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CORNING® ADVANCED-FLOW™ REACTORS
for Intensifying Two-Phase Processes
Daniela Lavric
Corning Reactor Technologies
Corning European Technology Center
Avon, France
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 2
Outline
• Introduction to Corning Incorporated
• Corning® Advanced-Flow™ Reactor Technologies
• Liquid-Liquid Mass Transfer
• Gas-Liquid Mass Transfer
• Applications
• Conclusion
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 3
Corning Incorporated
Founded:
1851
Headquarters:
Corning, New York
Employees:
~29,000 worldwide
2012 Sales:
$ 8,0 B
Fortune 500 Rank (2012):
326
~ 10 % of annual sales in R&D
• Corning is the world leader in specialty glass
and ceramics.
• We succeed through sustained investment
in R&D, 160 years of materials science and
process engineering knowledge, and a
distinctive collaborative culture.
Headquarters Manufacturing
Joint Ventures Sales offices
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 4
Corning Market Segments and Additional Operations
• Emerging Display
Technology
• Drug Discovery
Technology
• New Business
Development
• Equity
Companies – Cormetech, Inc.
– Dow Corning Corp.
– Eurokera, S.N.C.
– Samsung Corning
Advanced Glass, LLC
(SCG)
– Samsung Corning
Precision Materials Co.,
LTD (SCP)
• Cell Culture and
Bioprocess
• Assay and High-
Throughput
Screening
• Genomics and
Proteomics
• General
Laboratory
Products
• LCD Glass
Substrates
• Glass Substrates
for OLED and
high-performance
LCD platforms
• Optical Fiber and
Cable
• Hardware and
Equipment
– Fiber optic
connectivity
products
• Emissions
Control Products
– Light-duty gasoline
vehicles
– Light-duty and
heavy-duty on-road
diesel vehicles
– Heavy-duty non-
road diesel
vehicles
– Stationary
• Corning® Gorilla®
Glass
• Display Optics
and Components
• Optical Materials
– Semiconductor
materials
– Specialty fiber
– Polarcor™
• Optics
• Aerospace and
Defense
• Ophthalmic
Specialty
Materials
Other
Products
and Services
Life
Sciences Telecom
Display
Technology
Environmental
Technologies
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 5
1947
TV tube
mass
production
1879
Glass for
Edison’s
light bulb
1915
Heat-resistant
Pyrex®
glass
1970
Low-loss
optical fiber
1982
LCD glass
1934
Dow
Corning
silicones
1952
Glass
ceramics
2010
Thin-film
photovoltaic
glass
1972
Substrates
for catalytic
converters
Ultra
bendable
fiber
2007
Thin,
lightweight,
cover glass
Pre-1900 1910 1920 1930 1940 1950 1960 1970 1980 1990 2010 2000
2002
Fluidic
module
AFR*
* Advanced-Flow™ Reactors
Corning’s Continuous Flow Reactors Build on the Company’s
160 Years of Innovation
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 6
History of Corning Reactor Technologies One decade of expertise
2002 2003 2004 2005 2007 2008 2009 2010 2011 2006
Concept development
Customers collaborations
G1 reactor
Collaborations
with platforms
in Europe
G2 reactor
Bank concept
Low Flow
lab system
2012
G4
Ceramic reactor
G3 reactor
China applications lab MIT
collaboration
European
applications lab
• First introduced in 2002
• Technology leveraged for larger sizes with
advanced materials to increase throughput:
– Glass
– Ceramic
• Worldwide established business operations
India
applications lab
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 7
Corning® Advanced-Flow™ Reactors (AFR) Worldwide presence
NA ASIA EUROPE
SA
AFRICA
China India
S. Korea USA
