Calonaci Furnari Final Presentation

Matteo Calonaci Federica Furnari
A COMPUTATIONAL FRAMEWORK FOR THE

SIMULATION OF GAS-SOLID CATALYTIC REACTORS
BASED ON A MULTIREGION APPROACH

Anno accademico 2011-2012

Dipartimento di Energia &
Dipartimento CMIC Giulio Natta

Relatori: Dr. Alberto Cuoci & Dr. Matteo Maestri
Background
Catalytic Reactor Engineering
Catalytic Reactor Design
~90% of industrial
chemical processes
are catalytic
Background
~90% of industrial
chemical processes
are catalytic
Need for an accurate
design to provide
high yields ($)
Background
~90% of industrial
chemical processes
are catalytic
Need for an accurate
design to provide
high yields ($)
Need for a deep
understanding for
advanced design
Time [s]
Length
[m]
MICROSCALE

MESOSCALE

MACROSCALE

10
0
10
-6
10
-3
10
-9
10
-15
10
-6
10
0
(
*
)
Microkinetic analysis of complex chemical processes at surfaces
M. Maestri in New strategy for chemical synthesis and catalysis Wiley, 2011

Background
A Multiscale Phenomenon
Time [s]
Length
[m]
MICROSCALE

Making and breaking
of chemical bond
MESOSCALE

MACROSCALE

10
0
10
-6
10
-3
10
-9
10
-15
10
-6
10
0
(
*
)

Background
Time [s]
Length
[m]
MICROSCALE

Making and breaking
of chemical bond
MESOSCALE

Interplay among the
chemical events
MACROSCALE

10
0
10
-6
10
-3
10
-9
10
-15
10
-6
10
0
(
*
)

Background
Time [s]
Length
[m]
MICROSCALE

Making and breaking
of chemical bond
MESOSCALE

Interplay among the
chemical events
MACROSCALE

Mass and energy
transport phenomena
10
0
10
-6
10
-3
10
-9
10
-15
10
-6
10
0
(
*
)

Background
Time [s]
Length
[m]
MICROSCALE

Making and breaking
of chemical bond
MESOSCALE

Interplay among the
chemical events
MACROSCALE

Mass and energy
transport phenomena
Development
of a new solver
10
0
10
-6
10
-3
10
-9
10
-15
10
-6
10
0
(
*
)

Background
Time [s]
Length
[m]
MICROSCALE

MACROSCALE

10
0
10
-6
10
-3
10
-9
10
-15
10
-6
10
0
(
*
)

Background
MESOSCALE

Time [s]
Length
[m]
MICROSCALE

Detailed kinetic
mechanism
MACROSCALE

10
0
10
-6
10
-3
10
-9
10
-15
10
-6
10
0
(
*
)

Background
MESOSCALE

Time [s]
Length
[m]
MICROSCALE

Detailed kinetic
mechanism
MACROSCALE

10
0
10
-6
10
-3
10
-9
10
-15
10
-6
10
0
(
*
)

Background
MESOSCALE

Mean field
approximation
Time [s]
Length
[m]
MICROSCALE

Detailed kinetic
mechanism
MACROSCALE

CFD

10
0
10
-6
10
-3
10
-9
10
-15
10
-6
10
0
(
*
)

Background
MESOSCALE

Mean field
approximation
The Physical Problem
Phases of a Catalytic Reaction
Fluid Phase
Fluid Phase
Intra-solid phenomena not detailed
Fluid Phase
Intra-solid phenomena not detailed
Unacceptable if transport limitations
in the catalyst play a major role!
Fluid Phase
All steps of a catalytic reactive process
need to be described
Fluid Phase
Model intra-phase phenomena in the solid
Fluid Phase
multiRegion
Model intra-phase phenomena in the solid
Fluid Phase
Aim of the work
multiRegion
The solid phase needs to be
characterized:
Fluid Phase
Aim of the work
multiRegion
characterized:
Mathematical model to describe
transport and reactive phenomena
Fluid Phase
Aim of the work
multiRegion
characterized:
(
()
= kT +
()
+ = + +
+ = 0

Fluid Phase
Fluid Phase
Aim of the work
multiRegion
characterized:
(
()
= kT +
()
+ = + +
+ = 0

(
+ (
,
,
(
= k
T +
,
=
,

Fluid Phase
Solid Phase
Fluid Phase
Aim of the work
multiRegion
characterized:
(
()
= kT +
()
+ = + +
+ = 0

Separate pseudo-phase with effective
properties
(
+ (
,
,
(
= k
T +
,
=
,

Fluid Phase
Solid Phase
Fluid Phase
Aim of the work
multiRegion
characterized:
(
()
= kT +
()
+ = + +
+ = 0

Separate pseudo-phase with effective
properties
Need to correctly describe two
phase coupling at the interface
(
+ (
,
,
(
= k
T +
,
=
,

Fluid Phase
Solid Phase
Fluid Phase
Outline

MultiRegion Structure
Multiple meshes
Mixed BCs at the interface
Coupling partitioned approach

Outline

Multiple meshes

Numerical Tests
Coupling strategy effectiveness
Splitting operator testing
Test global architecture with cases of increasing complexity

