Objectives
This project aims to develop the tools necessary for
the design of future synthesis-gas and hydrogen
(SGH) fueled combustion turbines.
Generate a detailed experimental database of SGH
combustion at IGCC-like conditions.
Investigate fundamental chemical kinetics of
H2/CO/O2/N2/H2O/CO2 at pressures, temperatures, and
concentrations typical of SGH combustion in gas turbines
Develop detailed and reduced chemical mechanisms based
on this database, capable of predicting NOx formation
during SGH combustion.
Scope of Work
Obtain benchmark experimental
characteristics of syngas
data
for
combustion
Accomplishments - Year 1
Autoignition of dry H2/CO mixtures at elevated pressures
in a rapid compression machine.
Assessment of kinetics of syngas combustion at elevated
pressures using global uncertainty analysis methods.
Reaction kinetics of CO+HO2 ab initio calculations.
3 journal publications and 1 under review.
Preliminary experimentation on autoignition of wet H2/CO
mixtures at elevated pressures in a rapid compression
machine.
Preliminary experimentation to determine combustion
characteristics of wet H2/CO mixtures in a counterflow
configuration.
Outline
Autoignition of Dry H2/CO Mixtures
Conclusions
Future Work
Reactor
Cylinder end region
Cylinder
with quartz window,
pressure transducer,
thermocouple & gas line
Piston
stopping
groove
Spacers for
adjusting stroke
Air line
from tank
Hydraulic line for filling, draining, and solenoid release
Hydraulic Piston
Ports for
quartz
windows
Pressure
transducer
Thermocouple
Driver Piston
Creviced Piston
RCM Operation
Pneumatically driven
Reproducibility
60
Pressure (bar)
50
40
Ignition
Delay,
PC = 30 bar
TC = 999 K
30
20
10
0
-30
-20
-10
Time (ms)
10
Comparison of
RCM Experiment and Model
Simulation using CHEMKIN and SENKIN with volume specified
as a function of time in a homogeneous adiabatic system.
50
Pressure (bar)
40
PC= 30 bar
TC= 977 K
Experiment
Model
30
Nonreactive
(experiment and model)
20
10
0
-15
-10
-5
0
5
Time (ms)
10
15
20
RCO=[CO]/([H2]+[CO]): 0 0.80
Mixture #
RCO
H2
CO
O2
N2
Ar
1.0
12.5%
0%
6.25%
18.125%
63.125%
1.0
0.25
9.375%
3.125%
6.25%
18.125%
63.125%
1.0
0.50
6.25%
6.25%
6.25%
18.125%
63.125%
1.0
0.65
4.375%
8.125%
6.25%
18.125%
63.125%
1.0
0.80
2.5%
10%
6.25%
18.125%
63.125%
0.36
0.25
6.667%
2.222%
12.345%
14.418%
64.348%
0.72
0.25
6.667%
2.222%
6.173%
21.586%
63.352%
1.0
0.25
6.667%
2.222%
4.444%
23.600%
63.067%
1.3
0.25
6.667%
2.222%
3.419%
24.782%
62.910%
10
1.6
0.25
6.667%
2.222%
2.777%
25.511%
62.823%
Pressure (bar)
40
P0 = 640 Torr
TC = 1010.5 K
30
T0 = 298 K
20
Experimental
O'Conaire et al. (2004)
10
0
-15
-10
-5
0
5
Time (ms)
10
15
20
PC=15 bar
100
Experimental
Li et al.
Davis et al.
PC=30 bar
0.96
0.98
1
1.02
1000/T (1/K)
10
Experimental
Li et al.
Davis et al.
GRI-Mech 3.0
O'Conaire et al.
0.94
10
1
0.94
PC=50 bar
GRI-Mech 3.0
O'Conaire et al.
1.04
1.06
0.96
0.98
1
1.02
1000/T (1/K)
1.04
1.06
22
TC = 1010.5 K
PC = 30 bar
20
H2O2+H=HO2+H2
H2O2(+M)=OH+OH(+M)
19
HO2+HO2=H2O2+O2
18
HO2+HO2=H2O2+O2
17
HO2+OH=H2O+O2
13
H+O2(+M)=HO2(+M)
H+O2=OH+O
-60
-40
-20
20
40
60
Percent Sensitivity
100
Ignition Delay, (ms)
PC = 50 bar
0.80
0.65
0.50
0.25
RCO=0
10
1
0.96
0.98
1
1000/TC (1/K)
1.02
1.04
100
0.50
0.80
0.65
RCO=0
PC = 30 bar
0.25
10
RCO
0
0.25
0.50
0.65
10
0.80
PC = 15 bar
1
0.96
0.98
1
1.02
1000/TC (1/K)
1.04
1.06
0.94
0.96
0.98
1000/TC (1/K)
1.02
4
Ignition Delay, (ms)
30
Ignition Delay, (ms)
Li et al.
