University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

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Introduction
to Catalysis
David W. Agar
Short Course
26
th
June 4
th
July 2003
Chemical Engineering Department
IISc Bangalore
University of Dortmund
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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C
University of Dortmund
For those who were distracted from the engineering woods
by the chemical trees, a brief summary of yesterdays talk:
1. Transition metal ligand complexes
and now back to more familiar engineering territory..
Hydroformylation homogeneous catalysis for useful intermediates
(RCH=CH
2
RCH
2
CH
2
CHO)
2. Complex catalyst composition: - CoRh metallic active centre
- Triphenylphosphine ligands
- Triphenylphosphinesulfonate ligands
5. Two-phase catalysis extraction of water soluble catalyst
3. Well-defined cyclic mechanism (Heck-Breslow)
4. Mild conditions (100C, 10 bar), high selectivities (95% n-Aldehydes)
6. Reaction engineering: immobilisation, enhanced mass transfer
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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University of Dortmund
Course schedule:
26.06.03 Principles of catalysis
27.06.03 Ammonia synthesis catalysis
30.06.03 Automotive exhaust catalysis
01.07.03 Hydroformylation catalysis
02.07.03 Catalytic partial oxidation of propene
03.06.03 Catalysis in polymerisation
04.06.03 Enzymatic glucose isomerisation
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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Propene production
[1992 mio.t]
USA 10.3
Western Europe 9.7
Japan 4.5
Germany 2.0
GUS 1.3
world capacity 40
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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Propene production and consumption [1984]
(1) acetone, acrolein, acrylic acid, allyl chloride, carbon disulfide, chlorinated solvents, cresols, dichloropentadiene,
epichlorhydrin, ethylene-propylene rubber, 4-methyl 1-pentene, oxalic acid, polymethyl methacrylate, paramins...
(2) Steam cracking and catalytic cracking. In 1986 the worldwide production capacity of propylene was 28.310
6
t/a with
the following distribution:
geographic areas Western Europe United States Japan World
Uses (% product)
acrylonitrile 17 18 20 18
cumene 9 9 5 9
isopropanol 6 6 3 5
oxo alcohols 13 8 10 11
polypropylene 34 35 47 36
propylene oxide 10 11 6 9
oligomers 7 1 4
micellaneous
(1)
6 8 8
Total 100 100 100 100
Sources (% product)
steam cracking 86 53 89 75
catalytic caracking 14 47 11 25
Total 100 100 100 100
Production (10
6
t/a)
7.2 7.0 3.0 22.5
Capacity (10
6
t/a)
(2)
8.7 9.9 3.0 28.5
Consumption (10
6
t/a)
7.1 6.8 2.9 21.5
11
United States 9.7 Western Europe 8.2 Middle East 0.2
Canada 0.7 Eastern Europe 3.3 Japan 3.0
Latin America 1.3 Africa 0.1 Asia and Far East 1.8
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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polymerisation
47%
+NH3/O2
12%
+CO/H2
10%
+O2
10%
+benzene
7%
+H2O
4%
+O2
+Cl2
polypropylene
acrylonitrile
butanal
propylene oxide
cumene
isopropanol
acrylic acid
allyl chloride
isohexene
dimerisation
propene
polyacrylonitrile
acrylamide
adiponitrile
acetone
polyacrylic acid,
acrylates
epichlorhydrin
isoprene
phenol
acetone
propylenglycol
oligomer
n-butanol
2-ethylhexanol
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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Catalytic partial oxidation of propene
substrates
catalysts
products
propene +
oxygen
acrolein
acrylic
acid
acetone
propylene
oxide
acetic acid
1,5-hexa-
diene
benzene
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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Acrolein derivatives
acrolein
allyl alcohol
+H2 (cat.)
acrylic acid
+O2 (cat.)
methionine
3 stages
pyridine
+NH3
CHO
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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Acrylic acid derivatives
acrylic acid
acrylates (n-Bu,Et,Me,2-EH)
+alcohol
polyacrylic acid
polymeris.
copolymers
+ alkenes
acrylamide
salts
+NH3,
NaOH
COOH
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
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Acrylic acid production
Acrylic acid derivatives
Polyacrylic acid &
salts
n-Butylacrylate
Ethylacrylate
Methyl & 2-
Ethylhexylacrylates
specialty acrylates
miscellaneous
Worldwide production: 1.2 (2.0) Mio.tpa
End uses [%]: USA Europe Japan
Surface coatings 42 35 34
Textiles 23 18 16
Acrylic fibres 6 7 14
Adhesives 5 15 20
Others* 24 25 16
*superabsorber, detergents, water treatment, dispersants
Regional production of
acrylic acid & acrylates (1982)
USA
Europe
Japan
Other
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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Life cycles of acrylic acid syntheses
propene oxidation
new processes
Reppe process
Cyanohydrin
acrylonitrile &
propiolactone
process
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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Historical acrylic acid syntheses
Reppe process
low efficiency of acetylene manufacture
toxic & polluting nature of Ni carbonyls
2
140 ,200
2 2 2 2
.
bar C
NiBr CuBr
C H CO H O CH CHCOOH