Outline

Multiple meshes

Numerical Tests

Solver Validation
Comparison with experimental data
Importance of intra-solid phenomena description

Outline

Multiple meshes

Numerical Tests

Solver Validation

Conclusions

Outline

Multiple meshes

Numerical Tests

Solver Validation

Conclusions

New Structure
Multiple Meshes for Multiple Regions
MultiRegion nature of the solver
New Structure
Mesh 1: Fluid Region

Mesh 2: Solid Region 1

Multiple meshes


New Structure


Multiple meshes

Different properties
for each region


New Structure


Multiple meshes

for each region

Separate governing
equations on each cell


New Structure


Multiple meshes

for each region

Separate governing
equations on each cell

Full support for multi
region post-processing

Make Separate Regions Interact
Boundary conditions for coupled interfaces
How to couple at the
interface ?
interface ?
I NBR, I OWN,
) ( I NBR, ) ( I OWN,
T = T
T k = T k
I NBR I OWN
V V
( ) ( )
I NBR, I OWN,
C = C
C D = C D
I NBR NBR I OWN OWN
V V
2 different
approaches

interface ?
I NBR, I OWN,
) ( I NBR, ) ( I OWN,
T = T
T k = T k
I NBR I OWN
V V
( ) ( )
I NBR, I OWN,
C = C
C D = C D
I NBR NBR I OWN OWN
V V
Monolithic
works on multiple meshes
just for loose inter-equation
coupling

2 different
approaches

interface ?
I NBR, I OWN,
) ( I NBR, ) ( I OWN,
T = T
T k = T k
I NBR I OWN
V V
( ) ( )
I NBR, I OWN,
C = C
C D = C D
I NBR NBR I OWN OWN
V V
Monolithic
works on multiple meshes
just for loose inter-equation
coupling

Partitioned
Works on multiple meshes
even for stiff inter-equation
coupling

2 different
approaches

interface ?
I NBR, I OWN,
) ( I NBR, ) ( I OWN,
T = T
T k = T k
I NBR I OWN
V V
( ) ( )
I NBR, I OWN,
C = C
C D = C D
I NBR NBR I OWN OWN
V V
How to Couple at the Interface?
Mixed boundary
conditions at the
interface

I NBR, I OWN,
) ( I NBR, ) ( I OWN,
T = T
T k = T k
I NBR I OWN
V V
( ) ( )
I NBR, I OWN,
C = C
C D = C D
I NBR NBR I OWN OWN
V V
NBR
NBR
OWN
OWN
NBR
NBR NBR
OWN
OWN OWN
I.OWN
k
+
k

T k
+
T k
= T

NBR
NBR
OWN
OWN
NBR
NBR NBR
OWN
OWN OWN
I.OWN
D
+
C D
+
C D
= C

Mixed boundary
conditions at the
interface
I NBR, I OWN,
) ( I NBR, ) ( I OWN,
T = T
T k = T k
I NBR I OWN
V V
( ) ( )
I NBR, I OWN,
C = C
C D = C D
I NBR NBR I OWN OWN
V V
Partitioned Approach

1) Solve in each zone with mixed BCs

NBR
NBR
OWN
OWN
NBR
NBR NBR
OWN
OWN OWN
I.OWN
k
+
k

T k
+
T k
= T

NBR
NBR
OWN
OWN
NBR
NBR NBR
OWN
OWN OWN
I.OWN
D
+
C D
+
C D
= C

Mixed boundary
conditions at the
interface

I NBR, I OWN,
) ( I NBR, ) ( I OWN,
T = T
T k = T k
I NBR I OWN
V V
( ) ( )
I NBR, I OWN,
C = C
C D = C D
I NBR NBR I OWN OWN
V V


2) Update interface values and solve in the
neighboring region

NBR
NBR
OWN
OWN
NBR
NBR NBR
OWN
OWN OWN
I.OWN
k
+
k

T k
+
T k
= T

NBR
NBR
OWN
OWN
NBR
NBR NBR
OWN
OWN OWN
I.OWN
D
+
C D
+
C D
= C

Mixed boundary
conditions at the
interface

I NBR, I OWN,
) ( I NBR, ) ( I OWN,
T = T
T k = T k
I NBR I OWN
V V
( ) ( )
I NBR, I OWN,
C = C
C D = C D
I NBR NBR I OWN OWN
V V


neighboring region

3) Iterate till convergence is reached

NBR
NBR
OWN
OWN
NBR
NBR NBR
OWN
OWN OWN
I.OWN
k
+
k

T k
+
T k
= T

NBR
NBR
OWN
OWN
NBR
NBR NBR
OWN
OWN OWN
I.OWN
D
+
C D
+
C D
= C

Mixed boundary
conditions at the
interface

I NBR, I OWN,
) ( I NBR, ) ( I OWN,
T = T
T k = T k
I NBR I OWN
V V
( ) ( )
I NBR, I OWN,
C = C
C D = C D
I NBR NBR I OWN OWN
V V


neighboring region

3) Iterate till convergence is reached

Embedded in two newly coded libraries
NBR
NBR
OWN
OWN
NBR
NBR NBR
OWN
OWN OWN
I.OWN
k
+
k

