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ChemkinPro

Chemical Kinetics

ChemkinPro Installation
University of Cincinnati has a 20 Chemkin network licenses
Installation Procedure:
Step 1: Download 32 or 64 bit Chemkinpro from
http://www.ase.uc.edu/~chemkin/
Install both Chemkin (20) and ChemkinPro (1)
Step 2: Copy the license file, chemkin.lic
Step 3: Connect to university Network through VPN
Students can install on their personal laptops but for license file
connect to university network
The license is a Network license, so step 3 is always needed when
running ChemkinPro

The link in step 1 contains installation procedure, if


difficulties arise contact network administrator Rob Ogden
email: Rob.Ogden@uc.edu or bhayaruh@ucmail.uc.edu

Overview of Chemical Kinetics


activation
energy

O2

H C

H 2O
H
H

CH4

O2

CH3

OH

CO2

You need basic combustion concepts required to run the Chemkin software
Reaction occurs when two or more molecules collide
The probability of two molecules colliding is higher than three or more
molecules at an instant (bimolecular collision rates higher)
Assume during collision only one bond is broken
Inelastic collisions
- Involves conversion of KE to Internal energy/chemical energy
- Endothermic, exothermic

Overview of Chemical Kinetics


activation
energy
O2

O2

Control volume with


CH4 + O2
Presence of fuel and oxidizer in a control volume not necessarily mean there will be
a reaction
Needs Activation Energy to start the reaction process
Typical example: spark plug
Once the activation energy is given to a system with fuel and oxidizer a chain of
reaction occur which leads to conversion of reactants to products.

Overview of Chemical Kinetics

When activation energy is given the first reaction the starts is called chain initiation
In case of methane it is CH4+O2-> CH3+HO2
Once the reaction is started by chain initiation, the subsequent reactions are started
called chain propagation
Finally when there are reactions which leads to final conversion products. In this
case CO2 and H2O
The reactions further dont proceed as an when they reach their minimum state of
energy level represented by Gibbs Free Energy
As can be observed from the chain reaction diagram, the longer the path required to
convert from CH4 to CO2, the more time it takes. Its represented by Rate constant
or rate of reaction

Overview of Chemical Kinetics


- Based on the time given for the reaction to occur, if there is ample time
given for the reactions to occur, the reactants leads to the products
where they are at lowest energy state. A complete combustion is
achieved -> reaching equilibrium state or Chemical Equilibrium NASA
CEA code
- Chemical Equilibrium calculations will give a reasonable estimate of
products and temperatures. As one can guess the temperatures will be
higher
- From Chain Reactions, a Mechanism of conversion from reactants to
products, TIME factor is involved. Rate of Reaction-> time it takes for
the process to occur TIME -> How Much time

Overview of Chemical Kinetics


- In practical systems like gas turbine combustion or IC engines: Does the
system has enough time for all these reactions to occur: Quantitative ??
- If not sufficient time is given, non-equilibrium states are achieved
- Pollutant levels is a non-equilibrium
- Equilibrium = steady state = unsteady state
- Tchem vs Tflow, Tmixing, Tdiffusion
- Fast kinetics, Tchem << Tother
- Chemically frozen, Tchem >> Tother
- Time Dependent Processes
- Global Reactions (Fast Rate Chemistry) energy release rate vs
Elementary Reactions ignition, explosion, emissions

Reactants IN
At velocity
V1

Time spent by the


mixture in the control
volume
Tresidence time, Tchem
Damkhlar number

Products OUT at
velocity V2

Overview of Chemical Kinetics


Fuel/air
mixture IN
At velocity
V1

Time spent by the mixture


in the control volume
Tresidence time, Tchem, Tmixing

Fuel/air mixture
OUT at velocity V2

Damkhlar number

- Chamber/Reactor-where chemical reactions occur


- If there is no flow in and out during reaction-closed reactors (0D models)
- Constant volume or constant pressure reactors
- If there is flow in and out of the reactor during chemical reactions, open
reactors (0D models) Well Stirred Reactor
- If flow properties changes along the length of the reactor (1D models),
it is plug flow reactor

