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Hot topic 4
First-principles based
catalytic reaction engineering
Matteo Maestri
[CO]Rh + [OH]Rh CO
+ [H]Rh
RDS
CO2
[H2O]Rh + 2Rh
H2
H2O
“E pluribus unum”
Result of the interplay among phenomena at different scales
Temperature [°C]
1000
CO*+OH* → COOH*+*
COOH*+* → CO2*+H* 900
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
…
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
Catalytic wall
reactions
dt V j 1
j 1
k 1
NG NF NG
Cˆ dT Hˆ homhom 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 homhom 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
NU
NU NC
NC
Jacobian matrix:
Sparse
Unstructured
Blocks
Source term
Global system
Source term
Jacobian matrix:
Sparse
Diagonal
Transport term
Global system
Jacobian matrix:
Sparse
Unstructured
Operator-splitting algorithm
Global system
Navier-Stokes Eqs.
(PISO predictor) Main features:
CatalyticSMOKE OpenSMOKE
Surface microkinetics Complex gas-phase chemistry
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
Inlet
mixture
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
Inlet
mixture
10 mm
Inlet
mixture
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
jnα = v α M α TOF
104
jnα = v α M α TOF
104
jnα = v α M α TOF
104
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)
@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