CFD simulation of catalytic reactors
Olaf Deutschmann, Karlsruhe Institute of Technology (KIT)
Topsøe Catalysis Forum, Munkerupgaard, August 29-30, 2013
Institute for Chemical Technology and Polymer Chemistry (ITCP)
KIT – University of the State of Baden-Wuerttemberg and
National Research Center of the Helmholtz Association
Institute for Catalysis Research and Technology (IKFT)
www.kit.edu
THE CHALLENGE
2
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Multi-scale modeling:
From 10-10 m and 10-13 s to 1m and 10 s
1m
10 s
1 mm
10 ms
0.1 nm
3
1 nm
10 nm
10 m
100 s
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
THE DREAM
4
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Multi-scale modeling in catalysis:
From fundamental understanding to technology
Length and Time
Process simulation
Transients in heat &
mass transfer
Plants
Fluid mechanics
Reactors
DGM
MF
Reactor components
Porous supports
kMC
DFT
Multi-components, Additives
Single catalyst particles
Elementary reactions on surfaces
5
Complexity
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
THE REALITY
6
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Development of micro kinetic models for simulations of
catalytic reactors
Surface Science
Experimental
Reaction mechanism
and kinetics (idea)
Surface Science
Theoretical
Modeling of lab reactors
(including gas phase kinetics and
transport models)
Lab experiments
(conversion, selectivity,
ignition/extinction temperatures,
spatial & temporal profiles,
coverage)
Comparison of
experiment and
simulation
Thermodynamic
consistency
Technical reactor
Sensitivity & reaction
flow analyses
Revised reaction
mechanism
Cortesey of hte AG
7
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Development of micro kinetic models for simulations of
catalytic reactors
Surface Science
Experimental
Reaction mechanism
and kinetics (idea)
Surface Science
Theoretical
Modeling of lab reactors
(including gas phase kinetics and
transport models)
Lab experiments
(conversion, selectivity,
ignition/extinction temperatures,
spatial & temporal profiles,
coverage)
Comparison of
experiment and
simulation
Thermodynamic
consistency
Technical reactor
Sensitivity & reaction
flow analyses
Revised reaction
mechanism
Cortesey of hte AG
8
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Density Functional Theory (DFT) - simulation:
Periodic Slab approach
Binding energy of an oxygen atom as a
function of surface coverage
J.A. Keith, J. Anton, T.Jacob. Chapter 1 in Modeling and Simulation of
Heterogeneous Catalytic Reactions. O. Deutschmann (Ed.), 2011
9
