CERC3 „Brainstorming“ Meeting

Chemistry in Support of Sustainability

November 23 – November 25, 2001 Leibnizhaus, Hannover, Germany

2

List of Abstracts page Chris Adams An Industrial Perspective of Opportunities for 7 Catalysis in Sustainable Chemical Technology

J. Schoonman Advanced Deposition Techniques for Systems for 8 Conversion and Storage of Sustainable Energy

C. Vinckier New Cleaning Concepts in the Fabrication 9

Pierre Gallezot Catalytic Conversion of Renewable Resources 10

Riitta Keiski Environmental Catalysis - A Tool for Sustainability 11 of Integrated Circuits (IC’s)

Hans-Günther Schmalz Solid Phase Synthesis and Screening of New Modular 13 Ligands for Transition Metal Catalysis

Claude de Bellefont Application of high throughput experimentation, 14 parallel testing and combinatorial techniques to catalysis in support of sustainability

Peter Behrens Mesoporous and Macroporous Silicas 16 with Ordered Pore Structures as Supports

Michel Che The Functionalization of Oxides by Transition Metal 17 Complexes

Ulrich Kunz Development of Polymer/Carrier Composites 18 for Chemical Processes

Rainer Haag Dendritic Polymers as High-loading 19 Supports for Synthesis and Catalysis

Marc J. Ledoux The Use of Nanostructured Supports in Catalysis 20

Francois Cansell Supercritical Fluid Processing for 10 Chemistry in Support of Sustainability

C. Oliver Kappe The application of microwave dielectric heating 22 in high-speed organic and combinatorial chemistry

Ken. R. Seddon Ionic Liquids for Greeen Industrial Chemistry 23

Michel Vaultier New Applications of Ionic Resins and 24 Ionic Liquids in Organic Synthesis

Albert Renken Microstructured Reactors: Novel Approaches 25 for Heterogeneous Catalytic Reactions

Andreas Kirschning Polymer-Assisted Solution Phase Synthesis 26 with Novel Flowthrough Reactors

Michael Matlosz Microstructures for SMART Reactors: 29 Precision Performance in Industrial Production

Jacob A. Moulijn Structured Reactors, a Contribution 38 to Process Intensification Alle Bruggink Integration of biosynthesis and organic 39 synthesis - A new future for synthesis

Andreas Liese Bio-Inspired Catalysis Increasing Sustainability 41

Michael R. Buchmeiser Functional Supports via Metathesis: 43 Design, Synthesis and Applications Addresses of particiants 45 Map of central Hannover 48

3

Chemistry in Support of Sustainability

1. Introduction

“Sustainability“ has crept into many areas of modern societies. In general it deals with

our responsibility to make sensible and economical use of the earth´s resources that

will allow future generations to live on a livable and resourceful planet. For

successfully achieving long-term technological, environmental and societal

“sustainability” all members and groups of our societies will have to contribute by

making minimum use of irreplaceable natural sources and by providing and

developing new technologies. It is important to note that due to the fact that

„sustainability“ is a very broadly employed term, the various disciplines that need to

contribute to this process are still in the process of defining particularly fields that hold

great promise in this context. The ambiguity of the term “sustainability” is not

necessarily a disadvantage but rather a chance. It is a new challenge as it allows to

set different focus points based on background and interpretation and it sets the stage

for new creative concepts. And chemistry will definitely play a central role in the

pursuit of „sustainability“ as this product-oriented science is present in every

household worldwide.

2. Concepts for chemistry in support for “sustainability”

What will or can be the role of chemistry in this context?

The CERC3 „brainstorming“ meeting on chemistry in support for “sustainability” in

Hannover is supposed to stimulate cooperation in research, exchange information

and experience among the European chemists in the fields of

Synthesis with Functionalized Solid Phases

New Solid Phases for Synthesis and Catalysis

Reactor Design and Microreactors

Catalysis

Synthesis Under Unusual Conditions.

