Lecture 8:

Modeling Surface Reactions

15.0 Release

Advanced Combustion Modeling

1 2014 ANSYS, Inc. July 18, 2014 ANSYS Confidential

 Outline
Applications
Surface reaction models in Fluent
Resolved and Unresolved surface reaction models
Key features
Types of surface reactions
Material set-up
Surface reaction solvers
Appendix A: Examples
Kleijn CVD reactor
Catalytic combustion in a single channel
Carbon canister
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 Applications
Modeling deposition
Chemical Vapor Deposition (CVD)
Alternate Layer Deposition (ALD)
Modeling catalytic reactions
Catalytic combustion
Selective catalytic reduction
Modeling adsorption/desorption
CO2 adsorption
Hydrocarbon capture (Carbon canisters)

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 Surface Reaction Models

Resolved Surfaces Model Un-resolved Surface Model

Surface reaction on resolved wall Surface reactions in porous media
surfaces

Growth Rate of Gallium Arsenide in a Hydrocarbon capture in

vertical rotating disc reactor carbon canister
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 Surface Reactions: Key Features
Multi-step reactions with multiple sites and site species
Surface reaction products as reactants in other surface reactions
Local site balancing and desorption of gas-species from surface
Gas phase and surface species in a reaction
Ability to handle pure surface reactions
Different reaction mechanisms on different surfaces
Different surface reactions on each surface and boundary
Deposition of multiple bulk species on the same surface
Tungsten film growth
User defined outputs rate and uniformity in a
Separate tracking of deposition/etch rates for each bulk species 300-mm ALTUS system
Contour plots of site species concentration and open sites
UDFs to customize the surface reaction rate (DEFINE_SR_RATE)
UDFs to access adsorbed species concentrations on the surface
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 Unresolved Surface Reactions
Surface reactions in porous media
Catalyst represented as porous media

Specify anisotropic thermal conductivity

Specify anisotropic species diffusion
Actual velocity calculation
Accounts for fluid acceleration effects
Non-uniform porosity and resistance
distributions in porous media
UDF functionality
Non-equilibrium thermal model (NETM)
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 NETM for Porous Medium
Porous medium (solid) and fluid are not in thermal equilibrium
Separate governing equations for fluid and solid zones
Dual cell approach
Automatically creates cell zone for porous solid spatially coinciding with
the porous fluid
Fluid and solid zone interacts with each other through
convective heat transfer at the interface
Interfacial area per unit volume and heat transfer coefficient need
to be specified
Useful for start up/cyclic processes (Unsteady)

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 Types of Species Involved
Gas
Gas phase species Species
Species in the gas mixture Flow
Denoted by (g)
Surface

Surface/Site species
Species on the top-most layer of the solid
Denoted by (site) Site

Bulk/Solid species Bulk

Solid
Species in the solid below the surface
layer
Denoted by (s) or (b)
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 Types of Surface Reactions
AsH3(g)
Adsorption reaction AsH3(site)
Ga(site)
Using atomic site
AsH3(g) + Ga(site) AsH3(site) + Ga(b) Ga(b)
Using open site
Adsorption using atomic site
AsH3(g) + Open(site) AsH3(site) AsH3(g)
Desorption reaction
Open(site) AsH3(site)
AsH3(site) AsH3(g) + Open(site)
Can be using atomic site or open site Adsorption using open site
Deposition reaction AsH3(g)
AsH3(g) + Ga(site) AsH3(site) + Ga(b)
AsH3(site) Open(site)
Si Si(b)

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Desorption using open site
 Material Set-up
Gas, site and bulk species to be
defined as type fluid

Switch on wall surface reactions

in the species transport panel

Include required species

appropriately
Gas species
Define reactions
Volumetric
Wall surface Site species Bulk species

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 Surface Reaction Set-up

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 Surface Reaction Set-up (Cont)

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 Surface Reaction Import

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 Surface Reaction Import (Cont)

