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WS 07
Cat React Eng
Prof. Dr. Wendelin J. Stark
Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark
Agenda
activity stability
selectivity morphology
originality
cost
Catalyst preparation
Traditional
Supports –
keeping activity at the right place
Goal: optimal dispersion for active component and
stabilisation against sintering
ρ ~ 2160 kg m-3
Interlayer distance = 0.335 nm
Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark
Preparation of
Catalytic bed (e.g. M, MNx, MCx)
WC, MoC, W, Fe, CoN …
Quenching
Alloy (e.g. AlNi)
Solid solution Precipitation
Al
Digestion of
using NaOH
Zeolites
Aluminiumsilicates
> 600 m2/gr
Solid acids
Trapping of Ions and metal
complexes (ship in a bottle)
Isomer selective synthesis
Flame hydrolysis
2 H2 + O2 Æ H2O
SiCl4 + H2O Æ SiO2 + 4 HCl
Functionalization
O O
M
OH OMoCl4 O O
473 K 473 K
silica + MoCl5
silica silica
-HCl -HCl
anchored grafted
species species
Dipping
Drying,
calcination Reduction
T circa 400°C
Metal salt solution
Impregnated support
Active Catalyst
27. April 2005
Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark
Change of T, pH
or concentration
ÆDecrease
Metal salt solution
solubility of metal
Æ Flame spray
•Use of an organic liquid precursor
•Dispersing precursor with oxygen
•Igniting the spray using a premix
flame
L. Madler, H. K. Kammler, R. Mueller, S. E. Pratsinis, J. Aerosol Sci., 2002, 33, 369.
27. April 2005
Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark
© Reto Strobel
Products
Complex systems
Mixed oxides
(e.g YAG)
Composites
(e.g. Pt/CeO2/ZrO2)
J. Marchal, T. John, R. Baranwal, T. Hinklin, R. M. Laine, Chem. Mater., 2004, 16, 822.
W.J. Stark,
27. April 2005 L. Madler, M. Maciejewski, S.E. Pratsinis, and A. Baiker, Chem. Commun., 2003, 588-9.
Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark
100
V/TiO2
NOx removed / %
flame synthesis
50
commercial material
0
100 150 200 250
Process temperature / °C
Fine chemistry
OH OH
OOH
O
Ti/silica
1 2
100
Peroxid
90 Olefin 1
Selectivity / %
80
70
60
50
Shell- Aerogel TS-1 6 g/h 150 g/h 500 g/h
patent wet-phase
flame-made Ti/SiO2
olefin usage / %
OH
80 80
O
Lewis acid
(b)
Fe, Ti
60 Co 60
Cr 1 Co 3
Mn OH
Cr O
40
Fe
40
TBHP (5)
Mn
Fe (c)
Cr, Co
20 20
10 100 1000 1 10 4 100 1000
5 6
W. J. Stark, R. Strobel. D. Günther, S. E. Pratsinis, A. Baiker, J. Mater. Chem. 12, 3620 (2002)
75
50 commercial
25
0.8
0.4
50
Ceria/zirconia
for automotive Composite materials
exhaust gas
Excellent cold-start
cleaning
less Pt/Pd/Rh
0.5 Pt/ceria/zirconia
-1
Flame
Dyn. oxygen /mol kg
1.2
Wet phase
1.0
0.8
0.6
2 CeO2 Ce2O3 + "O"
0.4
CO CO2
0.2
H2 H2O
0.0 Reference powder
0 200 400 600 800 1000 1200 prepared from
precipitation and
Temperature / °C impregnation
1.2
1.0
0.8
0.6
st
Flame, 1
0.4 Flame, 2
nd
st
0.2
Wet phase, 1
nd
Wet phase, 2
0.0
0 200 400 600 800 1000 1200
Temperature / °C
Rohart et al, Rhodia Electronics & Catalysis, Top. Catal. 30/31, 2004.
Engelhard WO 02/30546, OMG-DMC2 EP 1181970; Daihatsu EP 1174174; Delphi US 6378338; Engelhard WO 02/22242;
Toyota EP 1172139
27. April 2005
Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark
Rohart et al, Rhodia Electronics & Catalysis, Top. Catal. 30/31, 2004.
Engelhard WO 02/30546, OMG-DMC2 EP 1181970; Daihatsu EP 1174174; Delphi US 6378338; Engelhard WO 02/22242;
Toyota EP 1172139
27. April 2005
Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark
Neck formation,
local equilibrium
Rapid sintering
Rohart et al, Rhodia Electronics & Catalysis, Top. Catal. 30/31, 2004.
Engelhard WO 02/30546, OMG-DMC2 EP 1181970; Daihatsu EP 1174174; Delphi US 6378338; Engelhard WO 02/22242;
Toyota EP 1172139
27. April 2005
Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark
Rohart et al, Rhodia Electronics & Catalysis, Top. Catal. 30/31, 2004.
Engelhard WO 02/30546, OMG-DMC2 EP 1181970; Daihatsu EP 1174174; Delphi US 6378338; Engelhard WO 02/22242;
Toyota EP 1172139
27. April 2005