratio so as to improve the thermal efficiency. But from 1970 teraethylead
41
began to be forbidden because of concerns over air and soil lead levels and the
42
accumulative neurotoxicity of lead. In 1979, MTBE (methyl tertiary butyl ether,
43
RON=118) is widely used as an oxygenate additive to enhance the octane number and
44
oxygen content, improve combustion and reduce engine knock. However, MTBE can
45
pollute the groundwater due to its high water solubility and make people sick,
46
vomiting and dizziness after contacting with it.2, 3 Since 2004, the United States and
47
some European countries began to reduce or ban the use of MTBE. But, in some Asia
48
countries, including China, there are still no restrictions about MTBE as a fuel
49
additive. The test results show that there are about 4-10% MTBE (%Wt) in gasoline
50
of China. Similarly with MTBE, ETBE (ethyl tertiary butyl ether, RON=117) also has
51
high octane number and good performance as gasoline additive but without the
52
drawbacks of MTBE.
53
Besides the method of liquid phase synthesis from ethanol and isobutene, ETBE
54
can also be synthesized from tert-butyl alcohol (TBA) and ethanol.4 ETBE can also be
55
considered as biofuel, since it can be produced from 47% bioethanol and 53%
56
isobutene. After many years of scientific and technological research, Kabuskiki
57
Kaisha IBF developed a competitive bioETBE mixture manufacturing technology,
58
which can produce ETBE from biomass completely. Table 1 gives the properties of
59
ETBE, MTBE, ethanol, iso-octane and gasoline.1, 5 ETBE, MTBE and ethanol have
60
higher octane number. The lower heating value (LHV) of ETBE (26.93 MJ/L) and
61
MTBE (26.04 MJ/L) is much closer to gasoline than that of ethanol (21.2 MJ/L), so
62
the power reduction of ETBE and MTBE is much less than that of ethanol when they
63
are added into gasoline. Reid vapor pressure (RVP) has an important impact on the
64
evaporative emissions of hydrocarbons in the gasoline supply system, so regulations
65
around the world have imposed strict restrictions on it.6 Despite the fact that ethanol
66
has the lowest RVP because of the strong intermolecular hydrogen boding interactions
67
between ethanol molecules, these additives (ETBE, MTBE, ethanol) and gasoline
68
mixtures’ RVP presents a completely opposite result. According to the research of
ACS Paragon Plus Environment
Page 2 of 40
Page 3 of 40 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
69
Silva3 and Rodrí guez-Antón6, the oxygenates (ETBE, ethanol), with exception of
70
ETBE, increase the RVP of gasoline. The positive deviation from Raoult’s Law with
71
the addition of ethanol occurs because the intermolecular interactions between ethanol
72
and hydrocarbon molecules are weaker than they are in two pure liquids and also due
73
to the formation of azeotrope that reduces the boiling point temperature and increases
74
the vapor pressure of the mixture.6 Thus, ETBE has the advantages of mixtures RVP
75
compared to MTBE and ethanol when they are added into gasoline. Additionally,
76
ethanol will absorb moisture from the atmosphere, thus causing the phase separation
77
of gasoline. In summary, with the advantages of low water solubility, being
78
biodegradable, producing from biomass, low harmfulness to people’s health, high
79
octane number, higher LHV, low mixture RVP and water absorbability, ETBE is a
80
better gasoline additive compared to MTBE and ethanol.
81
Generally, ETBE is blended with other fuels to combustion, so the relevant study of
82
ETBE is particularly important. At present, the research of ETBE is mainly focused
83
on production methods and processes, engine performance and chemical kinetics. In
84
2006, Malça and Freire7 found that the use of bioethanol as raw materials can increase
85
the yield of ETBE and bioETBE. Menezes et al.8 studied the optimization of the
86
ETBE production process and found that azeotropic mixtures of ETBE and ethanol
87
during the production process have a good prospect of application due to its higher
88
octane number, lower volatility and lower production cost. Besides, in the process of
89
synthesis of ETBE, an equivalent molar ratio of raw material (ethanol/isobutene)
90
should be used to reduce the production of azeotropic mixtures and increase ETBE
91
yield. However, under such conditions, the by-products of TBA and SBA (sec-butyl
92
alcohol) will be produced and the activity of catalysts will be reduced greatly. In
93
addition to being synthesized from chemical products (ethanol, isobutene, TBA)
94
completely or partly, ETBE can also be produced from biomass completely according
95
to the research results of Kabuskiki Kaisha IBF. With the development of Production
96
methods and processes, the cost of ETBE decreases and yield increases gradually,
97
which makes the use of ETBE as gasoline additive increasingly wide over the
98
developed countries. Despite the fact that the main gasoline additive is MTBE in
99
China due to the higher cost and lower yield of ETBE, ETBE will also be used as
100
additive widely with the upgrade of domestic production processes and manufacturing
101
equipment.
102
For engine performance research, ETBE is mainly used to study its reduction
ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
103
effects on engine emissions. According to the research of Croezen et al.,9 replacing
104
MTBE with ETBE in fuel will bring a reduction of greenhouse gas emissions by
105
1.94kg CO2/GJ fuels. And compared with other oxygenated additives, ETBE does not
106
cause photochemical smog.10 In 2010, Westphal et al.11 studied the toxicity and BTEX
107
(Benzene, Toluene, Ethylbenzene, Xylene) emissions of gasoline engine with the
108
addition of ETBE. The result indicated that the addition of ETBE to gasoline can
109
improve combustion and decrease emission of BTEX. As for diesel engine, Górski et
110
al.12 discovered that the diesel-ETBE blends can reduce emission of particulates and
111
soot by 36% and 70%, respectively. Besides the advantages of decreasing emission,
112
ETBE can also improve the spray characteristics and keep the change of physical and
113
chemical properties of diesel in acceptable range at the meanwhile. Also, compared
114
with ethanol, ETBE is more suitable to be added into diesel in terms of solubility and
115
stability. From the research above, we can learn that the addition of ETBE into
116
common fuels can reduce the emission of CO2, HC, NOX, aromatics, PM and soot and
117
improve spray characteristics, solubility and stability, which provides guidance and
118
basis for its wide application in actual fuels.
119
For chemical kinetics research of ETBE, many efforts have also been made by
120
some researchers over the last decades. In 1968, Daly and Wentrup13 found that ETBE
121
will decompose into ethanol and isobutene at the temperature range of 706-757 K and
122
put forward the four-center unimolecular decomposition mechanism. Dunphy and
123
Simmie14 measured the ignition delay times of ETBE in a shock tube over the high
124
temperature range from 1160 K to 1830 K and the pressure of 3.5 bar. They came to a
125
conclusion that the isobutene controls the ignition process and ETBE and MTBE have
126
similar ignition behaviors. A few years later, Cathonnet et al.15 carried out ETBE
127
oxidation experiments on a jet-stirred reactor (JSR) between 800 and 1150 K, at 10
128
bar and a large range of equivalence ratio (0.5-2). Meanwhile, El Kadi and Baronnet16
129
utilized a static reactor to study the oxidation of ETBE at 550-800 K and concluded
130
that the formation of isobutene could make an explanation for its antiknock effect.
131
Experiments covering the low and high temperature oxidation regimes were
132
conducted in a JSR by Dagaut et al.17 to demonstrate the inhibitory effects of ETBE
133
on n-heptane oxidation. Their findings indicated that ETBE strongly influences the
134
n-heptane oxidation rate only below 800 K and the presence of ETBE reduces the
135
emission of butadiene but increases the emission of formaldehyde and acetaldehyde
136
moderately. Experimental data attained by Goldaniga et al.18 in a JSR at a residence
ACS Paragon Plus Environment
Page 4 of 40
Page 5 of 40 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
137
time of 0.5 s and pressure of 10 bar were used to validate a semi-detailed oxidation
138
mechanism of ether oxidation and combustion, and the good agreement was observed
139
between model prediction and experimental data. In 2000, Glaude et al.19 developed a
140
kinetic mechanism automatically generated by EXGAS and modeled the JSR
141
experimental results of Dagaut et al.17 The discrepancy between modeling and the
142
experimental values was very small. Over the next few years, little work had been
143
done on chemical reaction kinetics of ETBE until 2007. In this year, Ogura et al.20
144
constructed an ETBE sub-mechanism from 2, 2-dimethyl-pentane and its derivatives
145
by replacing the CH2 group for an O atom in those species by KUCRS.21 Yasunaga et
146
al.22 from Currran’s research group studied the high temperature pyrolysis of ETBE
147
behind reflected shock waves coupled with single-pulse method and UV absorption
148
spectroscopy in the temperature range of 1000-1500 K and pressure of 1-9 bar and put
149
forward a 170-reaction mechanism. Almost at the same year, Yahyaoui et al.23
150
measured a series of ignition delay times of ETBE over a wide range of temperature
151
(1280-1750 K), pressure (2-10 bar) and equivalence ratio (0.25-1.5) and laminar
152
flame speeds of ETBE at room temperature and atmospheric pressure. In this study,
153
Yahyaoui et al.23 also compared the experimental ignition delay time and laminar
154
flame speed with the computed values calculated by a detailed chemical kinetic
155
reaction mechanism and analyzed the main pathways and sensitivity. Then Gong24
156
measured the laminar flame speeds of the blending of ETBE, TBA and ethanol at
157
different temperature (373 K, 423 K, 473 K) and different pressure (1 bar, 2.5 bar, 5
158
bar) and analyzed the flame instability of the blending. A high temperature chemical
159
kinetic mechanism of ETBE, MTBE, EME and DEE consisting of 215 species and
160
1051 reactions constructed by Yasunaga25 was validated by a series of shock tube
161
experimental data. Recently, Liu26 determined the oxidation characteristic and
162
products of ETBE using ARC (accelerating rate calorimetry) and considered that the
163
oxidation reaction process of ETBE with oxygen occurred through absorption of
164
oxygen by ETBE, followed by thermal decomposition and oxidation reaction. Liu
165
also found that ETBE is easy to absorb oxygen in the air and organic peroxides will
166
accelerate the oxidation of ETBE once generated. More recently, extinction limit
167
measurements for ethers were carried out by Hashimoto et al.27 using a counterflow
168
burner. According to the experimental results, ETBE, DIPE and TAME almost have
169
the same extinction strain rate and the extinction limit of ethers decreases with the
170
increase of carbon atoms. As has been said, many studies of ETBE available in the
ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
171
literature about chemical kinetics are mainly focus on the ignition delay times, mole
172
fractions of radicals and the developments of chemical kinetic reaction mechanism.