Allowed in Fluent Not Allowed in Fluent

Arrhenius reactions with third-body
efficiencies
Sticking coefficients (STICK)
Duplicate reactions (DUP)
Surface coverage modification
(COV)
Ion-Energy Dependent reaction
(ENRGDEP)
Bohm rate expressions (BOHM)
Ion-Enhanced reaction
Motz-Wise correction (MWON and
MWOFF)

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 Surface Chemistry Solver
Robust surface chemistry solver
ODE solver when Newton solver fails
User controls to select the type of solver manually using rp- ,
variables , = , ,

Default approach, calls Newton solver first, if it fails, then calls ODE
solver with same initial guess
(rpsetvar 'species/surf-stiff-chem-method 1) = ,

Use only Newton solver
(rpsetvar 'species/surf-stiff-chem-method 0) =
Use only ODE solver
(rpsetvar 'species/surf-stiff-chem-method 2)

Option to disable reaction-diffusion balance = , ,

Essentially specify infinite diffusivity =

Can be controlled using TUI

define/models/species/disable-diffusion-reaction-balance
Options to include heat and mass source due to mass deposition
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 Appendix A:
Examples
15.0 Release

Advanced Combustion Modeling

16 2014 ANSYS, Inc. July 18, 2014 ANSYS Confidential

 Example-1: Kleijn CVD reactor
Inlet

Susceptor Outlet

Inlet Temperature = 300 K

Inlet velocity = 0.0964 m/s Inlet Rotational
Inlet Silane (SiH4) mole fraction = 0.001 Periodic
Inlet Helium mole fraction = 0.999 (Angle= 45O)
Susceptor rotational speed = 1000 RPM
Susceptor Temperature = 1000 K Domain in Fluent
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 Models
Flow is laminar
26 volumetric and 13 surface
reactions
Kleijn
Stiff chemistry solver with ISAT
error tolerance of 1e-8 is used
Discretization schemes
Pressure PRESTO!
Momentum, Species and Energy Overall cell count is 100 K
Second Order Upwind
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 Volumetric Reactions

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 Surface Reactions

i sticking coefficien t
0 for Si3 H 8
M

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 Results: Axial Velocity
125.0

112.5

100.0

87.5
Axial Velocity (mm/s)

75.0 SPIN

62.5 Fluent

50.0

37.5

25.0

12.5

0.0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Height above Susceptor (mm)

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 Results: Temperature
1000

950

900 SPIN

850 Fluent

800

750
Temperature (K)

700

650

600

550

500

450

400

350

300
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Height from Susceptor (mm)

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 Results: Silicon Deposition Rate
2.5

2.4

2.3
Deposition Rate (nm/s)
SPIN - 1D[Ref = Kleijn]
2.2
2D - Sim[Ref = Kleijn]
3D-Fluent
2.1

1.9

1.8

1.7

1.6
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
Radial Coordinate (mm)

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 Example-2: Single Channel Case
Pt Catalyst, T=1290K

