Syngas and Hydrogen Combustion:

Ignition and Flame Propagation

Grant Number: DE-FG26-06NT42717
Development of Comprehensive Detailed and Reduced Reaction Mechanisms for
Syngas and Hydrogen Combustion

Principal Investigator: Chih-Jen Sung

Department of Mechanical and Aerospace Engineering
Case Western Reserve University
Cleveland, Ohio 44106
Collaborators: Hai Wang, University of Southern California
Angela Violi, University of Michigan
University Coal Research Contractors Review Conference
June 5-6, 2007

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

Conterflow Burner Apparatus

Laminar flame speeds
Extinction limits
Flame structure
Rapid Compression Machine
Ignition delays at elevated pressures

Develop comprehensive and computationally-efficient chemical

models

Assessment of available kinetic mechanisms

Theoretical calculations to determine critical rate constants
Mechanism optimization
Mechanism simplification and reduction

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

Characterization of Rapid Compression Machine

Ignition Delay Results
Brute Force Sensitivity Analysis
Global Uncertainty Analysis

Reaction Kinetics of CO+HO2 CO2 + OH: ab initio

Study and Master Equation Modeling
Laminar Flame Speeds of Wet H2/CO Mixtures with
Preheat
Counterflow Burner Apparatus
Preliminary Results

Conclusions
Future Work

Autoignition of Dry H2/CO Mixtures

High-Pressure Ignition and Oxidation

Rapid Compression Machine
(RCM)

Rapid sampling apparatus

Reactor
Cylinder end region
Cylinder
with quartz window,
pressure transducer,
thermocouple & gas line

Hydraulic piston seal

Hydraulic
Chamber

Piston
stopping
groove

Spacers for
adjusting stroke

Air line
from tank
Hydraulic line for filling, draining, and solenoid release
Hydraulic Piston

Port for gas

inlet/outlet valve

Ports for
quartz
windows

Pressure
transducer

Thermocouple

End Reaction Chamber

Driver Piston

Creviced Piston

Features of the Present RCM

RCM simulates a single compression stroke of an engine
simple and relatively easy to operate

Adjustable stroke and clearance

Fast compression (< 30 ms)
Compressed pressure up to 60 bar
Temperature 500 to 1100 K
Elevated pressure condition is sustained up to 100 ms
Optimized creviced piston for ensuring homogeneity of reacting mixture
Optically accessible
GC/MS and a fast sampling apparatus for species measurement
Direct measurement of ignition delay
Study of low-to-intermediate temperature chemistry

RCM Operation
Pneumatically driven

Hydraulically actuated and stopped

Reproducibility
60

Pressure (bar)

50
40

Ignition
Delay,

PC = 30 bar
TC = 999 K

30
20
10
0
-30

-20

-10
Time (ms)

10

Molar composition: H2/CO/O2/N2/Ar = 9.375/3.125/6.25/18.125/63.125

Initial conditions T0 = 298.7 K and P0 = 661 Torr

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

Dry H2/CO Experiments Specifications

Temperature (TC): 950 1100K

Pressure (PC): 15 50 bar

Equivalence ratio (): 0.36 1.6

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%

Hydrogen Ignition Delay (1)

Stoichiometric hydrogen mixtures (H2/O2/N2/Ar = 2/1/2.9/10.1)
50

Pressure (bar)

40

P0= 705.8 Torr

TC= 977 K

P0 = 640 Torr
TC = 1010.5 K

30
T0 = 298 K

20

Experimental
O'Conaire et al. (2004)

10

Davis et al. (2005)

Li et al. (2004)

0
-15

-10

-5

0
5
Time (ms)

10

15

20

Hydrogen Ignition Delay (2)

H2/O2/N2/Ar = 12.5/6.25/18.125/63.125
100

Ignition Delay, (ms)

PC=15 bar

Ignition Delay, (ms)

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

Brute Force Sensitivity Analysis

Reaction Number

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

Reactions involving formation and consumption of HO2

and H2O2 are important.

H2/CO Ignition Delay (1)

Effect of increasing RCO

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

Replacement of even small amounts of H2 with CO leads

to an inhibition of autoignition.

H2/CO Ignition Delay (2)

100

100

0.50
0.80
0.65

RCO=0

Ignition Delay, (ms)

Ignition Delay, (ms)

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)

The inhibition effect of CO addition is seen to be much

more pronounced at higher pressures.

1.02

H2/CO Ignition Delay (3)

Existing mechanisms fail to
describe the inhibition effect of
CO addition.
From mechanisms, inhibition
effect of CO is not observed
until it constitutes 80% of the
total fuel mole fraction.

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

Brute Force Sensitivity Analysis

29
28

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+HO2=CO2+OH appears to be the primary reaction responsible

for the mismatch of experimental and calculated ignition delays.

Global Uncertainty Analysis

Brute force local sensitivity analysis is a useful linear
analysis, but this cannot reveal interactions between kinetic
parameter values.
Uncertainties have to be assigned to all relevant parameters
and the response to variations within the assigned ranges must
be tested.
Global, non-linear, uncertainty analysis which simultaneously
considers variations in all kinetic parameters is required to
interpret the origins of the discrepancy (e.g. Morris-one-at-atime and Monte-Carlo methods).
in collaboration with Prof. J. F. Griffiths, University of Leeds

Morris Analysis (1)

The overall importance ranking of reactions is
determined by the absolute mean perturbation of the
predicted ignition delay across all simulations when
rate parameters are varied in a prescribed way within
their ranges of uncertainty.
The standard deviation reflects non-linear effects, i.e.
the extent to which the sensitivity of the ignition delay
may change if other parameters are adjusted.