T k
+
T k
= T

NBR
NBR
OWN
OWN
NBR
NBR NBR
OWN
OWN OWN
I.OWN
D
+
C D
+
C D
= C

Mixed boundary
conditions at the
interface

I NBR, I OWN,
) ( I NBR, ) ( I OWN,
T = T
T k = T k
I NBR I OWN
V V
( ) ( )
I NBR, I OWN,
C = C
C D = C D
I NBR NBR I OWN OWN
V V
The partitioned approach for heat and mass transfer coupling
Coupling Loop Structure
Fluid Region
with the mixed BCs on the interface:
SOL
SOL
FLU
FLU
SOL
SOL SOL
FLU
FLU FLU
k
+
T k
+
T k
= T

FLU I,
SOL
SOL
FLU
FLU
SOL
SOL SOL
FLU
FLU FLU
D
+
C D
+
C D
= C

FLU I,
( )
( ) ( ) ( )
( )
( ) ( ) ) (
i mix,
T C T k =
dt
T c d
Y Y D =
dt
Y d
mix
p
p mat
i i mix
i mix
V V V
V V V
FLU
FLU
SOL
SOL
FLU
FLU FLU
SOL
SOL SOL
D
+
C D
+
C D
= C

SOL I,

( )
( ) ( )
( )
( ) ( ) T k =
dt
T c d
Y D =
dt
Y d
p mat
i mix
i mix
V V
V V
i mix,
FLU
FLU
SOL
SOL
FLU
FLU FLU
SOL
SOL SOL
k
+
T k
+
T k
= T

SOL I,
Solid Region Fluid Region
with the mixed BCs on the interface: with the mixed BCs on the interface:
SOL
SOL
FLU
FLU
SOL
SOL SOL
FLU
FLU FLU
k
+
T k
+
T k
= T

FLU I,
SOL
SOL
FLU
FLU
SOL
SOL SOL
FLU
FLU FLU
D
+
C D
+
C D
= C

FLU I,
( )
( ) ( ) ( )
( )
( ) ( ) ) (
i mix,
T C T k =
dt
T c d
Y Y D =
dt
Y d
mix
p
p mat
i i mix
i mix
V V V
V V V
FLU
FLU
SOL
SOL
FLU
FLU FLU
SOL
SOL SOL
D
+
C D
+
C D
= C

SOL I,

( )
( ) ( )
( )
( ) ( ) T k =
dt
T c d
Y D =
dt
Y d
p mat
i mix
i mix
V V
V V
i mix,
FLU
FLU
SOL
SOL
FLU
FLU FLU
SOL
SOL SOL
k
+
T k
+
T k
= T

SOL I,
Solid Region Fluid Region
with the mixed BCs on the interface: with the mixed BCs on the interface:
SOL
SOL
FLU
FLU
SOL
SOL SOL
FLU
FLU FLU
k
+
T k
+
T k
= T

FLU I,
SOL
SOL
FLU
FLU
SOL
SOL SOL
FLU
FLU FLU
D
+
C D
+
C D
= C

FLU I,
Coupling Loop
Convergence Criteria
( ) ( )
, ,
( ) ( )
, ,
Y
k
i
k
i
T
k k
absTol Y Y
absTol T T
s
s
1
1
( ) ( )
, ,
( )
( ) ( )
, ,
( )
Y
k
i
k
i
k
i
T
k k k
relTol Y Y Y
relTol T T T
s
s

1 1
1 1
Coupling Method

1) Solve alternatively for every cell of
the 2 coupled regions

2) Check for convergence: if reached,
proceed to next time step

( )
( ) ( ) ( )
( )
( ) ( ) ) (
i mix,
T C T k =
dt
T c d
Y Y D =
dt
Y d
mix
p
p mat
i i mix
i mix
V V V
V V V
Solve Solid Solve Fluid
for each time step...
A Comprehensive Solver for Describing Multi-Region Phenomena
MultiRegion Solver Architecture
Solve Solid
Navier-stokes Equation
Pressure Corrector
Solve Fluid
P
I
S
O

p
r
e
d
i
c
t
o
r
-
c
o
r
r
e
c
t
o
r

l
o
o
p

Continuity Equation
Solve Solid
Pressure Corrector
Fluid Chemistry
Update Fluid Properties
Solve Fluid
P
I
S
O

p
r
e
d
i
c
t
o
r
-
c
o
r
r
e
c
t
o
r

l
o
o
p

Continuity Equation
Mass Transfer Equation
Heat Transfer Equation
Homogeneous reactions
Solve Solid
Solid Chemistry
Update Solid Properties
Pressure Corrector
Fluid Chemistry
Solve Fluid
P
I
S
O

p
r
e
d
i
c
t
o
r
-
c
o
r
r
e
c
t
o
r

l
o
o
p

Site species conservation
Homogeneous and heterogeneous reactions
Continuity Equation
Solve Solid
Solid Chemistry
Pressure Corrector
Fluid Chemistry
Solve Fluid
Coupling
Loop
Coupling
Loop
P
I
S
O

p
r
e
d
i
c
t
o
r
-
c
o
r
r
e
c
t
o
r

l
o
o
p

Coupling loop
convergence
check
Site species conservation
Homogeneous and heterogeneous reactions
Continuity Equation
Outline