+ + =
2 4
H SO aq.soln.
2 2 2 2 2
55-60C 175C
4 4
.

CH CH HCN HOCH CH CN CH CHCOOH
O NH HSO
+ =
+
Cyanohydrin process
toxicity of HCN & ethene cyanohydrin
waste salt by-product
Ketene process
toxicity of -propiolactone
multistep synthesis
2 2 4
3 2 2 2
750
2
.

H O H SO
HCHO
C
CH COOH CH C O CH C O CH CHCOOH
CH O

= = = =

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

University of Dortmund
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Production of acrylic acid from acetylene
(BASF process -
Reppe synthesis)
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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Acrylic acid synthesis via propene oxidation
3 2 2 2 2
3 2 2 2 2
2 2 2
3
. 594.9
2
. 340.8
1
. . 254.1
2
R
R
R
CH CH CH O CH CHCOOH H O H kJ
CH CH CH O CH CHCHO H O H kJ
CH CHCHO O CH CHCOOH H kJ
= + = + =
= + = + =
= + = =
Net Reaction:
Two step process:
limited yield of single step process (50-60%)
rapid deactivation of single step catalyst (TeO
2
)
1
st
step: Bi/Mo-Oxide - 300-400C - >85% yield
2
nd
step: Mo/V-Oxide 250-350C - >96% yield
gas composition: 10% propene, 50% air, 40% steam
pressure 1.3-2 bar - residence time: 1-3 s.
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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Acrolein
Degussa process
mixed aldol-condensation (obsolete)
CH3CHO + HCHO CH2=CHCHO + H2O
Na-silicates/SiO
2
300-320C
Direct oxidation of propene
mechanism: via allyl-radicals
catalyst: bismuth molybdate
phosphorus molybdate
selectivity: ~80% (by-products: acrylic acid, acetic acid, acetaldehyde)
CH2=CHCH3 + O2 CH2=CHCHO + H2O
R
H = -368 kJ/mol
Cat.
350-450C
+Fe-, Co-, Ti- oxides
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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Development of acrolein catalyst
>77 310-330 Bi, Mo, Fe, P, Ni, Co, W, Si, K 1970
60-70 330-350 Bi, Mo, Fe, P, Ni, Co 1964
50-60 350-400 Bi, Mo, Fe 1959
30-40 450-500 Bi, Mo 1957
Acrolein
yield [%]
Reaction
temp.[C]
Catalyst
composition
Year
catalyst lifetime: 3 years
transition metals lower operating temperature
Fe, Co, Ni regulate gas-lattice oxygen exchange
P & K maintain selectivity
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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Catalyic partial oxidation of propene
propene
acrolein
Propene
oxidation on
bismuth
molybdates
hydrogen
abstraction
allyl radical
adsorption
Desorption
reoxid-
ation
(high pO
2
)
eqm.
oxid.
step
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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Acrylic acid catalyst
production
Precipitation
Drying
Activation
active
phase
micro
porosity
Mechanical
properties of
the catalyst
pellet
Thermal
properties
pore
structure
pore
structure
active phase
catalyst
properties
Precipitation
Drying
Calcination
Grinding
Adding of formu-
lation excipients
Precompression
Shaping
Drying
Sieving
Activation/
Annealing
solution A solution B solution C
(NH
4
)
6
Mo
7
O
24
4H
2
O
H
3
PO
4
Ni(NO
3
)
2
6H
2
O
Fe(NO
3
)
2
6H
2
O
SiO
2
Bi(NO
3
)
3
5H
2
O
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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Development of acrolein oxidation catalyst
catalyst lifetime: >7 years
by-products: CO
2
, acetic acid, furfural, oligomers
two stage structured temperature profile
Catalyst composition Reaction Acrolein Acrylic acid
(O-free) temp.[C] conversion [%] yield [%]
