CECAM International Summer School

Hot topic 4

First-principles based
catalytic reaction engineering
Matteo Maestri

July 23, 2013

Conversationshaus - Norderney, Germany
 Catalytic cycle
Consists of the elementary steps through which
the reactants convert to the products

[CO]Rh + [OH]Rh CO
+ [H]Rh

[CO2]Rh +2[H]Rh [H]Rh +[OH]Rh + Rh

RDS
CO2
[H2O]Rh + 2Rh

H2
H2O
 “E pluribus unum”
Result of the interplay among phenomena at different scales

Microscale [CO]Rh + [OH]Rh CO Macroscale

COOH*+* → CO*+OH*
+ [H]Rh 1100
T catalyst

Temperature [°C]
1000
CO*+OH* → COOH*+*
COOH*+* → CO2*+H* 900

CO2*+H* → COOH*+* 800

CO2* + H2O* → COOH* + OH*
700
COOH* + OH* → CO2* + H2O*
CO2*+H* → HCOO** 600 T gas
HCOO** → CO2*+H*
[CO2]Rh +2[H]Rh [H]Rh +[OH]Rh + Rh 500
CO2* + OH* + *→ HCOO** + O*
400
HCOO** + OH* → CO2* + H2O* 2
CH* + H* → CH2* + *
CH* + * → C* + H*
C* + H* → CH* + *
RDS 1.5
CH
H
2
4

mmol/s
CH3* + O* → CH2* + OH* O CO
CH2* + OH* → CH3* + O*
CO2 1 2
CH* + OH* → CH2* + O*
CH2* + O* → CH* + OH* [H2O]Rh + 2Rh 0.5
HO
2
CO
2
…

~ 102 potential steps 0

0 2 4 6 8 10
@ different coverages Axial length [mm]
H2
H2O
 Need of bridging between the scales
Length

MACROSCALE
Reactor engineering and
transport phenomena

MESOSCALE
Interplay among the
chemical events

MICROSCALE
making and breaking of
chemical bonds
INTRINSIC FUNCTIONALITY

Time
From a “traditional” approach to CRE…
Length

MACROSCALE
Reactor engineering and
transport phenomena

MESOSCALE
Interplay among the
chemical events

MICROSCALE effective/simplified
making and breaking of approaches
chemical bonds

Time
…to a first-principles approach to CRE
Length

MACROSCALE
Reactor engineering and
transport phenomena
CFD

MESOSCALE
Interplay among the
chemical events
MK/kMC

MICROSCALE
making and breaking of Electronic
chemical bonds
structure theory
Time
Need of “bridging” between the scales
M. Maestri in “New strategy for
Length

MACROSCALE
chemical synthesis and catalysis”,
Wiley-VCH (2012)
Reactor engineering and
transport phenomena
CFD

MESOSCALE
Interplay among the
chemical events
MK/kMC

MICROSCALE
making and breaking of Electronic
chemical bonds
structure theory
Time
Need of “bridging” between the scales
Length

MACROSCALE
Reactor engineering and
transport phenomena
CFD
Complex
MESOSCALE geometries
Interplay among the
chemical events
MK

MICROSCALE
making and breaking of Electronic Microkinetic
chemical bonds
structure theory modeling
Time
 Outline
Length

 Methodology MACROSCALE
 Show-cases Reactor engineering and
transport phenomena

MESOSCALE
Interplay among the
chemical events

MICROSCALE
making and breaking of
chemical bonds M. Maestri & A. Cuoci
www.catalyticfoam.polimi.it

Time
 Outline
Length

 Methodology MACROSCALE
 Show-cases Reactor engineering and
transport phenomena

MESOSCALE
Interplay among the
chemical events

MICROSCALE
making and breaking of
chemical bonds M. Maestri & A. Cuoci
www.catalyticfoam.polimi.it