173
However, laminar flame speeds of ETBE are rare except the only experimental data23
174
at room temperature and atmosphere pressure. As we know, laminar flame speed is
175
also an important parameter of hydrocarbons and can be used to validate the chemical
176
kinetic mechanism, develop gasoline surrogate mechanism and provide the guidance
177
for combustor design of engine and numerical simulation of turbulent combustion.
178
Due to various advantages mentioned above of ETBE and the importance of
179
laminar flame speeds of ETBE for mechanism validation and development and
180
engineering application, propagating spherical flame method was applied to attain the
181
laminar flame speeds of ETBE at different temperatures and pressures in a constant
182
volume bomb in this study. The laminar flame speeds of MTBE, ethanol, iso-octane
183
and gasoline were also measured at certain conditions for the purpose of comparison
184
with ETBE. Additionally, two different chemical kinetic mechanisms of ETBE were
185
validated with the experimental results. Finally, the discrepancy of laminar flame
186
speeds of the tested fuels was explained by sensitivity analysis and radical
187
concentration analysis.
188
2. EXPERIMENTAL SETUP AND DATA PROCESSING
189
2.1. Experimental Setup
190
In this study, the laminar flame speeds were measured using the spherically
191
propagating flame in a constant volume vessel. The detailed description of the
192
apparatus has been introduced in literatures28, 29 and here only brief introduction is
193
provided. The combustion chamber is cylindrical with inner diameter of 180 mm and
194
volume of 5.8 L. Two glass windows for optical purpose with visible diameter of
195
80mm are mounted at both ends of the cylinder. The heating-tape surrounding outside
196
of the cylinder was used to heat the chamber and the temperature in the chamber was
197
monitored by a K-type thermocouple with the accuracy of ±2 K. High precision
198
pressure transmitter with relative pressure deviation of ±0.075% was used to prepare
199
the mixtures. The liquid fuel was injected into the chamber by micro syringes. The
200
mixtures are kept at least 3 minutes to guarantee full evaporation and high mixing
201
homogeneity before the mixtures was ignited with the electrodes located in the
202
chamber center. The spherical expanding flame was recorded by a high-speed camera
203
Phantom V611 at 10000 fps.
204
ETBE, MTBE, ethanol and iso-octane have the high purity of over 99%. The tests
ACS Paragon Plus Environment
Page 6 of 40
Page 7 of 40 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
205
of ETBE were performed with initial temperatures of 298 K, 373 K and 453 K and
206
initial pressure of 1atm, 3atm and 5atm. Under each temperature and pressure, the
207
equivalence ratios cover the range of 0.7-1.6. For comparison, the tests of MTBE,
208
ethanol, iso-octane and gasoline were conducted at certain conditions shown in Table
209
2.
210
2.2. Data Processing
211
The flame radius history Rf = Rf (t) could be acquired from schlieren pictures
212
recorded by the camera. Then the stretched flame propagation speed can be deduced
213
from the equation: Sb
dR f
(1)
dt
214
after getting the Sb , the unstreched flame propagation speed was extrapolated
215
employing the nonlinear expression of Frankel and Chen30, 31: Sb Sb0
2Sb0 Lb Rf
(2)
216
where Lb is Markstein length of the burned mixture. According to the mass
217
conservation across the flame front, the laminar burning velocities could be calculated
218
from the following equation: S u0 S b0
219
b u
(3)
where ρb and ρu are the density of the burned and unburned mixtures, respectively.
220
Various factors, such as mixture preparation, ignition, buoyancy, instability,
221
confinement, radiation, nonlinear stretch behavior, and extrapolation, will undermine
222
the accuracy of the laminar flame speeds obtained from outwardly spherical
223
propagating flames.32 In order to avoid the effect of ignition,33 space confinement34
224
and pressure increase during late flame propagation,35 the flame radius ranging from
225
9mm to 25mm were picked for the image processing. The uncertainty caused by
226
radiation could be modified with an expression of Yu et al.36 : S u0, RCFS S u0, Exp 0.82S u ,Exp (
S u0,Exp S0
) 1.14 (
Tu pu 0.3 )( ) T0 p0
(4)
227
where S0=1 cm/s, T0=298 K, and p0=0.1 MPa. S0u,RCFS and S0u,Exp are the
228
radiation-corrected laminar flame speed and the experimental values. In 1988, Moffat
229
et al.37 put forward a method of describing the uncertainties in an engineering
230
experiment considering both system errors and random errors, which is widely used in
ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
231
Page 8 of 40
evaluating uncertainty of laminar flame speed. The detail expression of the method is:
S ( BS ) 2 (t M 1.95 S ) 2 0 u
0 u
(5)
0 u
232
where tM-1.95 is the student’s t distribution at 95% confidence interval and the degrees
233
of M-1 and M is the experimental repetition times; S 0 means the standard deviation u
234
of S u0 ; BS 0 represents the total uncertainty of the measurement method, which can u
235
be acquired from:
BS 0 u
n
(ui i 1
Su0 ( xi ) 2 ) xi
(6)
236
where xi and ui are the influence factors of S u0 and the deviation of every factor xi,
237
respectively. Thus, the experimental uncertainty of this study was at the range of
238
about 1-4cm/s according to the above analysis.
239
2.3. Computational Methods
240
Laminar flame speed calculations were carried out using PREMIX code38 of
241
CHEMKIN-PRO package39. In present work, CRECK mechanism40 and Curran
242
mechanism25, 41 were used to simulate the laminar flame speeds of ETBE. CRECK
243
mechanism (Version 1412, PRF+PAH+Alcohols+Ethers) consists of 225 species and
244
7645 reactions, of which the ethers sub-mechanism is derived from Goldaniga18.
245
Curran mechanism is made up of 215 species and 1051 reactions. Besides, the
246
underlying mechanism of Curran mechanism was updated with AramcoMech2.042-48
247
and a modified mechanism, called Modified Curran mechanism, was developed. The
248
Modified Curran mechanism is given in the Supporting Information. For comparative
249
purpose, the ethanol mechanism of Leplat et al.,49 consisting of 36 species and 252
250
reactions which has been comprehensively validated, was used to calculate the
251
experimental results of ethanol. Similarly, a mechanism of iso-octane of Chaos et al.50
252
involving 107 species and 723 reactions which has been validated against a set of
253
experimental data, was used to simulate the experimental results of iso-octane. During
254
the simulation, Soret effect and mixture-averaged transport were considered.
255
3. RESULTS AND DIUCUSSION
256
3.1. Apparatus Validation
257
Figure 1 shows the laminar flame speed of ETBE at 1 atm and 298K, compared
258
with experimental data from Yahyaoui23 under the same experimental condition. The
259
two sets of data show good agreement with each other, which prove the good
260
performance of the experimental apparatus. Similarly, Figure 2 compares the laminar
ACS Paragon Plus Environment
Page 9 of 40 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
261
flame speed of ethanol at 1 atm and 373 K published by different research groups51-54.
262
It can be seen that the present data are very close to the data of Konnov,51 Broustail52
263
and Bradley,53 which can also verify the accuracy of the experimental data in this
264
study. All the measured laminar flame speed values and corresponding errors at
265
various temperatures and pressures are given in the Appendix.
266
3.2. Laminar Flame Speeds of ETBE
267
Generally, there is a close relationship between turbulent flame speed and laminar
268
flame speed. The turbulent flame speed can provide guidance for the combustion
269
modeling and engine design, so the laminar flame speed is very important in practical
270
application. The empirical formula of laminar flame speed by fitting the existing
271
experimental data is obviously vital for application. Because the laminar flame speed
272
varies with equivalence ratio, temperature and pressure, the following equation is
273
used to fit:
Su0 Su0,ref (
Tu pu ) ( ) Tu ,ref pu ,ref
(7)
274
where the Tu ,ref =298 K, pu ,ref =1 atm and the reference laminar flame speed Su0,ref ,
275
temperature dependence exponents β and pressure dependence exponents θ are regard
276
as a third order polynomial of equivalence ratio as following:
Su0,ref 0 1 2 2 3 3
(8)
0 1 2 2 3 3
(9)
0 1 2 2 3 3
(10)
277
During the fitting, the unconstrained minimization function fminunc in MATLAB
278
was employed to solve the twelve coefficients above and the detail results were
279
shown in Table 3.
280
Figure 3 shows the measured and fitting laminar flame speed of ETBE at different
281
temperatures and different pressures. The maximum value of laminar flame speed
282
appears near the equivalence ratio of 1.1 for each experimental condition. As is shown
283
in Figure 3(a), the laminar flame speed increases monotonically with the increase of
284
temperature, which is mainly due to the increase of adiabatic flame temperature with
285
initial temperature increasing. Additionally, the equivalence ratio of maximum
286
laminar flame speed slightly shifts to the direction of rich mixture with the increasing
287
temperature. And in Figure 3(b), we can see opposite tendency as the pressure
ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
288
increases compared with the result of various temperatures. Main reason behind this
289
phenomenon is the competition between the chain branching reactions and chain
290
termination reactions. As for the lines in Figure 3, they are the fitted results with Eq.(7)
291
using the fminunc function of MATLAB. The fitted results have good agreement with
292
the experimental results.
293
3.3.
