MAE 5310: COMBUSTION FUNDAMENTALS

Coupled Thermodynamic and Chemical Systems:

Well-Stirred Reactor (WSR) Theory

October 8, 2009

Mechanical and Aerospace Engineering Department

Florida Institute of Technology

D. R. Kirk

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 WELL-STIRRED REACTOR THEORY OVERVIEW
• Well-Stirred Reactor (WSR) or Perfectly-Stirred Reactor (PSR) is an ideal reactor
in which perfect mixing is achieved inside the control volume
• Extremely useful construct to study flame stabilization, NOx formation, etc.

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 APPLICATION OF CONSERVATION LAWS
Rate at which mass of i accumulates
within control volume Mass flow of i into control volume

dmi ,cv
= Vm i′′′+ m i ,in − m i ,out
dt Mass flow of i out of control volume

Rate at which mass of i is

generated within control volume

m i′′′= ω i MWi Relationship between mass generation rate of a

species related to the net production rate

m i = m Yi

ω i MWiV + m i (Yi ,in − Yi ,out ) = 0

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 APPLICATION OF CONSERVATION LAWS
ω i = f ( [ X i ] cv , T ) = f ( [ X i ] out , T ) Outlet mass fraction, Yi,out is equal
to the mass fraction within the reactor

Yi =
[ X i ] MWi Conversion of molar concentration into mass fraction

∑ [ X ]MW
N (see slide 2)
j j
j =1

Q = m ( hout − hin )
So far, N equations with N+1 unknowns, need to close set
Application of steady-flow energy equation

 N N

Q = m  ∑ Yi ,out hi ( T ) −∑ Yi ,in hi ( Tin ) 
 Energy equation in terms
of individual species
 i =1 i =1 
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 WSR SUMMARY
• Solving for temperature and species mass fraction is similar to calculation of adiabatic flame
temperature (Glassman, Chapter 1)
– The difference is that now the product composition is constrained by chemical kinetics
rather than by chemical equilibrium

• WSR (or PSR) is assumed to be operating at steady-state, so there is no time dependence

– Compared with the constant pressure and constant volume reactor models considered
previously
• The equations describing the WSR are a set of coupled (T and species concentration)
nonlinear algebraic equations
– Compared with constant pressure and constant volume reactor models which were
governed by a set of coupled linear, 1st order ODEs
– Net production rate term, although it appears to have a time derivative above it, depends
only on the mass fraction (or concentration) and temperature, not time
• Solve this system of equations using Newton method for solution of nonlinear equations
ρV
• Common to define a mean residence time, τ res, for gases in WSR τ res =
m
PMWmix
ρ=
RT 5
 EXAMPLE 1: WSR MODELING
• Develop a WSR model using same simplified chemistry and thermodynamic used in previous example
– Equal constant cp’s, MW’s, one-step global kinetics for C2H6
• Use model to develop blowout characteristics of a spherical reactor with premixed reactants (C2H6 and
Air) entering at 298 K. Diameter of reactor is 80 mm.
• Plot φ at blowout as a function of mass flow rate for φ ≤ 1.0 and assume that reactor is adiabatic

1.75
 P 
m (YF ,in − YF ) − kG MWV  YF0.1 ( 0.23YOx )
1.65
 =0
 RT 
1.75
 A  P 
m (YOx ,in − YOx ) −  kG MWV  YF0.1 ( 0.23YOx )
1.65
 =0
F  RT 
1 − YF − YOx − YPr = 0
h  f , F (YF − YF ,in ) + cP ( T − Tin ) = 0
• Set of 4 coupled nonlinear algebraic equations with unknowns, YF, YOx, YPr, 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 6
 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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 EXAMPLE 2: GAS TURBINE COMBUSTOR CHALLENGES
• Based on material limits of turbine (Tt4), combustors must operate below
stoichiometric values
– For most relevant hydrocarbon fuels, ψ s ~ 0.06 (based on mass)

• Comparison of actual fuel-to-air and stoichiometric ratio is called equivalence

ratio
– Equivalence ratio = φ = ψ /ψ stoich
– For most modern aircraft φ ~ 0.3

• Summary
– If φ = 1: Stoichiometric
– If φ > 1: Fuel Rich
– If φ < 1: Fuel Lean

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 EXAMPLE 2: WHY IS THIS RELEVANT?
• 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 φ > 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 Tt4 implies roughly φ < 0.5

• What do we do?
– Burn (keep combustion going) near φ =1 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

Turbine
Air Primary
Zone
φ ~0.3
Compressor

φ ~ 1.0
T>2000 K

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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 φ =1
1. Intermediate (Secondary Zone)
– Low altitude operation (higher pressures in combustor)
• Recover dissociation losses (primarily CO → CO2) 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 τ res)
– L/D ~ 0.7
1. 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

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 EXAMPLE 2: GAS TURBINE ENGINE COMBUSTOR
• Consider the primary combustion zone of a gas turbine as a well-stirred reactor with
volume of 900 cm3. Kerosene (C12H24) and stoichiometric air at 298 K flow into the reactor,
which is operating at 10 atm and 2,000 K
• The following assumptions may be employed to simplify the problem
– Neglect dissociation and assume that the system is operating adiabatically
– LHV of fuel is 42,500 KJ/kg
– Use one-step global kinetics, which is of the following form

ω fuel
 − Ea 
= −5 x10 exp
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[
 X fuel ] [X ]
0.25
ox
1.5

 RT 

– Ea is 30,000 cal/mol = 125,600 J/mol

– Concentrations in units of mol/cm3

• Find fractional amount of fuel burned, η

• Find fuel flow rate
• Find residence time inside reactor, τ res

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 EXAMPLE 2: FURTHER COMMENTS
• Consider again the WSR model for the gas turbine combustor primary zone, however now
treat temperature T as a variable.
– At low T, fuel mass flow rate and η are low
– At high T, η is close to unity but fuel mass flow rate is low because the concentration
[F] is low ([F]=χ FP/RT), which reduces reaction rate
– In the limit of η =1, T=Tflame and the fuel mass flow rate approaches zero
• For a given fuel flow rate two temperature solutions are possible with two different heat
outputs are possible

φ =1, kerosene-air mixture

V=900 cm3
P=10 atm

Q = ηm f LHV
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 EXAMPLE #3: HOW CHEMKIN WORKS
• Detailed mechanism for H2 combustion
• Reactor is adiabatic, operates at 1 atm, φ =1.0, and V=67.4 cm3
• For residence time, τ res , between equilibrium and blow-out limits, plot T, χ H2O, χ H2, χ OH,
χ O2, χ O, and χ NO vs τ res .

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 EXAMPLE #3: HOW CHEMKIN WORKS
Tflame and χ H2O
concentration drop as τ res
becomes shorter

H2 and O2 concentrations rise

Behavior of OH and O
radicals is more complicated

NO concentration falls rapidly

as τ res falls below 10-2 s

Input quantities in CHEMKIN:

Chemical mechanism
Reactant stream constituents
Equivalence ratio
Inlet temperature and pressure
Reactor volume
τ res (1 ms ~ essentially equilibrated conditions)

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