Mo
12
V
1.9
Al
1.0
Cu
2.2
(Al-sponge) 300 100 97.5
Mo
12
V
3
W
1.2
(SiO
2
) 240 98.0 87.0
Mo
12
V
3
W
1.2
Mn
3
255 99.0 93.0
Mo
12
V
2
W
2
Fe
3
230 99.0 91.0
Mo
12
V
3
W
1.2
Cu
1
Sb
6
272 99.0 91.0
Mo
12
V
4.6
Cu
2.2
W
2.4
Cr
0.6
(Al
2
O
3
) 220 100 98.0
Mo
12
V
2
(Li
2
SO
4
)
2
300 99.8 92.4
Mo
12
V
4.8
Cu
2.2
W
2.4
Sr
0.5
(Al
2
O
3
) 255 100 97.5
Mo
12
V
2.4
Cu
0.24
(SiC) 290 99.5 94.8
Mo
12
V
3
W
1.2
Ce
3
288 100 96.1
Mo
12
V
4.7
W
1.1
Cu
6.3
360 99.0 96.0
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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Acrylic acid synthesis via propene oxidation
Two-stage
process
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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Recuperative Heat Exchange
Multi-tubular reactor for partial oxidation reactions
Acrylic acid synthesis
h
salt bath
= 2000 W/m
2
K
h
gas
= 150 ~ 200 W/m
2
K
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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Temperature (& Concentration) profiles in
reactors may be manipulated using:
B. Recuperation
spatial segregation between reaction
medium & material/heat-sink/source
e.g. multitubular reactor
T
z
A. Convection
addition or withdrawal of sidestreams
e.g. cold-shot reactor
T
z
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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... or, less frequently:
C. Regeneration
chronological segregation between
reaction medium & material/heat -
sink/source
e.g. reverse flow reactor
T
z
D. Reaction
direct coupling of main reaction
with thermally/materially compatible
supplementary reaction
e.g. oxydehydrogenation
T
z
C D
A B
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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What are Hot-spots?
Unwanted temperature maxima arising in tubular reactors
with exothermic reactions due to heat transfer limitations
Heat exchange area (A)
~ 100 m/m
Heat transfer coefficient (h)
~ 100 W/mK
Hot-spot adversely effects:
- conversion
- selectivity
- safety
- catalyst lifetime
- choice of reactor materials
30K
100K
25 mm
25 000
tubes
Reactor feed
Coolant
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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Characteristic dimensions of heterogeneously
catalysed gas phase reactions in tubular reactors
Chemical activity (Nanostructure)
internal surface area ~ 100m/g
pore diameter ~ 10 nm
Pore diffusion (Microstructure)
Weisz-Modulus < 0,3
pellet diameter ~ 1mm
Heat transport (Macrostructure)
T < 50K
tube diameter ~ 1cm
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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Mechanisms of heat transfer in a fixed-bed
1a
1b
2a,b
3a
3b
Heat
flow
Fluid flow
1a
1b
2a
2b
3a 3b
1
2
3
Heat transfer in fixed-bed reactors
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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Classification of the continuum models
for steady-state fixed bed reactors
s
w
g
w
e
r
r
e
ax
h , h , , D , : Parameter
dispersion radial HT2 : HT3
, : Parameter
dispersion radial PH1 : PH3
0
l dimensiona two
, , : Parameter
gradients internal HT1 : HT2
, : Parameter
boundary phase the at gradients
reactor, flow plug Ideal : HT1
, : Parameter
dispersion axial PH1 : PH2
: Parameter
reactor flow plug Ideal : PH1
0
l dimensiona one
ous heterogene s homogeneou pseudo