4

It is the intention of this meeting to bring those research groups from all over Europe

together which are believed to develop improved preparation techniques and

production processes in its broadest sense by intense collaboration. Traditionally,

improved technologies with respect to “sustainability” are thought to be those that

make efficient use of chemicals, solvents and energy in industrial production.

Catalysis including biocatalysis was and will be by no doubt a key player in this field.

Additionally, chemistry under unusual conditions can lead to shorter reaction times, to

purer reaction products or even make chemical transformations possible which are

otherwise not feasable. Microwave assistance, ultrasound, and supercritical solvents

are only three examples to be mentioned here. In addition, reactor and process

design (micro and minireactors, batch processes versus continuous flow through

reactors) are important points on the agenda. However, the meaning of simple

workup has been underestimated when discussing sustainable processes. Workup,

as every chemist has experienced, can be very time consuming and costly

particularly when crystallization or distillation is not the purification technique of

choice. Indeed, often chemicals are not produced because of difficult purification.

Acarbose, a potent amylase inhibitor, is an example of a commercial high priced

compound, which is only available by very costly chromatographic purification.

Concepts for simple workup, like polymer-assisted synthesis have already seen

application in the laboratories, which can be ascribed to the demand of

pharmaceutical and agrochemical industries for rapid excess to large compound

libraries.

Still, the demand for fundamental research in all relevant areas is enormous since

many of the cited techniques are still in a quite empirical stage and have seen only

rather local and narrow applications. An important aim of modern chemistry is to

synthesize “properties”. Research directed towards “sustainability” is well in line with

this demand and will profoundly influence the future of applied preparative chemistry.

A. Kirschning, Hannover

5

PROGRAM

Friday, November 23rd 2001 12:00-13:00 Registration 13:00-13:30 Opening remarks: A. Kirschning (Universität Hannover) E. Winterfeldt (Universität Hannover) „Philosophy and aims of the conference” 13:30-13:55 “An Industrial Perspective of Opportunities for C. Adams (UK) Catalysis in Sustainable Chemical Technology” 13:55-14:20 “Advanced Deposition Techniques for J. Schoonman

Systems for Conversion and Storage (The Netherlands) of Sustainable Energy” 14:20-14:45 “New cleaning concepts in the fabrication C. Vinkier of integrated circuits” (Belgium) 14:45-15:10 “Catalytic Conversion of Renewable Resources” P. Gallezot (France) 15:10-15:35 “Environmental catalysis – a tool for R. Keiski (Finland) sustainability” 15:35-16:05 Coffee/Tea 16:05-16:30 “Solid phase synthesis and screening of H.-G. Schmalz new modular ligands for transition (Germany) metal catalysis” 16:30-16:55 “Application of high throughput experimentation, C. de Bellefont parallel testing and combinatorial techniques (France) to catalysis in support of sustainability” 16:55-17:20 “Mesoporous and Macroporous Silicas P. Behrens with Ordered Pore Structures as Supports” (Germany)

17:20-17:45 “The functionalization of oxides M. Che by transition metal complexes” (France) 17:45-18:10 “Development of polymer/carrier U. Kunz composites for chemical processes” (Germany) 18:10-18:35 “Dendritic polymers as high-loading R. Haag supports for synthesis and catalysis” (Germany)

20:00 Conference Dinner (Brunnenhof) Saturday, November 24th 2001 08:30-08:55 The use of nanostructured supports M. J. Ledoux in catalysis“ (France)

