Novel Process Windows

V. Hessel [email protected]

1 Institut für Mikrotechnik Mainz GmbHDirectorate Chemical Milli and Micro Process Technologies

2 Eindhoven University of TechnologyDepartment of Chemical Engineering and Chemistry

3 Technische Universität DarmstadtTechnische Chemie / Cluster of Excellence Smart Interfaces

Limburg Horhausen Mainz Eindhoven Darmstadt

March 22th, 2011CPAC Satellite Workshop, Rome / Italy

Novel Process Windows

- Gates to Intensified Flow Chemistry

GATEWAYS STAND FOR OPENNESSAND ENTRANCE INTO NEW WORLDS

Miyajima Torii – Miyajima Island, next to Hiroshima

Torii is commonly found at the entrance or within a Shinto shrine, where it symbolically marks the transition from the profane to the sacred

RESEARCH vs DEVELOPMENT

Top-Down

Enabling technologies

Business, Environment

Bottom-up

University research(ERC Advanced Grant,Cluster of Excellence)

New processing/Microfluidics

Catalysts/Reactors

Systems/Scale-up

Processes/Products

Applied research

Large-scale project coordination

‘Net-Present-Value’

‘Selectivity’

FABRICATIONCATALYSTS

REACTORS

PLANTS

PROCESSESOH

OH

OH

OH

COOHKHCO3 (aq)OH

OH

OH

OH

COOHKHCO3 (aq)

Aristotle (Αριστο τέλη ς; Aristoteles) (384 BC – 7 March 322 BC)

“The whole is more than the sum of its parts" – from Metaphysics 1041 b (VII 17, 1041b)“With regard to excellence, it is not enough to know, but we must try to have and use it.”

FULL-CHAIN, ALL-EMBRACING VIEWS IN ENGINEERING

Process Chemist’s View

High Level Group on the competitiveness of the European chemicals industry, 2009, Final Report: European Chemical Industry, Enabler of a Sustainable Future, European Communities

ROADMAP TO FUTURE CHEMICAL INDUSTRY

“In the next 20 years, these processes will undergo

substantial changes thanks to the smart design of the

synthetic route itself, micro process technologies,

integration and intensification of processes

combined with new catalyst concepts and the

development of in silico technologies”

(High Level Group, 2009)

CONTENTS

• Novel Process Windows (NPW) at selectivity-sensitive reactions

• NPW at multi-phase reactions – role of microfluidics

• Combined PI efforts – MW / conti / smart catalysts

• ERC Advanced Grant on NPW and new group at TU/e centering in NPW

• Outlook: NPW for material synthesis & process self-optimisation

COPIRIDE – One Page White Paper

• Epoxidation (Mythen; U Naples)

• Biodiesel production (Chemtex; Polito)

• Ammonia production (ITI Energy; U New castle)

• Polymer reaction 1 (Evonik-Degussa; U Stuttgart)

• Polymer reaction 2 (Evonik-Degussa)

• Sugar hydrogenation (Åbo Akademi)

Process Intensification Criteria

All-embracing, full-chain ‚Future Factory‘ approach, headed by industrial drivers

Modular plants: Container Flow Chemistry and Novel Process Windows

Enabling Technologies

COPIRIDE Plant & Process Innovations

Industrial Guidance / Commitment and Ex-Ante Cost & LCA Evaluation

Ex-Ante Evaluation: Cost & Life-Cycle Analysis

Top-Down

SustainabilityCompetitiveness of European Industries

Side product formation, Catalyst recovery, Productivity, Safety, Catalyst switch, Reactant consumption, Digestion time, Productivity, CO2

emissions, Capital costs, Plant operating costs, Plant volume, Space-time yield, Product properties, Feed ratios, Process integration

… 50% reduction, 5fold increase, CO2-neutral ….

