Documente Academic
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George Fitzgerald
Accelrys
Introduction
Catalysis is critical to modern chemical industry
Reaction energies HR
Energy barriers Ea
Location of intermediates
Z1
Without
Catalyst
Energy
Z2
Ea,0
Ea,1
Ea,2
R
With
Catalyst
HR
A*
P*
Reaction Coordinate
Roles of modeling:
Identify catalysts
Catalytic material
Mechanism
Active sites
Heterogeneous:
Zeolites
Heterogeneous:
Surfaces
Optimize catalyst
Optimize processes
Diffusion
Deactivation
Homogeneous Catalysis
Design and optimization of homogeneous catalysts such as
metallocenes
Typically designing ligands for
Control of activity
Control of molecular weight
Control of tacticity
R1
Z
N
R4
MX2
R2
R3
Solution:
Study both cationic vs. bimetallic forms with
theory and experiment
Polymerization Model
Experiment
1H and 13C NMR to identify species
Mass spec to study interaction of ionic
catalyst + ethylene
EPR to identify deactivation mechanism
Computation
Binding energies
Activation barriers
Comparison of reaction pathways for
multiple metals, co-catalysts
EHPP
Elastomeric homopolypropylene
Applications in
n
Isotactic Block
Hard Segment
Atactic Block
Soft Segment
isotactic PP
n
atactic PP
Stereoblock Polypropylene
R1
Zr
isotactic block
R1
atactic block
R1
Zr
R1
R1
Substituent orientation
leads to high isotactic vs.
syndiotactic
Zr
R1
R1
Zr
R1
Metallocene
Cl
Zr
Cl
Cl
Zr
Cl
-0.92
+1.6
elastomeric elastomeric
atactic
atactic
Observed
%mmmm
medium
39%
low
12%
medium
31%
high
75%
H 3C
H 3C
Cl
Zr Cl
CH 3
-0.29
elastomeric elastomeric
CH3
F 3C
F 3C
Cl
Zr
Cl
CF 3
CF 3
-5.3
isotactic
isotactic
Roles of modeling:
Identify catalysts
Catalytic material
Mechanism
Active sites
Heterogeneous:
Zeolites
Heterogeneous:
Surfaces
Optimize catalyst
Optimize processes
Diffusion
Deactivation
Pore size
Acidity
Extra framework cation
Framework composition
Simulation reveals
Roles of modeling:
Identify catalysts
Catalytic material
Mechanism
Active sites
Heterogeneous:
Zeolites
Heterogeneous:
Surfaces
Optimize catalyst
Optimize processes
Diffusion
Deactivation
Background
Claus reaction
2H2S + SO2
2H2O + 3Ssolid
Reduction of SO2 by CO
SO2 + 2CO
2CO2 + Ssolid
J. A. Rodriguez et al. JACS, 122, 12362 (2000).
Mg
SO2 + 2CO
Cr
100
80
60
40
20
0
MgO
Cr2O3
Cr0.06Mg0.94O
2-O,O
1-O
1-S
Cr
Cr
Cr
Mg
State can
hybridize
with the SO2
LUMO
looks like
4.0
best choice!
4.0
4.5
3.5
3.0
2.5
2.0
3.5
3.0
2.5
2.0
1.5 1.5
1.0 1.0
0.5 0.5
0.0 0.0
MgOZn Zn SnSn NiNi Co
Co Fe
Fe Mn
Mn
MgO
Cr
SO2 Conversion %
80
60
40
20
0
Cr0.06Mg0.94O
Zn0.05Mg0.95O
Fe0.06Mg0.94O
+K
Fe0.06Mg0.94O
Roles of modeling:
Identify catalysts
Catalytic material
Mechanism
Active sites
Heterogeneous:
Zeolites
Heterogeneous:
Surfaces
Optimize catalyst
Optimize processes
Diffusion
Deactivation
Fluid--Bed Reactor
Fluid-Bed Catalyst
Single Phase Material
No Added Hardening Agent
100 % Vanadyl Pyrophosphate (VO)2P2O7
Maleic
Anhydride
Experimental
Fresh
Used
100
200
300
700
800
900 1000
100
200
300
700
800
900 1000
Z1
Energy
Zr
R1
Z2
Ea,0
Ea,1
Ea,2
RG
HR
A*
With
catalyst
Calculation
Without
catalyst
P*
0
100
200
300
700
800
900 1000
Reaction Coordinate
Select catalyst
material
Guest molecule
docking
Reaction
modeling
Deactivation
Success!
Summary