HetCatEng Workshop USTUTT

INSTITUTE OF
CHEMICAL TECHNOLOGY
Heterogeneous Catalysis Engineering
E. Klemm
Topical Workshop Catalysis
DFG Priority Program 1362
Stuttgart, April 12, 2011
2
Outline
What is Heterogeneous Catalysis Engineering ?
Bulk Chemicals Manufacture
Space Time Yield
Selectivity-Conversion-Plots
Catalyst Life Time
Fine Chemicals Manufacture
Space Time Yield
Atom Efficiency (E Factor)
Time-to-Market
Bench Scale Reactors for Het. Cat. Eng.
3
Surface
Science
Reaction
Engineering
Operando Spectroscopy
Quantum Mechanics / DFT
Time Scale
Length Scale
Process
Engineering
Production
Level
Reaction Kinetics
Reactor Modelling
Scale-up
Separation units
Recycle
Quality Control
Longterm Stability
Material and
Pressure Gap
Heterogeneous
Catalysis
Research
Heterogeneous
Catalysis Engineering
Heterogeneous
Catalysis
Research
Heterogeneous
Catalysis
Engineering
4

Activity

Selectivity

Active
Site
Catal yst
Pellet
Reactor Process
Turnover
Frequency
Effective
Reaction Rate
Conversion /
Space Time Yield
Process
Conversion
Differential
Selectivity
on Active Site
Differential
Selectivity
on Pellet
Integral
Selectivity
Process
Selectivity

Reactor
Scale
E
E+P+SP
Molecular
Scale
E P
P SP
Particle
Scale
E P+SP
SP
E
E+P+SP
P+SP
P
E
Purge
Process
Scale
Heterogeneous
Catalysis Research
Heterogeneous
Catalysis Engineering
5
time
BenchScale
Experiments
Feasibility
Study
time
Space Time Yield,
Selectivity/Conversion,
catalyst life time etc.
Market Analysis
Profitability(CAPEX, OPEX)
PreliminaryFlow Sheet
Technical Reactor Concept
Front End
Engineering
Basic
Engineering
DetailedFlow Sheet
Dimensioningof Apparatuses
ExpenditureEstimation(CAPEX, OPEX)
Detailed
Engineering
MeasuringandControl
Dimensioningof Pipes
Ordering
Mechanical
Completion
Erectionof Plant
Commisioning
Commisoning
Heterogeneous
Catalysis
Engineering
(University/
Industry)
Heterogeneous
Catalysis
Engineering
(Industry)
Start of
Production
Start of
Production
6
The bench scale results were so good that we by-passed the pilot-plant
aus E.H. Stitt, Chem.Eng.J . 90(2002)47
7
Bulk Chemicals Fine Chemicals
Plant Capacity >10,000 metric tons per year
(usually: some 100,000 t/a)
<10,000 metric tons per year
(usually <1,000 t/a)
Space Time Yield 1-10 kilogram per
liter and hour
0.01-1 kilogram per
liter and hour
Processing continuous batch-wise
Phase gas (liquid) liquid
Reactor typically tube typically stirred tank
Plant dedicated multi-purpose
Product price <10 $/kg >10 $/kg
Lifecycle of product long relatively short
Added value low high
Raw materials quote high low
kg waste / kg product
(E Factor)
relatively low
(<1-5)
high
(5-50)

8
Outline
Space Time Yield
Selectivity-Conversion-Plots
Catalyst-Life-Time
Space-Time-Yield
Atom Efficiency (E Factor)
Time-to-Market
Bench Scale Reactors for Het. Cat. Eng.
9

Activity

Selectivity

Active
Site
Catal yst
Pellet
Reactor Process
Turnover
Frequency
Effective
Reaction Rate
Conversion /
Space Time Yield
Process
Conversion
Differential
Selectivity
on Active Site
Differential
Selectivity
on Pellet
Integral
Selectivity
Process
Selectivity

