Introducing CHEMKIN 4.

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Ellen Meeks CHEMKIN in Combustion Workshop August 6, 2006

Outline
Brief Introduction What is CHEMKIN? CHEMKIN 4.1 released July 2006
All New Graphical Post-processing Parameter-study Facility Particle Tracking Module (optional) More Complex Reactor Networks New Chemistry Formulations Reactor Model Enhancements

Future projects underway

Introduction

CHEMKIN software allows focus on chemistry using engineering approximations

Plug-flow Reactor (PFR) Perfectly Stirred Reactor (PSR) Partially Stirred Reactor

T v T v

Shear-layer Channel-flow Reactor Opposed-flow Diffusion Flame

N H2 CH2 O2
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Pre-mixed Flame

N 2 H2OCO CO O

Flame-speed Calculation

Equilibrium Calculator

The CHEMKIN approach provides efficient solutions with very short set-up time
Supports large chemical kinetic mechanisms
100s of species 1000s of reactions

Provides accurate information about reacting system

Trace species emissions
(parts per billion or smaller)

Accurate handling of kinetics time and length scales Complex dependency between major & minor species Dominant reaction paths Sensitivity of results to reaction parameters de facto standard for describing elementary kinetics

Computational time for single reactor ~ seconds-minutes

PC , Linux, UNIX
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Detailed kinetics are critical for accurately modeling chemical systems

Exhaust-gas emissions Ignition phenomena Engine knock Flame-speed Flammability limits Catalytic lightoff Chemical conversion Fuel reforming Material deposition Plasma processing
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Using CHEMKIN requires a chemistry set, reactor definition, and operating conditions
Choose a reactor model Define the geometry Specify operating conditions

Define or select a chemistry set Thermodynamic data Gas-phase reactions Surface reactions Transport-property data

Reactor models predict the varying state of the gas and/or surface
Thermodynamic state of the gas
Temperature / Enthalpy / Entropy Pressure / Density Rate of heat transfer to the environment

Chemical state of gas / surface / solid

Gas-phase composition Surface site coverage Instantaneous deposition or etch rates Species production rates Rate of progress of individual reactions

Flow state
Convective velocities Diffusive velocities Stefan velocity due to deposition

Predicted as a function of Time Distance Zone Parameter

Solution sensitivity to parameters

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Reactor networks are easily constructed using a visual diagram tool

Customizable palette of reactor modules Drag and drop diagrams for reactor networks and series simulations

Reactor templates guide user inputs for problem-specific applications

Reactor Models include:
Non-reactive Gas Mixer Chemical and Phase Equilibrium Calculations Mechanism Analyzer Closed Internal Combustion Engine Simulator Closed Homogeneous Batch Reactor Closed Partially Stirred Reactor Closed Plasma Reactor Perfectly Stirred Reactor (PSR) Plasma PSR Partially Stirred Reactor (PaSR) Plug Flow Reactor Honeycomb Plug Flow Reactor Plasma Plug Flow Reactor Planar Shear Flow Reactor Cylindrical Shear Flow Reactor Premixed Laminar Burner-stabilized Flame Premixed Laminar Flame-speed Calculation Diffusion or Premixed Opposed-flow Flame Stagnation Flow CVD Reactor Rotating Disk CVD Reactor Normal Incident Shock

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Descriptions of reactor configurations are through context-specific panels

Project tree with links to input panels

Input panels guide problem set-up and execution

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Users can also create their own Applications through use of the CHEMKIN/API
Subroutine Libraries are called from user programs
C/C++ or Fortran interfaces Functions for determining chemical terms and properties
Thermodynamic properties Gas-phase kinetics Surface kinetics Transport properties

Numerical solvers for transient and steady-state

Detailed examples provided in standard install

C++ and Fortran programs and makefiles Command-line / Scripting examples Extracting data from XML solution data file
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Summary of CHEMKIN Introduction

Chemistry simulation is increasingly a key to design CHEMKINs unique capabilities allow accurate kinetics

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State-of-the art reaction-rate formulations Advanced surface chemistry treatment Elementary or global kinetics expressions Multicomponent transport properties Solution algorithms designed to dynamically adapt to stiff chemistry Fast set-up and run time Visual diagramming of reactor networks Extensive graphical presentation of results Problem-oriented reactor models Application-oriented tutorials and sample projects API for advanced programming and command-line operation

CHEMKIN provides flexible, easy-to-use interfaces

CHEMKIN 4.1 Release Important New Capabilities

Several all-new capabilities are available with the release of CHEMKIN 4.1
New Visualizer / Post-processor New Parameter Study Facility New, advanced Particle Tracking Module (option)

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The new Graphical Post-processor takes CHEMKIN visualization to the next level

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New plot types expand visualization options

3-D Contour Plots
Interactive rotation

Mirrored Plots
Axes of symmetry

Multiple Y-axes

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Users have full interactive control over formatting and presentation

Plot format
Color, line type, thickness Symbol on/off, shape, size, color Axis line, label, text font, ticks Legend text font, spacing, outline Background color, transparency

Annotation insertions
Text boxes Drawing, shapes, arrows

Easy scaling of axes Sequential Undo (Cntrl-Z), for all operations!

