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How to make catalysts

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

ƒ Use of suported catalysts


ƒ What are weak points

ƒ Traditional catalyst preparation methods


ƒ Why can that be made better?

ƒ Novel functionalization methods


ƒ One-step methods

27. April 2005


Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark

Criteria for a good catalyst


Chemistry related Non-chemical

activity stability

selectivity morphology

thermal characteristics mechanical strength

originality
cost

27. April 2005


Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark

Why supported catalysts?

ƒ Most active materials are NOT:


ƒ Mechanically or thermally stable
ƒ of a open morphology
ƒ of low cost

Æ Good for making rings


Æ Useless Catalysts

27. April 2005


Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark

Catalyst preparation

Æ Good and stable dispersion necessary


27. April 2005
Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark

Traditional

ƒ (1) Produce a support with a high surface area

ƒ (2) Functionalize support using large range of surface


methods
ƒ Classical: Grafting, Precipitation, Impregnation
ƒ Modern techniques: Vapor deposition, layer deposition

27. April 2005


Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark

Supports –
keeping activity at the right place
ƒ Goal: optimal dispersion for active component and
stabilisation against sintering

ƒ How: Using ultra hard and chemically unreactive


materials with high melting points (SiO2, TiO2, Al2O3,
Carbon….)

ƒ With a large surface area (10-? m2/g)


ƒ How big is the SSA of a single carbon graphene sheet?

27. April 2005


Graphite
STM Image

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

Methods for preparation of supports


“anorganic materials at large scale”

ƒ Solid state reactions (precipitation, drying, coagulation)


ƒ Reduction, carbonization, leaching
ƒ Sol – gel (reactive chemistry)
ƒ Flame hydrolysis of chloride (high temp + gas phase)

27. April 2005


Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark

Reduction, carbonization: metallic


phases
ƒ Temperature controlled reaction
Bed of precursor material (usually oxide MOx)
Recative gases

(H2, CH4, NH3…)

ΔT (500- 1500°C) ~ 4-12 h

Preparation of
Catalytic bed (e.g. M, MNx, MCx)
WC, MoC, W, Fe, CoN …

27. April 2005


Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark

Alloy leaching, larger surfaces: Raney


nickel! Ni

Quenching
Alloy (e.g. AlNi)
Solid solution Precipitation

Al
Digestion of

less noble metal

using NaOH

Porous Ni with low particle size (Raney Nickel)


27. April 2005
Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark

Sol-Gel: mostly oxides

27. April 2005


Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark

Zeolites

ƒ Aluminiumsilicates
ƒ > 600 m2/gr
ƒ Solid acids
ƒ Trapping of Ions and metal
complexes (ship in a bottle)
ƒ Isomer selective synthesis

27. April 2005


Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark

Flame hydrolysis

ƒ 2 H2 + O2 Æ H2O
SiCl4 + H2O Æ SiO2 + 4 HCl

ƒ TiCl4, SnCl4, AlCl3, Fe(CO)5…

27. April 2005


Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark

Functionalization

ƒ Traditional Chemical methods


ƒ Grafting
ƒ Precipitation
ƒ Impregnation

ƒ Modern methods (mostly from electronics industry)


ƒ Chemical and Physical Vapor Deposition
ƒ Atomic Layer Deposition

27. April 2005


Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark

Anchoring and Grafting

ƒ Stable covalent bonds between


homogeneous transition metal

complex and inorganic support

O O
M
OH OMoCl4 O O
473 K 473 K
silica + MoCl5
silica silica
-HCl -HCl
anchored grafted
species species

27. April 2005


Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark

Impregnation Æ low loading

Support, often porous grains

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

Precipitation Æ high loading

Change of T, pH

or concentration

ÆDecrease
Metal salt solution
solubility of metal

Particle size of active species determined


by solubility + supersolubility (see TVT)
27. April 2005
Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark

Physical Vapor deposition (PVD)


or “how to transfer metals from A to B”

27. April 2005


Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark

What is flame spray synthesis?

