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Engineered reactors for Chemicals Industrial Production
PIN meeting April 26th, 2007
Philippe CAZE
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2Corning Restricted
Corning focus: The reactor and its integration into production system
Chemistry
C=OR
R’
Mass andheat transfer
System engineering
Reactor engineering
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Corning designs and manufacturesFrom glass microstructures to engineered reactors
3Corning Restricted
• Glass compositions– Chemical compatibility with chemicals and solvents– High chemical corrosion resistance with almost all chemicals
• Design of micro structures– Flexibility in design
• Unique, proprietary microstructure manufacturing technology
• Reactor engineering– Methodology and experience to leverage existing customer data/know-
how to define the continuous reactor– Basic and detailed engineering from pilot runs to full scale production
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4Corning Restricted
Corning productEngineered reactor and service
• Basic and detailed engineering – Reactor– Product synthesis module– Numbering up
• Feasibility studies• Customization• Engineering services• Start up assistance
Reactor
Product synthesis unit
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5Corning Restricted
Corning Microreaction technology
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6Corning Restricted
Mass and heat transfer are combined & integrated into each microstructure
Heat transfer
Mass transfer
Heat transfer
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7Corning Restricted
Micro reactor for Industrial Production
Targeted product Metric tons/Year per reactor Flow rate (Kg/hour)
Reactants concentration (wt%) 1 2 3 5 10 1210 1 2 2 4 8 1020 2 3 5 8 17 2030 2 5 7 12 25 3050 4 8 12 21 42 5070 6 12 17 29 58 70
100 8 17 25 42 83 100
Assumptions Conversion 100 %
Selectivity 95 %
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8Corning Restricted
Single-injection reactor
V/Q where
:rate flowconstant for
1
1
=
=
=
∑
∑
=
=
τ
ντ
ν
R
R
M
jjji
i
M
jjji
i
rddC
rdVdF
FEED PRE-HEAT/COOL
FEED PRE-HEAT/COOL REACT
A
/VN where ii
1
=
=∑=
C
rdt
dC RM
jjji
i ν
B
HE OUTHE IN
PRODUCT
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9Corning Restricted
Multi-injection reactor
FEED PRE-HEAT/COOL
FEED PRE-HEAT/COOL
SPLIT
REACT
A
PRODUCT
reactor.injection -multi for the
)1(1)/(
)2(
andreactorbatch -semi for the
)1(1)/(
)1(
BP
AB
BfAf
B
xQVkC
Lzddx
xtkCttd
dx
−−=
−−=
Acknowledgement:Michael T. Klein, Dean School of EngineeringRutgers, The State University of New Jersey
B
HE OUTHE IN
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Multi-injection: Better temperature management along the flow path
10Corning Restricted
( ) ( )cp TTVSUHkA
ddTC −⋅⋅−∆−= )(τ
ρ
Heat generation
Heat removal
0
0,2
0,4
0,6
0,8
1
0 2 4 6 8 10 12 14 16 18
NUMBER OF INJECTION POINTS
RE
DU
CTI
ON
OF
TEM
PER
ATU
RE
Single -injection
Multi -injection
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11Corning Restricted
Local molar ratio management
A = 1
A/B = 3A/B = 1
B = 1/3 B = 1/3 B = 1/3
A/B = 2 A/B = 1
A = 1A/B = 1
B = 1
In both cases, the incoming feeds molar ratio is the same
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12Corning Restricted
Multi-injection: Only two pumps are required
A
Pressure drop management and
fluid split within the micro-structuresB
Product
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13Corning Restricted
Multi injection reactor module
• Eliminate hot spots• Avoid local over concentration of active species
→ Less by product formation
time
T°CBatch
Multi injection
Batch
time
CHNO3
Multi injection
Example of use:
C6H6 → C6H6NO2 → C6H6(NO2)2
HNO3 HNO3
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14Corning Restricted
Multi-phase mass transferFeeds Mixing test Results Hydrodynamic
visualization
L Villermaux methodVillermaux & all, AIChE Symp. Ser. 88 (1991) 6, 286.
Mixing quality > 90% forflow rates > 1.8 L/h
50-100 nm particle size
0.5 - 10 mmHydrodynamic regime adapted to needs
L/L Polystyrene precipitationChem. Eng. Technol. 2005, 28, 324-330 Proc. of the 10th APCChE Congress, 2004, 4B-02
L/G Measure of slug sizePressure drop in monolith reactors, P. Woehl, R.L. Cerro, Catalysis Today 69 (2001) 171-174Flow patterns in liquid slugs during bubble-train flow inside capillaries, Chem Eng Sci 52 (1997) 2947-2962
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15Corning Restricted
End user application
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16Corning Restricted
Reactor engineering process
1. Chemistry know-how and reactor fundamentals– Chemistry know-how
• Reaction network and feed distribution• Thermodynamic & Kinetics• Feed characteristics
– Reactor fundamentals2. Basic engineering : Translate chemistry into a mass and heat transfer
question– Single injection / multi-injection– Mass and heat transfer principle
3. Detailed reactor engineering– Identify critical dimensions of the reactor– Design and sizing
Reactor fundamentals
Detailed reactor
engineering
Chemistry know-how Basic
reactor engineering
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Reactor fundamentals
Detailed reactor
engineering
Chemistry know-how Basic
reactor engineering
17Corning Restricted
Customer needs
• Safe and smooth production of 40 kg / week / reactor
• Raw material cost > 500 €/kg• More than 95% conversion• Impurities below 2%
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Chemistry know-how
18Corning Restricted
The chemistry know-how STEP 1
Reagent A and solvent are fed
STEP 2B is dosed
STEP 3C and solvent are
fed
STEP 4A+B reacted
mixture is dosed
STEP 5Aqueous solution
is dosed
Downstream operations PRODUCT
Hydrogen vent
Nitrogen
• A + B → C• C + D → E• E + H20 → Product + H2
• Exothermic• Highly reactive intermediate• No major side products
• Exothermic• Maximum temperature 10°C• Safety limit : 50 L batch vessel• Excess of C = Selectivity issue
• Exothermic• Hydrogen release
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Basic reactor
engineering
19Corning Restricted
Product synthesis unit
STEP 1Reagent A and solvent are fed
STEP 2B is dosed
STEP 3C and solvent are
fed
STEP 4A+B reacted
mixture is dosed
STEP 5Aqueous solution
is dosed
Downstream operations PRODUCT
Hydrogen vent
Nitrogen
A B
PRODUCT SYNTHESIS
UNIT
C
Aq.