Reactor
Scale
E
E+P+SP
Molecular
Scale
E P
P SP
Particle
Scale
E P+SP
SP
E
E+P+SP
P+SP
P
E
Purge
Process
Scale
10
Process Profitability =
f(Reactor Costs, Separation Costs, Recycle Costs, Feedstock Costs)
Separation Costs
= f(Selectivity)
Recycle Costs
= f(Conversion)
E+P+SP
E
E
P+SP
P
SP
Reactor Costs
= f(Space Time Yield)
Feedstock Costs
= f(Selectivity)
CAPEX OPEX
11
Process Profitability = f(Selectivity-Conversion-Plot, )
Educt Product Side Product
Molecular Scale:
Turnover Frequencies
ReducingFormation of Side Products
Particle Scale:
Avoiding Film andPore Diffusion
Limitation
Utilizationof Shape Selective Effects
Reactor Scale:
Avoiding Backmixing
Avoiding Hot Spots
Process Scale:
Recycle of Educt
Integration of Separation
12
with increasingconversionthe selectivity decreases
-> feed-stock costs increase
with increasingconversionless educt has to be
separatedand recycled
-> energycosts decrease
X
opt
13
Source: SRI Consulting
Reactor
C H
3
OH
O
C H
2
CH
2
C H
3
O
C
H
CH
2
O
+ + +
H
2
O
Pd/Au
0,5 O
2
VAM
X
C2H4
=8-10 % X
HAc
=15-35 %
S
VAM,C2H4
=88-96 %
14
Process Profitability = f(Reactor Costs,)
E+P+SP
E
E
P+SP
P
SP
Reactor Costs
= f(Space Time Yield)
15
f(Space Time Yield (STY), )

=
=

= =
h
Product
Reac
,
reac
,
reac
l
kg
M S X c
V
M S X c V
V
m
STY
P E P E Eo
P E P E Eo
P
Typical Values of STY:

1-10 kg product per 1 liter reaction volume
and hour
Residence Time
16
Space Time Yield
(STY):
Het. Catalysis: 1-10 kg/(lh)
Hom. Catalysis: 0.01 1 kg/(lh)
Biocatalysis: 0.001 0.01 kg/(lh)
hour and volume reaction of liter
product of kilogram
Reaction
temp.
Cat.
conc.
17
Process Profitability = f(Space Time Yield (STY), )
Wird beim Arbeiten im Kreislauf jeweils nur ein geringer Umsatz
der Reaktionsgase Stickstoff und Wasserstoff erreicht, so ist es
von grter technischer und wirtschaftlicher Bedeutung,
diese geringfgige Umsetzung noch bei schnellem
Durchleiten, also kurzer Berhrungszeit der Gase mit dem
Katalysator zu erreichen. Solch reiche Raum-Zeit-Ausbeute
ist nun nur mit Katalysatoren erreichbar, die den um 1905
bekannten an Wirksamkeit um ein Vielfaches berlegen sind.
Alwin Mittasch, Geschichte der Ammoniaksynthese, Verlag Chemie, Weinheim 1951.
18
undesired
time on stream(tos)
or process time
usually:
catalyst life time at least 8.000 hrs. (1 year)
catalyst activity
19
Bulk Chemicals Manufacture (Example I)
Direct Ring Oxidation of Aromatics with N
2
O
(E. Klemm et al., Direct Ring Oxidation of Aromatics, in: G. Ertl, H. Knzinger, J . Weitkamp(Hg.), Handbook of Heterogeneous
Catalysis, 2
nd
edition, WILEY-VCH, Weinheim, 2008)
A+B+NP
B+NP
NP
B
A
Purge
A B
A
A+B+NP
B NP
A B+NP
A
Strong adsorption andslow
diffusionof product
comparedto educt !
0
20
40
60
80
100
0 2 4 6 8 10 12
Verhltnis Benzol:N
2
O
S
e
l
e
k
t
i
v
i
t
t