25
PC = 30 bar
TC = 1010.5 K
GRI-Mech 3.0
GRI-Mech 3.0
PC = 50 bar
TC = 1044 K
Davis et al.
2.5
Experimental
2
1.5
1
0.5
Davis et al.
20
Li et al.
3.5
Experimental
15
0.2
0.4
0.6
0.8
RCO
10
(H2+CO)/O2/N2/Ar = 12.5/6.25/18.125/63.125
5
0
0.2
0.4
0.6
RCO
0.8
Reaction Number
27
TC = 1010.5 K
PC = 30 bar
26
CO+OH=CO2+H
CO+HO2=CO2+OH
CO+O2=CO2+O
CO+O(+M)=CO2(+M)
22
H2O2+H=HO2+H2
20
H2O2(+M)=OH+OH(+M)
19
HO2+HO2=H2O2+O2
RCO
18
HO2+HO2=H2O2+O2
HO2+OH=H2O+O2
0
0.50
0.80
17
13
H+O2(+M)=HO2(+M)
H+O2=OH+O
-60
-40
-20
20
40
60
Percent Sensitivity
CO + HO -> CO + OH
standard deviation / ms
H + O + M -> HO + M
HO + OH -> H O+ O2
2
2
0.4
HO + H2 -> H2O + H
2
2
REACTION
0.3
H + O -> OH + O
2
0.2
0.1
CO + OH -> CO + OH
2
CO+HO2 CO2+OH
(-10.702 -9.902)
H+O2+M HO2+M
(-11.272 -10.871)
H+O2 OH+O
(-7.207 -7.507)
H2O2+M 2OH+M
(19.146 19.546)
HO2+OH H2O+O2
(-10.905 -9.905)
HO2+H2 H2O2+H
(-19.667 -19.047)
0.0
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
Range of log A
(cm molecule s)
1.6
10
log A in primary
t/ms
Experimental
tign at 50 bar
and 1040 K
data set
The experimental
value for tign is
predicted in only a
few cases regardless
of all other
parameter values
0
-12.0
-11.5
-11.0
-10.5
-1
-1
log(A/molecule cm s )
-10.0
Normalised frequency
1.0
tign for log A = -10.3 and all other rate parameters are allowed to
vary over their uncertainty ranges (s.d ~ + 60%)
0.8
0.6
0.4
0.2
2.5
5.0
7.5
tign / ms
10.0
12.5
15.0
Conclusions from
Global Uncertainty Analysis
The currently accepted parameter values for CO + HO2 are
obviously not right.
Log A < -11 would fix it but the present analysis does not
permit us to do more than indicate that the overall reaction
rate is too fast.
This constraint arises from the uncertainty in other rate
parameters that gives the scatter in the predicted ignition
delays which is problem for any model validation using
ignition delay data.
Corrected parameters cannot be generated for this reaction
solely from ignition delay evaluations
Direct experimental or theoretical approaches are required to
determine the rate parameters.
Reaction Kinetics of
CO+HO2 CO2 + OH
ab initio Study and Master Equation Modeling
Motivation (1)
1011
Vandooren et al.
Azatyan et al.
Colket et al.
Atri et al.
Baldwin (1970)
Baldwin (1965)
Vardanyan
Mittal et al.
Burrows et al.
Davis et al.
Howard
Gramham
Simonaitis
Bohn et al.
Arustamyan et al.
Wyrsch et al.
Khachatrian et al.
Hoare and Patel
Hastie
Volman and Gorse
Sun et al.
Tsang and Hampson
109
107
Mueller et al.
105
Lloyd
103
101
10-1
CO+HO2=CO2+OH
10-3
0.5
1.0
1.5
2.0
1000K/T
2.5
3.0
3.5
Motivation (2)
Prior theoretical efforts are insufficient to ensure an
accurate rate coefficient.
In all cases, the hindered internal rotations in the
HOOCO adduct and the critical geometries were
inadequately treated.
The complexity of the potential energy surface due
to the trans- and cis-conformers and their mutual
isomerization was not considered.
In addition, the calculations of the potential energy
barriers may not be sufficiently reliable to obtain
accurate rate constant values.
Approach
A more detailed analysis of the potential energy
surface of CO+HO2 reaction using several high-level
quantum chemistry methods.
Our best estimates for the saddle point energies are
then incorporated in transition state theory
simulations that consider the full complexity of the
hindered rotational motions.
Furthermore, the possibility of collisional
stabilization and the dissociation of the adduct back
to CO + HO2 along the trans pathway is examined
via master equation simulations.