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 8
Corning® Advanced-Flow™ Reactors
Offer broad capability from feasibility to
production and enable the transition
from batch to continuous processes
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 9
quench
Corning® Advanced-Flow™ Reactors Product Design
• Engineered fluidic modules:
– glass or ceramic plates with integrated
mass and heat transfer
• Reactor design: a modular assembly
• Reactor:
Reactants End Product
Heat exchange
A
B
D
Corning® Advanced-Flow™ Reactor - Glass Corning® Advanced-Flow™ Reactor - SiC
A+B C C+D E
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 10
Fluidic Modules (HEART-based)
Increase throughput with similar:
- Mixing
- Residence time distribution
LF G1 G2 G3
5-9 ml 0.5 ml 20-25 ml
50-70 ml
- Heat Exchange
- Mass transfer in heterogeneous systems
2-10 g/min
G4
250 ml
30-175 g/min 150-600 g/min 1000-2300 g/min 1000-4600 g/min
D. Lavric and P. Woehl, Chemistry Today 27, 45-48 (2009)
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 11
Low Flow G1 G2 G3 G4
0.45 ml 8 – 11 ml 21 – 25 ml 55 – 65 ml 200 – 260 ml
T from - 60 to 200°C, P up to 18 bar, metal-free reaction path
G4
G3
G2
G1
25 50 75 100 125 150 175 200 225 250 275 300 325 350
Kg / h LF –
feasibility
studies
Continuous Flow Reactors Production Range
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 12
Glass & Ceramic Materials Superior corrosion resistance
Flow reactor characteristics
Transfer
• Superior mixing & mass-transfer
• Excellent HE with reaction integration
• Appropriate residence time
• Narrow RTD
Controls
• Reduced process fluid hold-up
• Accurate T,P, & RT control
Production
• Numbering-up to meet capacity
• Flexible to fit chemistry & market
needs
Weight loss
(mg/cm².year)* 316L SS Glass S-SiC
H2SO4-96% destroyed good good
HNO3-65% destroyed good good
NaOH-10% low T° good good good
NaOH30% High T° good destroyed good
HCl-32% destroyed good good
Glass transparency
• For development in the lab
• For photochemistry
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 13
For Production: Scale-up Combined with Internal and External
Numbering-up
Lab scale
Pilot scale
Production
Chemistry Today, 27 (3), 45-48 (2009)
Chemistry Today, 26 (5), 1-4 (2008)
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 14
Requirements of Chemical Reactions
Reactor capabilities
Contact between the molecules of
the reactants MIXING / MASS TRANSFER
Keep the molecules in contact during a sufficient
time to allow the completion of the reaction Residence
Time
Enable the same history of the
molecules in the reactor RTD
Provide isothermal condition HEAT
TRANSFER
Reaction needs
RT = 5 s
Intense Mass Transfer in Two-Phase Processes
in HEART-based Fluidic Modules
Periodic merging and break-up
of droplets/bubbles leads to a
constant renewal of the
interface and the active
interfacial area is used very
efficiently
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 16
20 g/min toluene-20g/min water 40 g/min toluene-40g/min water
Fluidic Module Performances Hydrodynamics in immiscible fluids: Toluene-Water
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 17
Fluidic Module Performances Mass transfer in immiscible liquids W/A/T
1Saien, J. et al., Chem. Eng. Sci. 2006, 61, 3942-3950 (2006) 2Kashid M. N., et al., 2011, Ind. Eng. Chem. Res., 50, 6906–6914 (2011)
Analysis: GC FID Misek, T., et al., Standard test systems for liquid extraction.
