Innovation Drives Green - industrialgreenchem.com

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)



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



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



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



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



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



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



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



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



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



Continuous Manufacturing of API Intermediate in cGMP Plant–Medichem (Spain) Dr. Ester Masllorens

2012Homemade

July 2013 G1

Dec 2013 G4



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



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



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



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



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



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



Growing list of industry & academic AFR customers*INDIA * Partial list

IIT DelhiNIT Warangal Osmania UniversityJNTU, Hyderabad

Anupam Rasayan India Ltd



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)



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

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Innovation Drives Green - industrialgreenchem.com