Innovation Drives Green Growth –Advanced-FlowTM Reactor Technology –Industrial Production Made RealContactPraveen GosainRegional Director – India S.E Asia and Australia
Corning Reactor Technologieswww.corning.com/[email protected]
Advanced-Flow™ Reactor Technologies 2.
© 2017 Corning Incorporated ..
Advanced Flow Reactors Offers - Green Synthesis Processes• Green process reduces the use of hazardous substances in synthesis.• Green Chemistry R&D Act (2007): major push by US Congress, and EU to use
safer and more sustainable products• Continuous-Flow reactors & processes can improve green metrics
Energy Waste LandEnergy Saving by 50-70%(up to 80,000 t-CO2/PlanT)
Waste/Solvent Reduction by 30-70%: up to 100,000 t-CO2/PlanT)
Plant Foot-Print Reduction by 50-75%
Foot-print was reduced 75%
400 MT/Y Selective Nitration Plant (Contineous Process foot-print reduced by 75%)
H-R. Marti et al (2009) P. Poechlauer, S.Brune (2010)
Advanced-Flow™ Reactor Technologies 3.
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Corning Patented “Heart-Cell” Fluid Module Designs offer excellent mixing (100X better), superior heat transfer (1000X enhancement)
Mixing of Two Liquid PhasesLiquid 1: BlueLiquid 2: YellowMixture: Green
HE Layer
Reactants1, 2 (in) Product (out)HE fluid outHE fluid in
HE Layer
Reaction Layer
HE area: 2500 m2/m3
HE area 2500m2/m3
U×(S/V) 1 MW/m3.K
multi-layer structure of fluidic module
Corning® AFR™ G1 Platform
G1 SiC
G1 Glass
Advanced-Flow™ Reactor Technologies 4.
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Continuous Innovation Led to Comprehensive Solutions -Seamless scale-up from lab to production
LFG1
G2G3 G4
SiC
SiC
LED Photo
Glass
SiC
Upto 5000 t/y
1000 t/y
250 t/y
80 t/y
5 t/y
Advanced-Flow™ Reactor Technologies 5.
© 2017 Corning Incorporated ..
Chemistry Types Applicable in AFR:Successfully tested more than 600 Chemistries Globally
HalogenationChlorinationBrominationFluorination
Hydrogenation
Low temperatures De-hydrogenHalogen exchange
Friedel–Crafts Friedel–Crafts acylationFriedel–Crafts Alkylation
Hydrogenation Reduction of nitro groupReduction of doule boundReduction of triple boundReduction of chloro group
De protection
NitrationNitration of alcoholNitration of amine
Nitration of Aromatic compounds
Nitrosation of alcohol
OxidationOxide double bond to alcohol
Oxide methene to carbonyl group
Oxide phenol to quinoneoxide acid or alcohol to peroxide
Others
Suzuki couplingHofmann degradation and rearrangement
AzideTo form diazomethane
To form diazo saltGrignard
Advanced-Flow™ Reactor Technologies 6.
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Selective Hydrogenation of Slurry Catalyst98%+ conversion & selectivity (impurity profiles within spec)
• highly exothermic (>400 kJ/mol)• 30 µm catalyst in slurry • significant catalyst reduction
-100.00
-80.00
-60.00
-40.00
-20.00
0.00 20.00 40.00 60.00 80.00 100.00
cat %
T
Conc%
Time
AFRBatch
Excellent G/L Mixing
Ref: Chemistry Today • Vol 27 n 6 / November-December 2009
30C 140C
0.1%0.4%
45%wt35%wt
90s10h
Batch Corning® AFR
Advanced-Flow™ Reactor Technologies 7.
© 2017 Corning Incorporated ..
HT Devices
Specific Area
S/V (m2/m3)
Global Heat Transfer Coeff.
U (W/m2.K)
U (S/V)
(kW/m3K)
Jacketed batch 2.5 400 1
Batch with external heat exchanger 10 1000 10
Shell and tubes (metallic; water/water; 1 m/s)
400 500 200
Metallic plates (4 mm spaced; water/water, 1 m/s)
800 1563 1250
Corning glass fluidic modules (water/water, ~ 0.7 m/s)
2500 680 1700
-D. Lavric, Proceedings of the Heat Transfer & Fluid Flow in Microscale III Conference (2008)-Z. Anxionnaz et al Chem Eng. & Process. 47, 2029 (2008)
Good Heat ExchangeHeat Transfer Performance in Different HT Devices
Advanced-Flow™ Reactor Technologies 8.
