Micro-Reactor developments Céline GUERMEUR Corning SAS CPAC SATELLITE WORKSHOPS 2007 Micro-reactors and Micro-Analytical – March 19-21, 2007

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%


Detailed reactor

engineering


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


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


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


Detailed reactor

engineering


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


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


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


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


A

B

Product

18Corning

Mass transfer

Heat transfer

Heat transfer

Mass and heat transfer are combined


19Corning

Optimum heat exchange

Reaction circuit: Toluene

Heat exchange circuit: Water

600 W/m2.K


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

Documents

Micro-Reactor developments Céline GUERMEUR Corning SAS CPAC SATELLITE WORKSHOPS 2007 Micro-reactors and Micro-Analytical – March 19-21, 2007