micro-reactor developments céline guermeur corning sas cpac satellite workshops 2007 micro-reactors...
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Micro-Reactor developmentsCéline GUERMEURCorning SAS
CPAC SATELLITE WORKSHOPS 2007Micro-reactors and Micro-Analytical – March 19-21, 2007
2Corning
Focus: The reactor and its integration into the production system
Chemistry
System engineering
Reactor engineering
C=OR
R’
Mass andheat transfer
3Corning
Micro reactor for Industrial ProductionThroughput in metric tons per year per reactor
Targeted product Metric tons/Year per reactor Flow rate (Kg/hour)
Reactants concentration (wt%) 1 2 3 5 10 12
10 1 2 2 4 8 10
20 2 3 5 8 17 20
30 2 5 7 12 25 30
50 4 8 12 21 42 50
70 6 12 17 29 58 70
100 8 17 25 42 83 100
Assumptions Conversion 100 %
Selectivity 95 %
4Corning
Reactor engineering process
Reactor fundamentals
Detailed reactor
engineering
Chemistry know-how Basic
reactor engineering
CUSTOMER NEEDS
Translation into a mass and heat transfer problem
Let’s go together through an example
REACTORPRODUCT SYNTHESIS UNIT
Reaction network and feed distributionThermodynamic & KineticsFeed boundaries
Design and sizingMaterial selection
5Corning
Customer needs
• Safe and smooth production of 40 kg / week / reactor• Raw material cost > 500 €/kg• More than 95% conversion• Impurities below 2%
Reactor fundamentals
Detailed reactor
engineering
Chemistry know-how Basic
reactor engineering
6Corning
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
The chemistry know-how
• 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
Chemistry know-how
7Corning
Product synthesis unit
PRODUCT SYNTHESIS
UNIT
Downstream operations
PRODUCT
A B
C
D
Internal volume < 0.1 LiterNo loading / unloading
Step 1Load A STEP 2
Dose with B
STEP 3Load C
STEP 4Dose with A+B
STEP 5Dose with D
Downstream operations
PRODUCT
Internal volume : 200 Liters5 loading / unloading
Basic reactor
engineering
8Corning
Basic engineering
• 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
Basic reactor
engineering
9Corning
Data needed: Mass and heat balance
20°C
15 Wreleased
0°C
150 Wreleased
0°C
480 W released
Feed 1
Feed 2
Feed 3
Feed 4
19 ml/min17 g/min0.5 cP @ 20°C
29 ml/min26 g/min0.5 cP@20°C
65 ml/min58 g/min0.7 Cp@0°C
43 ml/min39 g/min1.6 cP@ 0°C
Detailed reactor
engineering
10Corning
Hydrodynamic
10
100
1000
10000
100000
1000000
1 10 100 1000Q [ml/min]
dP
[m
bar
]
5cPo 300cPo
100cPo
Detailed reactor
engineering
11Corning
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
MASS TRANSFER: SINGLE AND MULTI-INJECTION
HEAT TRANSFER
13Corning
Single-injection reactor
V/Q where
:rate flowconstant for
1
1
R
R
M
jjji
i
M
jjji
i
rd
dC
rdV
dF
FEED PRE-HEAT/COOL
FEED PRE-HEAT/COOL
REACT
HE IN HE OUT
A
B
PRODUCT
/VN where ii
1
C
rdt
dC RM
jjji
i
Reactor fundamentals
14Corning
Multi-injection reactor
FEED PRE-HEAT/COOL
FEED PRE-HEAT/COOL
SPLIT
REACT
HE IN HE OUT
A
B
PRODUCT
reactor.injection -multi for the
)1(1)/(
)2(
and
reactorbatch -semi for the
)1(1)/(
)1(
BP
AB
BfAf
B
xQ
VkC
Lzd
dx
xtkCttd
dx
Acknowledgement:Michael T. Klein, Dean School of EngineeringRutgers, The State University of New Jersey
Reactor fundamentals
15Corning
cp TTVSUHkA
d
dTC )(
Multi-injection: Better temperature management along the flow path
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
CT
ION
OF
TE
MP
ER
AT
UR
E
Single -injection
Multi -injection
16Corning
Single and multi-injection
A = 1
A/B = 3
A/B = 1
B = 1/3 B = 1/3 B = 1/3
A/B = 2 A/B = 1
A = 1
A/B = 1
B = 1
Reactor fundamentals
Examples
In both cases, the molar ratio target is reached
17Corning
Multi-injection: Only two pumps are required
Pressure drop management and
fluid split within the micro-structures
Reactor fundamentals
A
B
Product
18Corning
Mass transfer
Heat transfer
Heat transfer
Mass and heat transfer are combined
Reactor fundamentals
19Corning
Optimum heat exchange
Reaction circuit: Toluene
Heat exchange circuit: Water
600 W/m2.K
Reactor fundamentals
20Corning
Heat exchange performanceReactor
fundamentals
Corning glass micro-reactor Example of metal mixer
(Internal testing)
Reaction circuit: Toluene – Same flow rate
Heat exchange fluid: Water
Heat exchange: Integrated Heat exchange: Agitated bath
600 W/m2.K 60 W/m2.K
21Corning
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
L/L Polystyrene precipitationChem. Eng. Technol. 2005, 28, 324-330
Proc. of the 10th APCChE Congress, 2004, 4B-02
50-100 nm particle size
L/G Measure of slug sizePressure drop in monolith reactors, P. Woehl, R.L. Cerro, Catalysis Today 69 (2001) 171-174
Flow patterns in liquid slugs during bubble-train flow inside capillaries, Chem Eng Sci 52 (1997) 2947-2962
0.5 - 10 mm
Hydrodynamic regime adapted to needs
22Corning
Module approach enable bridging
Specific reaction(s)
Standard modules
Synthesis unit kg-lab testing
Dedicated production
Multipurpose production
Test applicability on reaction portfolio
23Corning
Nitration
Feed 1
Feed 2
DT
DT MJ
MF
DT
DT MJ
MF
Feed 3
DT SJFeed 4
DT
PRODUCT OUTPUT
24Corning
Organometalic reaction
Feed 2
Feed 1
DT
DT
MF
MJ
Feed 3
Product outlet
DT MF
MJ
DT
Feed 4
SJ
25Corning
Example of 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
26Corning
Generate value in production, increase safety and product quality using micro-reactors
Courtesy of Lonza