EFCE Publication Series 1985, 46
G3
LF
G1
G2
G4
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 18
Fluidic Module Performances Mass transfer in immiscible liquids hexane-water
M. Jose Nieves-Remacha, A. A. Kulkarni, and K. F. Jensen, Ind. & Eng. Chem. Res. 51 ,16251 – 16262 (2012)
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 19
Fluidic Module Performances Hydrodynamics in Gas-Liquid: water-N2
First HEARTs 2nd row of HEARTs
50 mL/min G 100 NmL/min
100 mL/min G 200 NmL/min
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 20
Fluidic Module Performances Mass transfer in Gas-Liquid from Low Flow to G4
CO2 absorption in NaHCO3/Na2CO3 buffer solutions Contacting equipment Volumetric mass transfer
coefficient, kLa (s-1)
Plate column1 0.01–0.05
Packed column1 0.005–0.02
Gas bubble column1 0.005–0.01
Stirred bubble absorber1 0.02–0.2
Spray column1 0.0007–0.015
Jet (loop)1 0.1–3.0
Multi-stage ELALR1 0.01–0.05
Microchannel2:
V = 25 µL
QG = 15 – 375 mL/min
QL = 2.5 – 30 mL/min
0.3-21
Corning® G1:
V = 8 mL
QG = 20 – 600 mL/min
QL = 20 – 130 mL/min
0.08-0.55
Corning® G4
V = 250 mL
QG = 3000 – 30000 mL/min
QL = 600 – 3000 mL/min
0.045-0.65
1K. Mohanty et al., Chemical Engineering Journal 133, 257–264 (2007). 2 J. Yue et al., Chem. Eng. Sci. 62, 2096-2108 (2007).
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 21
Fluidic Module Performances Gas - Liquid specific surface area and power consumption
1.M.W Losey et al., Ind. Eng. Chem. Res. 40, 2555–2562 (2001).
2. K.K. Yeong et al., Chem. Eng. Sci. 59, 3491-3494 (2004).
3. K. Jähnisch et al., J. Fluorine Chem. 105, 117-128 (2000).
4. B. Chevalier et al., Chemistry Today 26(2), 53-56 (2008).
5. M. Jose Nieves-Remacha, A. A. Kulkarni, and K. F. Jensen, Ind. & Eng. Chem. Res. 52, 8996 – 9010 (2013).
Type of micro reactor Specific interfacial area
[m2/m3]
Micropacked bed 16.000 (1)
Microbubble column
(1100 µm x 170 µm) 5.100
Micro bubble column
(300 µm x 100 µm) 9.800
Micro bubble column
(50 µm x 50 µm) 14.800
Falling film microreactor
(300 µm x 100 µm)
9.000-15.000 (2)
27.000 (3)
Corning G1 fluidic module 7000-14.000 air / water (4)
Air-water CO2-NaOH
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 22
Fluidic Module Performances Mass transfer in G-L systems
400 µm
V = 270 µL
Kuhn, S., ECCE 8, September 25-29, Berlin, Germany (2011)
400 µm
V = 240 µL
Courtesy of S. Kuhn CO2 - NaOH
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 23
Fluidic Module Performances Mass transfer in G-L systems
400 µm
V = 270 µL
V = 8.7 mL
Courtesy S. Kuhn Kuhn, S., ECCE 8, September 25-29, Berlin, Germany (2011)
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 24
Corning® Advanced-Flow™ Reactors
Minimize scale-up failures and drastically reduce
the time from laboratory to production
Applications
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 26
Nitration Reactions in Corning® AFR Reduced solvent usage, higher yield and safer operation
• Shorter Development Cycle
• Value generated from: reduced solvent usage, higher yield & significant safety improvement
Substrate
Solvent
HNO 3
H 2 O NaOH NaOH NaOH
Product
Flush H 2 O
Feed preparation
Nitration Quench and neutralization
Excellent Mixing of immiscible liquids
Commercial scale demonstration
HO R OH + HNO3
HO R
ONO2 O2NO
R ONO2 X
Product Explosive by-Product
Braune, S. et al.,Chemistry Today, 26 (5), 1-4, (2008)
• Strict control of reaction parameters is
crucial for both quality and safety:
• Temperature
• Stoechiometry
• Residence time
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 27
Scale-up and Numbering-up as well
DSM presentation Scale-up conference 2010
From concept validation in the lab… …to the industrial production.
