1

Simple Reactors
Coupled Thermodynamic and Chemical Systems
2
Four Simple Reactor Models
3
SUMMARY OF USEFUL RELATIONS
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=
=
=
= =
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= =
=
= =
|
|
.
|

\
|
=
i
i
i
i i
mix
i
i i mix
i i
i
mix
i i i i
j
j
i
i
mix
i i i
j
j j
i i
i
i
i
i
i mix
i
i
mix
i i
X
MW X
MW
MW MW
MW
Y
MW
MW X Y
X
X
MW RT
P
X
MW X
MW X
Y
MW
Y
RTMW
Y PMW
X
MW
MW
Y
_

_

_ _

_
1
Mole / mass fraction relation
Mass fraction / molar concentration
Mole fraction / molar concentration
Mass concentration
MW
mix
defined in terms of mass fractions
MW
mix
defined in terms of mole fractions
MW
mix
defined in terms of molar concentrations
_
i
: mole fraction
Y
i
: mass fraction
[X
i
]: molar concentration
4
1. CONSTANT PRESSURE, FIXED MASS REACTOR
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| | ( )
| | ( )
| |
| |
| |
(
(
(

+ =
=

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=

=
=
c
c
=
(

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+
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=

dt
dT
T X
X
dt
X d
MW X
m
V
c X
h
V
Q
dt
dT
V
dt
dN
X V N
dt
dT
c
dt
dT
T
h
dt
h d
dt
h d
N
dt
dN
h
m dt
dh
dt
dh
m Q
i
i
i
i
i i
i
i
i i
i
p i
i
i i
i
i
i i
i p
i i
i i
i
i i
i
1
1
,
e
e
e
e

1
st
Law
Differentiation of enthalpy
Note that enthalpys are on per mole basis
Calorically perfect gas
short hand notation for net production rate for
complete mechanism
Substitution into 1
st
Law
Volume expression
Expression for rate of change of molar concentrations
i
e

5
2. CONSTANT VOLUME, FIXED MASS REACTOR
| | ( )
| |( ) ( )
| |

+ =

+
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.
|

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=

|
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.
|

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=
=
i
i
i
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i
p i
i
i i
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i
i
v i
i
i i
dt
dT
X R RT
dt
dP
R c X
h RT
V
Q
dt
dT
c X
u
V
Q
dt
dT
dt
du
m Q
i
i
e
e e
e

1
st
Law
Substitution into 1
st
Law
In terms of molar enthalpys (instead of
internal energy)
Expression for time rate of change of pressure
Very useful for explosion calculations
6
Constant Volume Combustion: Engine Knock
Compressed gasoline-air mixtures have a
tendency to ignite prematurely rather than
burning smoothlyEngine Knock
Octane number of gasoline - resistance to
knock
Octane number is determined by
comparing the characteristics of a
gasoline to isooctane (2,2,4-
trimethylpentane) and heptane.
Isooctane is assigned an octane
number of 100. It is a highly
branched compound that burns
smoothly, with little knock.
Heptane is given an octane rating of
zero. It is an unbranched compound
and knocks badly.
7
EXAMPLE: ENGINE KNOCK
In spark ignition engines, knock occurs when unburned fuel-air mixture ahead of flame reacts
homogeneously, i.e., it autoignites
Rate of pressure rise is a key parameter in determining knock intensity and propensity for mechanical
damage to piston-crank engine assembly
Pressure vs. time traces for normal and knocking combustion in a spark-ignition engine shown below
Note very rapid pressure rise in case of heavy knock.
Piston exposed to long
terms effects of knock
http://www-cms.llnl.gov/s-t/int_combustion_eng.html
8
EXAMPLE: ENGINE KNOCK
Create a simple constant volume model of autoignition process and determine temperature, pressure and fuel
and product concentrations as a function of time
Assume that initial conditions corresponding to compression of a fuel-air mixture from 300 K and 1 atm to
TDC for a compression ratio of 10:1. Initial volume before compression is 3.68x10
-4
m
3
which corresponds to
an engine with both bore and a stroke of 75 mm. Use ethane, C
2
H
6
, as fuel.
Other assumptions:
1. One-step global kinetics using rate parameters for ethane
2. Fuel, air and products all have equal molecular weights, MW=29
3. Specific heats for the fuel, air, and products are constant and equal, cp=1,200 J/kg K
4. Enthalpy of formation of air and products is zero and enthalpy of formation of fuel is 4x10
7
J/kg
5. Stoichiometric air-fuel ratio is 16, and combustion is restricted to stoichiometric or lean cases
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| | | |
n m
y x
a
y x
k
y x
O H C
RT
E
A
dt
H C d
O H
y
xCO O
y
x H C
global
2
2 2 2
exp
2 4
|
.
|