Mechanism Validation and Optimization
294
In this part, the laminar flame speeds of ETBE were simulated using the latest
295
ethers mechanisms (Curran mechanism and CRECK mechanism). Figure 4 gives the
296
comparison between the measured and simulated laminar flame speeds at different
297
temperatures and pressures. From this figure, we can see that both Curran and
298
CRECK mechanism do not give satisfactory prediction overall and even all the peak
299
values of Curran mechanism appear at the equivalence ratio of 1.2. Only when the
300
equivalence ratio is larger than 1.3, the simulated results deviate from experimental
301
results relatively slightly. When the equivalence ratio is smaller than 1.3, the
302
simulated results of Curran mechanism are larger than the measured results and the
303
simulated results of CRECK mechanism are smaller than the corresponding measured
304
results. Additionally, with the increase of temperature and pressure, the deviation
305
between simulated results and experimental data also increase. Therefore, the
306
prediction performance of Curran and CRECK mechanisms does not meet the
307
requirements of understanding the chemical kinetics deeply.
308
To improve the prediction performance of Curran mechanism and understand the
309
chemical kinetics of ETBE, some refinements were done for the Curran mechanism.
310
As mentioned in section 2.3, the underlying mechanism of Curran mechanism was
311
updated and a mechanism called Modified Curran mechanism was developed. The
312
Modified Curran mechanism was employed to simulate the experimental results, as
313
shown in Figure 5. Compared to the Curran mechanism, the Modified Curran
314
mechanism gives good prediction for such experimental conditions globally. Firstly,
315
the maximum laminar flame speed lies at the equivalence ratio of 1.1, which is
316
consistent with the experimental results. Secondly, the prediction performance
317
improves greatly for lean mixtures and stoichiometric mixture. Finally, the deviation
318
from experimental data becomes smaller than that of Curran mechanism with the
319
increase of temperature and pressure.
320
The ignition delay time was also validated for the Modified Curran mechanism.
321
Figure 6 shows the comparison of measured and simulated ignition delay time of
ACS Paragon Plus Environment
Page 10 of 40
Page 11 of 40 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
322
ETBE. The agreement between Modified Curran mechanism and measured data is
323
more satisfactory than that of Curran mechanism, especially for the conditions of high
324
temperature. But when the temperature is lower than 1400K, Modified Curran
325
mechanism still over-predicts the experimental data slightly, which means there are
326
still some works to do on the Modified Curran mechanism.
327
To clearly understand why the Modified Curran mechanism behaves better on
328
predicting laminar flame speed than Curran and CRECK mechanisms, the normalized
329
sensitivity analysis for ETBE was carried out using these three mechanisms
330
respectively, as shown in Figure 7. We can see that the three mechanisms’ sensitivity
331
analysis differs greatly from each other. Firstly, the three most important reactions
332
promoting laminar flame speed are: R1, O2+HO+OH, R2, CO+OHCO2+H,
333
and R3, HCO+MH+CO+M for the three mechanisms and the two most important
334
reactions inhibiting the laminar flame speed are: R4, H+OH+MH2O+M and R5,
335
H+O2(+M)HO2(+M). But the reaction rate constants of the five reactions are
336
different from each other, as the underlying mechanism was different, which may
337
account for the differences of laminar flame speed. The Curran and CRECK
338
mechanism were developed in 2011 and 2014, respectively and nobody updated them
339
until now with the quick development of chemical reaction kinetics. So the authors
340
update
341
AramcoMech2.0 mechanism which includes the sub-mechanisms of C1-C4 based
342
hydrocarbon and oxygenated fuels. Secondly, the reactions involving IC4H8, IC4H7
343
and IC4H9 appear to be sensitive for Curran mechanism, but such phenomenon does
344
not happen to the other two mechanisms. We can infer that the production of IC4H8
345
dominates the reaction of the system partly for Curran mechanism, but the system
346
reaction is not restricted by IC4H8 broadly for Modified Curran and CRECK
347
mechanisms, which probably means the three mechanisms may differ in the IC4H8
348
sub-mechanism thus causing different prediction performance. Thus the explanation
349
will be developed around the above two main differences with reaction pathway
350
analysis, comparison of reaction rates and laminar flame speed calculations.
the
Curran
mechanism’s
underlying
mechanism
with
the
latest
351
First of all, the reaction pathway analysis of IC4H8 coupling with reaction rates was
352
conducted to illustrate the differences. As shown in Figure 8, the reaction pathway of
353
IC4H8 differs greatly from each mechanism. In order to explain the differences, the
354
comparison of mole fraction of OH, H and O radicals (Figure 9) and rate constants for
355
different consumption pathways of IC4H8 (Figure 10) between Curran, Modified
ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
356
Page 12 of 40
Curran and CRECK mechanism was carried out.
357
There are six kinds of main consumption pathways of IC4H8 in the three
358
mechanisms. And with the exception of reaction pathway of IC4H8+HIC4H7+H2,
359
the other five pathways differs greatly among the three mechanisms. From the Figure
360
R10(a), we can find the rate constant of IC4H8+HIC4H9 in Modified Curran
361
mechanism is far less than that in Curran and CRECK mechanism and thus there
362
almost no IC4H8 reacts with H radical to produce IC4H9 in Modified Curran
363
mechanism. As the AramcoMech2.0 mechanism includes the latest detailed
364
sub-mechanism of IC4H8, so the IC4H8 sun-mechanism is more accurate and
365
comprehensive in Modified Curran mechanism than the other two mechanisms. Thus
366
we may conclude that the rate constants of IC4H8+HIC4H9 are too high in Curran
367
and
368
IC4H8+OHIC4H7+H2O, the consumption branching ratio in Modified Curran
369
mechanism is higher than that in the other two mechanism. Because of the similarities
370
in OH radical mole fractions and rate constants in three mechanisms, we can’t explain
371
the branching ratio difference by rate constants. But as some IC4H8 is consumed by
372
the reaction of IC4H8+HIC4H9 in Curran and CRECK mechanisms, the
373
consumption percentages of IC4H8+OHIC4H7+H2O are lower naturally. Not like
374
Curran and Modified Curran mechanisms, the pathway of IC4H8+HC3H6+CH3 is
375
absence in CRECK mechanism, which means the sub-mechanism of IC4H8 in
376
CRECK is incomplete. From Figure 9, we can find mole fractions of O radical are
377
close in the three mechanisms, so the consumption percentages of IC4H8 are
378
determined by the rate constants of IC4H8+OIC4H7+OH. Since the rate constants
379
of IC4H8+OIC4H7+OH in Curran mechanism is far less than that in Modified
380
Curran and CRECK mechanism, IC4H8 is hardly consumed by O radicals in Curran
381
mechanism, which means there are some problems in the rate constants of
382
IC4H8+OIC4H7+OH in Curran mechanism. Generally the H atoms of IC4H8 at two
383
locations can be removed by OH radical, but there exits only one kind of
384
H-abstraction reaction by OH radical in Curran and CRECK mechanisms, which
385
means the sub-mechanisms of IC4H8 of Curran and CRECK mechanisms are
386
incomplete.
CRECK
mechanisms.
As
for
the
IC4H8
consumption
pathway
of
387
Like IC4H8, the comparison of rate constants for different consumption pathways
388
of IC4H7 (Figure 11) between Curran, Modified Curran and CRECK mechanism was
389
also carried out to explain the reaction pathway differences of IC4H7. From Figure 8,
ACS Paragon Plus Environment
Page 13 of 40 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
390
we can find that IC4H7 is mainly consumed by reaction of IC4H7AC3H4+CH3
391
(59.53%) and the other IC4H7 is consumed by reaction of IC4H7+HIC4H8 in
392
Modified Curran mechanism (34.34%). On the contrary, IC4H7 is mainly consumed
393
by reaction of IC4H7+HIC4H8 (64.59%) in Curran mechanism. It can be find that
394
the rate constants of IC4H7+HIC4H8 in Curran and Modified Curran mechanisms
395
are close to each other during the whole reaction temperature range from Figure 11(a),
396
which can’t account for the higher branching ratio of IC4H7+HIC4H8 in Curran
397
mechanism. Also we can find the rate constants of IC4H7AC3H4+CH3 in Modified
398
Curran mechanism is at least 3 times higher than that in Curran mechanism, which
399
can account for the higher branching ratio of IC4H7+AC3H4+CH3 in Modified
400
Curran mechanism. After replacing the rate constants in Curran mechanism with that
401
of
402
IC4H7+HIC4H8 and IC4H7AC3H4+CH3 are changed to 34.94% and 62.03%
403
respectively, which is very close to that of Modified Curran mechanism. Thereby, we
404
can draw a conclusion that the rate constant of IC4H7AC3H4+CH3 in Curran
405
mechanism is too low. As for CRECK mechanism, another reaction pathway of
406
IC4H7+OCH2CCH3+CH3 appears and its branching ratio is the highest among the
407
three reaction pathways. But there doesn’t include such reaction pathway of
408
IC4H7+OCH2CCH3+CH3 in Modified Curran mechanism, which perhaps mean
409
this pathway isn’t reasonable in CRECK mechanism.
Modified
Curran
mechanism,
we
can
find
the
branching
ratio
of
410
Secondly, the rate constants comparison of the three most important reactions
411
promoting laminar flame speed (R1-R3) and two most important reactions inhibiting
412
laminar flame speed (R4-R5) was also conducted in order to explain the differences of
413
Curran, Modified Curran and CRECK mechanisms. As the hydrogen oxidation
414
mechanism is a central part of many combustion systems, the precision of the rate
415
constants are of great importance (R1, R4, R5). The correlative reactions of CO are
416
also of great importance for hydrocarbon fuels (R2, R3). Figure 12 gives out the
417
detailed comparison of rate constants of R1-R5. Rate constants of many gas-phase
418
elementary reactions’, which have been measured by several groups and at a given
419
temperature, typically have an uncertainty of 10-30%, even for the best know
420
reactions.55 The chain-branching reaction R1: H+O2OH+H is the best known
421
elementary reaction and even considering an uncertainty of 10% on its rate constants,
422
it can cause an accuracy of 30% on the prediction of mechanisms56. From Figure
423
12(a), we can find the difference of rate constants of R1 is about 10% at temperature
ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
424
above 1000K between Curran and Modified Curran mechanisms. The corresponding
425
difference between CRECK and Modified Curran mechanisms is about 20-50%,
426
which means the rate constants of R1 in CRECK mechanism are too high. As for R2:
427
CO+OHCO2+H, we can find there has 3 times difference of rate constants
428
between CRECK and modified mechanisms at temperature about 1000 K and the rate
429
constants are very similar among the three mechanisms at temperature above 1600 K.