How To Use ChemkinPro


Software

ChemkinPro Tutorials
Four Problems will be discussed
Problem 1: Adiabatic Flame Temperature : Chemical
Equilibrium Calculations
Problem 2: Steady-state Gas-phase Combustion : PSR
Problem 3: Plug Flow Reactor
Problem 4: Gas Turbine Network : PSRs+ PFRs

ChemkinPro Tutorials

Start Menu
Things to Observe

A project is created for each Network


model
Contains 0D and 1D models,
A series of these models are used for to simulate a gas
turbine combustor

ChemkinPro Tutorials
Mathematical Model to simulate combustion related engineering problems
Reactor models typically used in
IC Engines: Closed volume
Well stirred reactor (WSR or PSR) typically used in Gas
Turbine combustion modeling: open volume means flow
in and out
Flow Reactors to simulate the flow
Models to simulate the Flame, to study flame
extinction, lean blowout limits, flammability limits

Example 1
Adiabatic Flame Temperature
Chemical Equilibrium Calculations
(For Hydrogen and Air)
Parameters:
Initial Temperature 300,400,500,600 K
Pressure 1 atm
Equivalence Ratio 1
H2 1
Fuel
N2 0.79 O2 .21 Air

Example 1

Examples can be found here

Example 1

Chemical equilibrium calculations


Similar to NASA SP273 or CEA code

Select Models and select chemical


equilibrium icon, drag and drop in the
diagram view

Example 1

Recollect:
For chemical Equilibrium calculations,
Thermodynamic data, species involved in the reaction
mechanism are needed
Select Preprocessing

Example 1

For chemical kinetics,


example 2
Reaction Rate: Activation
Energy: Arrhenius Equation
parameters
Thermodynamic data
Mixing = flame zone,
recirculation, flame speed
In the preprocessing stage, we mention what is required to define a
chemical reaction
Thermodynamic data File
Reaction Mechanism File (Reaction Mechanisms Kinetics)
Transport Properties File

Example 1

Run the pre-processor to


update the boundary
conditions

For Equilibrium calculations reactions rates


are irrelevant. Just mention the species that
are expected

Example 1

Give the concentration of


species in moles or normalized
mole fractions
If equivalence ratio is
given then make sure
that
complete
combustion products
are included(H2O, N2)
Select the problem type,
constant pressure enthalpy

Example 1

If an effect of a parameter has to be studied, give that parameter and the


range you want to study in continuations
Here we are studying the effect of initial temperature on equilibrium
temperature

Example 1

Click on Run Calculations to


carry out the calculations

Before you Run Calculations, you can change solver settings.


These settings are mainly to control how the ODEs are solved.
Typically you can leave the default settings. At advanced level
calculations solver settings need to be changed for solution
convergence, mainly depends on the stiffness of the problem

Example 1

Once the calculations


are carried out, the
software
gives
an
output
of
several
parameters
We
can
plot
the
information
using
analyze results
In this example we wish
to see the effect of initial
temperature
on
equilibrium temperature

Example 1

Homework 1: Can we compare Equilibrium Calculations between


Chemkin and NASA CEA code. If So, Compare the Equilibrium
Temperature between both the software for H2+Air and CH4+Air. For 5
equivalence ratios. Make sure that the number of species selected are
same

ChemkinPro Tutorials
In equilibrium calculations we have not given any Rate parameters like how
fast the reaction takes to complete. Only initial state is required.
Now We will take an example where chemical kinetics are linked with fluid
and thermodynamic systems
Not in Chemical Equilibrium
The process of conversion from reactants to products as a function of time
Species concentrations as a function of time
Well Stirred Reactor (we assume perfectly mixed mixture and the spatial
variations are fully ignored, 0D reactor)
Plug Flow Reactor
Partially Stirred Reactor etc are used to model the flow