V. Hessel Chem. Eng. Technol. 32, 11 (2009) 1655-1681.

NOVEL PROCESS WINDOWS

German NPW Research Cluster: 7 projects

ERC Advanced Grant NPW

V. Hessel, B. Cortese, M.H.J.M. de Croon Chem. Eng. Sci. (2010) available online.

NOVEL PROCESS WINDOWS EXTEND MUCH THE OPERATIONAL POSSIBILITIES

T. Razzaq, C. O. Kappe, Chem. Asian J. 5, 6, 1274-128.

Other reviews

M. Damm, T. N. Glasnov, C. O. Kappe, Translating High-Tempera-ture Microwave Chemistry to Scalable Continuous Flow Processes, Org. Process Res. Dev.14 (2010) 215-224.

T. Razzaq, T. N. Glasnov, C. O. Kappe, Continuous-flow micro-reactor chemistry under high-temperature/pressure conditions, European J. Org. Chem. (2010) 1321-1325.

T. Razzaq, T. N. Glasnov, C. O. Kappe, Accessing Novel Process Windows in a high<temperatur/ pressure capillary flow reactor, Chem. Eng. Technol. 32, 11 (2009) 1–16.

2010 EXAMPLES FOR SUPERHEATED µ-PROCESSING (‘high T,P’)

High-T, high-p processing

B. Gutmann, J.-P. Roduit, D. Roberge, C. Oliver Kappe“Synthesis of 5-substituted 1H-tetrazoles from nitriles and hydrazoic acid by using a safe

and scalable high-temperature microreactor approach”Angew. Chem. 122 (2010) 7255 –7259

J. F. Ng, Y. Nie, G. K. Chuah, S. Jaenicke“A wall-coated catalytic capillary microreactor for the direct formation of hydrogen

peroxide”J. Catalysis 269 (2010) 302–308

T. Razzaq, T. N. Glasnov and C. O. Kappe “Accessing Novel Process Windows in a high-temperature/pressure capillary flow reactor”

Chem. Eng. Technol.32, 11 (2009) 1702–1716

H. Kawanami, M. Sato, M. Chatterjee, N. Otabe, T. Tuji, Y. Ikushima, TakayukiIshizaka, T. Yokoyama, T. M.Suzuki

“Highly selective non-catalytic Claisen rearrangement in a high-pressure and high-temperature water microreaction system”

Chem. Eng. J. (2011) online

M. W. Bedore, Nikolay Zaborenko, K. F. Jensen, T. F. Jamison“Aminolysis of epoxides in a microreactor system: A continuous flow approach to b-amino

alcohols”

Org. Process Res. Dev. 14 (2010) 432–440

L. Kong, X. Lv, Qi Lin, X. Liu, Y. Zhou, Y. Jia“Efficient synthesis of imidazoles from aldehydes and 1,2-diketones under superheating

conditions by using a continuous flow microreactor system under pressure”

Org. Process Res. Dev. 14, 4 (2010) 902–904

N. Zaborenko, M. W. Bedore, T. F. Jamison, K. F. Jensen “Kinetic and scale-up investigations of epoxide aminolysis in microreactors at hightemperatures and pressures”

Org. Process Res. Dev. 15, 1 (2011) 131–139

S. Marre, A. Adamo, S. Basak, C. Aymonier, K. F. Jensen“Design and packaging of microreactors for high pressure and high temperature

Applications”

Ind. Eng. Chem. Res. 49, 22 (2010) 11310–11320

PROCESS INTENSIFICATION: INCREASE IN SPACE-TIME YIELD BY HIGH-p,T PROCESSING

V. Hessel, C. Hofmann, P. Löb, J. Löhndorf, et al. Org. Proc. Res. Dev. 9, 4 (2005) 479-489.V. Hessel, U. Krtschil, P. Löb, A. Stark, et al. Org. Proc. Res. Dev. 13, 5 (2009) 970-982.U. Krtschil, V. Hessel, A. Stark, D. Reinhard Chem. Eng. Technol. 32, 11 (2009) 1774-1789.