430
The difference of rate constants of R3 between Curran and Modified Curran
431
mechanisms is 20%, but the difference between CRECK and Modified Curran
432
mechanisms is about 3 times at temperature over 2000K. Compared to R1-R3, the
433
differences of rate constants of R4 and R5 are relatively small, which are no more
434
than 30% and 15% for R4 and R5, respectively. In order to evaluate such differences’
435
effects on the prediction performance of mechanisms, the rate constants of R1-R5 in
436
Curran and CRECK mechanisms were replaced with that of Modified mechanism
437
respectively to calculate laminar flame speed of ETBE at temperature of 373 K and
438
pressure of 1 atm, as shown in Figure 13.
439
As it can be seen from Figure 13(a), replacing rate constants of R2, R3 and R5
440
has little effects on the modeling result of Curran mechanism. And after replacing rate
441
constants of R1 and R4, there have lower and higher modeling results for R1 and R4
442
respectively. However, all the replacing of rate constants doesn’t give better
443
prediction performance and the phenomenon of equivalence ratio deviation still exists.
444
Thus we may come to a conclusion that the crux of Curran mechanism lies on IC4H8
445
sub-mechanism instead of R1-R5. Unlike Curran mechanism, the replacing brings a
446
different outcome for CRECK mechanism. Except R2 and R5, changing rate
447
constants of the other three sensitive reactions creates larger effects on laminar flame
448
speed calculation results. Changing rate constants of R3 and R4 makes the modeling
449
results further deviate from experimental results. Only when the rate constant of R1 is
450
replaced, CRECK mechanism presents a better prediction performance than original
451
CRECK mechanism. Consequently, we may consider the difference of between
452
CRECK and Modified mechanisms not only lies on IC4H8 sub-mechanism, but also
453
some central elementary reactions, such as R1-R5.
454
3.4. Comparison of Laminar Flame Speed
455
Before the ETBE was widely used as gasoline antiknock additive, MTBE played
456
the role of antiknock additive in some Europe and American countries. And the flame
457
speed is vital in spark ignition engine design. So, in order to clarify if replacing
ACS Paragon Plus Environment
Page 14 of 40
Page 15 of 40 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
458
MTBE with ETBE as additive will have an effect on the flame speed of gasoline, the
459
comparison of laminar flame speeds between ETBE and MTBE was conducted.
460
Figure 14 illustrates the laminar speed of ETBE and MTBE at atmospheric pressure.
461
It can be seen that the two ethers’ laminar flame speeds are very close to each other
462
and the biggest discrepancy is less than 3 cm/s at the whole range of equivalence
463
ratio.
464
The laminar flame speed similarity of the two ethers indicates a corresponding
465
similarity with the flame structure and processes in the flame. Ji et al.57 stated that
466
since the initial fuel reacts to form fuel fragments relatively fast, it is the fuel fragment
467
products that enter the active oxidation zone and their subsequent reactions, that
468
control the heat release and the flame propagation. Figure 15 shows the temperature
469
and heat release profiles for the two ethers calculated with Modified Curran
470
mechanism. It is seen that the temperature and heat release profiles for the two ethers
471
are almost identical. Generally speaking, these two parameters are the most important
472
factors influencing the chemical reactions and flame propagation. The congruence of
473
their profiles is consistent with the result that the flame speeds are so similar.
474
Besides the similarities of temperature and heat release profiles for the two ethers,
475
we can find that their key reactions and corresponding sensitivity coefficients are also
476
basically identical from Figure 16. Table 4 gives the ETBE and MTBE’s main
477
consumption pathways at 373 K, 1atm and . We can see that both ETBE and
478
MTBE are predominantly consumed by H-abstraction reactions instead of
479
decomposition reactions and the consumption pathways are very similar. Additionally,
480
we can know that ETBE and MTBE consume nearly at the same rate along the whole
481
reaction zone from the Figure 17 of the fuel fractions of ETBE and MTBE. According
482
the analyses above, we can know that all of the flame structure, sensitivity analysis,
483
main consumption pathways and fuel fraction of ETBE and MTBE are similar, which
484
perhaps give supports to the observed similarity in the laminar flame speed. In the
485
research of Dunphy and Simmie14, we can learn that ETBE and MTBE almost have
486
the same ignition delay times and their oxidation rates are very close based on the
487
shock tube experiment results. The ignition delay times and laminar flame speeds of
488
ETBE and MTBE show similarities, which means replacing MTBE with ETBE as
489
additive is absolutely feasible and reasonable on the fundamental combustion
490
characteristics.
491
Besides MTBE and ETBE, ethanol is also added into gasoline as gasoline additive.
ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
492
Iso-octane is commonly used as the surrogate or representative species for gasoline
493
fuels. Thus, the laminar flame speed of ETBE is also compared with that of ethanol,
494
iso-octane, as well as gasoline. Figure 18 shows the laminar flame speed of ETBE,
495
ethanol, iso-octane and gasoline at 373 K and 453 K and corresponding simulated
496
results of ethanol and iso-octane. It is seen that the peak of laminar flame speed for
497
these four fuels appears at the equivalence ratio around 1.1 at both 373 K and 453 K.
498
Among the four fuels, ethanol has the largest laminar flame speed. For the other three
499
fuels, the differences among their laminar flame speeds are relatively small, especially
500
for the iso-octane and gasoline. Overall, in the lean mixture conditions, laminar flame
501
speed between ETBE, iso-octane and gasoline differs little and the difference is no
502
more than 3 cm/s. While in rich mixture conditions, the maximum gap is less than 6
503
cm/s and ETBE has the largest flame speed among the three fuels. Therefore mixing
504
ETBE with gasoline as additive will not influence the flame speed of gasoline greatly.
505
To explain the reasons for this discrepancy of laminar flame speed of ETBE,
506
ethanol and iso-octane, the thermodynamic analysis and chemical kinetic analysis
507
were conducted. Figure 19 depicts the adiabatic flame temperature of ETBE, ethanol
508
and iso-octane at 373 K and 453 K. It can be seen that ethanol has the lowest adiabatic
509
flame temperature; ETBE and iso-octane have almost the same adiabatic flame speed
510
and the largest difference is less 6 K.
511
Combining Figure 18 and Figure 19, the laminar flame speed and adiabatic flame
512
temperature of ethanol, ETBE and iso-octane presents the opposite tendency, which
513
means chemical kinetic plays a more important role in determining the laminar flame
514
speed than thermodynamic factor. In order to further interpret the laminar flame speed
515
differences, the sensitivity analyses of ethanol, ETBE and iso-octane were also
516
provided at the condition of T=373K, p=1atm, =1.0, as shown in Figure 14. The
517
reaction of O2+HO+OH has the largest positive coefficient among the 20 most
518
sensitive reactions for the three fuels.
519
Figure 20(a) gives the 20 most sensitive reactions of ETBE. There are four
520
reactions involving species of IC4H8, which generates IC4H7 by dehydrogenation
521
reaction. IC4H8 and IC4H7 will consume large amount of H and OH radicals and are
522
inactive. So they will inhibit the combustion and lower the globle reactivity of ETBE.
523
Similarly, among the sensitive reaction of iso-octane as shown in Figure 20(b),
524
there are also some reactions involing IC4H8 and IC4H7, as well as C3H6. C3H6 will
525
consume OH radical and produce propenyl C3H5-A. Like IC4H8 and IC4H7, C3H6 and
ACS Paragon Plus Environment
Page 16 of 40
Page 17 of 40 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
526
C3H5-A will also consume active radicals and are less active. So These radicals will
527
reduce the reactivity of iso-octane.
528
In Figure 20(c), all the sensitive reactions are the elementary reactions involving
529
only C1-C2 species for ethanol. Thus the ethanol generates small species quickly and
530
has higher chemical reactivity. Additionally, the small species diffuse faster than
531
larger species generally. Thereby, ethanol has the larger laminar flame speed
532
compared to ETBE and iso-octane.
533
According to the analysis above, ETBE and iso-octane have lower laminar flame
534
speed than ethanol, though ethanol has lower adiabatic flame temperature the ETBE
535
and iso-octane. As for who has higher laminar flame speed between ETBE and
536
iso-octane, more experiments and deep thermodynamic, diffusion and kinetic analysis
537
should be done to come to a clear conclusion.
538
To support the analysis from the sensitivity analysis, the mole fractions of some
539
active species (H, OH, O) and inactive species (IC4H8, IC4H7, C3H6, C3H5-A) are
540
shown in Figure 21. The mole fractions of H, OH and O of ethanol are higher than
541
that of ETBE and iso-octane, especially for the H radical, so the reactivity of ethanol
542
is the highest. And the differences between ETBE and iso-octane are very small in
543
terms of mole fractions of active species. Unlike ETBE and iso-octane, ethanol
544
generates very little IC4H8, IC4H7, C3H6, C3H5-A, which consume large amount of
545
active radicals and inhibit the overall reactivity during the combustion process, as
546
shown in Figure 21(b). Meanwhile, mole fractions of some inactive species between
547
ETBE and iso-octane differ little. Therefore, the results of radical analysis are
548
consistent with the results of sensitivity analysis, which proves the validity of the
549
laminar flame speed results.
550
3.5. Markstein length
551
Markstein length represents the flame sensitivity to stretch and characterize the
552
flame instability. Positive Markstein length means stable flame front and negative
553
Markstein length means unstable flame front. And Bradley58 put forward that the
554
flame keeps stable until the critical flame radius is reached when the Markstein length
555
is larger than 1.5. Although the Markstein lengths of different fuels vary from each
556
other, the change rule of Markstein length respect to the equivalence ratio is very clear.
557
In order to reduce the uncertainty, the Markstein length is the average of three times
558
experimental results. Figure 22 shows the Markstein length of ETBE at different
559
temperatures and different pressures.
ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
560
At each temperatures and pressures, the Markstein length of ETBE decreases with
561
the increase of equivalence ratio, so the flame stability decreases gradually. The
562
reasons are that ETBE is heavier than air and the heat diffusion and mass diffusion are
563
non-equal. From Figure 22(a), we can see that temperature has little significant effect
564
on Markstein length. The differences between the Markstein lengths under different
565
temperatures are almost less than 0.4mm. The effects of pressure on Markstein length
566
are shown in Figure 22(b). As the pressure increases, the Markstein length decreases
567
and the flame becomes more and more unstable. The same conclusion can be drawn
568
based on the experimental schilieren images under different pressures. The higher the
569
pressure, the earlier the cellularity appears.
570
The measured Markstein lengths of ETBE, ethanol, iso-octane and gasoline were
571
also compared with each other, as shown in Figure 23. With the increase of
572
equivalence ratio, the Markstein lengths of all tested fuels decrease at both
573
temperatures. Among the tested fuels, gasoline has the smallest Markstein lengths at
574
both temperatures, which means its flame front is the most unstable at the tested
575
conditions. Additionally, the differences of Markstein lengths between ETBE and
576
iso-octane are very small at the whole range of equivalence ratio. When 1.2, the result is just contrary. Therefore, under lean conditions, the flame fronts of
579
ETBE and iso-octane might be more stable and under rich conditions, the flame front
580
of ethanol might be the most stable.
581
4. CONCLUSIONS
582
In this work, the laminar burning characteristics of ETBE were conducted at
583
different temperatures (298K, 373K, 453K) and pressures (1atm, 3atm, 5atm) using a
584
constant volume bomb. Besides, the laminar burning characteristics of MTBE,
585
ethanol, iso-octane and gasoline were compared to that of ETBE. The CRECK
586
mechanism, Curran mechanism and modified Curran mechanism were used to model
587
the laminar flame speeds of ETBE. Sensitivity analyses of the tested fuels were made
588
to interpret the differences between the Curran and modified Curran mechanism and
589
the differences of laminar flame speed between the tested fuels. The main conclusions
590
are as follows:
591
(1) Laminar flame speeds of all the tested fuels reach the peak value at the
592
equivalence ratio of 1.1. As the ignition delay times, the laminar flame speeds of
593
ETBE and MTBE are very close with each other, which indicates that replacing
ACS Paragon Plus Environment
Page 18 of 40
Page 19 of 40 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
594
MTBE with ETBE in gasoline is absolutely feasible and reasonable. Ethanol
595
shows the fastest laminar flame speed and the other three fuels (ETBE,
596
iso-octane, gasoline) have similar laminar flame speeds. Sensitivity analysis of
597
ethanol indicates that the sensitive reactions of ethanol only involve species
598
whose number of C atoms is below 3. However, the sensitive reactions of ETBE
599
and iso-octane consist of several large species, such as IC4H8, IC4H7, C3H6 and
600
C3H5-A. Thus the laminar flame speed of ethanol is faster than that of ETBE and
601
iso-octane.
602
(2) Both the CRECK mechanism and Curran mechanism can’t well predict the
603
laminar flame speed of ETBE. The modified Curran mechanism has a better
604
prediction performance over the tested conditions. The sensitivity analysis and
605
pathway analysis of ETBE using Curran, Modified Curran and CRECK
606
mechanisms shows that the update of reaction rate constants for critical sensitive
607
reactions accounts for the better prediction performance.
608
(3) The results of Markstein length show that temperature has little effects on
609
Markstein lengths of ETBE and the Markstein lengths decrease as the pressure
610
increase. Among the tested fuels, gasoline has the lowest Markstein length and
611
its flame is the most unstable. Under lean conditions, the flame front of ETBE
612
and iso-octane might be more stable and under rich conditions, the flame front of
613
ethanol might be the most stable one.
614 615
ASSOCIATED CONTENT
616 617
Supporting Information
618
The measured laminar flame speeds and errors at various temperatures and pressures.
619
The Modified Curran mechanism (mechanism, thermodynamic data, transport data).
620
AUTHOR INFORMATION
621
Corresponding Authors *
623 624
E-mail:
[email protected] (Erjiang Hu) State Key Laboratory of Multiphase Flow in Power Engineering, Xi'an Jiaotong University, Xi'an, 710049, People’s Republic of China
625
ORCID
626
Erjiang Hu: 0000-0002-0762-9018
622
ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
627 628 629
Notes The authors declare no competing financial interest.
630 631
ACKNOWLEDGEMENTS
632
This study is supported by the National Natural Science Foundation of China (Grants
633
91641124 and 91441118). The support from the Fundamental Research Funds for the
634
Central Universities is also appreciated.
635 636 637 638 639 640 641 642 643 644 645 646 647 648 649 650 651 652 653 654 655 656 657 658 659 660 661 662 663 664 665 666 667 668
REFERENCES (1) Tran, L. S.; Sirjean, B.; Glaude, P. A.; Fournet, R. PROGRESS IN DETAILED KINETIC MODELING OF THE COMBUSTION OF OXYGENATED COMPONENTS OF BIOFUELS. Energy 2012, 43 (1), 4-18. (2) Squillace, P. J.; Zogorski, J. S.; And, W. G. W.; Price, C. V. Preliminary Assessment of the Occurrence and Possible Sources of MTBE in Groundwater in the United States, 1993−1994. Rev.fac.nac.salud Pública 1996, 30 (5), 39-42. (3) Silva, R. D.; Cataluña, R.; Menezes, E. W. D.; Samios, D.; Piatnicki, C. M. S. Effect of additives on the antiknock properties and Reid vapor pressure of gasoline. Fuel 2005, 84 (7–8), 951-959. (4) Yang, B. L.; Yang, S. B.; Yao, R. Q. Synthesis of ethyl tert -butyl ether from tert -butyl alcohol and ethanol on strong acid cation-exchange resins. Reactive & Functional Polymers 2000, 44 (2), 167-175. (5) Wu, X.; Li, Q.; Jin, F.; Tang, C.; Huang, Z.; Daniel, R.; Tian, G.; Xu, H. Laminar burning characteristics of 2,5-dimethylfuran and iso- octane blend at elevated temperatures and pressures. Fuel 2012, 95 (1), 234-240. (6) Rodríguez-Antón, L. M.; Hernández-Campos, M.; Sanz-Pérez, F. Experimental determination of some physical properties of gasoline, ethanol and ETBE blends. Fuel 2013, 112 (10), 178-184. (7) Malça, J.; Freire, F. Renewability and life-cycle energy efficiency of bioethanol and bio-ethyl tertiary butyl ether (bioETBE): Assessing the implications of allocation. Energy 2006, 31 (15), 3362-3380. (8) Menezes, E. W. D.; Cataluña, R. Optimization of the ETBE (ethyl tert -butyl ether) production process. Fuel Processing Technology 2008, 89 (11), 1148-1152. (9) Croezen, H.; Kampman, B. The impact of ethanol and ETBE blending on refinery operations and GHG-emissions. Energy Policy 2009, 37 (12), 5226-5238. (10) Matsumoto, N.; Sano, D.; Elder, M. Biofuel initiatives in Japan: Strategies, policies, and future potential. Applied Energy 2009, 86 (11), S69-S76. (11) Westphal, G. A.; Krahl, J.; Brüning, T.; Hallier, E.; Bünger, J. Ether oxygenate additives in gasoline reduce toxicity of exhausts. Toxicology 2010, 268 (3), 198-203. (12) Górski, K.; Sen, A. K.; Lotko, W.; Swat, M. Effects of ethyl-tert-butyl ether (ETBE) addition on the physicochemical properties of diesel oil and particulate matter and smoke emissions from diesel engines. Fuel 2013, 103 (1), 1138-1143. (13) Daly, N. J.; Wentrup, C. The thermal decomposition of t-butyl ethyl ether. Australian Journal of Chemistry 1968, 21 (6), 1535-&. (14) Dunphy, M. P.; Simmie, J. M. Preliminary observations on the high temperature oxidation of ethyl tert‐ butyl ether. International Journal of Chemical Kinetics 1991, 23 (6), 553-558. (15) Dagaut, P.; Reuillon, M.; Cathonnet, M.; Presvots, D. Gas chromatography and mass spectrometry identification of cyclic ethers formed from reference fuels combustion. Chromatographia 1995, 40 (3-4), 147-154.