Time
 Governing equations
Catalytic wall

Gas-phase

∂ρ
+ ∇ ⋅ ( ρv) =0 continuity
∂t
∂  
∂t
( )
ρ v + ∇ ⋅ ( )
ρ vv = −∇ p + ∇ ⋅ 

µ ∇ v (
+ ∇ vT
−
2
3
µ ( )
∇ v ) I 

+ ρg momentum

∂
( ρωk ) + ∇ ⋅ ( ρωk v ) = −∇ ⋅ ( ρωk Vk ) + Ω hom k = 1,..., NG mass
∂t
k

∂T NG NG
ρCP
ˆ + ρCP v∇T = ∇ ⋅ ( λ∇T ) − ρ ∑ CP ,k ωk Vk − ∑ Hˆ khomΩ
ˆ ˆ  hom energy
∂t
k
= k 1= k 1
 Governing equations
Non-catalytic walls Detailed microkinetic models
COOH*+* → CO*+OH*
∇ ωk =
0
inert CO*+OH* → COOH*+*
COOH*+* → CO2*+H*
T inert
= f ( t ,T ) CO2*+H* → COOH*+*
CO2* + H2O* → COOH* + OH*
∇T inert
g ( t ,T )
= COOH* + OH* → CO2* + H2O*
CO2*+H* → HCOO**
Catalytic walls HCOO** → CO2*+H*
CO2* + OH* + *→ HCOO** + O*
HCOO** + OH* → CO2* + H2O*
ρ Γ k ,mix ( ∇ωk ) catalytic =  het
−α cat Ω k k=
1,..., NG CH* + H* → CH2* + *
CH* + * → C* + H*
NR
C* + H* → CH* + *
−α cat ∑ ∆H het
λ ( ∇T ) catalytic = j rj
 het CH3* + O* → CH2* + OH*
j =1 CH2* + OH* → CH3* + O*
CH* + OH* → CH2* + O*
∂θ i  het CH2* + O* → CH* + OH*
σ cat =
Ω i=
1,..., NS
∂t
i
…
Adsorbed (surface) species

M. Maestri, Microkinetic analysis of complex chemical processes at surface, in “New strategy for chemical
synthesis and catalysis”, Wiley-VCH (2012)
 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
 Numerical solution
Fully segregated algorithms
 easy to implement and computationally efficient
Detailed kinetic  unfeasible when large, stiff kinetic mechanisms Complex
schemes are used geometries

Strong non linearity of reaction terms

High stiffness

Fully coupled algorithms Operator-splitting methods

 all the processes and their interactions are
considered simultaneously
 natural way to treat problems with multiple stiff
processes
 the resulting system of equations can be
extremely large and the computational cost
prohibitive
 usually avoid many costly matrix operations
 allow the best numerical method to be used
for each type of term or process
 the resulting algorithms can be very complex
and usually differ from term to term
 Operator-splitting algorithm
Diffusion,
Reaction
convection...

Strang splitting scheme

Z. Ren, S. B. Pope, Journal of Computational Physics, 2008

M. Maestri, A. Cuoci, Chemical Engineering Science, 96 (2013) 106-117

 Reactor network
Catalytic wall
Each computational cell
behaves as a chemical
Gas mixture reactor in the splitting-
operator algorithm (chemical
step)

Each reactor is described by a

set of stiff ODE, which must
be integrated on the time step
Δt

Batch reactor Batch reactor

M. Maestri, A. Cuoci, Chemical Engineering Science, 96 (2013) 106-117

 Reactor network

 1  NF  
d k het 
NF NG
Homogeneous 
  hom  cat 
 k    j A j k , j  k   j A j  k , j  
het cat   k=1,NG

Catalytic wall
reactions 
 dt V j 1 
  
  j 1
 k 1 


 NG NF NG
Cˆ dT   Hˆ homhom  1
 P
 dt
 k k 
V j 1
 j A j   het
cat
 ˆ het
k , j Hk , j  Hk 
ˆ hom


k 1 k 1

 i , j

cat   het i =1,...,NS j =1,...,NF
Catalytic wall 
 t
i, j



 1  NF  
d k het 
NF NG

   
 k    j A j k , j  k   j A j  k , j  
hom cat het cat   k=1,NG
Homogeneous 
 dt V j 1 
  
reactions   j 1
 k 1 


 NG NF NG
Cˆ dT   Hˆ homhom  1
 P
 dt
 k k 
V j 1
 j A j   het
cat
 ˆ het
k , j Hk , j  Hk 
ˆ hom


k 1 k 1

 i , j

cat   het i =1,...,NS j =1,...,NF

 t
i, j

 Operator-splitting algorithm

ti ti+1 ti+2

ti ti+1 ti+2

ti ti+1 ti+2

The procedure is iterated on the next time step

M. Maestri, A. Cuoci, Chemical Engineering Science, 96 (2013) 106-117

 Jacobian matrix
Global system

NU

NU NC

NC

Jacobian matrix:
 Sparse
 Unstructured
 Blocks
 Source term
Global system

Source term

Jacobian matrix:
 Sparse
 Diagonal
 Transport term
Global system

Source term Transport term

Jacobian matrix:
 Sparse
 Unstructured
 Operator-splitting algorithm
Global system

Source term Transport term

 Solution procedure

Navier-Stokes Eqs.
(PISO predictor) Main features:

Reactor network  Solution of the Navier-Stokes

(Strang predictor) equations (laminar and turbulent
regime)
Properties evaluation

 No limit to the number of species

Transport Eqs. and reactions
(Strang corrector)
 No limit in geometry
Pressure Eqn.
Velocity correction
(PISO corrector)
 catalyticFOAM structure
www.catalyticfoam.polimi.it

Numerical library for

OpenFOAM stiff ODEs system
Complex CFD (LSODE, RADAU5, CVODE,
BzzMath, etc.)