àReaction time reduction at best up to 2000 times; increase in space-time yield by factor 3200

4 t / a

64200 kg/(m³ h)

4 s

Flow chem (9 ml)

Batch (1 l)

2 h – 7200 s

20 kg/(m³ h)

1 t / aat high temperatures and for longer residence times:ð minor variation in yield

at high temperatures and for longer residence times:ð minor variation in yield



ð substantial increase in selectivity




Capillary reactor, O.D. 1/8 inch 35 bar

0

5

10

15

20

25

30

35

40

45

0,0000 0,0100 0,0200 0,0300 0,0400 0,0500 0,0600 0,0700 0,0800 0,0900

Residence time [s] (reciprocal)

Yie

ld2

,4-D

HB

A a

nd

2,6

-DH

BA

[%

] ((

2,4-DHBA, 160°C2,4-DHBA, 180°C2,4-DHBA, 200°C

2,6-DHBA, 160°C2,6-DHBA, 180°C2,6-DHBA, 200°C

130385 33 25 20 17 1113

1

65

O OH

OH

OH

rearrangement

DT

O

OHOH

OHDT

OH

OH

+ CO2

2,4-Dihydroxybenzoic acid 2,6-Dihydroxybenzoic acid Resorcinol

SYNTHESIS OF 3-CHLORO-2-HYDROXYPROPYL PIVALOATE

OO

Cl Cl

O O

ClOH

O O

Cl

OH

48 h for batch operation: high conversions + 60% yield

Similar yields at 180– 200ºC for 5-10 min

by superheated continuous processingAt 30 s - 240-fold reduction

M. Escribà, V. Hessel, J. Eras, R. Canela, S. Rothstock, P. Löb, Green Chemistry (2011) in press.

0102030405060708090

100

180 190 200 210 220 230 240

Temperature [°C]

Co

nv

ers

ion

, Y

ield

[%

] Conversion

Yield (Monoproduct)

Yield (Diproduct)

Residence time = 20'

0

10

20

30

40

50

60

70

80

90

100

200 210 220 230 240 250 260

Temperature [°C]

Co

nv

ers

ion

, S

ele

cti

vit

y [

%] Conversion

Selectivity (Monoproduct)

Selectivity (Diproduct)

Residence time = 30''

NOVEL PROCESS WINDOWS FOR THE SYNTHESIS OF 3-CHLORO-2-HYDROXYPROPYL PIVALOATE


0

20

40

60

80

0 500 1000 1500 2000 2500 3000 350080

100120140160180200220240260

Yie

ld (%

)

t (min)

T (

ºC)

Continous processBatch process

0

20

40

60

80

0

1000

2000

3000

80120

160200

240


OO

Cl Cl

O O

ClOH

O O

Cl

OH

NOVEL PROCESS WINDOWS FOR THE SYNTHESIS OF 3-CHLORO-2-HYDROXYPROPYL PIVALOATE


OO

Cl Cl

O O

ClOH

O O

Cl

OH


ProcessNet – Jahrestagung 2010 / 21-23 Sept. Seite [email protected]

SYNTHESIS of tert.-BUTYLPEROXYPIVALAT IN GENERAL

1st Stage: Deprotonation of tert.-Butylhydroperoxide to Potassium tert.-butylperoxide

? DTad = 25 K ( slightly exothermic)

? Single phase reaction

2nd Stage: Formation of tert.-Butylperoxypivalate

? DTad = 72 K (exothermic)

? Temperature sensitive

+ KOHaq CH3

CH3

CH3

O

O-

K+

CH3

CH3

CH3

O

OH

CH3

CH3

CH3

O

O-

K+

+CH3

CH3

CH3O

Cl

CH3

CH3

CH3O

O

O

CH3

CH3

CH3

? Biphasic reaction ? Corrosive


POTASSIUM tert.-BUTYLPEROXIDE - FROM BATCH TO CONTINUOUS PROCESSING

0

10

20

30

40

50

60

70

80

90

100

Continuous- modet=0.4 s

Continuous- modet=4 s

Me

an

co

nve

rsio

n a

nd

me

an

yie

ld / %

Mean conversion tert.-butyl hydroperoxide Mean conversion pivaloyl chloride Mean yield tert.-butyl peroxypivalate