ACS Paragon Plus Environment
Page 20 of 40
Page 21 of 40 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
669 670 671 672 673 674 675 676 677 678 679 680 681 682 683 684 685 686 687 688 689 690 691 692 693 694 695 696 697 698 699 700 701 702 703 704 705 706 707 708 709 710 711 712
Energy & Fuels
(16) Kadi, B. E.; Baronnet, F. Study of the oxidation of unsymmetrical ethers (ETBE, TAME) and tentative interpretation of their high octane numbers. Journal de Chimie Physique et de Physico-Chimie Biologique 1995, 92, 706-725. (17) Dagaur, P.; Koch, R.; Cathonnet, M. The Oxidation of N-Heptane in the Presence of Oxygenated Octane Improvers: MTBE and ETBE. Combustion Science & Technology 1997, 122 (1-6), 345-361. (18) Goldaniga, A.; Faravelli, T.; Ranzi, E.; Dagaut, P.; Cathonnet, M. Oxidation of oxygenated octane improvers: MTBE, ETBE, DIPE, and TAME. Symposium on Combustion 1998, 27 (1), 353-360. (19)Glaude, P. A.; Battin-Leclerc, F.; Judenherc, B.; Warth, V.; Fournet, R.; Côme, G. M.; Scacchi, G.; Dagaut, P.; Cathonnet, M. Experimental and modeling study of the gas-phase oxidation of methyl and ethyl tertiary butyl ethers. Combustion & Flame 2000, 121 (1–2), 345-355. (20) Ogura, T.; Sakai, Y.; Miyoshi, A.; Koshi, M.; Dagaut, P. Modeling of the Oxidation of Primary Reference Fuel in the Presence of Oxygenated Octane Improvers: Ethyl Tert-Butyl Ether and Ethanol. Energy Fuels 2007, 21 (6), 3233-3239. (21) Miyoshi, A. In OS3-1 KUCRS - Detailed Kinetic Mechanism Generator for Versatile Fuel Components and Mixtures(OS3 Application of chemical kinetics to combustion modeling,Organized Session Papers), The ... international symposium on diagnostics and modeling of combustion in internal combustion engines, 2017; 2017; pp 116-121. (22) Yasunaga, K.; Kuraguchi, Y.; Hidaka, Y.; Takahashi, O.; Yamada, H.; Koike, T. Kinetic and modeling studies on ETBE pyrolysis behind reflected shock waves. Chemical Physics Letters 2008, 451 (4–6), 192-197. (23) Yahyaoui, M.; Djebailichaumeix, N.; Dagaut, P.; Paillard, C. E. Ethyl Tertiary Butyl Ether Ignition and Combustion Using a Shock Tube and Spherical Bomb. Energy & Fuels 2008, 22 (6), 3701-3708. (24) Gong, J.; Jin, C.; Huang, Z.; Wu, X. Study on Laminar Burning Characteristics of Premixed High-Octane Fuel−Air Mixtures at Elevated Pressures and Temperatures. Energy & Fuels 2010, 24 (24), 965-972. (25) Yasunaga, K.; Simmie, J. M.; Curran, H. J.; Koike, T.; Takahashi, O.; Kuraguchi, Y.; Hidaka, Y. Detailed chemical kinetic mechanisms of ethyl methyl, methyl tert -butyl and ethyl tert -butyl ethers: The importance of uni-molecular elimination reactions. Combustion & Flame 2011, 158 (6), 1032-1036. (26)Liu, X.; Ito, S.; Wada, Y. Oxidation characteristic and products of ETBE (ethyl tert-butyl ether). Energy 2015, 82, 184-192. (27) Hashimoto, J.; Hosono, J.; Shimizu, K.; Urakawa, R.; Tanoue, K. Extinction limits and flame structures of ETBE, DIPE and TAME non-premixed flames. Proceedings of the Combustion Institute 2017, 36 (1), 1439-1446. (28) Hu, E. J.; Huang, Z. H.; He, J. J.; Jin, C.; Miao, H. Y.; Wang, X. B. Measurements of laminar burning velocities and flame stability analysis for hydrogen-air-diluent mixtures. Chinese Science Bulletin 2009, 54 (5), 846-857. (29) Tang, C.; Huang, Z.; Wang, J.; Zheng, J. Effects of hydrogen addition on cellular instabilities of the spherically expanding propane flames. International Journal of Hydrogen Energy 2009, 34 (5), 2483-2487. (30) FRANKEL, M. L.; SIVASHINSKY, G. I. On Effects Due To Thermal Expansion and Lewis Number in Spherical Flame Propagation. Combustion Science & Technology 1983, 31 (3-4), 131-138. (31) Chen, Z. On the extraction of laminar flame speed and Markstein length from outwardly propagating spherical flames. Combustion & Flame 2011, 158 (2), 291-300. (32) Chen, Z. On the accuracy of laminar flame speeds measured from outwardly propagating spherical flames: Methane/air at normal temperature and pressure. Combustion & Flame 2015, 162 (6), 2442-2453. (33) Bradley, D.; Gaskell, P. H.; Gu, X. J. Burning velocities, markstein lengths, and flame quenching for spherical methane-air flames: A computational study. Combustion & Flame 1996, 104 (1–2), 176-198. (34) Burke, M. P.; Chen, Z.; Ju, Y.; Dryer, F. L. Effect of cylindrical confinement on the determination of laminar
ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
713 714 715 716 717 718 719 720 721 722 723 724 725 726 727 728 729 730 731 732 733 734 735 736 737 738 739 740 741 742 743 744 745 746 747 748 749 750 751 752 753 754 755 756
flame speeds using outwardly propagating flames. Combustion & Flame 2009, 156 (4), 771-779. (35) Zhang, Z.; Huang, Z.; Wang, X.; Xiang, J.; Wang, X.; Miao, H. Measurements of laminar burning velocities and Markstein lengths for methanol–air–nitrogen mixtures at elevated pressures and temperatures. Combustion & Flame 2008, 155 (3), 358-368. (36) Yu, H.; Han, W.; Santner, J.; Gou, X.; Sohn, C. H.; Ju, Y.; Chen, Z. Radiation-induced uncertainty in laminar flame speed measured from propagating spherical flames. Combustion & Flame 2014, 161 (11), 2815-2824. (37) Moffat, R. J. Describing uncertainties in experimental results. Exp Therm Fluid Sci J 1:3-7. Experimental Thermal & Fluid Science 1988, 1 (1), 3-17. (38) Kee, R. J.; Grcar, J. F.; Smooke, M. D.; Miller, J. A.; Meeks, E. PREMIX. A Fortran Program for Modeling Steady Laminar One-dimensional Premixed Flames. 1985, 143 (5), 65. (39) Reaction Design: San Diego, C.-P., CHEMKIN-PRO 15112, Reaction Design: San Diego, 2011. 2011. (40) Ranzi, E.; Corbetta, M.; Manenti, F.; Pierucci, S. Kinetic modeling of the thermal degradation and combustion of biomass. Chemical Engineering Science 2014, 110 (7), 2-12. (41) Yasunaga, K.; Gillespie, F.; Simmie, J. M.; Curran, H. J.; Kuraguchi, Y.; Hoshikawa, H.; Yamane, M.; Hidaka, Y. A multiple shock tube and chemical kinetic modeling study of diethyl ether pyrolysis and oxidation. Journal of Physical Chemistry A 2010, 114 (34), 9098-9109. (42) Li, Y.; Zhou, C. W.; Somers, K. P.; Zhang, K.; Curran, H. J. The oxidation of 2-butene: A high pressure ignition delay, kinetic modeling study and reactivity comparison with isobutene and 1-butene. Proceedings of the Combustion Institute 2017, 36(1), 403–411. (43) Zhou, C. W.; Li, Y.; O'Connor, E.; Somers, K. P.; Thion, S.; Keesee, C.; Mathieu, O.; Petersen, E. L.; Deverter, T. A.; Oehlschlaeger, M. A. A comprehensive experimental and modeling study of isobutene oxidation. Combustion & Flame 2016, 167, 353-379. (44) Burke, U.; Metcalfe, W. K.; Burke, S. M.; Heufer, K. A.; Dagaut, P.; Curran, H. J. A detailed chemical kinetic modeling, ignition delay time and jet-stirred reactor study of methanol oxidation. Combustion & Flame 2016, 165 (5), 125-136. (45) Burke, S. M.; Burke, U.; Mc Donagh, R.; Mathieu, O.; Osorio, I.; Keesee, C.; Morones, A.; Petersen, E. L.; Wang, W.; DeVerter, T. A.; Oehlschlaeger, M. A.; Rhodes, B.; Hanson, R. K.; Davidson, D. F.; Weber, B. W.; Sung, C.-J.; Santner, J.; Ju, Y.; Haas, F. M.; Dryer, F. L.; Volkov, E. N.; Nilsson, E. J. K.; Konnov, A. A.; Alrefae, M.; Khaled, F.; Farooq, A.; Dirrenberger, P.; Glaude, P.-A.; Battin-Leclerc, F.; Curran, H. J. An experimental and modeling study of propene oxidation. Part 2: Ignition delay time and flame speed measurements. Combustion and Flame 2015, 162 (2), 296-314. (46) Burke, S.; Metcalfe, W.; Herbinet, O.; Battinleclerc, F.; Haas, F.; Santner, J.; Dryer, F.; Curran, H. J. In An experimental and modeling study of propene oxidation. Part 1: Speciation measurements in jetstirred and flow reactors, International Symposium on Web and Wireless Geographical Information Systems, 2014; 2014; pp 171-186. (47) Metcalfe, W. K.; Burke, S. M.; Ahmed, S. S.; Curran, H. J. A Hierarchical and Comparative Kinetic Modeling Study of C 1 − C 2 Hydrocarbon and Oxygenated Fuels. International Journal of Chemical Kinetics 2013, 45 (10), 638–675. (48) Kéromnès, A.; Metcalfe, W. K.; Heufer, K. A.; Donohoe, N.; Das, A. K.; Sung, C. J.; Herzler, J.; Naumann, C.; Griebel, P.; Mathieu, O. An experimental and detailed chemical kinetic modeling study of hydrogen and syngas mixture oxidation at elevated pressures. Combustion & Flame 2013, 160 (6), 995-1011. (49) Leplat, N.; Dagaut, P.; Togbé, C.; Vandooren, J. Numerical and experimental study of ethanol combustion and oxidation in laminar premixed flames and in jet-stirred reactor. Combustion & Flame 2011, 158 (4), 705-725. (50) Chaos, M.; Kazakov, A.; Zhao, Z.; Dryer, F. L. A high‐temperature chemical kinetic model for primary
ACS Paragon Plus Environment
Page 22 of 40
Page 23 of 40 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
757 758 759 760 761 762 763 764 765 766 767 768 769 770 771 772 773 774
Energy & Fuels
reference fuels. International Journal of Chemical Kinetics 2007, 39 (7), 399-414. (51) Konnov, A. A.; Meuwissen, R. J.; Goey, L. P. H. D. The temperature dependence of the laminar burning velocity of ethanol flames. Proceedings of the Combustion Institute 2011, 33 (1), 1011-1019. (52) Broustail, G.; Seers, P.; Halter, F.; Moréac, G.; Mounaim-Rousselle, C. Experimental determination of laminar burning velocity for butanol and ethanol iso-octane blends. Fuel 2011, 90 (1), 1-6. (53) Bradley, D.; Lawes, M.; Mansour, M. S. Explosion bomb measurements of ethanol–air laminar gaseous flame characteristics at pressures up to 1.4 MPa. Combustion & Flame 2009, 156 (7), 1462-1470. (54) Egolfopoulos, F. N.; Du, D. X.; Law, C. K. A study on ethanol oxidation kinetics in laminar premixed flames, flow reactors, and shock tubes. Symposium on Combustion 1992, 24 (1), 833-841. (55) Turányi, T.; Nagy, T.; Zsély, I. G.; Cserháti, M.; Varga, T.; Szabó, B. T.; Sedyó, I.; Kiss, P. T.; Zempléni, A.; Curran, H. J. Determination of rate parameters based on both direct and indirect measurements. International Journal of Chemical Kinetics 2012, 44 (5), 284–302. (56) Miller, J. A.; Pilling, M. J.; Troe, J. Unravelling combustion mechanisms through a quantitative understanding of elementary reactions. Proceedings of the Combustion Institute 2005, 30 (1), 43-88. (57) Ji, C.; Dames, E.; Wang, Y. L.; Wang, H.; Egolfopoulos, F. N. Propagation and extinction of premixed C 5 – C 12 n -alkane flames. Combustion & Flame 2010, 157 (2), 277-287. (58) Bradley, D.; Lawes, M.; Liu, K.; Verhelst, S.; Woolley, R. Laminar burning velocities of lean hydrogen–air mixtures at pressures up to 1.0 MPa. Combustion & Flame 2007, 149 (1), 162-172.