Flame spray as a one step method


to functionalized catalysts

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

Gas phase synthesis of nanomaterials

© Reto Strobel

Stark, W.J., Mädler L., Pratsinis S. E., WO 2004005184


27. April 2005
Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark

How useful is it?

27. April 2005


Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark

How useful is it?

27. April 2005


Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark

Products

ƒ Complex systems
ƒ Mixed oxides
(e.g YAG)
ƒ Composites
(e.g. Pt/CeO2/ZrO2)

ƒ Excellent product dispersion

CeO2/ZrO2 transmission electron micrograph

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

VOx / titania for DeNOx


O2
NO + NH3 N2 + H2O

100
V/TiO2

NOx removed / %
flame synthesis

50

commercial material
0
100 150 200 250
Process temperature / °C

W. J. Stark, K. Wegner, S. E. Pratsinis, A. Baiker, J. Catal., 197, 182 (2001)


W. J. Stark, A. Baiker, S. E. Pratsinis, Part. Part. Sys. Charact., 19, 306-311 (2002).
27. April 2005
Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark

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

W. J. Stark, S. E. Pratsinis, A. Baiker, A., J. Catal., 203, 516 (2001).


W. J. Stark, H. K. Kammler, R. Strobel, D. Günther, A. Baiker, S. E. Pratsinis, Ind. Eng. Chem. Res., 41, 4921 (2002).
27. April 2005
Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark

Highest purity catalysts


result better selectivity
OH OH
TBHP (5)
O (a)
100 100 Ti
1 2
peroxid usage / %

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

Heavy metal content / ppm heavy metal content / ppm


OH H + 0.5 O2 (d)
O Cr, Mn, Fe, Co O

5 6

W. J. Stark, R. Strobel. D. Günther, S. E. Pratsinis, A. Baiker, J. Mater. Chem. 12, 3620 (2002)

27. April 2005


Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark

Pt/alumina: 50 % less Pt required


for enantioselective hydrogenations
100 flame
Conversion / %

75

50 commercial
25
0.8

dV/dlog(D) / cm3 nm-1 g-1


1000
0.6
E4759 5Pt3/3
75
ee / %

0.4
50

E4759 (reference) 0.2


25
5Pt3/3 (this work)
0
0
1 10 100
0 50 100 150 200
Pore diameter / nm
time / min

R. Strobel, W. J. Stark, L. Mädler, S. E. Pratsinis, A. Baiker, J. Catal., 294-304, 213 (2002).


27. April 2005
Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark

High temperature stability


ceramic materials

Ceria/zirconia
for automotive Composite materials
exhaust gas
Excellent cold-start
cleaning
less Pt/Pd/Rh

27. April 2005


Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark

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

27. April 2005


Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark

0.5 Pt/ceria/zirconia: Thermal stability


-1
Dyn. oxygen /mol kg

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

27. April 2005


Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark

Morphology and particles size strongly


influence the sintering stability

ƒ Rhodia, 2004: fractal like structures of ceria based


oxides:
ƒ Highest thermal stability.
ƒ 14 m2/g for Ce/ZrOx after 1100 °C, 4h
ƒ 23 m2/g for Pr-doped Ce/ZrOx after 1100 °C, 4h

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

Larger flame spray burners

Pilot scale flame spray


synthesis at 750 g / h

only 45 m2/g as prep.


27. April 2005
Institute of Chemical and Bioengineering
Catalyst Preparation ETH Hönggerberg, HCI E 107
8093 Zürich
Prof. Dr. Wendelin J. Stark

Large vs. small starting powders

as prep. 1100 °C, 4 h, air

Lab scale, 120-160 m2/g for 4.5 m2/g

res. time 5-10 μsec 0.5 wt% Pt / CeZrO4

Pilot scale, 40-45 m2/g 26-29 m2/g

res. time >30 μsec 0.5 wt% Pt / CeZrO4 14 m2/g*

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

Large vs. small starting powders

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

Large vs. small starting powders

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

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