CFD code for reacting flows with

heterogeneous reactions

CatalyticSMOKE OpenSMOKE
Surface microkinetics Complex gas-phase chemistry

M. Maestri, A. Cuoci, Chemical Engineering Science, 96 (2013) 106-117

 Outline
Length

 Methodology MACROSCALE
 Show-cases Reactor engineering and
transport phenomena

MESOSCALE
Interplay among the
chemical events

MICROSCALE
making and breaking of
chemical bonds M. Maestri & A. Cuoci
www.catalyticfoam.polimi.it

Time
 Show-case I: Rashig-ring bed
1.5 cm

Inlet
mixture

5 cm

1 cm
Rashig-ring:
0.5 cm

0.2 cm

Mesh generation in collaboration with Dr. S. Lipp – BASF SE, DE

 Show-case I: Rashig-ring bed

Laminar flow (Re = 50)

Inlet
mixture

Operating conditions C1 microkinetic model on Rh:

Internal diameter 1.5 cm
Total length 5 cm 82 reaction steps
H2 mole fraction 0.04 (-) 13 adsorbed species
O2 mole fraction 0.01 (-) UBI-QEP and DFT refinement
N2 mole fraction 0.95 (-)
Temperature 473.15 K M. Maestri et al., AIChE J., 2009
Inlet velocity 0.2 m/s
 Show-case I: Rashig-ring bed
Inlet mixture
 Show-case I: Rashig-ring bed
Inlet mixture Flow-field
 Show-case I: Rashig-ring bed
Inlet mixture Flow-field
recirculation

u [m/s]

By-pass zone
 Show-case I: Rashig-ring bed
Gas-phase species
Inlet mixture
 Show-case I: Rashig-ring bed
Gas-phase species
Inlet mixture
 Show-case I: Rashig-ring bed
Adsorbed species at the catalyst surface

Inlet mixture
 Show-case I: Rashig-ring bed
Adsorbed species at the catalyst surface

+ - + -
zx zy
Inlet mixture
Show-case I: Rashig-ring bed
Dynamics of the system
Show-case I: Rashig-ring bed
Dynamics of the system
Show-case II: packed bed of spheres
4 mm

Inlet
mixture

10 mm

Catalytic particle:
600 µm

Mesh generation in collaboration with Prof. Freund – Erlangen University, DE

Show-case II: packed bed of spheres
4 mm

Inlet
mixture

10 mm

3D Unstructured Mesh: ~2,000,000 cells

Homogeneous reactors: ~1,000,000
Heterogeneous reactors: ~1,000,000
Show-case II: packed bed of spheres

Laminar flow (Re = 20)

Inlet
mixture

Operating conditions C1 microkinetic model on Rh:

Inlet diameter 4 mm
Total length 10 mm 82 reaction steps
H2 mole fraction 0.036(-) 13 adsorbed species
O2 mole fraction 0.014(-) UBI-QEP and DFT refinement
N2 mole fraction 0.95 (-)
Temperature 573 K M. Maestri et al., AIChE J., 2009
Inlet velocity 1.7 m/s
 Show-case II: packed bed of spheres
Flow-field

Inlet mixture

By-pass zone
Show-case II: packed bed of spheres
Flow-field
Show-case II: packed bed of spheres
Gas-phase species
y

x
 A “first-principles” approach to CRE
Length

MACROSCALE
Reactor engineering and
transport phenomena
CFD
MESOSCALE In collaboration with:
K. Reuter and S. Matera (TUM)
Interplay among the
chemical events
kMC

MICROSCALE
making and breaking of
chemical bonds
MK M. Maestri & A. Cuoci
www.catalyticfoam.polimi.it
Time
 First-principles kinetic Monte Carlo
• Evaluate the statistical interplay of
large number of elementary processes
• open non-equilibrium system → need
to explicitely follow the time evolution
• rare event dynamics → Molecular
Dynamics simulations unsuitable. Map
adsorbed O
on a lattice model adsorbed CO
bridge rows
→ Markov jump process description cus rows

P ( x ,t )= ∑ k ( x , y) P ( y , t )− ∑ k ( y , x) P ( x , t )
d
dt y y

• Each site a has own entry in x denoting

its adsorbate state xa
• Simulate trajectories x(t) (kinetic Monte
Image courtesy of Dr. S. Matera (TUM)
Carlo)
K. Reuter and M. Scheffler, Phys. Rev. B 73, 045433 (2006)
 Linking the scales
• Continuum equations need boundary
conditions for the mass fluxes jα at the
surface: Ts = 600K, ps(O₂)= 1atm

jnα = v α M α TOF
104

TOF(x 1015 cm-2s-1)