N
2
O

z
u

P
h
e
n
o
l

[
%
]
Solutia:
20
Bulk Chemicals Manufacture (Example II: DEMiS
)
equal
up
E. Klemm et al., Ind. Eng. Chem. Res. 2008, 47, 2086.
gas
TS-1 cat.
3 cm
Labor
Ti O Si
H
2
O
2
Si
O H
olefin

Si
O H
epoxid
H O
Ti
O
Si
O H
H O
Ti
O
OH
Ti
H2O
TS-1
hydroperoxid
species
oxygen transfer
dehydratation
Foto: TU-Chemnitz
Lab Scale
1 m
0,6 m
Industrieller Mastab
Foto: Uhde GmbH / Degussa AG
Pilot Scale
21
)
According to: E. Ananieva, A. Reitzmann, Chem. Eng. Sci., 59 (2004) 5509 - 5517
22
)
3 8 hydrogen peroxide
in gas [vol%]
>1 substrate/hydrogen
peroxide
1 reaction pressure
[bar]
100-
150
reaction temperature
[C]
Reaction conditions
Catal yst TS-1
in gas [vol%]
peroxide
1 reaction pressure
[bar]
100-
150
[C]
Reaction conditions
Catal yst TS-1
0
20
40
60
80
100
0 20 40 60 80 100
X (propene) / %
S

(
p
r
o
p
y
l
e
n
e

o
x
i
d
e
,

p
r
o
p
e
n
e
)

/

%
Lab scale fixed bed (C3H6/H2O2=1,0)
Lab scale micro reactor (C3H6/H2O2=1,4)
Pilot scale micro reactor (C3H6/H2O2=1,4)
gas
TS-1 cat.
23
)
in gas [vol%]
peroxide
1 reaction pressure
[bar]
100-
150
[C]
Reaction conditions
Catal yst TS-1
in gas [vol%]
peroxide
1 reaction pressure
[bar]
100-
150
[C]
Reaction conditions
Catal yst TS-1
0
20
40
60
80
100
0 20 40 60 80 100
X (H2O2) / %
S

(
p
r
o
p
y
l
e
n
e

o
x
i
d
e
,

H
2
O
2
)

/

%
Lab scale fixed bed (C3H6/H2O2=1,0)
gas
TS-1 cat.
24
)
E. Klemm, G. Mathivanan, T. Schwarz, S. Schirrmeister,
Evaporation of Hydrogen Peroxide with a Microstructured
Falling Film, Chem. Eng. Proc, submitted.
E. Klemmet al.,
Method for Obtaining a Gaseoues Phase From a Liquid
Medium and Device for Carrying Out the Same,
Disclosure WO 2004/036137 A2, 29.04.2004.
gas
TS-1 cat.
S. Heinrich, M. Plettig, E. Klemm,
Role of the Ti(IV)-Superoxide Species in the Selective
Oxidation of Alkanes with Hydrogen Peroxide in the Gas
Phase on Titanium Silicalite-1 an In-Situ EPR
Investigation Catal. Lett. 141(2011)251.
T. Schwarz, S. Schirrmeister, H. Dring, E. Klemm,
Herstellung von Wandkatalysatoren fr Mikrostruktur-
reaktoren mittels der Niederdruckspritztechnologie,
Chem. Ing. Tech. 82(2010)921.
S. Schirrmeister, K. Bker, M. Schmitz-Niederau, B.
Langanke, A. Geielmann, F. Becker, R. Machnik, G.
Markowz, T. Schwarz, E. Klemm,
Katalytisch beschichtete Trger, Verfahren zu dessen
Herstellung und damit ausgestatteter Reaktor sowie
dessen Verwendung,
Disclosure DE 10 2005 019 000 A1, 26.10.2006.
E. Klemm et al., Ind. Eng. Chem. Res. 2008, 47, 2086.
25
Virtual, but realistic example:
Fine chemical synthesis with Y
P,E
=80 %, c
Eo
= 1 mol/l
and M
P
= 100 g/mol
(assuming stirred tank reactor witch V
reac
= 2 m
3
)
3-shift batch-wise operation:
Production Capacity: ca. 170 t / a
Space Time Yield: ca. 0.01 kg per liter and hour
day kg
mol g l mol l
M Y c V m
E P Eo reac
/ 480
/ 100 8 . 0 / 1 000 , 2 3
3
P , y Product/da
=
= =
= =
26
f(Space Time Yield (STY), )