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
DFT - Simulation: Periodic Slab approach:
H2 oxidation over Pt(111)
J.A. Keith, J. Anton, T.Jacob. Chapter 1 in Modeling and Simulation of
Heterogeneous Catalytic Reactions. O. Deutschmann (Ed.), 2011
10
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Kinetic Monte Carlo Simulation of surface reactions
and diffusion: CO oxidation on Pt nanoperticle
2 CO + O2 -> 2 CO2
CO: blue O: red
Catalyst atom (Pt): white
Washcoat molecule (Al2O3): grey
Adsorption sites: yellow
L. Kunz et al., Chapter 4 in Modeling Heterogeneous Catalytic Reactions. O. Deutschmann (Ed.), 2011
11
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Modeling heterogeneous reactions: Concept of rate
equations (mean-field approximation)
Surface coverage
Θi si M i
c

Θi  i i
t
Γ
Γ
Locally resolved reaction rates depending on gasphase concentration and surface coverages
Surface reaction rate
 'jk
si   ik kf k  c j
kR
jS
Rate expression
k f k  Ak T
12
βk
  Eak  N s μik
 εik Θi 
exp 
exp
Θ
 i


RT
RT

1
i




O. Deutschmann. in Handbook of Heterogeneous Catalysis, 2nd Ed.,, G. Ertl,
H. Knözinger, F. Schüth, J. Weitkamp (eds.), p. 1811, Wiley-VCH, 2008
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Development of micro kinetic models for simulations of
catalytic reactors
Surface Science
Experimental
Reaction mechanism
and kinetics (idea)
Surface Science
Theoretical
Modeling of lab reactors
(including gas phase kinetics and
transport models)
Lab experiments
(conversion, selectivity,
ignition/extinction temperatures,
spatial & temporal profiles,
coverage)
Comparison of
experiment and
simulation
Thermodynamic
consistency
Technical reactor
Sensitivity & reaction
flow analyses
Revised reaction
mechanism
Cortesey of hte AG
13
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Example
Development of a microkinetic model for
CH4 + CO2  2 H2 + 2 CO
CH4 + H2O  3 H2 + CO
CH4 + ½ O2  2 H2 + CO
CH4 + 2 O2  2 H2O + CO2
over Ni-based catalysts
to be used for numerical simulation
of technical reactors
DryRef: FKZ 0327856
14
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Micro kinetic model for conversion of methane over Ni
A(cm,mol,s) β(-) Ea(KJ/mol)
Reaction
R1
R2
R3
R4
R5
R6
R7
R8
R9
R10
R11
R12
R13
R14
R15
R16
R17
R18
R19
R20
R21
R22
R23
R24
R25
R26
R27
R28
R29
R30
R31
R32
R33
R34
R35
R36
R37
R38
R39
R40
R41
R42
R43
R44
R45
R46
R47
R48
R49
R50
H2
H(Ni)
O2
O(Ni)
CH4
CH4(Ni)
H2O
H2O(Ni)
CO2
CO2(Ni)
CO
CO(Ni)
O(Ni)
OH(Ni)
OH(Ni)
H2O(Ni)
OH(Ni)
O(Ni)
O(Ni)
CO(Ni)
CO2(Ni)
O(Ni)
CO2(Ni)
COOH(Ni)
COOH(Ni)
CO(Ni)
CO(Ni)
C(Ni)
HCO(Ni)
CO(Ni)
HCO(Ni)
O(Ni)
CH4(Ni)