Braune, S. et al., Chemistry Today, 26 (5), 1-4, (2008)
R. Guidat, D. Lavric, CHISA 2010, 28 August-1 September, Prague, Czech Republic (2010)
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 28
TEMPO Reaction: Parametric Study in Low-Flow Improved efficiency of a two-phase L/L reaction by fine-tuning the conditions
Higher yield achieved at pH = 8 but, the bleach is less stable
Solved by optimized set-up with 3 feeds for pH in-line
adjustment
pH and set-up optimization
• Initially developed by Anelli et al. (JOC, 1987, 52, 2559)
• Difficult scale-up due to exothermicity and bleach stability
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 29
TEMPO Reaction: Strong Impact of Mixing The unique HEART design allows a permanent and efficient mixing quality
• Qualitative comparison for the same residence time: – T-mixer + tubes (0.32 mm or 0.16 mm internal diameter) slugs at the outlet
– 1 Low Flow fluidic module + tube 0.16 mm emulsion + slugs
– 7 Low Flow fluidic modules emulsion
• Permanent mixing Constant emulsion quality
Higher mass transfer
Octanol 0.5M in dichloromethane
• TEMPO 0.05%
• Temperature: 20ºC (no HE for tubes)
• Bleach: 1.2 equivalents (9.7%)
• Buffer: phosphate 1 M (1 eq. / pH=8)
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 30
TEMPO Reaction: Scale-up from Low-Flow to G1 Optimized conditions implemented in G1 allow higher productivity
1.2 eq bleach, 0,2%mol TEMPO
K2HPO4 CH2Cl2-H2O, pH = 8, 20°C
Low-Flow G1
Internal volume 5.7 ml 61.7 ml
Residence Time 49 s 30 s
Flow rate 7 ml/min 120 ml/min
Production 0.18 mol/h 3.6 mol/h
• In-line generation and easy management of unstable reagent
• Fast (30-60 s) and selective conversion of primary alcohols to corresponding aldehydes
• Higher volumetric heat and mass transfer coefficients than in batch enable higher productivity
• Successful scale-up from Low-Flow to G1 with improvement of productivity by a factor 20
80,00%
85,00%
90,00%
95,00%
100,00%
0 20 40 60 80 100 120
Co
nv
ers
ion
(%
)
Residence time (s)
TEMPO in LFR and G1
G1
LFR
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 31
Selective Hydrogenation with Slurry Catalyst 98%+ conversion & selectivity (impurity profiles within spec)
• highly exothermic (>400 kJ/mol)
• 30 µm catalyst in slurry
• significant catalyst reduction
Excellent G/L Mixing
30 °C 140 °C
0.1% 0.4%
45%wt 35%wt
90s 10h
Batch Corning® AFR
B.Buisson et al., Chemistry Today, 27(6), 12-15 (2009)
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 32
Scale-up from lab to pilot
Lab G1
80 t/y
Production, G4
2000 t/y
G1 G4
Yie
ld
Multiphase application: L/L/G
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 33
How well do we know our product?
Testing on fluidic modules
Testing on reactor
1HPA11090002
1HPA11089001
1HPA11082002
1HPA11095002
1HPA11083002
1HPA11108001
Design X4SJHSDesign X4RT
N4 Layer above
Sharp angle
Oblong
feature
Breakage analysis - fractography
Example of lifetime model
Long duration lifetime testing
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 34
Reliability and auxiliaries characterization
Apparatus for gaskets testing
Samples of
gaskets after
testing
Impact of vibration on flow
meter measurement stability Control of rupture pressure of piping
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 35
Continuous Flow Reactor Technology is More than Reactor
Corning has an unique and global experience in delivering or
advising for complete flow reactor systems for specific needs
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 36
Massachusetts Institute of Technology
(MIT)
Shandong Brother Tech
上海师
范大学
This is one of the reason why
more and more customers trust us*
* Partial list
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 37
Instead of Conclusion….
To be successful, you have to have your
HEART in your business,
and your business in your heart
Thomas J. Watson, Sr. chairman and CEO of IBM from 1914 to 1956
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 38
A special Thank to the CORNING AFR Team, particularly
the Research & Development Group
the Reliability and Characterization Group
the Global Application Engineer Team
the Quality Control Service
lavricd@corning.com
Acknowledgements
for making this presentation possible
Advanced-Flow™ Reactor Technologies © 2013 Corning Incorporated 39
THANK YOU FOR YOUR ATTENTION
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