\
|

=
+
|
.
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|
+ +
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SOLUTION: MATLAB SIMULATION, CONSTANT VOLUME
Fuel
Oxidizer
Products
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SOLUTION: EXPANDED SCALE ON TOP PLOT
Fuel
Oxidizer
Products
Large temperature increase in ~0.1 ms
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EXAMPLE RESULTS AND COMMENTS
Equations are integrated numerically using Excel
Temperature increases only about 200 K in first 3 ms, then T rises extremely
rapidly to adiabatic flame temperature, T
ad
~ 3300 K, in less than 0.1 ms
This rapid temperature rise and rapid consumption of fuel is characteristic of a
thermal explosion, where the energy released and temperature rise from reaction
feeds back to produce ever-increasing reaction rates because of the (-E
a
/RT)
temperature dependence of the reaction rate.
It can also be shown that huge pressure derivatives are associated with exploding
stage of reaction, with peak values of dP/dt ~ 1.9x10
13
Pa/s !!!
Although this model predicted explosive combustion of mixture after an initial
period of slow combustion, as is observed in real knocking combustion, single-step
kinetics mechanism does not model true behavior of autoigniting mixtures
In reality, induction period, or ignition delay, is controlled by formation of
intermediate species (radicals)
To accurately model knock, a more detailed mechanism would be required
17
EXAMPLE 1: WSR MODELING
Develop a WSR model using same simplified chemistry and thermodynamic used in previous example
Equal constant cps, MWs, one-step global kinetics for C
2
H
6
Use model to develop blowout characteristics of a spherical reactor with premixed reactants (C
2
H
6
and
Air) entering at 298 K. Diameter of reactor is 80 mm.
Plot | at blowout as a function of mass flow rate for | 1.0 and assume that reactor is adiabatic
( ) ( )
( ) ( )
( ) ( ) 0
0 1
0 23 . 0
0 23 . 0
,
,
Pr
65 . 1
1 . 0
75 . 1
,
65 . 1
1 . 0
75 . 1
,
= +
=
=
|
.
|

\
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.
|

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|

=
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in P in F F
F f
Ox F
Ox F G Ox in Ox
Ox F G F in F
T T c Y Y h
Y Y Y
Y Y
RT
P
MWV k
F
A
Y Y m
Y Y
RT
P
MWV k Y Y m

Set of 4 coupled nonlinear algebraic equations with unknowns, Y

F
, Y
Ox
, Y
Pr
, and T
Treat mass flow rate and volume as known parameters
To determine reactor blowout characteristic, solve nonlinear algebraic equations on previous slide for a
sufficiently small value of mass flow rate that allows combustion at given equivalence ratio
Increase mass flow rate until failure to achieve a solution or until solution yields input values
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EXAMPLE 1: RESULTS AND COMMENTS
Decreasing conversion of fuel to products as mass flow rate is increased to blowout condition
Decreased temperature as flow rate is increased to blowout condition
Mass flow rate for blowout is about 0.193 kg/s
Ratio of blowout temperature to adiabatic flame temperature is 1738 / 2381 = 0.73
Repeat calculations at various equivalence ratios generates the blowout characteristic curve
Reactor is more easily blown out as the fuel-air mixture becomes leaner
Shape of blowout curve is similar to experimental for gas turbine engine combustors
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GAS TURBINE COMBUSTOR CHALLENGES
Based on material limits of turbine (T
t4
), combustors must operate below
stoichiometric values
For most relevant hydrocarbon fuels,
s
~ 0.06 (based on mass)
Comparison of actual fuel-to-air and stoichiometric ratio is called equivalence ratio
Equivalence ratio = | = /
stoich
For most modern aircraft | ~ 0.3-0.4
Summary
If | = 1: Stoichiometric
If | > 1: Fuel Rich
If | < 1: Fuel Lean
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Most mixtures will NOT burn so far away from
stoichiometric
Often called Flammability Limit
Highly pressure dependent
Increased pressure, increased
flammability limit
Requirements for combustion, roughly | > 0.8
Gas turbine can NOT operate at (or even near)
stoichiometric levels
Temperatures (adiabatic flame temperatures)
associated with stoichiometric combustion are
way too hot for turbine
Fixed T
t4
implies roughly | < 0.5
What do we do?
Burn (keep combustion going) fuel rich with
some of ingested air
Then mix very hot gases with remaining air to
lower temperature for turbine
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SOLUTION: BURNING REGIONS
Air
C
o
m
p
r
e
s
s
o
r
T
u
r
b
i
n
e
| ~ 1.0
T>2000 K
|~0.3
Primary
Zone
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COMBUSTOR ZONES: MORE DETAILS
1. Primary Zone
Anchors Flame
Provides sufficient time, mixing, temperature for complete oxidation of fuel
Equivalence ratio near |=1
2. Intermediate (Secondary Zone)
Low altitude operation (higher pressures in combustor)
Recover dissociation losses (primarily CO CO
2
) and Soot Oxidation
Complete burning of anything left over from primary due to poor mixing
High altitude operation (lower pressures in combustor)
Low pressure implies slower rate of reaction in primary zone
Serves basically as an extension of primary zone (increased t
res
)
L/D ~ 0.7
3. Dilution Zone (critical to durability of turbine)
Mix in air to lower temperature to acceptable value for turbine
Tailor temperature profile (low at root and tip, high in middle)
Uses about 20-40% of total ingested core mass flow
L/D ~ 1.5-1.8
Assumptio
ns
Input
Important
EXCEL
File