Multiple meshes

Numerical Tests

Solver Validation

Conclusions

Coupling Strategy Testing
1-D Conjugate Heat Transfer
Compare with
analytical
solution
at steady state
Compare with
fully-coupled
Matlab solver
Compare with
analytical
solution
during transient
at steady state
Alluminium
Steel
Hot side:
Fixed T = 500 [K]
Cold side:
Fixed T = 300 [K]
Initial T =
uniform 400 [K]
Interface
Compare with
fully-coupled
Matlab solver
Compare with
analytical
solution
during transient
at steady state
2
2
2
2
2 2
1
2
1
1
1 1
T k =
t
T
Cp
T k =
t
T
Cp
V
c
c
V
c
c
( ) ( )
( ) ( )
( )
( )
( ) | |
( ) | |
( ) | | K = x, T
K = T
K = T
= t T
= t T
t T = t T
t
x
T
k = t
x
T
k
400 0
500 0,0.1
300 0,0
300 0.1,
500 0,
0.05, 0.05,
0.05, 0.05,
2
1
2
1
2 1
2
2
1
1
c
c
c
c Model equations
Boundary Conditions
Initial Conditions
Alluminium
Steel
Hot side:
Fixed T = 500 [K]
Cold side:
Fixed T = 300 [K]
Initial T =
uniform 400 [K]
Interface
Compare with
fully-coupled
Matlab solver
Compare with
analytical
solution
during transient
at steady state
Transient
Solution
Accurate prediction of T profiles
along the two bars :

Compared to fully-coupled solution
during transient

Compared with the analytical solution
at steady state
Steady State
Solution
300
320
340
360
380
400
420
440
460
480
500
0 1 2 3 4 5 6 7 8 9 10
T
e
m
p
e
r
a
t
u
r
e

[
K
]

Bar Length [cm]
CatalyticFOAM
Solution
Analytical
Solution
Does our splitting scheme make sense?
Testing MultiRegion Splitting Method
How to test for validity of our splitting scheme ?
CatalyticFOAM
Multi-Region
Solver
CatalyticFOAM
Multi-Region
Solver
CatalyticFOAM
Multi-Region
Solver
CatalyticFOAM
Multi-Region
Solver
Matlab
Fully Coupled
Solver
Effect of time
step
CatalyticFOAM
Multi-Region
Solver
Matlab
Fully Coupled
Solver
Effect of time
step
Effect of mesh
refinement
CatalyticFOAM
Multi-Region
Solver
Matlab
Fully Coupled
Solver
Effect of time
step
Effect of mesh
refinement
Test in different
conditions
CatalyticFOAM
Multi-Region
Solver
Matlab
Fully Coupled
Solver
Test Case:

200 Fluid Cells

200 Solid Cells

2 Gas Phase Species

1 Reaction: A->B
Description:

Transport in the fluid region

Diffusion + Reaction in the solid region

Coupling at the interface

A
0.6
A
0.4
Effect of time
step
Effect of mesh
refinement
Test in different
conditions
CatalyticFOAM
Multi-Region
Solver
Matlab
Fully Coupled
Solver
Decreasing time step

-
0.010
0.012
0.014
0.016
0.018
0.020
0.022
0.024
0.0 0.2 0.4 0.6 0.8 1.0
C
A

[
m
o
l
/
m
3
]

Slab Length [cm]
dt=1e-4
dt=1e-5
dt=1e-6
fully coupled
dt = 110
-4
dt = 110
-5
dt = 110
-6

8.3810
-5
2.6510
-5
5.2410
-6

Euclidean norm of the error

-
Using a finer mesh

0.010
0.012
0.014
0.016
0.018
0.020
0.022
0.024
0.0 0.2 0.4 0.6 0.8 1.0
C
A

[
m
o
l
/
m
3
]

Slab Length [cm]
dt=1e-4
dt=1e-5
dt=1e-6
fully coupled
0
0.005
0.01
0.015
0.02
0.025
0.03
0 0.5 1
C
A

[
m
o
l
/
m
3
]

Slab Length [cm]
10 Cells
50 Cells
100 Cells
Fully Coupled - 600 Cells
dt = 110
-4
dt = 110
-5
dt = 110
-6

8.3810
-5
2.6510
-5
5.2410
-6

10 cells 50 cells 100 cells
6.4110
-4
5.7110
-5
1.8610
-5


-
Using a finer mesh

0.010
0.012
0.014
0.016
0.018
0.020
0.022
0.024
0.0 0.2 0.4 0.6 0.8 1.0
C
A

[
m
o
l
/
m
3
]

Slab Length [cm]
dt=1e-4
dt=1e-5
dt=1e-6
fully coupled
0
0.005
0.01
0.015
0.02
0.025
0.03
0 0.5 1
C
A

[
m
o
l
/
m
3
]

Slab Length [cm]
10 Cells
50 Cells
100 Cells
y = 0.0232x
0.602

1.0E-06
1.0E-05
1.0E-04
1.0E-03
1.E-07 1.E-05 1.E-03
e
r
r
o
r

time step [s]
dt = 110
-4
dt = 110
-5
dt = 110
-6

8.3810
-5
2.6510
-5
5.2410
-6

Convergence Order 0.6 (ideal 1)
6.4110
-4
5.7110
-5
1.8610
-5


-
0.010
0.012
0.014
0.016
0.018
0.020
0.022
0.024
0.0 0.2 0.4 0.6 0.8 1.0
C
A

[
m
o
l
/
m
3
]