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Extensive save / reapply options reduce time needed for repetitive tasks
Save / Reapply plot-set selections
Selections can be saved on a project-by-project basis

Save and apply user-defined plot styles Record and apply macros for other operations
Mouse clicks and key strokes can be recorded

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The Parameter-Study Facility automates a series of simulations

Choose one or more user-specified input(s) to vary
User-interface panel inputs Chemistry-set parameters

Variations are controlled by:

Tables of discrete values Specification of Min, Max, Increment Specification of Min, Max, # of runs Linear or Logarithmic interpolation

Available for multiple-cluster reactor networks

Allows system studies Shows effects of upstream variation on downstream results

Complements existing continuation capability

Each cluster model can contain continuations Each run starts from user-specified initial conditions and generates a separate solution file
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Visualization of parameter-study results includes added parametric dimension

Solutions are harvested from multiple runs
User selects variables for post-processing Data is extracted out of multiple solution files 2-D plot sets automatically constructed

Vary engine compression ratio

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Multiphase CHEMKIN: the new Particle Tracking Module (PTM)

Nucleation of particles from gas-phase species
e.g., poly-aromatic hydrocarbons (PAHs) for soot Rates controlled by collision frequencies

Growth by coagulation of particles

Collision-regime options

Growth and reduction by general surface reactions

Vapor-deposition type reactions Condensation of large species

Tracking of particles
Moment Method calculates moments of size distribution Provides particle mean diameter, mass & volume fractions Average surface state and total surface area

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The PTM can be used with any mechanism for particle growth and reduction
Coagulation
Particle collision frequency

Nucleation reactions
Precursor collision frequency

R0 R1

G0 G1

S0 S1

Surface reactions
Oxidation Growth Condensation

DM r = Rr + Gr + S r Dt
Moment Equations

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Particle nucleation and growth/reduction are described within the surface chemistry input
MATERIAL SOOT_PARTICLE DISPERSED END SITE/PolyC/ SDEN/3.341E-9/ H(se) open(se) ! se indicates edge or active site. END BULK C(B) /1.8/ END REACTIONS ! nucleation from PAH 2A4 => 32C(B)+20H(se)+28.72open(se) 6.0E10 0.5 0.0 NUCL ! HACA growth H+H(se) => open(se)+H2 4.2E13 0.0 13000.0 open(se)+H2 => H(se)+H 3.9E12 0.0 9320.0 open(se)+H => H(se) 2.0E13 0.0 0.0 H(se)+OH => H2O+open(se) 1.0E10 0.734 1430.0 H2O+open(se) => OH + H(se) 3.68E8 1.139 17100.0 open(se)+C2H2 => H(se)+2C(B)+H 8.0E7 1.56 3800.0 ! PAH condensation C6H6+open(se) => H(se)+6C(B)+5H 0.1 0.0 0.0 STICK FORD/open(se) 2.0/ DCOL/4.E-8/

Indicate a dispersed phase and activates the soot module Precursors for nucleation Inception particle class Particle bulk composition Nucleation reaction

Grow particle by 2 classes Grow particle by 6 classes Sticking coefficient Collision diameter for benzene

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The PTM is available for use with All Homogeneous 0-D and Flow Reactors
Closed Homogeneous Reactors Perfectly Stirred Reactors Plug Flow Reactors Shear Layer Flow Reactors

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We have applied the new PTM in soot particle formation studies

Reaction Mechanisms Tested: Ethylene combustion, which determines PAH precursors
From Appel, Bockhorn, Frenklach

Nucleation by single path

Particle Concentration (gm/cc)

MIT JSR/PFR Experiments with Ethylene (Marr, 1993)

2.5E-07 2.0E-07 1.5E-07 1.0E-07 5.0E-08 0.0E+00 0 5 10 15 PFR Residence Time (ms) 20 Expt: soot Expt: tar Expt: sum Simulation