CH3(Ni)
CH3(Ni)
CH2(Ni)
CH2(Ni)
CH(Ni)
CH(Ni)
C(Ni)
O(Ni)
CH3(Ni)
O(Ni)
CH2(Ni)
O(Ni)
CH(Ni)
O(Ni)
C(Ni)
H(Ni)
OH(Ni)
+2(Ni)
+H(Ni)
+2(Ni)
+O(Ni)
+(Ni)
>(Ni)
+(Ni)
>(Ni)
+(Ni)
>(Ni)
+(Ni)
>(Ni)
+H(Ni)
+(Ni)
+H(Ni)
+(Ni)
+OH(Ni)
+H2O(Ni)
+C(Ni)
+(Ni)
+(Ni)
+CO(Ni)
+H(Ni)
+(Ni)
+(Ni)
+OH(Ni)
+CO(Ni)
+CO2(Ni)
+(Ni)
+H(Ni)
+(Ni)
+CH(Ni)
+(Ni)
+H(Ni)
+(Ni)
+H(Ni)
+(Ni)
+H(Ni)
+(Ni)
+H(Ni)
+CH4(Ni)
+OH(Ni)
+CH3(Ni)
+OH(Ni)
+CH2(Ni)
+OH(Ni)
+CH(Ni)
+OH(Ni)
+CO(Ni)
+C(Ni)
CH4(g)
*
CH4*
*
CH3*
*
CH2*
*
CH*
O2(g)
15
>H(Ni)
>2(Ni)
>O(Ni)
>2(Ni)
>CH4(Ni)
+CH4
>H2O(Ni)
+H2O
>CO2(Ni)
+CO2
>CO(Ni)
+CO
>OH(Ni)
>O(Ni)
>H2O(Ni)
>OH(Ni)
>O(Ni)
>OH(Ni)
>CO(Ni)
>O(Ni)
>O(Ni)
>CO2(Ni)
>COOH(Ni)
>CO2(Ni)
>CO(Ni)
>COOH(Ni)
>C(Ni)
>CO(Ni)
>CO(Ni)
>HCO(Ni)
>O(Ni)
>HCO(Ni)
>CH3(Ni)
>CH4(Ni)
>CH2(Ni)
>CH3(Ni)
>CH(Ni)
>CH2(Ni)
>C(Ni)
>CH(Ni)
>CH3(Ni)
>O(Ni)
>CH2(Ni)
>O(Ni)
>CH(Ni)
>O(Ni)
>C(Ni)
>O(Ni)
>C(Ni)
>H(Ni)
+H(Ni)
+H2
+O(Ni)
+O2
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
-1.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
-1.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
-0.7
0.7
0.00
92.21
0.00
420.95
0.00
37.55
0.00
60.79
0.00
25.98
0.00
109.27-50ƟCO(Ni)
97.90
36.09
42.70
91.76
100.00
102.86
148.00
100.24-50ƟCO(Ni)
89.32
123.60-50ƟCO(Ni)
166.00
87.00
38.00
111.00
326.00-50ƟCO(Ni)
155.00
0.00+50ƟCO(Ni)
132.23
81.91
109.97
57.70
61.58
100.00
55.33
97.10
79.18
18.80
161.11
75.30
30.37
110.10
23.62
126.80
47.07
48.10
128.61
110.05-50ƟCO(Ni)
30.00
R21 CO2(Ni) +(Ni)
>O(Ni)
H*
*
R22 OH*
O(Ni)
+CO(Ni)
H2O* >CO2(Ni)
R23 CO2(Ni) +H(Ni)
>COOH(Ni)
R24 COOH(Ni) +(Ni)
>CO2(Ni)
O*
+(Ni)
R25 COOH(Ni)
+(Ni)
+H(Ni)
R26 CO(Ni)
+OH(Ni)
+(Ni)
+H(Ni)
+H2O(Ni)
R27 CO(Ni)
+OH(Ni)
+(Ni)
R28 H*
C(Ni)
H*
+C(Ni)
+CO(Ni)
+(Ni)
+(Ni)
+H(Ni)
+OH(Ni)
+(Ni)
+CO2(Ni)
+CO(Ni)
+H(Ni)
+(Ni)
+CH(Ni)
+(Ni)
+H(Ni)
+(Ni)
+H(Ni)
+(Ni)
+H(Ni)
+(Ni)
+H(Ni)
+(Ni)
+OH(Ni)
+CH4(Ni)
+OH(Ni)
+CH3(Ni)
+OH(Ni)
+CH2(Ni)
+OH(Ni)
+CH(Ni)
+OH(Ni)
+CO(Ni)
R19 O(Ni)
*
R20 CO(Ni)
R27 CO(Ni)
R28 C(Ni)
+C(Ni)
+(Ni)
OH*
R49 H(Ni)
R50 OH(Ni)
O*
+CO2(Ni)
*
+CO(Ni)
CO(g)
>CO(Ni)
>O(Ni)
*
CO2*
+(Ni)
+C(Ni)
OH*
+CO(Ni) >C(Ni)
+CO2(Ni) >CO(Ni)
O*
+CO(Ni)
+(Ni)
H2O(g)
+(Ni)
+H(Ni)
>CO(Ni)
+OH(Ni)
CO2(g)
>COOH(Ni) +(Ni)
+CO(Ni) >C(Ni)
H2(g) >CO(Ni)
+CO2(Ni)
R39 CH(Ni)C* +(Ni)
R40 C(Ni)
+H(Ni)
R47 O(Ni)
CHO*
R48 C(Ni)
*
1.000E-02
2.545E+31
1.000E-02
4.283E+20
8.000E-03
8.705E+15
1.000E-01
3.732E+12
7.000E-06
6.447E+07
5.000E-01
3.563E+11
5.000E+22
1.781E+21
3.000E+20
2.271E+21
3.000E+21
6.373E+23
3.400E+19
1.759E+11
4.653E+23
2.000E+19
7.230E+18
3.230E+19
2.740E+23
3.200E+23
3.200E+18
3.700E+21
3.700E+21
4.019E+20
3.792E+15