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Corning AFR vs. Tube Reactor: Excellent mixing matters
Tube Reactor
Corning AFR (LF-7FM)
1.2 eq bleach, 0.2%mol TEMPO
K2HPO4, CH2Cl2-H2O, pH=8, 20°C
Perfect emulsion
Immiscible slugsOrganic-Aqueous immiscible mixture phases
Advanced-Flow™ Reactor Technologies 9.
© 2017 Corning Incorporated ..
AFR™ Offers Superior G-L, L-L Mass Transfer Performance with Much Lower Energy Consumption (or Pressure-Drops)
Corning AFR
Volu
met
ric m
ass t
rans
fer c
oeffi
cien
t
Volu
met
ric m
ass t
rans
fer c
oeffi
cien
t
Bioreactor
Gas-inducing impellersMechanically agitated contactor
Bubble column
Static mixer
Agitated contactor
Corning AFR
Batch reactor
Capillary microchannel
L-L System: Ind. Eng. Chem. Res., 2012, 51 (50), pp 16251–16262G-L System: Ind. Eng. Chem. Res., 2013, 52 (26), pp 8996–9010
María José Nieves-Remacha,† Amol A. Kulkarni,†,‡ and Klavs F. Jensen; “Gas Liquid Flow and Mass Transfer in an Advanced-Flow Reactor”, Ind. Eng. Chem. Res. 2013, 52, 8996 9010María José Nieves-Remacha,† Amol A. Kulkarni,‡ and Klavs F. Jensen:” Hydrodynamics of Liquid Liquid Dispersion in an Advanced-Flow Reactor”, Ind. Eng. Chem. Res. 2012, 51(50), 16251-16262
Advanced-Flow™ Reactor Technologies 10.
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Green Process Development using Corning AFR
A + B HATPethyl acetate
10~15oC
Expt B/A (Mol.ratio)
A flowrate(ml/min)
B flowrate(ml/min)
T(oC) Yield% HATP Content (%)
UsingSolvent
AFR 1.02 28 19.5 15 ~100 97.8 (no separation need) noBatch 1.10 Stirred for 7-9 hours 10-15 67-75 85 (after distillation 97) yes
Batch Process Challenges: Making 1kg targeted product (HATP), has to use 3 kg solvent (got 2.14kg solvent recycled), also produces 5.36kg waste-water, 0.93kg waste organics
Ref: Modern Chemical Industry, No. 3 (2012), p71-75 –in Chinese
Advanced-Flow™ Reactor Technologies 11.
© 2017 Corning Incorporated ..
Flow Chemistry Helped Deliver Green Continuous Process: Eliminated solvent use & extraction, distillation etc steps
HATP Batch AFR
Yield 67%-75% Quantitative Yield
Purity >97.0% >97.0%
B/A Molar Ratio 1.10 1.02
Production Stability
The quality varies by batch
Stable
Solvent Yes No
Waste Water Yes No
Energy Use Distillation Min to control Temp
Process
ExtractionConcentration
DryingFractional Distillation
No. Pump off volatile
30t/y CMO production in Laviana China (2012)
Courtesy of Laviana
Courtesy of Laviana
Advanced-Flow™ Reactor Technologies 12.
© 2017 Corning Incorporated ..
Continuous Manufacturing of API Intermediate in cGMP Plant–Medichem (Spain) Dr. Ester Masllorens
2012Homemade
July 2013 G1
Dec 2013 G4
Advanced-Flow™ Reactor Technologies 13.
© 2017 Corning Incorporated ..
FDA’s QbD Initiative
Implying current regulatory environment is in favor of continuous flow process
• Enables continuous process parameter design based on scientific principles
• Incorporates PAT monitoring tools
• Standardizes operating conditions for scale up
• Maintains operating conditions for high quality output
• Enables for continuous yield and quality
• improvement through process optimization
Advanced-Flow™ Reactor Technologies 14.
© 2017 Corning Incorporated ..
Operation Cost
Comparison
CapexInvestmentComparison
Opex reduced 34%Solvent down 70%Lab cost down 60%Waste water down 30%Water down 30%Organic SM down 20%
Capex reduced 28%Equipment up 8 timesBuilding down 88%Facility down 65%Tubes, DCS down 60%Storages down 50%
Project background: Nitration plant(400 ton Product/year, 2400 ton Fluid/year
Corning AFR helped nitration plant save total investment 30%
0
5,000,000
10,000,000
15,000,000
20,000,000
25,000,000
30,000,000
Batch AFR
Capex Batch/AFR = 100 : 72
0
10
20
30
40
50
60
Batch AFRCost Batch/AFR = 100 66
Advanced-Flow™ Reactor Technologies 15.
© 2017 Corning Incorporated ..