Batch - modet=1200 s

TBHP

KOH

22.7%

PIVCl

mixer 1mixer 2

TIR

TIR

PI

TIRPI

C l

O

O

O

O

O

O H

5mL/min

3.1mL/min

2.2mL/min

CH3

CH3

CH3

O

O-

K+

? Reaction temperature 20 – 25 °C

? Flow rate 8.1 mL/min

? Reduction of reaction time to 0.4 s shows similar performance as in batch mode

Successful transfer into continuous mode[1] T. Illg et al., ChemSusChem, 2011, 4, 392-398


[1] T. Illg et al., ChemSusChem, 2011, 4, 392-398[2] T. Illg et al., Chem. Eng. J., 2011,167, 504-509[3] T. Illg et al., in Proc. IMRET-11; Editors: -, Kyoto, Japan, 2010

tert.-BUTYLPEROXIPIVALATE – CONTINUOUS PROCESSING USING ORIFICES AS EMULSIFICATION UNITS

KOH22.7wt%

TBHP

PIVCl

mixer 1mixer 2

Orifice 1ID 0.25mm

Orifice 2ID 0.25mm

Orifice 3ID 0.25mm

TIR

TIRPI

PI

Orifice 4ID 0.25mm

Orifice 5ID 0.25mm

0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4 1,6

0

10

20

30

40

50

60

70

80

90

100 Conversion tert.-Butylhydroperoxide Conversion Pivaloylchloride Yield tert.-Butylperoxypivalate

Co

nve

rsio

n a

nd

yie

ld / %

Time / s



? Reaction time (2nd Stage) 1.5 s

Successful transfer into continuous mode using orifices as emulsification units


tert.-BUTYL PEROXIPIVALATE SYNTHESIS AT INCREASED REACTION TEMPERATURE

10 20 30 40 50

0

10

20

30

40

50

60

70

80

90

100 Conversion tert.-Butylhydroperoxide Conversion Pivaloylchloride Yield tert.-Butylperoxypivalate

Co

nve

rsio

n a

nd

yie

ld / %

Reaction temperature / °C


for both steps


? Reaction time (2nd Stage) 1.5 s

? No negative impact of reaction temperature 30 – 50 °C due to short impact

Using micro reactor technology will lead to a more flexible process control compared to high volume batch systems.


ORIFICE CONCEPT - BENCHMARK

[4] Azzawi et al. Method for the production of organic peroxide by means of micro reaction technique, US20090043122, 2009

? 9 Orifices

? 10x52 cm Loops

? RT: 40°C

? YTBPP: 78%

? t: 15 s

? STY: 55600 g/Lh

Micro reactor process [4]

? RT: 10 - 20°C

? YTBPP: 93 % bei ~6 min

? STY: 3600 g/Lh (-10 - 20°C)

3 x 350 L Cascaded batch [4]

? RT: 10 - 20 °C

? YTBPP: 84% bei ~100 min

? STY: 190 g/Lh (8 - 20°C)

? 9 Orifices

? 10x5 cm Loops

? RT: 40°C

? YTBPP: 64%

? t: 1.5 s

? STY: 469000 g/Lh

Reactor length Temperature controlCombination

Optimum design

PAGE 20

ANNULAR BUBBLY

PARALLEL SLUG

f (flow, flow ratio, diameter, length, ∆P, T, fluid properties, wall wetting properties)

Flow patterns

PhD Jovanonic

PAGE 21

ANNULAR BUBBLY

PARALLEL SLUG

Flow ratio

Slug flow:

5000 m2/m3

40000 m2/m3

Flow rate

80000 m2/m3

180000 m2/m3

Bubbly flow:

ml/min range > l/min range

Flow patterns: Fluidic control

PhD Jovanonic

PAGE 22

Reaction time of 10 min

Controlling the slug size : Conversion and Selectivity control

Fluidic control of phase transfer catalysis

Decoupling of kinetics and mass transfer

Fast kinetic screening

Selective synthesis

PhD Jovanonic

PAGE 23

∆Ptotal = ∆Pdispersed + ∆Pinterface + ∆Pcontinous

∆Ptotal ~ 1/D2

D < 300 µm:

∆Pinterface is > 50 % of ∆Ptotal

Flow in porous media: Surface tension

∆Pinterface

Resistance to flow

∆Pdispersed ∆Pcontinous∆Pinterface

D

Pressure drop

PhD Jovanonic

PAGE 24

Process characteristics Conventional PTC Microprocess PTC

Yield, % 90 99

Reaction time 3 h 1 min

Temperature <85 °C 105 °C

Base NaOH, KOH none

Solvent Toluene, benzene, chloroform, … none

Post reaction workup Washing + distillation Washing

98.8 % selectivity

“Green” process, no bases, no solvents, no distillation

Pilot plant: 1-10 t/year

up to 250,000 m2/m3

Scale-up using interdigital mixer

PhD Jovanonic

0

1

2

3

4

5

6

7

8

0.005 0.050 0.500 5.000

Oxi

ran

en

um

be

r

Time (minutes)

N.E. = f(t,T)

30

60

90

120

150

180

210

240

270

Time [min]

Micro process technology – 2h à ~10min

Novel Process Windows – 10 min à 300 ms

Temperature [°C]8

7

6

5

4

3

2

1

0 0.005 (0.3 s) 0.050 (3 s) 0.50 (30s)

Soybean Oil Epoxidation: Potential of Superheated Micro Processing

‘Single phase’ modeling – mass transfer limitations will give longer reaction times

30

60

90

120

150

180

210

240 270

H2O2 + HCOOHH

+

HCOOOH + H2O

H2O2 H2 + 0.5 O2

+ Nu R1

OH

Nu

R2

O

R1 R2

+ H2O2 R1

OH

OOH

R2

O

R1 R2

R1 R2 + HCOOOH R1

OR2

H2O2 H2 + 0.5 O2

+ Nu R1

OH

Nu

R2

O

R1 R2

+ H2O2 R1

OH

OOH

R2

O

R1 R2

R1 R2 + HCOOOH R1

OR2R1 R2 + HCOOOH R1

OR2

Gan, Goh, Ool, JAOCS69, 4 (1992) 347-351

Oxir

an

e n

um

ber

[a.u

.]


Soybean Oil Epoxidation- Heat Releases and Cascaded Reactor Design

Single-Stage (150°C)

Multi-Stage (100, 120, 160°C)

Yield

Yield

Temperature

Temperature

Micro heat exchanger, 4000 W/m2 K


Evotrainer, container plant – ‘Future Factory’

Option for automatic filling

Raw material logitics transport

can

Option for air conditioning

Desaster collection pan (WHG)

Element for environmental

protection

Control room

Ex zone gate

Extinguishing installation

Constructive fire protectionReduced emissionse.g. nois

Bus integration: a) lightingb) Ex controlc) cabel ways, powerd) Pneumatic systeme) Field busf) compressed air, gasesg) cooling water, soleh) local area networki) air ventilationj) etc.

* Easy entry* integrated emergency exits* montage doors

integrated elements for construction

On demand CMP- a./o. clean room condition

Modular measure and control technology

Patent pending

Think big @ plant invest is one option

Großinvestition (4 Mio €) versus verteilte Investition (4*1,2 Mio €)

-10.000

0

10.000

20.000

30.000

Periodennummer

Periode

T-E

UR

-2.000

-1.000

0

1.000

2.000

3.000

4.000

5.000

Periode

T-E

UR

Investitionssumme ohne Bauzeitzinsen 4 Mio € Investitionssumme ohne Bauzeitzinsen 4,8 Mio € vert.

kumuliert abgezinster Cash Flow 4 Mio € kumuliert abgezinster Cash Flow 4,8 Mio € vert.

Result: big plants are not the best option!

One big plant (4 Mio €) versus 4 small, time shifted plants (4*1,2 Mio €)Cash-flow calculation

MICROWAVE-MICROREACTOR (‚µ2‘) OPERATION – ULLMANN ETHER SYNTHESIS

Metallic Cu 75 µm Traces

Metallic Cu 45 µm 3% yield

Metallic Cu 3 µm 20% yield

Nano Cu 10 nm 80% yield

Benaskar, Engels, Patil, Rebrov, Meuldijk, Hessel, Hulshof, Jefferson, Schouten, Wheatley, Tetrahedron Letters 5, 2 (2010) 248-251.