Example 2
Steady-state Gas-phase Combustion
Perfectly Stirred Reactor (PSR)
(For Hydrogen and Air)
Parameters:
Residence Time 0.03 ms-0.2ms
Pressure 1 atm
Equivalence Ratio 1
H2 0.8 N2 0.2 Fuel
N2 0.79 O2 .21 Air

Example 2
Watch out: closed and open reactors
Well stirred reactor (PSR) is an open 0D Reactor

In this example, we demonstrate the effect of residence time on the final


temperature attained by products

Example 2

3 Columns
Observe the difference between
example 1 and this example
The
three
column
contains
Arrhenius constants for elementary
reactions: information on rate of
reactions-> Time

Example 2

Need to mention mole and mass fraction


as inputs

Example 2
Residence time in the reactor.
Also defined by volume flow rate
or mass flow rate or velocity

Example 2

In the continuations this time,


we give residence time as a
parameter of interest.
Give typical residence times in
gas turbines

Example 2

Homework 2: Compare the temperature with Equilibrium and how much residence
time it required to reach to the equilibrium temperature for CH4+Air for 5
equivalence ratios. USE GRI Mech 3.0

Debugging Errors
Open File Editor window.
Look for <filename>.out

If there are input boundary


conditions are missing or if the
solver cannot converge to the
solution, software gives out an
error

Example 3
Plug Flow Reactor (Diffuser)
Parameters:
Initial Temperature 1500 K
Pressure 1 atm
Equivalence Ratio 1
Length 5 cm, Diameter varying from 2-5 cm
Axial Velocity 25 cm/2
Species mixture:
AR 0.8, CO 0.006, CO2 0.065, H2O .09,N2 .002895, NH3 .002, NO
.001, O2 0.007,OH .00005

Example 3
Why do we need a Plug Flow Reactor? What does it used for?
Used to simulate flow in nozzles, diffusors where there is an area change
Change in geometrical conditions effects the flow properties like T, P,
species composition
The reactor also takes into consideration heat losses

Example 3

Thermodynamic data can be


seen in graphical form with this
option

Example 3

Mention here the variation of


cross sectional area

Simulate with Heat Flux

Example 3
Use the example problem in
Chemkin software for plug flow
reactor.
Homework 3. Simulate a diffuser
with inlet with diameter A cm to exit
with diameter B cm. The length of
the diffuser to be C cm. Simulate
with Heat Flux D and initial
Temperature E
Choose A,B,C,D,E which are
realistic

Why does the temperature


Increase ?

Example 2 : PSR

Example 3 : PFR

Network Modeling
Aerodynamics

Flow control

RCS
exhaust

inlet

combustor

nozzle

Each Individual component is mathematically modeled based on fundamentals


The exit conditions of one component are the input conditions for the next
component
To study the overall performance of the combined system, all the individual
components have to be integrated into one system
Then one can study the system performance and can carry a systematic
parametric analysis during its flight path
Further for much detailed study, each individual component contains further
subcomponents which are modeled

Typical Gas Turbine Combustor

Most mixtures will NOT burn so far away from


stoichiometric Often called Flammability Limit
Gas turbine can NOT operate at (or even near)
stoichiometric levels as temperatures are way
too hot for turbine
Fixed Tt4 implies roughly f < 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

Typical Gas Turbine Combustor

Simulating Gas Turbine Combustor

Compressor

Air

Turbine

APPLICATION TO COMBUSTION SYSTEM


MODELING
Primary
Zone
~ 1.0
T~2500 K

~0.3

44

Conceptual model of a gas-turbine combustor using 2 WSRs and 1 PFR

Example 4

Example 4
Gas Turbine Network Model
PSRs+ PFRs
Parameters:
Initial Temperature 650 K, Pressure 10 atm
Primary Air: 50 g/s, Premixed Air: 500 g/s, Cooling Air 100g/s
Equivalence Ratio 0.6
Mixing Zone: Residence time 0.5 ms, Temp 800K
Flame Zone: Residence time 1.5 ms, Temp 1600K
Recirculation Zone: Residence time 1.5 ms, Temp 1600K
Split recirculation zone gases 0.15: 0.85
split of gases from flame zone to post flame zone 0.15:0.85
Post flame zone length 5 cm, diameter 10 cm