775 776
ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
List of Tables and Figures
777 778
Table 1. Properties of tested fuels.1, 5
779
Table 2. Experimental conditions of tested fuels.
780
Table 3. Fitting coefficients of reference laminar flame speed, temperature and
781
pressure.
782
Table 4. Comparison of the main consumption pathways between ETBE and MTBE.
783
Figure 1. Comparison of laminar flame speed of ETBE at 1 atm and 298 K.
784
Figure 2. Comparison of laminar flame speed of ethanol at 1 atm and 373 K.
785
Figure 3. Laminar flame speeds of ETBE at different temperatures and pressures.
786
Figure 4. Comparison of measured (symbols) and simulated laminar flame speeds
787
(Dot line: Curran mechanism, dash line: CRECK mechanism) of ETBE.
788
Figure 5. Comparison of measured (symbols) and simulated laminar flame speeds
789
(Dot line: Curran mechanism, solid line: Modified Curran mechanism) of ETBE.
790
Figure 6. Comparison of measured (symbols) and simulated ignition delay time (Dot
791
line: Curran mechanism, solid line: Modified Curran mechanism) of ETBE.
792
Figure 7. Comparison of sensitivity analyses of ETBE between Curran, Modified
793
Curran and CRECK mechanism.
794
Figure 8. Comparison of reaction pathway analyses of IC4H8 between Curran,
795
Modified Curran and CRECK mechanism.
796
Figure 9. Comparison of mole fractions of OH, H and O radicals between Curran,
797
Modified Curran and CRECK mechanism.
798
Figure 10. Rate constants comparison for different consumption pathways of IC4H8
799
between Curran, Modified Curran and CRECK mechanism.
800
Figure 11. Rate constants comparison for different consumption pathways of IC4H7
801
between Curran, Modified Curran and CRECK mechanism.
802
Figure 12. Comparison of rate constants of R1-R5 between Curran, modified Curran
803
and CRECK mechanisms.
804
Figure 13. Effects of replacing rate constants of R1-R5 on the prediction of laminar
805
flame speed.
806
Figure 14. Comparison of laminar flame speed between ETBE and MTBE.
807
Figure 15. Temperature and heat release profiles for ETBE and MTBE flames
808
calculated with Modified Curran mechanism, =1.0, T=373 K, p=1 atm.
809
Figure 16. Sensitivity analysis comparison of ETBE and MTBE, =1.0, T=373 K, p=1
810
atm.
ACS Paragon Plus Environment
Page 24 of 40
Page 25 of 40 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
811
Figure 17. Fuel fraction of ETBE and MTBE at 373 K, 1 atm and =1.0.
812
Figure 18. Laminar flame speed of ETBE, ethanol, iso-octane and gasoline at 373K
813
and 453K.
814
Figure 19. Adiabatic flame temperature of ETBE, ethanol and iso-octane at 373K and
815
453K.
816
Figure 20. Sensitivity analysis of ethanol, ETBE and iso-octane at =1.0, T=373K,
817
p=1atm.
818
Figure 21. Mole fractions of some main species of ethanol, ETBE, iso-octane flames
819
at T=373K, p=1atm, =1.0.
820
Figure 22. Measured Markstein length of ETBE at different temperatures and
821
pressures.
822
Figure 23. Measured Markstein length of ETBE, ethanol, iso-octane and gasoline at
823
373K and 453K.
824
ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
825
Page 26 of 40
Table 1. Properties of tested fuels.1, 5 ETBE
MTBE
Ethanol
Iso-octane
Gasoline
C4H9OC2H5
C4H9OCH3
C2H5OH
(CH3)2CHCH2C(CH3)₃
C4-C14
102.17
88.14
46.07
114.23
≈102
Oxygen content (Wt%)
15.7
18.2
34.8
0
≈1.8
RVP (kPa)
30.6
55
15.6
-
45-85
Density (kg/m3)
750
740
790
691.9
0.74
Boiling point (K)
346.0
328.5
351.6
372.0
303-473
LHV (MJ/kg)
35.9
35.2
26.8
44.3
42.7
LHV (MJ/L)
26.93
26.04
21.2
30.7
31.60
RON/MON
117/101
118/101
109/90
100/100
92-98/82-88
12.16
11.74
9.00
15.13
14.18
Chemical formula MW (g/mol)
Stoichiometric A/F ratio
826 827
Table 2. Experimental conditions of tested fuels.
Initial temperature T/K Initial pressure p/atm Equivalence ratio
ETBE
MTBE
Ethanol
Iso-octane
Gasoline
298、373、453
298、373
373、453
373、453
373、453
1、3、5
1
1
1
1
0.7-1.6
0.7-1.6
0.7-1.6
0.7-1.6
0.7-1.6
828 829
Table 3. Fitting coefficients of reference laminar flame speed, temperature and
830
pressure.
Su0,ref
β
θ
α0
-137.51
β0
-0.57
θ0
0.12
α1
377.34
β1
5.15
θ1
-1.99
α2
-255.62
β2
-4.81
θ2
2.48
α3
48.24
β3
1.82
θ3
-0.91
831 832 833 834 835
ACS Paragon Plus Environment
Page 27 of 40
836
Table 4. Comparison of the main consumption pathways between ETBE and MTBE. Reactions
Consumption Pathway/ %
ETBE+HTC4H9OC2H4S+H2 ETBE+HC2H5OC4H8I+H2 ETBE(+M)IC4H8+C2H5OH(+M) ETBE+OHC2H5OC4H8I+H2O ETBE+HTC4H9OC2H4P+H2 ETBE+OHTC4H9OC2H4P+H2O ETBE+OC2H5OC4H8I+OH ETBE+OTC4H9OC2H4S+OH ETBE(+M)C2H4+TC4H9OH(+M) ETBE(+M)C2H5O+TC4H9(+M)
33.74 22.16 12.49 10.45 7.39 3.48 3.45 1.52 1.21 1.04
Reactions
Consumption Pathway/ %
MTBE+HTC4H9OCH2+H2 MTBE+HCH3OC4H8I+H2 MTBE+OHCH3OC4H8I+H=O MTBE(+M)IC4H8+CH3OH(+M) MTBE+OCH3OC4H8I+OH MTBE+OTC4H9OCH2+OH MTBE+OHTC4H9OCH2+H2O MTBE+HO2CH3OC4H8I+H2O2 MTBE(+M)CH3O+TC4H9(+M) MTBE(+M)CH3+TC4H9O(+M)
837
40
ETBE T=298K p=1atm
0
Su (cm/s)
30
20
Present work Yahyaoui [24]
10 0.6
0.8
1.0
838 839
1.2
1.4
1.6
Figure 1. Comparison of laminar flame speed of ETBE at 1 atm and 298 K.
70 60
ethanol T=373K p=1atm
50 Present work Konnov [52] Broustail [53] Bradley [54] Egolfopoulos [55]
40
0
Su (cm/s)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
30 20 10 0.6
0.8
1.0
1.2
1.4
1.6
840 841
Figure 2. Comparison of laminar flame speed of ethanol at 1 atm and 373 K.
ACS Paragon Plus Environment
71.41 10.65 8.32 4.91 1.69 1.05 0.58 0.50 0.20 0.18
Energy & Fuels
70 60
(a)
ETBE p=1atm
0
Su (m/s)
50 40 30
T=298K T=373K T=453K Line:fitting line
20 10 0.6
0.8
1.0
1.2
1.4
1.6
842
50
(b)
ETBE T=373K
30
p=1atm p=3atm p=5atm Line:fitting line
0
Su (m/s)
40
20 10 0.6
0.8
1.0
843 844
1.2
1.4
1.6
Figure 3. Laminar flame speeds of ETBE at different temperatures and pressures.
80 70
ETBE p=1atm
(a)
60 50
0
Su (cm/s)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
40 30 20
T=298K T=373K Dot line: Curran T=453K Dash line:CRECK
10 0 0.6
845
0.8
1.0
1.2
1.4
1.6
ACS Paragon Plus Environment
Page 28 of 40
Page 29 of 40
ETBE T=373K
50
(b)
0
Su (cm/s)
40 30 20
p=1atm p=3atm Dot line: Curran p=5atm Dash line:CRECK
10 0 0.6
0.8
1.0
1.2
1.4
1.6
846 847
Figure 4. Comparison of measured (symbols) and simulated laminar flame speeds
848
(Dot line: Curran mechanism, dash line: CRECK mechanism) of ETBE.
849 80 70
ETBE p=1atm
(a)
60
0
Su (cm/s)
50 40 30 20 10 0 0.6
T=298K T=373K Dot line: Curran T=453K Solid line:Modified Curran 0.8 1.0 1.2 1.4 1.6
850 50
(b)
ETBE T=373K
40
0
Su (cm/s)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
30 20
p=1atm p=3atm Dot line: Curran p=5atm Solid line:Modified Curran
10 0 0.6
851
0.8
1.0
1.2
1.4
1.6
852
Figure 5. Comparison of measured (symbols) and simulated laminar flame speeds
853
(Dot line: Curran mechanism, solid line: Modified Curran mechanism) of ETBE.