Engels, Benaskar, Patil, Rebrov, Hessel, Hulshof, Jefferson, Vekemans, Karwal, Schouten, Wheatley, Org. Process Res. Dev. 14, 3 (2010) 644-649.

Engels, Benaskar, Jefferson, Johnson, Wheatley, Dalton Transactions39 (2010) 6496-6502.

J. Org Chem. (2010) submitted.

Nanoparticulate catalyst development

PAGE 30

N

Cl OK

N

O

N

O

N

Cl

+

OKDMA

18-crown-6

Cu/TiO2/SiO2

Single-mode

microwave 140 oC

2) Support synthesisTiO2 deposition on

SiO2-surface

1) Cat-synthesisCu nanoparticle

colloid synthesis

3) Cat depositionNPs impregnation

ZnO and TiO2

4) Reactor packing

5) Reactor testing

Process design for MW-flow Ullmann chemistry

Non-porous TiO2 MesoporousTiO2

Ti K

Ti K

Cu K

Cu K

Ti K

Ti K

Cu K

Cu K

Mesoporous titania much higher Cu loading

F. Benaskar/ TUe

N

Cl OKO

+ 18-crown-6

DMA

PAGE 31

Continuous milli-processing in single mode MW-cavity

Micro-Mixer Micro-HEX

F. Benaskar/ TUe

Fixed-bed milli reactorSingle-mode

cavity

Multi-cavity single-mode microwave

N

Cl OKO

+ 18-crown-6

DMAOil-bath

PAGE 32

Cost-analysis on integrated µ 2-conceptOperating and capital cost

• Division of plant

Raw materials

Waste materials Energy

Personnel

Capital costCatalyst unit

Microwave & micoprocess plant

Post-treatment

Pre-treatment

Catalyst-free chemistry

Cu-catalyzed chemistry

PAGE 33

Cost-analysis on integrated µ 2-conceptProposed scenarios

• Proposal of several scenario studies

• Study parameters• Heating:

• Multimode microwave cavity

• Singlemode microwave multi-cavity

• Electrical heating

• Chemistry:

• Ullmann reaction: Catalyzed process with expensive raw materials

• Aspirin synthesis: Non-catalyzed process with cheap raw materials

• Catalyst:

• Slurry-type catalyst in flow and batch

• Supported catalyst as fixed-bed or wall-coated

PAGE 38

Cost-analysis on integrated µ 2-conceptResults: “Profitability”

• Overall cost results

Homogenous systems: clear go!!

Heterogeneous systems: only adapted systems!!

PAGE 39

• Catalyst performance on initial rates and yields

• Cat-loading most effective for unsupported systems

• Temperature most effective for supported systems

Testing supported Cu-catalyst systems

low

high

low

high0

0.2

0.4

0.6

0.8

1140 oC

120 oC

Iin

itia

lra

tes

(mm

ol*

L-1

*s-1

) Reaction time: 5 min

Cat loadings (mol%) Cu/MP-TiO2 Cu/NW-ZnO Cu/ML-TiO2 CuZn-NPs’

High 0.05 0.001 0.001 0.3

Low 0.2 0.004 0.004 1.2

N

Cl OKO

+ 18-crown-6

DMA

low

high

lowhigh

0

20

40

60

80

100140 oC

120 oC

Yie

ld (

%)

Reaction time: 90 min

F. Benaskar/ TUe

PAGE 40

Supported Cu nanoparticles in microprocessing“Ullmann reaction towards aromatic ethers”

• Development of support film for wall-coated and fixed-bed reactors in microreactors

PAGE 41

CuZn X-ray photoelectron spectroscopy“Zn as oxidative stabilizer”

X-ray Photo-electron and 65Cu-Nuclear Magnetic Resonance spectroscopy provided in parallelan explanation on the role of Zn as promoting metal in Cu-catalyst:

“Sacrificial Anode effect”

Cu(0) state was observed in the presence of the Zn promoter in XPS spectra of the CuZn catalysts after 4 hrs reaction time. After 12 h on-stream the copper was oxidized simultaneous with

decreasing zinc signal, signifying a “sacrificial anode” effect.