4.604E+20
3.700E+21
6.034E+21
3.700E+24
1.293E+23
3.700E+21
4.089E+24
3.700E+23
4.562E+21
1.700E+24
9.876E+22
3.700E+24
4.607E+21
3.700E+19
1.457E+23
3.700E+21
1.625E+21
4.945E+21
2.769E+22
H*
COOH*
+CO2(Ni)
+CO(Ni)
CO*
>C(Ni)
>CH(Ni)
+H(Ni)
+(Ni)
+CH(Ni)
H*
+OH(Ni)
>C(Ni)
>O(Ni)
+OH(Ni)
+CH(Ni)
+CO(Ni)
+C(Ni)
>C(Ni)
>H(Ni)
+OH(Ni)
+CO(Ni)
L. Maier, B. Schädel, K. Herrera Delgado, S. Tischer,
O. Deutschmann, Top Catal: 54 845 (2011)
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Development of micro kinetic models for simulations of
catalytic reactors
Surface Science
Experimental
Reaction mechanism
and kinetics (idea)
Surface Science
Theoretical
Modeling of lab reactors
(including gas phase kinetics and
transport models)
Lab experiments
(conversion, selectivity,
ignition/extinction temperatures,
spatial & temporal profiles,
coverage)
Comparison of
experiment and
simulation
Thermodynamic
consistency
Technical reactor
Sensitivity & reaction
flow analyses
Revised reaction
mechanism
Cortesey of hte AG
16
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Dry-reforming of CH4: Small olefins can lead to gas-phase
molecular-weight growth and carbon deposits
CH4/CO2 = 1; 10 % H2; 5 % Ar
u0 = 0,366 m/s, ~1200 K, 20 bar
A. Li, O. Deutschmann. Chemical Engineering Science, 62 (2007) 4976.
L.C.S. Kahle, T. Roussière, L. Maier, K. Herrera Delgado, G. Wasserschaff, S.A. Schunk, O. Deutschmann. Ind. & Eng. Chem. Res. 52 (2013) 11920
17
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Development of micro kinetic models for simulations of
catalytic reactors
Surface Science
Experimental
Reaction mechanism
and kinetics (idea)
Surface Science
Theoretical
Modeling of lab reactors
(including gas phase kinetics and
transport models)
Lab experiments
(conversion, selectivity,
ignition/extinction temperatures,
spatial & temporal profiles,
coverage)
Comparison of
experiment and
simulation
Thermodynamic
consistency
Technical reactor
Sensitivity & reaction
flow analyses
Revised reaction
mechanism
Cortesey of hte AG
18
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Spatially - resolved sampling techniques for catalytic
reactors
Stagnation flow reactor (0d)
N.E. McGuire, N.P. Sullivan, O. Deutschmann, H. Zhu, R.J. Kee.
Appl. Catal. A 394 (2011) 257.
C. Karakaya, O. Deutschmann, Chem. Eng. Sci. 89 (2013) 171
Monolithic Catalysts (1d)
G. Fischer et al., 2006
R. Horn, N. J. Degenstein, K. A. Williams, L. D. Schmidt Catal. Lett. 110, 169-178 (2006)
A. Donazzi, D. Livio, M. Maestri, A. Beretta, G. Groppi, E. Tronconi, P. Forzatti, Angew. Chem.
Int. Ed. 2011, 50, 3943.