6

08:55-09:20 “Supercritical fluid processing for F. Cansell (France) chemistry in support of sustainability” 09:20-9:45 “The application of microwave C. O. Kappe dielectric heating in high-speed (Austria) organic and combinatorial chemistry” 09:45-10:10 “Ionic Liquids for Green Industrial Chemistry” K. R. Seddon (UK) 10:10-10:35 “New Applications of Ionic Resins and M. Vaultier Ionic Liquids in Organic Synthesis” (France) 10:35-10:55 Coffee/Tea 10:55-11:20 “Microstructured Reactors: Novel Approaches A. Renken for Heterogeneous Catalytic Reactions” (Switzerland) 11:20-11:45 “Polymer-assisted solution phase synthesis A. Kirschning

with novel flowthrough reactors“ (Germany) 11:45-12:10 “Microstructures for smart reactors: Precision M. Matlosz performance in industrial production” (France) 12:10-12:35 “Structured Reactors, a Contribution J. A. Moulijn to Process Intensification” (The Netherlands) 12:35-13:30 Lunch 13:30-13:55 “Integration of biosynthesis and organic A. Bruggink synthesis - A new future for synthesis” (The Netherlands) 13:55-14:20 “Bio-inspired catalysis increasing A. Liese sustainability” (Germany) 14:45-15:10 “Functional supports via metathesis: M. R. Buchmeiser

design, synthesis and applications” (Austria) 15:10-15:30 Brief discussion and instruction of team work 15:30-16:00 Coffee/Tea with first meeting of possible discussion groups 16:00-18:00 Workshop in 3 or 4 groups 19:30 Dinner (Paulaner) Sunday, November 25th 2001

08:30-09:00 Reports from the groups 09:00-10:00 Discussion of the conference results (definition of relevant research

fields) 10:00-10:30 Coffee/Tea 10:30-12:30 Workshop in groups (collection of project ideas etc.) 12:30- 13:00 Closing remarks Riekkola (Chairman CERC 3)

7

An Industrial Perspective of Opportunities for Catalysis in Sustainable Chemical Technology

Chris Adams The Institute of Applied Catalysis, Kings Buildings, Smith Square

London SW1P 3JJ Phone 020 7963 6719, E-mail: chris.adams@iac.org.uk

___________________________

The talk will address industrial aspects of catalytic technologies which are essential

for producing a more sustainable manufacture and use of chemicals. It will also

highlight the implications for catalysis research.

8

Advanced Deposition Techniques for Systems for Conversion and Storage of Sustainable Energy

J. Schoonman Laboratory for Inorganic Chemistry, Delft Institute for Sustainable Energy’

Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands e-mail: j.schoonman@tnw.tudelft.nl

___________________________ Solid state electrochemical systems usually comprise thin films of the active

components. A variety of thin-film deposition techniques are presently available. In this

presentation Chemical Vapour Deposition (CVD) will be compared with Atomic Layer

Chemical Vapour Deposition (AL-CVD), Electrostatic Spray Deposition (ESD), and

Laser-Assisted Chemical Vapour Deposition (LA-CVD).

A new approach towards an all-solid state sensitised solar cell is a so-called nano-

structured hetero-junction cell. It comprises a nano-porous, wide band gap n-type

semiconductor, covered with a thin p-type absorber film. Due to the nano-porous

structure of the solar cell, the distance that photo-excited electrons in the p-type

absorber film must pass within their lifetime can be reduced to less than 100 nm. The

enlarged p-n junction area is also beneficial with regard to light scattering and boosts

the light absorbing capacity of the thin film cell. The potentials of AL-CVD will be

discussed.

Thin-films of electrode materials for rechargeable Li-ion batteries and Intermediate-

Temperature Solid Oxide Fuel Cells with special surface morphologies can be

deposited with ESD. Recent results will be discussed to illustrate this deposition

technique.

The introduction of a hydrogen economy requires safe storage of hydrogen, which is

preferably produced using sustainable energy. To date, nano-structured materials are

being investigated for this purpose. Their synthesis can be achieved using LA-CVD.