27
ECCSD(T)/cc-pVQZ ECCSD(T)/cc-pVTZ
37
1
EFCC/CBS ECCSD(T)/CBS + ECCSD(T)/cc-pVTZ ECCSD/cc-pVTZ
5
Configuration Interaction truncation error
-63.3
6.3
18.3
12.0
19.3
15.5
33.3
-61.0
7.2
18.3
13.4
19.3
16.4
33.7
-61.8
6.5
17.9
12.7
18.9
15.8
34.1
-61.7
6.0
17.3
11.8
18.2
15.3
34.0
Literature
value
-61.60.1
33.60.1
TS3 (cis)
TS1 (trans)
18.9
17.9
TS2 (trans)
12.7
trans-HOOCO
6.5
CO+HO2
0
Theory
TS1
PT2(5e,5o)/CBS
17.1
PT2(9e,8o)/CBS
18.2
PT2(11e,11o)/CBS
18.4
cis-HOOCO
CO2+OH
-61.8
Internal Rotation
Asymmetric characteristics
TS1TS3
Potential Energy
V03
V02
V01
V04
1.149
1.758
1.150
TS3
1.742 0.968
TS1
TS1
/2
3/2
Rotation Angle,
TS1
1.391
12 4
1 kBT
Qh ( T ) =
2 B
i / 2
(
i =1
i 1) 2
d e V
TS3
1.400
0.969
kBT
Density of States
( 2, n )
I L (1, n )I R (1, n )
I L (1, n ) + I R (1, n )
(3, 4 )
2
3
U
iy
i
(1,1)
=I
+
m L + mR
I
i
i =1
Results (1)
T(K)
Harmonic
oscillator
Free rotor
with I(3,4)
I(2,1)
I(2,3)
I(3,4)
500
2.1103
3.8104
2.9103
1.5103
1.7103
1000
5.6107
6.1108
1.1108
6.3107
6.5107
1500
2.6109
2.11010
5.5109
3.4109
3.2109
2000
2.21010
1.41011
4.71010
2.91010
2.71010
2500
8.81010
4.61011
1.91011
1.21011
1.11011
Results (2)
Vandooren et al.
Azatyan et al.
Colket et al.
Atri et al.
Baldwin (1970)
Baldwin (1965)
Vardanyan
Mittal et al.
Burrows et al.
Davis et al.
Howard
Gramham
Simonaitis
Bohn et al.
Arustamyan et al.
Wyrsch et al.
Khachatrian et al.
Hoare and Patel
Hastie
Volman and Gorse
1011
109
107
105
103
this work
101
10-1
CO+HO2=CO2+OH
10-3
0.5
1.0
1.5
2.0
2.5
3.0
3.5
1000K/T
No pressure dependence up to 500 atm.
Supports the notion advanced in RCM studies that the literature rate values are too
large.
Uncertainty Analysis
1011
Sources of Uncertainty:
Upperlimit (this work)
k (cm3/mol-s)
1010
108
107
300 K, a factor of 8;
106
1000 K, a factor of 2;
0.6
0.8
1.0
1.2
1.4
1000K/T
The error bars reject almost all of the rate values
reported in earlier studies.
Pc = 15 Bar
Tc = 1028.5 K
10
25
Pc = 30 Bar
Tc = 1010.5 K
20
15
10
5
0
5
Pc = 50 Bar
Tc = 1044 K
2
1
0
0.0
0.2
0.4
0.6
RCO
0.8
1.0
Summary
The current theoretical analysis supports lower rate
value for CO+HO2=CO2+OH.
Recommended rate expression:
Bypass
Nebulizer
Air
Mixing
Chamber
O2
N2
Syringe
Pump
Temperature
Controller
Nozzle Heating
Pad
N 2 Coflow
Heating Rope
Uz
Laser Head
Burner
DPIV Measurement
0.5
Reference Speed
1.5
0.6
Radial Velocity Gradient
0.4
0.2
stretch rate, K
0
-0.2
-0.4
-0.6
Reference Point
0
-3
0
0.5
1
1.5
2
2.5
3
Distance from Nozzle Exit, z (mm)
-2
-1
0
1
Radial Axis, r (mm)
Linear Extrapolation
=0.7, RCO=0.95, H2O=15%, Tu=323 K
100
100
80
60
40
20
200
400
600
800
80
60
20
200
400
600
H2O=[H2O]/([H2]+[CO]+[H2O])
800
H2O=0%
H2O=0%
H2O=25%
H2O=25%
Conclusions
Need comprehensive detailed and reduced mechanisms for
syngas and hydrogen combustion.
Discrepancies between simulations and the newly obtained
experimental data are discussed.
Comparison of experimental and computational results will
enable the re-evaluation and optimization of current
mechanisms.
The lack of accurate/meaningful experimental data has in the
past hampered the progress in the development of kinetic
mechanism.
Need extensive benchmark data of high fidelity.
Future Work
Obtain detailed experimental data for combustion characteristics of SGH
mixtures using rapid compression machine and counterflow burner.
Effects of CO2 and H2O addition on the autoignition of H2/CO mixtures.
Measurements of laminar flame speeds and strain-induced extinction limits of
premixed SGH flames.
Acknowledgements
Work supported by DOE/NETL
Contract Monitor: Rondle E. Harp.
Former and current graduate students:
Gaurav Mittal, Kamal Kumar, Xiaoqing You, and
Apurba Das.