=
=
=
h
Product
Reac
,
Reac
, Reac
Reac
l
kg
t
M Y c
t V
M Y c V
t V
m
STY
P E P Eo
P E P Eo
P
Process Time
for batch-wise
operation
Typical Values of STY:
0.01 1 kg product per 1 liter reaction
volume and hour
27
Space Time Yield
(STY):
Het. Catalysis: 1-10 kg/(lh)
Hom. Catalysis: 0.01 1 kg/(lh)
Biocatalysis: 0.001 0.01 kg/(lh)
hour and volume reaction of liter
product of kilogram
Reaction
temp.
Cat.
conc.
28
Plant Capacity E Factor
(kg waste / kg product)
Oil Refining >1 Mio t / year <0.1
Bulk Chemicals 10.000 t / year
up to
1 Mio t / vear
<1-5
Fine Chemicals <10.000 t / year 5-50
Pharmaceuticals <1 t / year 25-100

Accordingto: R.A. Sheldon, The E factor: fifteen years on, Green Chemistry 9 (2007) 1273.
Process Development for the Reduction of the E factor in Fine
Chemicals and Pharmaceuticals Manufacture due to
reduction of negative environmental impact
reduction of cost of disposingof waste
29
From: A. Stankiewicz, Process IntensificationWorkshop, DECHEMA, 29.05.2006.
Process time in batch-wise fine chemical manufacture is mostly
limited by heat and mass, and not by the chemical reaction itself.
Due to increasing V and decreasingA/V, process time increases
when scaling up frombench to production scale.
30
From: Dr. J . Lang, Evonik Degussa
26 cm
36 cm
Granulatdosierung
Zerkleinern/Feinmahlen
Granulatspeicher
Feinkorndosierung
Lsemittelpuffer
Flssigdosierung
berhitzung
Druckdosierung
Filtration
Filterkuchenaustrag
Rckstandspeicher Produkt
Extraktion
310 ml
48 sec
23 L/h
204 tons/year
V=ca. 40 l
31
Shifting from batch-wise to continuous operation:
Fine chemical synthesis withY
P,E
=80 %, c
E0
= 1 mol/l
and M
P
= 100 g/mol
(assuming continuous reactor with V
reac
= 40 l and
reaction time of 1 min):
Production Capacity: ca. 1,533 t / a
Space Time Yield: ca. 4.8 kg per liter and hour
higher capacity or shorter time-to-market
day t day kg
mol g l mol l
M Y c V
m
E P Eo
/ 6 , 4 / 608 , 4
min 1
/ 100 8 . 0 / 1 40
P , reac
Product
= =
=

=
=

=
32
J . Yoshida, A. Naganki, T. Yamada, Chem. Euro. J . 14(2008)7450.
33
34
Bench Scale Reactors for Heterogeneous Catalysis
Catalytic Wall
Reactors
Tube
Reactor
Recycle
Reactor
(Type Berty)
Stirred Autoclave Reactor
Source:
Lehrstuhl Technische Chemie,
Universitt Erlangen-Nrnberg
Universitt Stuttgart
Slug Flow Reactor
35
List of Symbols
Symbol Dimension Description
c
E,0
mol m
-3
concentration of educt species E at the beginning of the reaction

M
E
g mol
-1
molar mass of educt E
P
m
kg s
-1
productivity (mass flow of the product P)
S
P,E
- selectivity to product P related to educt E
t s process time
V
reac
m
3
reaction volume
V

m
3
s
-1
volumetric flow rate
X
E
- conversion of educt E
Y
P,E
- yield of product P related to educt E

s residence time

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