Corning Incorporated - USAFounded: 1851
Headquarters: Corning, New York
Employees: ~34,800 worldwide
2015 Sales: $9.8 Billions
US Fortune 500 Rank (2015): 297
Corning is the world leader in specialty glass and ceramics
Corning Reactor Technologies: Program started 2002, Commercial started 2006
Business Headquarters: Fontainebleau, France
Provide innovative Corning® Advanced-Flow™ Reactor (AFR) products and full engineering services for
Pharma ChemicalsFine ChemicalsSpecialty ChemicalsBase ChemicalsAgro ChemicalsPetro Chemicals
Corning European TechnologyCenter (CETC), FranceCorning New York, USA
Advanced-Flow™ Reactor Technologies 16.
© 2017 Corning Incorporated ..
The Patent Scorecard™ ranks corporate innovation using a series of metrics to determine patent quality, technological strength, and breadth of impact.
Research and DevelopmentCorning’s Patent Portfolio First Among Top Technology Firms
2014 Patent Scorecard™ Category: Industrial Materials
Source: The Patent Board™ as of 5/16/2014
Previous Qtr Rank
Current Rank Company
Patents Granted
Science Strength™
Innovation Cycle Time™
Industry Impact™
Technology Strength™
Research Intensity™
1 1 Corning Incorporated 356 2600 11.7 1.64 404.34 1.83
2 2 Valinge Innovation AB 27 0 16.4 12.56 236.97 0.22
3 3 Compagnie de Saint-Gobain 202 378.8 16.5 0.92 128.94 1.21
4 4 Guardian Industries Corp. 81 286.5 10.1 2.13 119.68 1.88
6 5 Graphic Packaging Holding Co. 56 0 19.8 1.94 75.22 0
5 6 Kobe Steel Ltd 87 30 10 1.11 67.27 0.64
16 7 Reynolds Group Holdings Ltd 48 2.3 20.5 1.88 62.82 0.15
7 8 Prysmian SpA 24 151 10.4 3.62 60.79 2.07
9 9 Fujikura Ltd 103 98 11.8 0.79 56.09 0.95
12 10 NGK Insulators Ltd 143 43 13.7 0.55 53.87 0.74
Advanced-Flow™ Reactor Technologies 17.
© 2017 Corning Incorporated ..
Corning AFR Technology: 15 Year Innovation
2010 2011 2012
G4 Oxidation Industrial
Trial (China)
G3 Reactor Launch
Entering ChinaCorning India Joint Lab
G3 Installation in Shandong
G4 SiC Launch
Corning-CZU Joint Lab
2002-2006Tech Develop..
2007-2009EMEA
Develop..
2010-2012Asia Develop..
2013->Growth in
Asia
2002 2003 2004 2005 2006
G1 product launch
Flow Module Development
CRTC (China) Opening
2013
G4 Industrial Commission
2014
G1 Photo Reactor Launch
G4 Trial in Europe
Corning Certified Reactor Application Lab
20092007 2008
DSM-G2 X12 commission
LFR Launch
MIT Collaboration
2002: AFR development started at CETC in France
2015Commercial Installations
in IndiaG1 Photo Reactor2000 TPA G4 Plant3500 TPA G4 Plant
2016
Advanced-Flow™ Reactor Technologies 18.
© 2017 Corning Incorporated ..
AFR™ technology & manufacturing have received many certificates, and awards in Europe and Asia
TÜV PED Quality Certificate (G4 SiC)ASMEChina SELO A4 (SiC)EU ATEX II 2 G c IIC T4 Certificate (G1, G3)FDA Certificates for compliancesISO 14001
Received 2013 NationalInnovation Award by ChinaPetroleum & ChemicalIndustry Federation CPCIF
Corning's AFR technology receivedthe ‘Best Contribution to Academia’Award at the 2016 India Chemtradeshow
Advanced-Flow™ Reactor Technologies 19.
© 2017 Corning Incorporated ..
Growing list of industry & academic AFR customers*INDIA * Partial list
IIT DelhiNIT Warangal Osmania UniversityJNTU, Hyderabad
Anupam Rasayan India Ltd
Advanced-Flow™ Reactor Technologies 20.
© 2017 Corning Incorporated ..
Growing list of industry & academic AFR customers*
Shandong Brother Tech
* Partial list
HeNan Academy of Sciences
Nanjing Refinery Co., Ltd.
Massachusetts Institute of Technology (MIT)
Advanced-Flow™ Reactor Technologies 21.
© 2017 Corning Incorporated ..
Corning® Advanced-Flow™ Reactor Value Proposition-Revolutionary Improvement vs. the BatchCompared with traditional batch reactor1000 x heat transfer improvement100 x mixing enhancement1/1000 x batch reactor volumeSeamless scale up from lab to production