D. Livio, C. Diehm, A. Donazzi, A. Beretta, G. Groppi, O. Deutschmann, Appl. Catal. A (2013)
Reactors with catalytic surfaces (2d)
OH LIF
U. Dogwiler, J. Mantzaras, C. Appel, P. Benz, B. Kaeppeli, R.
Bombach, A. Arnold. Proc. Combust. Inst. 27 (1998) 2275
19
NO LIF
A. Zellner, O. Deutschmann, 2012
O. Deutschmann, J.-D. Grunwaldt. Chem.Eng. Technol. 85 (2013) 595
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Stagnation flow reactor for kinetic studies: Resolution of
external and internal boundary layer
Oxidation of CH4
over Rh/Al2O3
catalyst
gas-phase
Tsurf = 700°C
Software: DETCHEMSTAG, H. Karadeniz, S. Tischer, O. Deutschmann
20
C. Karakaya, O. Deutschmann, Chem. Eng. Sci. 89 (2013) 171
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Resolution of species profiles and temperature in flow
direction with movable capillaries: CPOX of EtOH over Rh/Al2O3
20
Stoffmengenanteil (%)
H2
15
EtOH
CO
10
O2
H2O
5
CO2
0
-15
-10
-5
0
5
10
15
20
25
Axiale Koordinate (mm)
Stoffmengenanteil (%)
2,0
C/O = 0,65
C/O = 0,70
C/O = 0,75
C/O = 0,80
C/O = 0,85
1,5
Acetaldehyd
1,0
0,5
0,0
-15
M. Hettel, C. Diehm, B. Torkashvand, ,O. Deutschmann, Catal. Today (2013)
D. Livio, C. Diehm, A. Beretta, G. Groppi, O. Deutschmann, Appl. Catal. A (2013)
21
-10
-5
0
5
10
15
20
25
Axiale Koordinate (mm)
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Development of micro kinetic models for simulations of
catalytic reactors
Surface Science
Experimental
Reaction mechanism
and kinetics (idea)
Surface Science
Theoretical
Modeling of lab reactors
(including gas phase kinetics and
transport models)
Lab experiments
(conversion, selectivity,
ignition/extinction temperatures,
spatial & temporal profiles,
coverage)
Comparison of
experiment and
simulation
Thermodynamic
consistency
Technical reactor
Sensitivity & reaction
flow analyses
Revised reaction
mechanism
Cortesey of hte AG
22
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Strategy for mechanism development:
Hierarchical approach
H2 oxidation
CO oxidation
H2
CO
O2
Sub-mechanism for H2/O2 systems
Sub-mechanism for CO/O2 systems
Preferential oxidation of CO
H2
R-WGS
CO2
H2
O2
O2
CO
Varying
composition,
temperature,
residence time
WGS
CO
H2O
Sub-mechanism for CO/O2/H2/CO2/H2O systems
POx of CH4
CH4
O2
Dry reforming of CH4
CO2
CH4
Ox of CH4
CH4
O2
SR of CH4
CH4
Ni/Al2O3 (KIT)
New Ni cat (BASF)
Ni … cats (lit.)
H2O
Final mechanism for CO/O2/H2/CO2/H2O/CH4 systems
23
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Development of micro kinetic models for simulations of
catalytic reactors
Surface Science
Experimental
Reaction mechanism
and kinetics (idea)
Surface Science
Theoretical
Modeling of lab reactors
(including gas phase kinetics and
transport models)
Lab experiments
(conversion, selectivity,
ignition/extinction temperatures,
spatial & temporal profiles,
coverage)
Comparison of
experiment and
simulation
Thermodynamic
consistency
Technical reactor
Sensitivity & reaction
flow analyses
Revised reaction
mechanism
Cortesey of hte AG
24
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Dry reforming of natural gas over Ni-based catalyst:
Influence of H2 addition
Experimental conditions:
Nickel based catalyst (BASF)
100-900oC , 4 SLPM, 1bar
1.6%CH4, 2.1%CO2, 1.8%H2 in N2
25
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Dry reforming of natural gas over Ni-based catalyst:
Influence of H2O addition
Experimental conditions:
Nickel based catalyst (new BASF catalyst)