Slab Length [cm]
dt=1e-4
dt=1e-5
dt=1e-6
fully coupled
0
0.005
0.01
0.015
0.02
0.025
0.03
0 0.5 1
C
A

[
m
o
l
/
m
3
]

Slab Length [cm]
10 Cells
50 Cells
100 Cells
6.4110
-4
5.7110
-5
1.8610
-5

y = 0.0232x
0.602

1.0E-06
1.0E-05
1.0E-04
1.0E-03
1.E-07 1.E-05 1.E-03
e
r
r
o
r

time step [s]
y = 0.022x
1.5312

1.E-05
1.E-04
1.E-03
0.001 0.1
e
r
r
o
r

step size [cm]
dt = 110
-4
dt = 110
-5
dt = 110
-6

8.3810
-5
2.6510
-5
5.2410
-6

Using a finer mesh

Diff/k 0.1 1 10 1000
2 10
-6
2 10
-5

2 10
-4

0
0.005
0.01
0.015
0.02
0.025
0 0.2 0.4 0.6 0.8 1
CatalyticFOAM
Fully Coupled
0
0.005
0.01
0.015
0.02
0.025
0 0.2 0.4 0.6 0.8 1
CatalyticFOAM
Fully Coupled
0
0.005
0.01
0.015
0.02
0.025
0 0.2 0.4 0.6 0.8 1
CatalyticFOAM
Fully Coupled
0
0.005
0.01
0.015
0.02
0.025
0 0.2 0.4 0.6 0.8 1
CatalyticF
Fully Coupled
0
0.005
0.01
0.015
0.02
0.025
0 0.2 0.4 0.6 0.8 1
CatalyticFOAM
Fully Coupled
0
0.005
0.01
0.015
0.02
0.025
0 0.2 0.4 0.6 0.8 1
CatalyticFOAM
Fully Coupled
0
0.005
0.01
0.015
0.02
0.025
0 0.2 0.4 0.6 0.8 1
CatalyticFOAM
Fully Coupled
0
0.005
0.01
0.015
0.02
0.025
0 0.2 0.4 0.6 0.8 1
CatalyticFOAM
Fully Coupled
0
0.005
0.01
0.015
0.02
0.025
0 0.2 0.4 0.6 0.8 1
CatalyticFOAM
Fully Coupled
0
0.005
0.01
0.015
0.02
0.025
0 0.2 0.4 0.6 0.8 1
CatalyticFOAM
Fully Coupled
0
0.005
0.01
0.015
0.02
0.025
0 0.2 0.4 0.6 0.8 1
CatalyticFOAM
Fully Coupled
0
0.005
0.01
0.015
0.02
0.025
0 0.2 0.4 0.6 0.8 1
CatalyticFOAM
Fully Coupled
Does our splitting scheme work with more complex cases?
Testing Full Solver Architecture
2D Case : pipe with
cylindrical obstacle

solid catalyst
2D Case : pipe with

full solver architecture tested
solid catalyst
2D Case : pipe with

non-elementary geometry

solid catalyst
2D Case : pipe with

detailed kinetic scheme
(H2 on Rh : 18 reactions, 5 adsorbed species)

solid catalyst
Resolution of Navier-Stokes equations
in fluid domain

2D Case : pipe with


solid catalyst
Intra-solid profiles can
be investigated
2D Case : pipe with


Radial Profile
solid catalyst
2D Case : pipe with


Intra-solid profiles can
be investigated
Axial Profile
solid catalyst
Outline

Multiple meshes

Numerical Tests

Solver Validation

Conclusions

Combustion of a fuel-rich H
2
over Rh catalyst in an annular
reactor
(
*
)
.
(
*
)
Two-dimensional detailed modeling of fuel-rich H
2
combustion over Rh/Al
2
O
3
catalyst.
M. Maestri, A. Beretta, T. Faravelli, G. Groppi, E. Tronconi, D.G. Vlachos Chem. Eng. Sci. 2008

Solver Validation
Case Description
Operating conditions
Inner radius 0.235 cm
Outer radius 0.450 cm
Reactor length 1.5 cm
H
2
mole fraction 0.04 (-)
O
2
N
2
Pressure 1 atm
Catalytic layer width 50 m

Flow rate 0.274 Nl/min

(
*
)
2D detailed modeling of fuel-rich H
2
2
O
3
catalyst.
M. Maestri, A. Beretta, T. Faravelli, G. Groppi, E. Tronconi, D. Vlachos CES 2008

Solver Validation
Comparison with Experimental Data
2
over Rh catalyst in an annular reactor
(
*
)

0
0.2
0.4
0.6
0.8
1
1.2
0 100 200 300 400 500 600
O
2

C
o
n
v
e
r
s
i
o
n

[
%
]

Temperature [C]
(
*
)
2
2
O
3
catalyst.

Solver Validation
2
(
*
)

0
0.2
0.4
0.6
0.8
1
1.2
0 100 200 300 400 500 600
O
2

C
o
n
v
e
r
s
i
o
n

[
%
]

Temperature [C]
Previous Models
(no description of the solid phase)
(
*
)
2
2
O
3
catalyst.