+

+
=

= =

e s
r
g
r g
r w
e
g
g
ax
s g s g s g s g
D , h, , , k
D , h
D h, k U,
h k U,
D U,
U
T T ; c c T T ; c c
r
r
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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Mean conversions & axial temperature profile
in multitubular partial oxidation reactor
z (m)
x
A
m

x
B
m

x
C
m
x
Am
x
Bm
x
Cm
T'
m
T
'
m
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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Multitubular partial
oxidation reactor
Radial temperature profiles
at various bed depths
T

=
T
-
T
o
R
r
Hot-spot scale-up
problems:
catalyst activation
thermoelement dis-
tortions
coolant side non-uni-
formities
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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University of Dortmund - Chemical Engineering Department - Institute for Reaction Engineering
How can hot-spots be eliminated?
Improved co-ordination between the rates
of heat generation & heat removal in reactor
Cooling
Reaction
Hydrodynamics
Microreactor
Benchmark:
Multitubular
reactor
Debottlenecking Strategies:
- diminish catalyst activity
catalyst dilution
- enlarge heat exchange surface (A)
Linde-reactor
- raise heat transfer coefficient (h)
Fluidised bed
- increase both A & h
Microreactor
Millireactor
Fluidised bed
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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Improved co-ordination of reaction &
cooling using a fluidised bed reactor
Increased heat transfer coefficients due to efficient convective-
regenerative particle transport mechanism
+ excellent isothermal behaviour (h~600 W/mK)
+ higher degree of catalyst utilisation
+ facile catalyst regeneration
very mechanically resilient catalyst needed
limited hydrodynamic loading range
undesirable backmixing
scale-up?
e.g. Ammonoxidation of propene to
acrylonitrile (Sohio process)
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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Limitations of catalytic activity
the chemical processes occurring at the active sites impose an upper
limit on reaction rate (~1mol/g.cat.s*) and heat generation (~500kW/m*)
for chemically limited kinetics, a specific heat exchange surface of
~1,000 m/m is usually adequate to ensure rapid heat removal.
Microreactors offer excessive
heat exchange surface
reactor dimensions of 1-5mm,
i.e. Millireactors
* for typical industrial synthesis reactions W.Gerhardt, DECHEMA-GVC, Wernigerode, 06.04.00
0,01
0,1
1
10
100
0,001 0,01 0,1 1 10 100 1000
k [1/s]
d

[
m
m
]
Da =2
NTU =100
Nu = 3,7
a =10
-5
m/s
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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Developments
extension to similar reaction systems e.g. methacrylic acid
use of propane instead of propene
operation in rich & even ex- composition region
Explosion limits: 2.0 LEL-11.1(15.3) UEL % C
3
H
6
use of microreactors to improve heat removal
cut losses due to unwanted polymerisation
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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Methyl Methacrylate
Previously
Propylene
Cumene
Acetone
Cyanhydrine
Methacryl Amide
Methyl Methacrylate
Benzene
Hydrocyanic Acid
Sulfuric Acid
Methanol
Now
Ethylene
Propionaldehyde
Methacrolein
Methacrylic Acid
Methyl Methacrylate
CO/H2
Formaldehyde
Air
Methanol
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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Acrylate via acrylic acid esterification
Yield: 95% based on acrylic acid
University of Dortmund Chemical Engineering Department Chair for Reaction Engineering
University of Dortmund
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University of Dortmund
Course schedule:
26.06.03 Principles of catalysis
27.06.03 Ammonia synthesis catalysis
30.06.03 Automotive exhaust catalysis
01.07.03 Hydroformylation catalysis
02.07.03 Catalytic partial oxidation of propene
03.06.03 Catalysis in polymerisation
04.06.03 Enzymatic glucose isomerisation
Disposable cats?