100-900oC, 4 SLPM , 1bar
1.7%CH4, 2.1%CO2, 2.1%H2O
26
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Partial oxidation of CH4 in a fixed-bed reactor
Experimental conditions:
Nickel based catalyst (new BASF catalyst)
200-900 oC, 4 SLPM, CH4/O2=1.6 in N2, 1bar
No coke formation according to spent catalyst analysis
27
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Development of micro kinetic models for simulations of
catalytic reactors
Surface Science
Experimental
Reaction mechanism
and kinetics (idea)
Surface Science
Theoretical
Modeling of lab reactors
(including gas phase kinetics and
transport models)
Lab experiments
(conversion, selectivity,
ignition/extinction temperatures,
spatial & temporal profiles,
coverage)
Comparison of
experiment and
simulation
Thermodynamic
consistency
Technical reactor
Sensitivity & reaction
flow analyses
Revised reaction
mechanism
Cortesey of hte AG
28
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
APPLICATIONS
success stories
29
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
TWC emission control
30
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Simulation at real driving conditions is very challenging:
Continuous variation of all inlet variables
J. Braun, T. Hauber, H. Többen, J. Windmann, P. Zacke, D. Chatterjee, C. Correa, O. Deutschmann, L. Maier, S.Tischer, J. Warnatz, SAE paper 2002-01-0065
31
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
DETCHEMMONOLITH: Computer program for the numerical
simulation of transients in catalytic monoliths
MONOLITH
Temperature of the solid structure incl. canning
by a 2D / 3D heat balance
transient
quasi-steady-state
temperature profile
at the wall
time scale ~ 1 s
heat source term
residence time < 100 ms
CHANNEL or PLUG
1D or 2D-flow field simulations for a representative number of
channels using boundary layer or plug flow equations
gas phase concentrations
temperature
chemical source term
transport coefficients
DETCHEM - Library
Thermodynamic and transport properties
Detailed reaction mechanisms for gas-phase & surface
S. Tischer, O. Deutschmann, Catal. Today 105 (2005) 407, www.detchem.de
32
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Pollutant reduction in a three-way catalyst during
cold start-up: Simulation of a driving cycle
J. Braun, T. Hauber, H. Többen, J. Windmann, P. Zacke, D. Chatterjee, C. Correa, O. Deutschmann, L. Maier, S.Tischer, J. Warnatz, SAE paper 2002-01-0065
33
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Cumulative CO emission in MEVG cycle:
Experiment vs. simulation
8
inlet
inlet (cum.)
experiment (cum.)
simulation (cum.)
7
CO emission [%]
6
80
5
60
4
40
3
2
20
1
0
0
Funded by Corning, 2006-2009
34
200
400
600
time [s]
800
1000
cumulative CO emission [g]
100
0
1200
Tischer et al. SAE Technical paper 2007-01-1072 2007
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Auxiliary power units (APU)
with on-board reforming
Courtesy of Steve Shaffer, Delphi, 2008 SECA Review
35
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
On-board catalytic partial oxidation of logistic fuels
provides electricity and reduces pollutant emissions
Tailgas recycling (CO2/H2O)
CPOx Reformer
AIR
H2, CO
WGS
Improved Start‐up
Fuel
36
Idle state: < 5%
Full load: < 30%
el. efficiency
H2
SOFC
PEM
40‐60% el. efficiency
H2 ‐ SCR
Catalytic Converter
Exhaust
Exhaust
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Conversion of logistic fuels (i-octane) to hydrogen:
