CORNING ADVANCED-FLOW™ REACTORS - Traxxys · 2019. 1. 31. · Daniela Lavric Corning Reactor...

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


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


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


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


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


Corning® Advanced-Flow™ Reactors (AFR) Worldwide presence

NA ASIA EUROPE

SA

AFRICA

China India

S. Korea USA


Corning® Advanced-Flow™ Reactors

Offer broad capability from feasibility to

production and enable the transition

from batch to continuous processes


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


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)


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


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


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)


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


20 g/min toluene-20g/min water 40 g/min toluene-40g/min water

Fluidic Module Performances Hydrodynamics in immiscible fluids: Toluene-Water


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


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)


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


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).


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


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


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)


Corning® Advanced-Flow™ Reactors

Minimize scale-up failures and drastically reduce

the time from laboratory to production

Applications


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


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)


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


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)


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


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)

http://www.uk-cpi.com/index.html


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


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


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


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


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

http://www.jaas.co.jp/index.html



http://www.abachem.com/cn/index/


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


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

[email protected]

Acknowledgements

for making this presentation possible


THANK YOU FOR YOUR ATTENTION

CORNING ADVANCED-FLOW™ REACTORS - Traxxys · 2019. 1. 31. · Daniela Lavric Corning Reactor...

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Transcript of CORNING ADVANCED-FLOW™ REACTORS - Traxxys · 2019. 1. 31. · Daniela Lavric Corning Reactor...