1023.3 1020.6 1017.9

C

PS

(a.

u.)

Zn 2p Cu 2p Ti 2p

CuZn/TiO2 12h

CuZn/TiO2 4h

CuZn/TiO2 fresh

Cu/TiO2 12h

Cu/TiO2 4h

Cu/TiO2 fresh

CuZn NP

468 462 456

960 948 936

Binding energy (eV)

Cu NP

PAGE 42

Synchrotron beam-time:“In-situ oxidation behavior of CuZn catalyst”

• Why synchrotron X-ray analysis?• XPS results indicated a “Sacrificial Anode effect”

• Bulk or atomic effect?

• XPS provides only surface information, i.e. less representative for porous systems

• Synchrotron-EXAFS provides atomic-scale crystal environment of catalyst

• What to do now?• Powdered catalyst synthesis :

• Previously only films

• Own reactor cell design

• No ESRF user shares Cell information

• XRD, XPS, TPX and S(TEM) pre-analysis required

PAGE 43

CuZn-XANES“Temperature programmed reduction of CuZn catalyst”

• Results of Cu and Zn XANES edges under H2 flow

• Cu reduction at 200 oC

• Zinc still complicated “metal”

1

2 3

8.96 8.98 9.00 9.02 9.04

3.10

3.15

3.20

3.25

3.30

Inte

nsity (

A.U

.)

Energy (keV)

RT

400 oC

200 oC

Pre-edge peak

9.62 9.64 9.66 9.68 9.70 9.72 9.74

2.20

2.24

2.28

2.32

2.36

Inte

nsity (

A.U

.)

Energy (keV)

RT

400 oC

200 oCCu Zn

44

ERC Advanced Grant 2010 - NPW

Graphic scheme of the project overall view

45

Sub-project 1: Cross Project on Generic Aspects of Novel Process Windows

• Develop a coordinated methodology for identifying, classifying, detailing and evaluating of Novel Process Windows

• Give the frame for the actions in the sub-projects 2-5

• Create a ‘superficial process level’ with extended generic insight

• Create a techno-economic-ecological evaluation of the NPW options –cost and life-cycle analysis (Fig. 1).

Fig. 1Life-cycle analysis of process variants of the Kolbe-Schmitt synthesis [1]

[1] V. Hessel, D. Kralisch, et al., Energy Environ. Sci., 1, pp. 467-478 (2008)

46

Sub-project 2: New Direct or Integrated Chemical Transformations

Fig. 2 The reaction pathway for the direct oxidation of cyclohexene to adipic acid with aqueous H2O2

[2]

2. Develop a one-flow multi-step route for Click chemistry

1. Investigate a direct oxidation route (see Fig. 2)

Fig. 3 “Sharpless-type click reaction” – Triazole [3]

[2] K. Sato, M. Aoki, et al., Science, 281, pp. 1646 (1998)[3] H. C. Kolb, M. G. Finn, et al., Angew. Chem. Intern. Ed., 40(11), pp. 2004-2021 (2001)

47

Sub-project 3: Boosting Reactivity at High-Temperature / High-Pressure

• Speeding-up can be easily done at the microscale by using capillaries and HPLC pumps (Fig. 4)

Fig. 4 Schematic high-temperature/pressure capillary flow reactor [4]

• Perform organic reactions under much higher temperature and high pressure .

Fig. 5 Claisen rearrangement [5]

• Claisen rearrangement (Fig. 5): Experimental study on selectivity effects, stereo-and regioselectivity effects, solvents effects, catalysts effects and pressure effects; thorough kinetic study.