Morris Analysis (2)

0.8CO + 0.20H2 at 50 bar and1040 K using 76 irreversible reaction
scheme (Davis et al., 2005)
0.5

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

H2O + M -> 2OH + M

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

absolute mean perturbation / ms

1.4

Range of log A
(cm molecule s)

1.6

Monte Carlo Analysis (1)

Significance of k of CO+HO2 in predicting ignition delay
12

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 )

This is why we think k for CO + HO2 is wrong.

-10.0

Monte Carlo Analysis (2)

Relationship of various values of k of CO+HO2 with predicted ignition delays

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

tign for log A = -11 and all other rate

parameters are allowed to vary over their
uncertainty ranges (s.d ~ + 40%)

0.6

0.4

These variations arise even in a 76

reaction scheme for which the data are

0.2

generally well known. BE WARNED!

0.0
0.0

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.

Quantum Chemistry Calculation

CCSD(T)/CBS energy (Halkier, 1998)
ECCSD(T)/CBS ECCSD(T)/cc-pVQZ +

27
ECCSD(T)/cc-pVQZ ECCSD(T)/cc-pVTZ

37

FCC/CBS energy (He, 2000)

Basis set correction

1
EFCC/CBS ECCSD(T)/CBS + ECCSD(T)/cc-pVTZ ECCSD/cc-pVTZ

5
Configuration Interaction truncation error

Energies (kcal/mol) at 0 K relative to CO + HO2

Products/
G3B3
transition state
CO2+OH
HOOCO
TS1
TS2
TS3
TS4
HCO+O2

-63.3
6.3
18.3
12.0
19.3
15.5
33.3

CCSD(T)/ CCSD(T)/ CCSD(T)/ FCC/CBS

cc-pVTZ cc-pVQZa
CBS
-59.9
8.1
18.8
14.4
19.9
17.2
33.1

-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

Potential Energy Surface

CO+HO2products (CCSD(T)/CBS//CCSD(T)/cc-pVTZ, kcal/mol)

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

Hindered internal rotation contributions

h ( E ) = h 1 ( E ) + h 2 ( E ) + h 3 ( E ) + h 4 ( E )

Total density of states

Treatment of the Moment of Inertia

At lower level approximation

( 2, n )

I L (1, n )I R (1, n )

I L (1, n ) + I R (1, n )

At higher level approximation (East and Radom,

1997)
I

(3, 4 )

2
3

U
iy
i
(1,1)

=I

+
m L + mR

I
i
i =1

Results (1)

Effects of internal rotor and I treatment on k (cm3/mols)

Hindered rotor

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)

TS1, TS3 barrier: 1 kcal/mol

k (cm3/mol-s)

1010

Internal rotation barrier: 1

kcal/mol
109

State counting: 50%

This work

108

107

Rate constant Uncertainty:

Lowerlimit (this work)

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.

2000 K, a factor of 1.7.

Modeling vs. RCM Experiments

15

Pc = 15 Bar
Tc = 1028.5 K

Molar composition: (H2+CO)/O2/N2/Ar

=12.5/6.25/18.125/63.125.

10

Dashed lines: Model of Davis et al. (2005)

25

Pc = 30 Bar
Tc = 1010.5 K

20
15

Solid lines: updated model.

10
5
0
5

1. CO+HO2=CO2+OH (this work)

Pc = 50 Bar
Tc = 1044 K

2. CO+OH=CO2+H (Joshi and Wang)

3. HO2+OH=H2O+O2 (Sivaramakrishnan et al.)

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:

k cm3 mol s = 1.57 105T 2.18e9030 T

(300T2500 K, P 500 atm)

Laminar Flame Speeds of

Wet H2/CO Mixtures with Preheat

Counterflow Twin-Flame Configuration

Sonic
Nozzle

Bypass

Nebulizer
Air

Mixing
Chamber

O2
N2
Syringe
Pump

Temperature
Controller
Nozzle Heating
Pad

N 2 Coflow

Heating Rope

Counterflow Twin Flames

Uz

DPIV System for Velocity Measurement

Gemini PIV-Nd:YAG Dual Lasers
15 Hz repetition rate
120 mJ/pulse at 532 nm
3-5 ns pulse width

Laser Head

Dantec PIV 2100

Processor

Burner

Dantec HiSense CCD

Camera
12801024 pixels
6.7 m 6.7 m
9 frames/sec

DPIV Measurement

0.5

Reference Speed

Radial Velocity at Reference Point (m/s)

Axial Velocity (m/s)

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

Reference Flame Speed (cm/s)

Reference Flame Speed (cm/s)

100

80

60

Laminar Flame Speed

40

20

200

400

600

Stretch Rate (s-1)

800

=0.7, RCO=0.95, H2O=25%, Tu=323 K

80

60

Laminar Flame Speed

40

20

200

400

600

Stretch Rate (s-1)

H2O=[H2O]/([H2]+[CO]+[H2O])

800

Effect of Water Addition on

Flame Propagation
Fixed Volumetric Flow Rate
=0.7, RCO=0.75, Tu=323 K

Fixed Volumetric Flow Rate

=1.3, RCO=0.95, Tu=323 K

H2O=0%

H2O=0%

H2O=25%

H2O=25%

laminar flame speed decreases with

increasing H2O

laminar flame speed increases with

increasing H2O

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.

Assess kinetic mechanism against the newly acquired experimental data,

thereby enabling re-evaluation and optimization of rate constants and
mechanism.
Conduct ab initio quantum chemistry calculation and master equation
modeling for certain key reactions, including HO2+HO2H2O2+O2 and
HO2+OHH2O+O2.
Notable influence on SGH oxidation rates under high-pressure, low-tointermediate temperature conditions.
Complex temperature and pressure dependences that cannot be easily resolved
through mechanism optimization.

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.