CH4 D=2mm
air
L = 10cm

Boundary Conditions
Volume Fraction: 3% CH4
Inlet velocity: 5 m/s
Inlet temperature: 600 K
Gas species
CH4, O2, H2, H2O, CO, CO2, N2, OH
Surface species
Pt(s), H(s), O(s), OH(s), H2O(s), H3(s), CH2(s), CH(s), C(s), CO(s), CO2(s)
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 Surface Reaction Mechanism
Reaction A B E(J/kmol)
H2+2PT(s) => 2H(s) 4.36E7 0.5 0.0
2H(s) => H2+2PT(s) 3.7E20 0.0 6.74E7
O2+2PT(s) => 2O(s) 1.8E17 -0.5 0.0
O2+2PT(s) => 2O(s) 2.01E14 0.5 0.0
2O(s) => O2+2PT(s) 3.7E20 0.0 2.13E8
H2O+PT(s) => H2O(s) 2.37E8 0.5 0.0
H2O(s) => H2O+PT(s) 1.0E13 0.0 4.03E7
OH+PT(s) => OH(s) 3.25E8 0.5 0.0
OH(s) => OH+PT(s) 1.0E13 0.0 1.93E8
H(s)+O(s) => OH(s)+PT(s) 3.7E20 0.0 1.15E7
H(s)+OH(s) => H2O(s)+PT(s) 3.7E20 0.0 1.74E7
OH(s)+OH(s) => H2O(s)+O(s) 3.7E20 0.0 4.82E7
CO+PT(s) => CO(s) 7.85E15 0.5 0.0
CO(s) => CO+PT(s) 1.0E13 0.0 1.25E8
CO2(s) => CO2+ PT(s) 1.0E13 0.0 2.05E7
CO(s)+O(s) => CO2(s)+PT(s) 3.7E20 0.0 1.05E8
CH4+2PT(s) => CH3(s)+H(s) 2.3E16 0.5 0.0
CH3(s)+PT(s) => CH2(s)+H(s) 3.7E20 0.0 2.00E7
CH2(s)+PT(s) => CH(s)+H(s) 3.7E20 0.0 2.00E7
CH(s)+PT(s) => C(s)+H(s) 3.7E20 0.0 2.00E7
C(s)+O(s) =>CO(s)+PT(s) 3.7E20 0.0 6.28E7
CO(s)+PT(s) => C(s)+O(s) 1.0E17 0.0 1.84E8
OH(s)+PT(s) => H(s)+O(s) 1.56E18 0.0 1.15E7
H2O(s)+PT(s) => H(s)+OH(s) 1.88E18 0.0 1.74E7
H2O(s)+O(s) =>OH(s)+OH(s) 4.45E20 0.0 4.82E7

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 Mass Fraction of Major Gas Species

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 Surface Coverage Profiles

Major species Minor species

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 Example-3: Carbon canister
Devices used in automotive to capture
hydrocarbon vapor losses
Activated carbon elements in the
canister adsorb fuel vapor and feed it
back into the engine
Saves the fuel and reduces hydrocarbon
emission
Carbon canister

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 Test case
n-butane vapor + air n-butane vapor and air enter at the inlet
Mass flow rate = 1e-5 kg/s
n-butane mass fraction = 0.675
n-butane is captured at three porous
zones using surface reactions
Porous Made up reaction rates
zones Outer walls: adiabatic
Fluid and solid temperatures in the
porous zones are monitored using non
equilibrium thermal model in Fluent 14

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 Setup: Species properties
n-butane and air
Properties from Fluent database
n-butane-site
Standard state enthalpy
Assumed such that the adsorption reaction is exothermic
Standard state entropy = 0
Open-site
Molecular weight = 0
Standard state enthalpy = 0
Standard state entropy = 0

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 Set-up
Reactions:
Reaction Pre- exponential constant
C4H10 + Open_s C4H10_s 10000
C4H10_s C4H10 + Open_s 10

Solid material: Carbon-BAX-1500

Density 448 kg/m3
Specific Heat 900 J/kg-K
Thermal Conductivity 1.5 W/m-K

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 Setup: Non equilibrium thermal model

Inputs
Interfacial area density
Surface area to volume ratio
Heat transfer coefficient
Note: Set surface area to
volume ratio in reaction tab
as well

NOTE: Before enabling the non-equilibrium thermal model, click OK in the Fluid dialog box, in order to save settings in the Porous
Zone tab. If it is not saved, they will be reset to the default values while enabling the non-equilibrium thermal model
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 Solution parameters
Pressure based segregated solver
P-V coupling: SIMPLE
Discretization:
Momentum, species and energy
Second order
Simulation: Transient
Time step size: 10s
Total flow time: ~1500s

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 Hydrocarbon (n-butane) capture

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 Temperature variation
Fluid side

0 Time t
Solid side

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 Temperature at center of porous zone-1

Temperature (K)

(s)

Higher temperature on fluid side when reaction front reaches this location
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 Summary
Surface reactions
Resolved & unresolved surfaces
Options to import mechanism in CHEMKIN format
Robust surface stiff chemistry solvers
Examples & applications
Kleijn CVD reactor
Single channel case
Carbon canister
Tutorials
Catalytic combustion tutorial
CVD tutorial
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