Pyrene (A4) dimerization From Frenklach

HACA growth by C2H2 addition

From Frenklach and Wang

T=1620 K

PAH condensation Particle coagulation Soot oxidation

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The model allows differentiation of contributions from mechanism components

HACA cannot account for observed growth PAH condensation important for growth Large PAHs are under-predicted by gas mechanism
10
0

2.5E-07

10-1
-2

H2
Soot Mass Concentration (gm/cm3) 2E-07

Data (Marr 1993) HACA+PAH HACA only

10 Mole Fraction

C2H 2
-3

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1.5E-07

Benzene
-4

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Phenyl Acetylene
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1E-07

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Naphthalene Pyrene

5E-08

10

-6

T =1620 K P = 1 atm =2.2

0 5 10 PFR Residence Time (ms) 15 20

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10 PFR Residence Time (ms)

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20

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Users have full control over the particletracking simulation from the user interface
Dispersed phases are identified in the Surface Kinetics Input file User options include
Initial particle density Coagulation parameters Solver controls
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Many other important enhancements are introduced in CHEMKIN 4.1 Some Highlights:
Expansion of reactor-networking capability New reaction-rate formulations Improved solver convergence Advanced ignition-delay calculations Entrainment flow-rate profile for Plug Flow Multiple materials option for Shear Layer Flow Improved consistency between input panels Easier-to-use diagramming and file browsing Ability to plot ignition delay & flame-speed in parameter studies
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Enhancements to reactor networking add flexibility in describing complex systems

Splitter allows flow splits to multiple reactors Parallel streams enabled Stored file icon allows initialization from previously saved solution Visual emphasis on flow streams
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New chemistry formulations make it easier to transcribe and estimate rates

Collision probability for gas-phase reactions
Rate based on collision frequency User specifies reaction probability between 0 and 1

New surface-reaction UNITS options

Facilitates direct use of published catalysis data Partial-pressure units for gas-phase species Site-fraction (coverage) units for surface species

Dependence of surface species heats of formation on local coverage

Facilitates estimation of catalysis rates using BondOrder-Conservation methods Improved thermodynamic consistency
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Several options allow more accurate prediction of ignition delay

Choices for ignition criteria:
Specified temperature threshold for ignition Specified T above initial temperature Peak dT/dt (inflection point) Peak concentration of any species (e.g., OH) User-defined criteria in user subroutine
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Propane / air ignition delay

Flow-rate profile option for PFRs allows gradual entrainment of gases

CHEMKIN Profile Tool

Additional inlets in PFR allow varying of flow rate vs. distance Example for CH4/NH3 oxidation
0.2% CH4, 0.06% NH3 in N2

8% O2, 4% H2O in N2

Temperature varied: 1000-1500K

Based on Experiments by Grcar,J.F., Glarborg, P., Bella, J.B., Day, M.S., Loren, A., Jensen, A.D. Proceedings of the Combustion Institute, 30 (2004)

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Summary CHEMKIN 4.1 saves you time

Parameter study More robust solutions Save/restore & macros for plotting Advanced visualization Easily plot single values from parameter study of 1-D simulations (e.g., flame speed, ignition) Improved diagramming 64-bit LINUX now available for AMD/Intel chips

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Projects underway for future releases

A new Uncertainty Module is under development for use with CHEMKIN

Currently in Alpha Testing Scheduled for release in Q1 2007 Plug-in module to CHEMKIN (4.1 or Later) Based on polynomial chaos expansion theory
10-1000 X faster than Monte Carlo approaches User Specifies
Variant Inputs
P(k1) k1 P(km) km
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Uncertainty Module Predicts

CHEMKIN Model y1 = f (k1,k2,,km) y2 = f (k1,k2,,km) Variant Outputs
P(y1) y1 P(y2)

...

y2

Other major projects

Implementation of tear-stream algorithm for heterogeneous reactor networks Extraction of reactor network from CFD solutions Particle Tracking Module option added to Flame Simulations Advanced mechanism-analysis tools Further improvements in solver speed and robustness

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Discussion

Two years ago, we launched the Teaching Forum on our website

How many have used accessed the information there? Is the site useful? Do you plan to contribute a problem to the site? What would you like to see improved or changed?

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What technology enhancements would you find helpful to your work?

New reactor models? New reaction rate formulations? More user-routine capabilities? Extended reactor connectivity options? Optimization or other add-on capability? Other thoughts or comments?

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What aspects of CHEMKIN do you find the most difficult?

Flame-code convergence? Finding / accessing chemistry data? Manipulating solution data? Linking to the API? Other thoughts / comments?

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Of the recent enhancements, what do you find to be the most valuable?

?

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CHEMKIN 4.1 Demo