Example 4

Create clusters when there is recirculation or downstream


conditions effect the upstream conditions, to isolate with
remaining flow
Change the temperature in the flame zone and check the
effect on the species concentration and temperature in the
reactors. Which Temperature should be higher flame zone
temperature or recirculation zone temperature

Example 4

One can study how the flow conditions effect the NOX and CO
formation and in which zones of the combustor NOX formation is high
Based on these initial analysis one can redesign the combustor
Chemkin is integrated with CFD softwares like CFX and Fluent in
Ansys to obtain reactor network model

Typical Gas Turbine Combustor Simulation in


Chemkin

Homework 4: Carry out a literature survey on the RQL and LPP combustor. Get
typical engine conditions.
Create a Reactor Network model for RQL combustor and LPP combustor and
predict the NOx Levels in the combustor.

MID TERM PROJECT WORK


Simulate Real Gas Turbine Combustor
and Obtain Temperature and NOX
distribution in the combustor and obtain EI
of emissions

Mid Term Project : A network of ideal reactors


Example 2 : PSR

PSR
PSR
Inlet

PSR

Example 3 : PFR

Inlet

Inlet

PSR
Inlet/
inlets

PSR

mixer

mixer

PFR

PSR
PSR
PSR
PSR
PSR

Example 4 : Simple Gas


turbine Combustor Network
model

PROJECT WORK

PFR

outlet

Engine Annular Combustor Dimension (unit = cm)

Proposed E3 annular combustion chamber design


it has 24 fuel injectors

Engine Conditions

Comparison of combustor operating conditions

Combustor Air Flow Distribution

remaining % air for Turbine cooling


Use 10 PSRs for primary zone, each PSR occupies equal volume in the
primary zone
Calculate primary zone equivalence ratios at different engine power conditions
scale up or down the equivalence ratio based on the distribution shown in this
chart if the primary zone is not operated at equivalence=1.0

Mid Term Project


Estimate the emission index of CO, NO, CO2 at 5
engine power conditions at two different flight
conditions
A written report should be submitted (~ 10 pages)
You need to certify that you have conducted this
project independently when you submit the project
report.
Due Date

ChemkinPro : Further Information


Where to Find Reaction Mechanisms and Thermodynamic data
Reaction Design Website has links to several research groups webpages
where a constant update of reaction mechanisms are available
http://www.reactiondesign.com/support/chemical-mechanisms-data/
GRI Mech for methane
http://combustion.berkeley.edu/Combustion_Laboratory/gri-mech/
Constant update of reaction mechanisms for Jet A
http://web.eng.ucsd.edu/mae/groups/combustion/mechanism.html
For IC engines
http://www.erc.wisc.edu/chemicalreaction.php
Reduced order mechanisms
http://lcg.princeton.edu/research/chemical-kinetic-mechanisms.aspx

Chemical Kinetics: Final Note


(CH4+2O2<--> CO2+2H20) GRI Mech. for
consists of 325 reactions that involve 53
species
Reactions occur through multiple paths
Each path, an elementary reaction is
controlled by rate of reaction, k(T)
How can we be sure that such an
elementary reaction occurs and how to get
parameters like k
These are measured laser absorption
techniques for species detection or
predicted through simulations

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Chemical Kinetics: Final Note


H2 combustion 7 species 20 reactions
CH4 combustion 30 species 200
reactions
C3H8 combustion 100 species 400
reactions
Real Fuels are complex mixtures of
several components
Gasoline contains components ranging
from 6<C<10
Jet A contains components ranging from
9<C<13
Diesel contains components ranging from
13<C<22
C12H26+ Jet A fuel combustion
Species ??? reactions

???

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