[4] T. Razzaq, T. N. Glasnov, et al., Chem. Eng. Technol., 32(11), pp. 1702–1716 (2009)[5] L. Abraham, R. Czerwonka, et al., Angew. Chem. Int. Ed., 40(24), pp. 4700-4703 (2001)

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Sub-project 4:Innovative Reaction Environments

• Reduce the amount of solvent for a given process, to yield solvent-less operation, down to zero-solvent loads, solvent-free operation.• Supercritical fluids, being transient between gas and liquid state, have physical properties favourable for the reaction kinetics (Fig. 6)• Supercritical processing, in particular via the addition of carbon dioxide, will be used to have improved control of rates and selectivity in chemical reactions. Hydroformylation will be chosen (Fig. 7).

Fig. 6 [6] Supported ionic liquid catalysis used in the hydroformylation reaction of 1-hexene to form n,i-heptanal

Fig. 7 Hydroformylation [7].

[6] C. P. Mehnert, R. A. Cook, et al., J. Am. Chem. Soc., 124, pp. 12932-12933 (2002)[7]Cornils, Herrmann, Rasch, Angew. Chem. Int. Ed. 33, pp. 2144 (1994)

49

Sub-project 5:Process Simplification and Integration

• Provide a systematic experimental and theoretic investigation on the simplification of the downstream purification through increasing selectivity by microstructured reactors.

• Compare the performance of the three-step chain of reaction-distillation/extraction-filtration to that of the reduction to two steps, reaction-filtration.

• The reactions in projects 2 and 4 will be considered, and this project will build bridges to these two projects.

Figure 8 Hydroformylation process flow sheet for n-valeraldehyde [8]

[8] N. Harris, A. J. Dennis, et al., US patent 4287370 (1981)

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Volker Hessel’s new group in TU/e

Dr. Q. Wang, Postdoc

Dr. L. Protasova, Postdoc

Ing. Tobias Illg, Ph.D student

MSc. B. Cortese, Ph.D student

MSc. I. Dencic, Ph.D student

MSc. C. A. Sanchez Pedraza, Ph.D student

4 new recruited Ph.D students, N.N. starting > April 1st

Associate professor, N.N.

51

Process Technology in TU/evSix professorsvThree of them – awarded ERC Advanced GrantsvOne of them – awarded ERC Starting Grant

FSFSI SSFSI

Ascorbic acid, PVA, mass ratio polymer/Au 10

FSFSIF: Fast mixing – high flow rateS: Slow reducer ascorbic acidF: Fast particle growth -assumed S: Slow diffusion - long-chain PVA I: Intense binding – PVA

Mixing: low to high flow rateReducer: ascorbic acid to NaBH4

Particle growth: not impacted Stabilization: PVP; PVA

mix

ing

mix

ing

M. Luty-Blocho, F. Fizner, V. Hessel, P. Löb, M. Maskos, Chem. Eng. J. (2010) submitted.

GOLD NANOPARTICLES THROUGH ASCORBIC ACID REDUCTION

A) Mixing

- slow (S) / fast (F) --- Flow rate (mixing quality)

B) Nucleation

- slow (S) / fast (F) --- Chemicals; temperature; concentration / ratio

C) Particle growth

- slow (S) / fast (F) --- impact unclear

D) Particle stabilization

- slow (S) / fast (F) --- Flow rate; chain length, temperature- intense (I) / weak (W) --- chain length; chemicals;

concentration / ratio

FFFSI, SSFSI, FFFSW, …

Vision: Integrated device with sequential units

A B C D ?

A, B

C, D

Image taken from Prof. Köhler,Handbook of Micro Process Technology

NOVEL PROCESS WINDOWS AND INTEGRATED REACTOR DESIGN … TO MATERIAL SCIENCE

Self-Optimising Reaction Systems (1)

McMullen, Jensen et al. Angew. Chem. Int. Ed. 49 (2010) 7076 –7080McMullen, Jensen et al. Org. Process Res. Dev. 14, 5 (2010) 1169–1176

Reactor System

Process Control (New FP7 topic)

Lab Self-Optimisation

Scale-out

Standardisation(New FP8 topic)

Self-Optimising Reaction Systems (2)

Rasheed, Wirth Angew. Chem. Int. Ed. 50 (2010) 357 – 358

Process windows in time and temperature

Documents

Novel Process Windows