Solver Validation
2
(
*
)

0
0.2
0.4
0.6
0.8
1
1.2
0 100 200 300 400 500 600
O
2

C
o
n
v
e
r
s
i
o
n

[
%
]

Temperature [C]
Previous Models
Overestimated conversions
in the mid T range
Identification of the calculation domain
Cylindrical symmetry
(
*
)
2
2
O
3
catalyst.

Solver Validation
Case Setup
2D domain
Lower computational
effort
(
*
)
2
2
O
3
catalyst.

Solver Validation
Case Setup
2D domain
Lower computational
effort
(
*
)
2
2
O
3
catalyst.

Solver Validation
Case Setup
(
*
)
Determination of the effective diffusion coefficient in porous media including
Knudsen effects. D. Mu, Z.S. Liu, C. Huang, N. Djilali 2008

Solver Validation
2
(
*
)

0
0.2
0.4
0.6
0.8
1
1.2
0 100 200 300 400 500 600
O
2

C
o
n
v
e
r
s
i
o
n

[
%
]

Temperature [C]
multiRegion
Better fit due to the
description of intra-solid
phenomena
1% 1%
Main catalytic bed
(
*
)

Solver Validation
2
(
*
)

0
0.2
0.4
0.6
0.8
1
1.2
0 100 200 300 400 500 600
O
2

C
o
n
v
e
r
s
i
o
n

[
%
]

Temperature [C]
multiRegion
phenomena
1% 1%
Main catalytic bed
= ()

(
*
)

Solver Validation
2
(
*
)

0
0.2
0.4
0.6
0.8
1
1.2
0 100 200 300 400 500 600
O
2

C
o
n
v
e
r
s
i
o
n

[
%
]

Temperature [C]
multiRegion
phenomena
1% 1%
Main catalytic bed
= ()
= .
= .
/
(
*
)
2
2
O
3
catalyst.

Solver Validation
2
(
*
)

multiRegion
0
0.2
0.4
0.6
0.8
1
1.2
0 100 200 300 400 500 600
O
2

C
o
n
v
e
r
s
i
o
n

[
%
]

Temperature [C]
1% 1%
Main catalytic bed
= .
= .
= .
/
(
*
)
2
2
O
3
catalyst.

Solver Validation
2
(
*
)

0
0.2
0.4
0.6
0.8
1
1.2
0 100 200 300 400 500 600
O
2

C
o
n
v
e
r
s
i
o
n

[
%
]

Temperature [C]
multiRegion
Same results obtained with
refined mesh
1% 1%
Main catalytic bed
600 cells 1200 cells
Solver Validation
Different controlling
regimes at different T
multiRegion
Solver Validation
0.000
0.002
0.004
0.006
0.008
0.010
0.012
0.014
0.016
0 10 20 30 40 50
O
2

m
a
s
s

f
r
a
c
t
i
o
n

Catalytic Layer Width [m]
0.0E+00
5.0E-04
1.0E-03
1.5E-03
2.0E-03
2.5E-03
3.0E-03
3.5E-03
4.0E-03
0 10 20 30 40 50
O
2

m
a
s
s

f
r
a
c
t
i
o
n

Different controlling
regimes at different T
0.E+00
1.E-04
2.E-04
3.E-04
4.E-04
5.E-04
6.E-04
7.E-04
8.E-04
0 10 20 30 40 50
O
2

m
a
s
s

f
r
a
c
t
i
o
n

multiRegion
0.E+00
1.E-05
2.E-05
3.E-05
4.E-05
5.E-05
6.E-05
7.E-05
8.E-05
9.E-05
0 10 20 30 40 50
O
2

m
a
s
s

f
r
a
c
t
i
o
n

373 K
423 K
523 K
823 K
0.E+00
2.E-03
4.E-03
6.E-03
8.E-03
1.E-02
1.E-02
0 10 20 30 40 50
O
2

m
a
s
s

f
r
a
c
t
i
o
n

373 K
423 K
523 K
823 K
Outline

Multiple meshes

Numerical Tests

Solver Validation

Conclusions

Conclusions
Segregated approach (operator splitting)
Multiple meshes for multiple regions
Partitioned approach with coupling at the interface for
multiRegions handling
Solver
Structure
multiRegion
Conclusions
multiRegion
Operator splitting strategy for reactive and transport terms
Partitioned approach for coupling at the interface between
two different phases
Solver
Structure
Conclusions
multiRegion
Solver
Structure
Conclusions
multiRegion
Solver
Structure
Conclusions
Comparison with analytical and numerical solutions in
cases with increasing complexity
Validation of the solver through comparison with
experimental data
Tests and
Validation
multiRegion
Solver
Structure
Conclusions
experimental data
Tests and
Validation
multiRegion
Solver
Structure
Conclusions
experimental data
Tests and
Validation
multiRegion
Solver
Structure
Conclusions
experimental data
Tests and
Validation
multiRegion
Detailed description of intra-solid phenomena
Complex kinetic schemes
Arbitrary number of regions with different properties
Handles geometries of arbitrary complexity
Solver
Potential
Solver
Structure
Conclusions
experimental data
Tests and
Validation
multiRegion
Solver
Potential
Solver
Structure
Conclusions
experimental data
Tests and
Validation
multiRegion
Solver
Potential
Solver
Structure
Conclusions
experimental data
Tests and
Validation
multiRegion
Solver
Potential
Solver
Structure
Conclusions
Solver
Structure
experimental data
Tests and
Validation
multiRegion
Solver
Potential
Show Case
Case Setup
Mesh Size: 8700 Cells