ACS Paragon Plus Environment
Energy & Fuels
10000
Ignition delay time (s)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
p5=3.5bar 1000
100 Yahyaoui [24] Dunphy and Simmie [15] Curran Modified Curran
10
1 6.0
854
0.3% ETBE + 4.5% O2 + 95.2% Ar
6.4
6.8
7.2 4
7.6
8.0
-1
10 /T (K )
855
Figure 6. Comparison of measured (symbols) and simulated ignition delay time (Dot
856
line: Curran mechanism, solid line: Modified Curran mechanism) of ETBE.
857
858 859
Figure 7. Comparison of sensitivity analyses of ETBE between Curran, Modified
860
Curran and CRECK mechanism.
861
ACS Paragon Plus Environment
Page 30 of 40
Page 31 of 40 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
862 863
Figure 8. Comparison of reaction pathway analyses of IC4H8 between Curran,
864
Modified Curran and CRECK mechanism.
865
866 867
Figure 9. Comparison of mole fractions of OH, H and O radicals between Curran,
868
Modified Curran and CRECK mechanism.
869
ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
(a) IC4H8+HIC4H9
Page 32 of 40
(b) IC4H8+OIC4H7+OH
870
Figure 10. Rate constants comparison for different consumption pathway of IC4H8
871
between Curran, Modified Curran and CRECK mechanism.
872
(a) IC4H7+HIC4H8
(b) IC4H7AC3H4+CH3
873
Figure 11. Rate constants comparison for different consumption pathways of IC4H7
874
between Curran, Modified Curran and CRECK mechanism.
875
ACS Paragon Plus Environment
Page 33 of 40 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
(a) R1: H+O2O+OH
(b) R2: CO+OHCO2+H
(c) R3: HCO+MH+CO+M
(d) R4: H+OH+MH2O+M
(e) R5: H+O2(+M)HO2(+M) 876 877
Figure 12. Comparison of rate constants of R1-R5 between Curran, modified Curran
878
and CRECK mechanisms.
879
ACS Paragon Plus Environment
Energy & Fuels
(a) Curran mechanism
(b) CRECK mechanism
880
Figure 13. Effects of replacing rate constants of R1-R5 on the prediction of laminar
881
flame speed.
882 60
p=1atm
T=373K
50 40
0
Su (cm/s)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 34 of 40
T=298K
30 20 ETBE MTBE
10 0 0.6
883 884
0.8
1.0
1.2
1.4
1.6
Figure 14. Comparison of laminar flame speed between ETBE and MTBE.
885
ACS Paragon Plus Environment
Page 35 of 40
×10
10 2400
Temperature
2100 1800
6
1500
4
ETBE MTBE
1200 900 600
2 Heat release 0 0.10
0.15
Temperature (K)
8
Heat release rate (erg·cm-3·s-1)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
300 0 0.25
0.20
Distance (cm)
886 887
Figure 15. Temperature and heat release profiles for ETBE and MTBE flames
888
calculated with Modified Curran mechanism, =1.0, T=373 K, p=1 atm.
889 H+OH+MH 2O+M H+O2(+M)HO 2(+M) CH3+H(+M)CH=(+M) HCO+HCO+H 2 HO2+HH2+O 2 C2H3+HC2H2+H2 IC4H8+OHIC4H7+H2O HCO+O2CO+HO 2 H2+OHH+H 2O
MTBE ETBE
CH3+OHCH 2OH+H H2+OH+OH
T=373K p=1atm =1
CH3+HO2CH3O+OH HO2+H2OH HCO+MH+CO+M CO+OHCO 2+H O2+HO+OH
-0.2
-0.1
0.0
0.1
0.2
0.3
0.4
Normalized sensitivity coefficients
890 891
Figure 16. Sensitivity analysis comparison of ETBE and MTBE, =1.0, T=373 K,
892
p=1 atm.
893
ACS Paragon Plus Environment
Energy & Fuels
ETBE MTBE
1.0
T=373K p=1atm
Fuel fraction
0.8 0.6 0.4 0.2 0.0 0.12
0.13
895
0.14
0.15
0.16
0.17
0.18
Distance (cm)
894
Figure 17. Fuel fraction of ETBE and MTBE at 373 K, 1 atm and =1.0.
70 60
T=373K p=1atm
(a)
0
Su (m/s)
50 40
ETBE ethanol isooctane gasoline
30 20
Leplat-ethanol Chaos-isooctane
10 0.6
0.8
1.0
1.2
1.4
1.6
896 90 80
T=453K p=1atm
(b)
70 60
0
Su (m/s)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ETBE ethanol isooctane gasoline
50 40 30
Leplat-ethanol Chaos-isooctane
20 10 0.6
0.8
1.0
1.2
1.4
1.6
897 898
Figure 18. Laminar flame speed of ETBE, ethanol, iso-octane and gasoline at 373K
899
and 453K.
ACS Paragon Plus Environment
Page 36 of 40
Page 37 of 40
2400
p=1atm Adiabatic flame temperature (K)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
2300 2200 ETBE-373K ethanol-373K isooctane-373K ETBE-453K ethanol-453K isooctane-453K
2100 2000 1900 0.6
0.8
1.0
1.2
1.4
1.6
900 901
Figure 19. Adiabatic flame temperature of ETBE, ethanol and iso-octane at 373K and
902
453K.
903 H+OH+MH2O+M H+O2(+M)HO2(+M) CH3+H(+M)CH4(+M) HCO+HCO+H2 HO2+HH2+O2 C2H3+HC2H2+H2 IC4H8+OHIC4H7+H2O HCO+O2CO+HO2 IC4H8+HIC4H7+H2 IC4H8IC4H7+H C2H4+H(+M)C2H5(+M) IC4H8+OHIC4H7-I1+H2O H2+OHH+H2O CH3+OHCH2OH+H H2+OH+OH CH3+HO2CH3O+OH HO2+H2OH HCO+MH+CO+M CO+OHCO2+H O2+HO+OH
-0.2 904
-0.1
(a)
Modified Curran ETBE T=373K p=1atm =1
0.0 0.1 0.2 0.3 Normalized sensitivity coefficients
ACS Paragon Plus Environment
0.4
Energy & Fuels
H+OH+MH2O+M H+CH3(+M)CH4(+M) IC4H8IC4H7+H C3H6+OHC3H5-A+H2O H+HCOH2+CO H+O2(+M)HO2(+M) HCO+O2HO2+CO HO2+OHH2O+O2 OH+HCOH2O+CO O+CH3H+CH2O
O+CH3=>H+H2+CO O+H2H+OH HO2+CH3OH+CH3O IC4H7C3H4-A+CH3 CH2+O2=>2H+CO2 HCO+H2OH+CO+H2O HCO+MH+CO+M OH+CH3CH2(S)+H2O OH+COH+CO2 H+O2O+OH
-0.2 905
(b)
Chaos iso-octane T=373K p=1atm =1
-0.1 0.0 0.1 0.2 Normalized sensitivity coefficients
0.3
906 H+O2+MHO2+M H+HO2H2+O2 CH3+H(+M)CH4(+M) OH+HO2H2O+O2 HCO+O2CO+HO2 H+OH+MH2O+M HCO+HCO+H2 2CH3(+M)C2H6(+M) CH3CHOH+O2CH3HCO+HO2 O+H2OH+H OH+H2H+H2O CH2+O2CO2+2H CH3CHOH+HO2CH3HCO+2OH CH3+HO2CH3O+OH HCO+MH+CO+M CH3+OHCH2(S)+H2O HCO+H2OH+CO+H2O H+HO22OH CO+OHCO2+H O2+HO+OH
(c)
A
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 38 of 40
-0.2 907
Leplat ethanol T=373K p=1atm =1
-0.1 0.0 0.1 0.2 Normalized sensitivity coefficients
0.3
908
Figure 20. Sensitivity analysis of ethanol, ETBE and iso-octane at T=373K, p=1atm,
909
=1.
ACS Paragon Plus Environment
Page 39 of 40
Species mole fraction
0.012
T=373K p=1atm =1.0
Pink line: ethanol Red line: ETBE Blue line: isooctane
(a)
Solid line: H Dash line:OH Dot line:O
0.008
0.004
0.000 0.0
0.1
0.2
0.3
0.4
0.5
Distance (cm)
910
0.004
Species mole fraction
T=373K p=1atm =1.0
Red line: ETBE Blue line: isooctane Solid line:
0.000 0.00
(b)
IC4H8
Dash line:
IC4H7
Dot line:
C3H6
Dash dot line: C3H5-A
0.002
0.05
0.10
0.15
0.20
Distance (cm)
911 912
Figure 21. Mole fractions of some main species of ethanol, ETBE, iso-octane flames
913
at T=373K, p=1atm, =1.0.
914 4 (a) 3 2
Lb (mm)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
1 0 -1 -2 0.6
915
ETBE p=1atm T=298K T=373K T=453K 0.8
1.0
1.2
1.4
1.6
ACS Paragon Plus Environment
Energy & Fuels
3
(b)
Lb (mm)
2 1
ETBE T=373K
0
p=1atm p=3atm p=5atm
-1 -2 0.6
0.8
1.0
1.2
1.4
1.6
916 917
Figure 22. Measured Markstein length of ETBE at different temperatures and
918
pressures. 4 (a) 3
Lb (mm)
2 1 0 -1
ETBE ethanol isooctane gasoline
T=373K p=1atm
-2 0.6
0.8
1.0
1.2
1.4
1.6
919
2.0
(b)
1.5 1.0
Lb (mm)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
0.5 0.0 -0.5 -1.0
ETBE ethanol isooctane gasoline
T=453K p=1atm
-1.5 0.6
0.8
1.0
1.2
1.4
1.6
920 921
Figure 23. Measured Markstein length of ETBE, ethanol, iso-octane and gasoline at
922
373K and 453K.
ACS Paragon Plus Environment
Page 40 of 40