• Coupled problem: to determine the TOF
102 kMC (raw)
with 1p-kMC the pressures at the surface
are needed, but the pressure field
depends on the TOF 100

• kMC too expensive for direct coupling to kMC (interpolation)

the flow solver 10 -2

• Run kMC beforehand and interpolate 0.005 0.5 50

(Modified Shepard) ps(CO) (atm)
• Very efficient
• Easily extendable to more complex
geometries S. Matera and K. Reuter, Catal. Lett. 133, 156-159 (2009);
Phys. Rev. B 82, 085446 (2010).
 Linking the scales
• Continuum equations need boundary
conditions for the mass fluxes jα at the
surface: Ts = 600K, ps(O₂)= 1atm

jnα = v α M α TOF
104

TOF(x 1015 cm-2s-1)

• Coupled problem: to determine the TOF
102 kMC (raw)
with 1p-kMC the pressures at the surface
are needed, but the pressure field
depends on the TOF 100

• kMC too expensive for direct coupling to kMC (interpolation)

the flow solver 10 -2

• Run kMC beforehand and interpolate 0.005 0.5 50

(Modified Shepard) ps(CO) (atm)
• Very efficient
• Easily extendable to more complex
geometries S. Matera and K. Reuter, Catal. Lett. 133, 156-159 (2009);
Phys. Rev. B 82, 085446 (2010).
 Linking the scales
• Continuum equations need boundary
conditions for the mass fluxes jα at the
surface: Ts = 600K, ps(O₂)= 1atm

jnα = v α M α TOF
104

TOF(x 1015 cm-2s-1)

• Coupled problem: to determine the TOF
102 kMC (raw)
with 1p-kMC the pressures at the surface
are needed, but the pressure field
depends on the TOF 100

• kMC too expensive for direct coupling to kMC (interpolation)

the flow solver 10 -2

• Run kMC beforehand and interpolate 0.005 0.5 50

(Modified Shepard) ps(CO) (atm)
• Very efficient
• Easily extendable to more complex
geometries S. Matera and K. Reuter, Catal. Lett. 133, 156-159 (2009);
Karsten’s tutorial this afternoon
Phys. Rev. B 82, 085446 (2010).
Show-case: the “reactor STM”
 Show-case: the “reactor STM”
Rasmussen et al., Review of scientific instrument, 69 (1998) 3879

CO oxidation on Ru2O
• Rate constants k(x,y) from DFT and
harmonic Transition State Theory
outlet • Model system: CO oxidation on
RuO2(110)
inlet
– 2 types of sites, bridge and cus
CO + O2
K. Reuter and M. Scheffler, Phys. Rev. B 73,
045433 (2006)
Operating conditions
T: 600 K
P: 1 atm
Inlet: CO + O2 (66%, 34% Vol)
Inlet velocity: 5 cm/s
Catalytic Wall
Catalyst: Ru2O
catalyticFOAM (interpolated kMC)
www.catalyticfoam.polimi.it
 Show-case: the “reactor STM”
Rasmussen et al., Review of scientific instrument, 69 (1998) 3879

d = 2 mm

outlet

inlet
CO + O2

Operating conditions
T: 600 K
P: 1 atm
Computational details
Inlet: CO + O2 (66%, 34% Vol)
Mesh: unstructured, ~90,000 cells
Inlet velocity: 5 cm/s Catalytic Wall Discretization: 2nd order, centered
Catalyst: Ru2O Max time step: 10-4 s
CPU time: ~2 s per time step
Results
Stream lines

Strong
recirculations

Catalytic Wall
Catalyst: Ru2O
 Conclusions & perspectives
 Efficient coupling between heterogeneous microkinetic models and
computational fluid dynamics (complex and fundamental chemistry
with complex and general geometries)

 Description of the solid phase (diffusion/conduction and reaction

within the solid: assessment of internal mass transfer limitation)

 Implementation of the interpolated kMC methodology in

catalyticFOAM (in collaboration with K. Reuter/S. Matera, TUM)

 Multiscale framework for the first-principles analysis of catalytic

processes
www.catalyticfoam.polimi.it
 Acknowledgements

@polimi.it
M. Maestri & A. Cuoci
Tiziano Maffei, G. Gentile, F. Manelli, S. Rebughini,
S. Goisis, A. Osio, M. Calonaci, F. Furnari, B. Baran, Y. Niyazi
 Thank you for your Politecnico di Milano
attention! Raffaello, The school of Athens, 1509, Apostolic Palace, Roma

www.catalyticfoam.polimi.it matteo.maestri@polimi.it