H
2
O
2
N
2
Pressure 1 atm
Show Case
Case Setup

1 Fluid Region and 4 Solid Regions

H
2
O
2
N
2
Pressure 1 atm
Show Case
Case Setup

Different Properties for each catalytic
solid

H
2
O
2
N
2
Pressure 1 atm
Show Case
Case Setup

solid
Detailed H
2
on Rh kinetic scheme
(18 reactions, 7 gas species, 5 adsorbed species)

H
2
O
2
N
2
Pressure 1 atm
Show Case
Velocity Profiles
solid
Detailed H
2
on Rh kinetic scheme
(18 reactions, 7 gas species, 5 adsorbed species)

Show Case
Transient Simulation
Show Case
Oxygen mass fraction profiles
0.0E+00
2.0E-03
4.0E-03
6.0E-03
8.0E-03
1.0E-02
1.2E-02
0 0.2 0.4 0.6 0.8 1 1.2
O
2

m
a
s
s

f
r
a
c
t
i
o
n

Catalytic Layer Width [mm]
0.0E+00
4.0E-03
8.0E-03
1.2E-02
1.6E-02
0 0.2 0.4 0.6 0.8
O
2

m
a
s
s

f
r
a
c
t
i
o
n

0.0E+00
2.0E-03
4.0E-03
6.0E-03
8.0E-03
1.0E-02
1.2E-02
0 0.2 0.4 0.6 0.8
O
2

m
a
s
s

f
r
a
c
t
i
o
n

Different regimes inside the catalyst
regions depending on their properties
Show Case
Oxygen mass fraction profiles
Generality and flexibility of the solver
0.0E+00
2.0E-03
4.0E-03
6.0E-03
8.0E-03
1.0E-02
1.2E-02
0 0.2 0.4 0.6 0.8 1 1.2
O
2

m
a
s
s

f
r
a
c
t
i
o
n

0.0E+00
4.0E-03
8.0E-03
1.2E-02
1.6E-02
0 0.2 0.4 0.6 0.8
O
2

m
a
s
s

f
r
a
c
t
i
o
n

0.0E+00
2.0E-03
4.0E-03
6.0E-03
8.0E-03
1.0E-02
1.2E-02
0 0.2 0.4 0.6 0.8
O
2

m
a
s
s

f
r
a
c
t
i
o
n

Different regimes inside the catalyst
regions depending on their properties
Acknowledgements
Thank you for your
attention!
Acknowledgements
Any questions?
BACK-UP SLIDES
Numerical challenges
Dimensions of the system
Proportional to the number of species
Proportional to the number of cells

Stiffness
Different temporal scales involved
Different spatial scales involved

Non-linearity
Source term non linear in
concentrations and temperature
Coverage dependence of activation
energy
, , , ,
=

catalyticFOAM structure
OpenFOAM

Complex CFD
CatalyticSMOKE
Surface microkinetics
OpenSMOKE
Complex gas-phase
chemistry
Numerical library for
stiff ODEs system
(LSODE, RADAU5, CVODE,
BzzMath 6.0)

catalyticFOAM

CFD code for reacting flows on
surface with detailed kinetic
Operator splitting scheme
= +
Reaction
Diffusion,
convection...
(
*
)
Second-order splitting schemes for a class of reactive systems
Z. Ren, S. B. Pope Journal of Computational Physics - 2008

Strang splitting scheme
Operator splitting scheme
Global system
Source term
=
Transport term
= +
Jacobian matrix:
Sparse
Unstructured
Jacobian matrix:
Sparse
Diagonal
Blocks
Solution procedure
Main features:
Solution of the Navier-Stokes
equations (laminar and
turbulent regime)
No limit to the number of
species and reactions
Isothermal and adiabatic
conditions
Navier-Stokes Eqs.
(PISO predictor)
Batch series
(Strang predictor)
Properties
evaluation
Transport Eqs.
(Strang corrector)
Pressure Eqn.
Velocity correction
(PISO corrector)
+
=
+
Interface Coupling Validation
1-D Diffusion
CH4
=
1 [w/w]
O2
=
1 [w/w]

- FluidSx: 2e-5 [m^2/s]
- FluidDx: 1e-5 [m^2/s]
Diffusion coefficients
CH4-O2 Diffusion in a
N2-full volume
(T = 573[K],P=1[atm])
0
0.005
0.01
0.015
0.02
0.025
0.03
0.035
0 2 4 6 8 10
C
o
n
c

A

[
m
o
l
/
m
3
]