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Translation into a mass andheat transfer question
Basic reactor
engineering
20Corning Restricted
• Step 1 : – Mixing and heat exchange
integrated– Single injection
• Step 2 : • Mixing and heat exchange
integrated• No excess of C
• Step 3: – Mixing and heat exchange
integrated– Single injection
Feed 1
Feed 2
DT
DT SJ
Feed 3
Product outlet
DT MJ
MF
SJ
DT
DT
Feed 4
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21Corning Restricted
Mass and heat balance: data for reactor sizing
Detailed reactor
engineering
20°C
15 Wreleased
0°C
150 Wreleased
0°C
480 W released
Feed 1
19 ml/min17 g/min0.5 cP @ 20°C
Feed 2
29 ml/min26 g/min0.5 cP@20°C
Feed 365 ml/min58 g/min0.7 Cp@0°C
Feed 443 ml/min39 g/min1.6 cP@ 0°C
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Product synthesis unit
22Corning Restricted
Feed 1
Feed 2
DT
DT SJ
Feed 3
Product outlet
DT MJ
MF
SJ
DT
DT
Feed 4
Throughput: 40 kg/week99 % conversionImpurities < 1%
Pressure: Up to 18 barsTemperature : -50°C to 40°CInternal volume : 70 ml
Reactor fundamentals
Detailed reactor
engineering
Chemistry know-how Basic
reactor engineering
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Product synthesis unit
23Corning Restricted
1. For each unit operation, design the best engineered reactor module to fit your chemistry
2. Combine several engineered reactor modules into an optimized continuous operation
3. Combine several product synthesis module in order to achieve the capacity according to your needs
1. Chemistry has to be adapted to the equipment
2. Cascade of discontinuous unit operations in agitated vessels in order to make the product
3. Manufacturing capacity is obtained through complex plant and manufacturing train management in campaign
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24Corning Restricted
Reduction reaction
Feed 1
Feed 2
DT
DT SJ
Feed 3
Product outlet
DT MJ
MF
SJ
DT
DT
Feed 4
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25Corning Restricted
NitrationFeed 1
Feed 2
DT
DT MJ
MF
DT
DT MJ
MF
Feed 3
DT SJFeed 4
DT
PRODUCT OUTPUT
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26Corning Restricted
Organometalic reaction
Feed 2
Feed 1
DT
DT
MF
MJ
Feed 3
Product outlet
DT MF
MJ
DT
Feed 4
SJ
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27Corning Restricted
Multipurpose productionPRODUCTION 1CAMPAIGN 1
PRODUCTION 1CAMPAIGN 2
Feed 1
Feed 2
DT
DT SJ
Feed 3
Product outlet
DT MJ
MF
SJ
DT
DT
Feed 4
Feed 2
Feed 1
DT
DT
MF
MJ
Feed 3
Product outlet
DT MF
MJ
DT
Feed 4
SJ
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28Corning Restricted
Multipurpose or dedicated productionSpecificreaction(s)
Standard reactormodules
Synthesis unit kg-lab testing
Dedicatedproduction
Multipurpose production
Test applicabilityon reactionportfolio
• Flexibility for process development• Flexibility for Multipurpose production• Flexibility for adapting production capacity to needs
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29Corning Restricted
Integration into production system
Chemistry
C=OR
R’
Mass andheat transfer
System engineering
Reactor engineering
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30Corning Restricted
Integrated approach in process development, reactor design & system engineering• Changing to continuous requires a different approach from
lab, through piloting to processing at the commercial scale– Corning & Zeton bring this approach in practice– Support of customer in their testing of chemistry in lab, pilot
and production phase– Dedicated or multi purpose reactors by Corning– Overall engineering, automation, process integration and
construction of facilities by Zeton
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31Corning Restricted
• Corning capabilities
– Microprocessing technology using a process intensified approach
– Reactor design conform process & chemistry requirements
– Assistance in the development from batch to continuous processing
– Support in testing of chemistry at customer’s facility
– Strength in R&D and innovation– 150 years experience in
materials and process
• Zeton capabilities
– Engineering & Construction of highly automated built plants
– Support in development of projects through basic design studies
– Custom design – fit for purpose – 20 years experience in
continuous processing– Design low flow & severe
conditions– Delivery conform ATEX & PED– Fast track project approach– Smart solution on small scale
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32Corning Restricted
Industrial mobile multi purpose microreactor unit• Independent operation• Highly automated• Adaptable to most chemistries
• 3 liquid feeds• 2 gas feeds• ATEX EEx Zone II• T= -80 / +250°C• Output up to 50 t/y• Data collection
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Thank you for your attention
33Corning Restricted
Courtesy of Lonza
Zeton - Corning