Computed profiles in the reformer
Rh catalyst at ~1000°C converts
hydrocarbons fuels to CO and H2
in less than 5 ms without any additional
energy supply
CnHm+ n/2 O2
n CO + m/2 H2
H2
Surface: 111 reactions / 31 surface species
Gas-phase: 7193 reactions/ 857 species
37
L. Maier, M. Hartmann, O. Deutschmann, Combust. Flame 158 (2011) 796–808.
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
CPOX of i-octane: Coke precursors are formed in the gas
phase both in the catalytic zone and downstream
10 nm
carbon layer
Rh
Al2O3
support
Rh
C/O = 1.0 5 slpm
catalyst
catalyst
L. Maier, M. Hartmann, O. Deutschmann, Combust. Flame 158 (2011) 796–808.
38
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
SOFC operated with HC fuels: Complex interaction of electrochemistry, thermo-catalytic chemistry, mass and heat transport
H. Zhu, R. J. Kee, V.M. Janardhanan, O. Deutschmann, D.G. Goodwin. J. Electrochemical Soc. 152 (2005) A2427
39
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Modeling Solid-Oxide Fuel Cells:
Spatial profiles in the fuel channel and Ni/YSZ anode
H. Zhu, R. J. Kee, V.M. Janardhanan, O. Deutschmann, D.G. Goodwin. J. Electrochemical Soc. 152 (2005) A2427
40
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Anode-supported, planar SOFC: Computed temperature
distribution in the electrodes (adiabatic condition)
Impact of endothermic reforming and temperature difference between fuel and air
streams on temperature distribution
Anode
750 m
Cathode
30 m
Fuel stream: 40% CH4, 60% H2O at 800°C
Cathode stream: Air at 650°C
41
V.M. Janardhanan, O. Deutschmann. Chem. Eng. Sci. 62 (2007) 5473
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Anode-supported, planar SOFC: Impact of anode
thickness on current density (adiabatic condition)
Competition of H2 production/consumption, endothermic reforming, and heat release
Fuel stream: 40% CH4, 60% H2O at 800°C
Cathode stream: Air at 650°C
V.M. Janardhanan, O. Deutschmann. J. Power Sources 177 (2007) 296
42
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Anode-supported, planar SOFC: Impact of anode
thickness on efficiency and power density
V.M. Janardhanan, O. Deutschmann. ECS Transactions 7 (2007) 1939
43
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
SOFC Stack Structure












44
Planar architecture
Membrane-electrode
assembly
Interconnect carries current
Stacked layers build voltage
Electrolyte (e.g.,YSZ)
Polycrystalline ceramic
O2- ion conductor
Electrical insulator
Impervious to gas flow
Electrodes
Porous cermet composite
Anode supports MEA
Interconnect
High electrical conductivity
Maintains equal potential
Flow channels
Formed in interconnect
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
SOFC stack: Simulation of stack temperature caused by
change in voltage
Start-up and step change in voltage from 0.7V to 0.8V in a SOFC stack
V. Menon, V.M. Janardhanan, S. Tischer, O. Deutschmann. J. Power Sources 214 (2012) 227
45
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Simulation of technical catalytic reactors from first principles:
STILL A LONG WAY TO GO
Length and Time
Process simulation
Transients in heat &
mass transfer
Plants
Fluid mechanics
Reactors
DGM
MF
Reactor components
Porous supports
kMC
DFT
Multi-components, Additives
Single catalyst particles
Elementary reactions on surfaces
46
Complexity
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Acknowledgements
Many colleagues at KIT
Deutschmann group at KIT 2011
47
R.J. Kee, A.M. Dean, N.P. Sullivan (CSM)
L. D. Schmidt (U Minnesota)
G. Eigenberger, U. Nieken (U Stuttgart)
V.M. Janardhanan (IIT Hyderabad)
H.-G. Bock (U Heidelberg)
A. Beretta (Politecnico Milano)
K. Norinaga (Fukuoka U)
R.J. Behm (U Ulm)
T. Bauer, R. Lange (TU Dresden)
U. Riedel (DLR Stuttgart)
A. Worayingyong, P. Viravathana (Kasetsart U)
W. Zhang (Beijing), S. Zhang (Xi’an)
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry
Thank you for your attention!
Hydrodynamics and mass transfer in Taylor flow
Rising bubble swarm
Ö. Keskin, M. Wörner, H.S. Soyhan,T. Bauer, O. Deutschmann, R. Lange. AIChE J 56
(2010) 1693
48
Olaf Deutschmann
Institute for Chemical Technology and Polymer Chemistry