Slab length [cm]
Steady state
solution
analytical solution CH4
catalyticFOAM solution CH4
analytical solution O2
catalyticFOAM solution O2
Steady
state
Analytical Validation of Solver with Integrated Reaction Term
Diffusion and Reaction in a Solid Slab
Solid slab with constant
massive fraction on the sides
Reaction: A->B
Analytical solution:
|
|
|
.
|
\
|
|
|
.
|
\
|
|
|
.
|
\
|
|
|
.
|
\
|
|
|
.
|
\
|
L
Diff
k
x
Diff
k
C = C
s
A A
cosh
cosh
A
= 0.3

A
= 0.3

0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0 0.5 1 1.5 2
A

w
t
/
w
t

Slab length [cm]
Steady state
solution
analytical solution
catalyticFOAM solution
A
Solve Solid
0 = +
dt
d
mix
V
( )
( )
sites Rh
cat
SOL
cell
i tot i
mix
i
tot
MW
dV
Y dm MW R +
R
=
dt
dY
m
i gas,
i hom,
mix p
c
Q + Q
=
dt
dT
mix
het hom
sites
i
R
=
dt
d
i surf,
Solid Chemistry
Rho Eq.
U Eq.
*
v =
a
P
p
V
|
|
.
|
\
|
V
V
Pressure Eq.
mix
i
R
=
dt
dY
i hom,
mix p
c
Q
=
dt
dT
mix
hom
Fluid Chemistry
( )
( ) ( ) ( )
i i mix
i mix
Y Y D =
dt
Y d
V V V
mix i,
( )
( ) ( ) ( ) T c T k =
dt
T c d
p mat
mat
V V V
mat p
Mass Transfer Eq.
HeatTransfer Eq.
( )
( ) ( )
i mix
i mix
Y D =
dt
Y d
V V
mix i,
Mass Transfer Eq.
( )
( ) ( ) T k =
dt
T c d
mat
mat
V V
mat p
Heat Transfer Eq.
Solve Fluid
Pimple
Loop
Pimple
Loop
P
I
S
O

p
r
e
d
i
c
t
o
r
-
c
o
r
r
e
c
t
o
r

l
o
o
p

PIMPLE
convergence
check
A Comprehensive Solve for Describing Multi-Region Phenomena
(
+()-
2

=
2D Cases: Chemical/Diffusive Regimes
U profile
developement
Material diffusion
through interface
Heterogeneous
reactions on the solid
surface inside the
solid volume
Homogeneous
reactions in the fluid
volumes
O2
H2
N2
O2
H2
N2
Detailed microkinetic
description of surface
chemistry
2D Case : solid slab between 2 fluid
channels
more complex geometry:3 regions, 2 coupled
interfaces
Detailed heterogeneous kinetic model
Solution of Navier-Stokes equation
Resolution of Navier-Stokes equation in fluid
domain

Intra-solid profiles can be investigated

0
0.2
0.4
0.6
0.8
1
1.2
0 100 200 300 400 500 600
O
2

C
o
n
v
e
r
s
i
o
n

[
%
]

Temperature [C]
(
*
)
2
2
O
3
catalyst.

2
(
*
)

Solver Validation
Previous Models
Overestimate conversions in
the mid T range
Underestimate conversions
in the high T range
0
0.2
0.4
0.6
0.8
1
1.2
0 100 200 300 400 500 600
O
2

C
o
n
v
e
r
s
i
o
n

[
%
]

Temperature [C]
(
*
)
2
2
O
3
catalyst.

Main catalytic bed
Solver Validation
2
(
*
)

multiRegion
0
0.2
0.4
0.6
0.8
1
1.2
0 100 200 300 400 500 600
O
2

C
o
n
v
e
r
s
i
o
n

[
%
]

Temperature [C]
(
*
)
2
2
O
3
catalyst.

Main catalytic bed
Solver Validation
2
(
*
)

multiRegion
phenomena
0
0.2
0.4
0.6
0.8
1
1.2
0 100 200 300 400 500 600
O
2

C
o
n
v
e
r
s
i
o
n

[
%
]

Temperature [C]
(
*
)
2
2
O
3
catalyst.

Solver Validation
2
(
*
)

multiRegion
phenomena
Main catalytic bed
0
0.2
0.4
0.6
0.8
1
1.2
0 100 200 300 400 500 600
O
2

C
o
n
v
e
r
s
i
o
n

[
%
]

Temperature [C]
(
*
)
2
2
O
3
catalyst.

Solver Validation
2
(
*
)

multiRegion
phenomena
1% 1%
Main catalytic bed
When an extended bed is
considered.
Solver Validation
Adsorbed species
profiles
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0 0.3 0.6 0.9 1.2 1.5
S
i
t
e

F
r
a
c
t
i
o
n

[
%
]

Reactor Length [cm]
H(S)
O(S)
OH(S)
Rh(S)
multiRegion
(
*
)

Solver Validation
2
(
*
)

0
0.2
0.4
0.6
0.8
1
1.2
0 100 200 300 400 500 600
O
2

C
o
n
v
e
r
s
i
o
n

[
%
]

Temperature [C]
phenomena
1% 1%
Main catalytic bed
= ()
= .
= .
=
2
3

=
1.5

=
2
1 0.5

= 1 (1 )
0.46

Calonaci Furnari Final Presentation

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Calonaci Furnari Final Presentation

Uploaded by

Copyright:

Available Formats

Matteo Calonaci Federica Furnari

A COMPUTATIONAL FRAMEWORK FOR THE

You might also like