9

New Cleaning Concepts in the Fabrication of Integrated Circuits (IC’s)

C. Vinckier, F. De Smedt, H. Vankerckhoven and S. De Gendt*

Department of Chemistry KULeuven, Celestijnenlaan 200F, 3001 Heverlee

Belgium E-mail: Chris.Vinckier@chem.kuleuven.ac.be

___________________________

About 30% of the process time in the manufacturing of semiconductor devices is

devoted to cleaning processes. One of the most used cleaning agents for removing

organic substances is concentrated sulfuric acid. It is very efficient as oxidizer, but its

environmental burden is becoming very high. One is left with a high purity reagent

which gets contaminated by organic residues and which must be considered as

waste. In addition very large quantities of ultra pure DI-water (de-ionized) are needed

to remove the acid left on the IC-structures in order to obtain a clean surface.

An overview will be given of current research on the possible uses of ozone in

solution as a very attractive alternative for sulfuric acid. First its solubility and stability

in pure water will be described. Its reactivity has to be seen in terms of ozone itself (

direct mechanism) or by its radical decomposition products (indirect mechanism).

Besides its effectiveness as oxidizer of organic contamination or for the removal of

photoresist material, ozone is also a powerful agent for purifying the process rinse

water. In this way the rinse baths can be re-used and the amounts of waste water will

be reduced. Better analytical techniques are needed to quantify the organic reaction

products left in the process waters in order to optimize the parameters ( pH,

temperature, additives,..) of the ozone cleaning process.

A major barrier for the implementation of the process on an industrial scale is the

difficulty of the transfer of gaseous ozone from the gas phase through the liquid film

on the solid surfaces.

10

Catalytic Conversion of Renewable Resources

Pierre Gallezot Institut de Recherches sur la Catalyse-CNRS

2, avenue Albert Einstein, 69626 Villeurbanne cédex, France. gallezot@catalyse.univ-lyon1.fr

________________________________________________

There are strong incentives to develop chemical processes starting from

biosustainable resources (e.g., carbohydrate- or triglyceride-containing crops), which

in contrast with petroleum-derived feedstocks are renewable and contribute to

decrease CO2 emissions. These raw materials consisting of highly functionalized

molecules can be converted by clean catalytic processes into highly priced

derivatives used as food additives, and specialties or fine chemicals. In this lecture, a

general survey of catalytic transformations of crop-derived feedstocks will be given.

Then, a few examples of metal-catalyzed conversion of carbohydrates obtained from

maize or other starch-containing crops will be described.

11

Environmental Catalysis - A Tool for Sustainability

Riitta Keiski

University of Oulu, Department of Process and Environmental Engineering, P.O.Box 4300, FIN-

90014 University of Oulu (+358-8-553 2348, +358-8-553 2304, riitta.keiski@oulu.fi)

_______________________

Catalysis – both environmental and process catalysis – has proved its role as a tool in

pollution prevention. Catalysis has long been utilized in increasing yield, selectivity and

efficiency of chemical processes. Nowadays catalytic procedures have been

implemented according to the green chemistry principles and good industrial

examples are found that fulfil several of the twelve principles of green chemistry at the

same time (Anastas et al., 2000).

The use of catalysts has brought many environmental benefits and important

advances in chemistry and chemical industry. The use of large quantities of reagents

has been avoided by changing the reaction to be catalytic instead of stoichiometric.

One good example is oxidation chemistry, which has become very important in

chemical industry and at the same time it is one of the most polluting chemical

technologies. The new oxidation chemistries with lower polluting effects are catalytic

rather than stoichiometric. The use and generation of little or no hazardous

substances and maximum efficiency of atom incorporation are the goals to be

achieved in the future.

Our research group concentrates for the time being on the use of catalysis as an

environmental technology. Automotive exhaust gas catalysis, catalytic combustion

of volatile organic compounds as well as malodorous sulfur compounds, and catalytic

wet oxidation of the organic load in the water circulations in pulp and paper integrates

are research areas that are for the time being going on actively in our group.

Micro-structured heat-exchange reactors, prepared with porous alumina layers,

are in demand. These reactors are powerful devices in several environmentally

related catalytic reactions. Hydrogen production from alcohols (e.g. CH3OH) and

hydrocarbons (natural gas, gasoline, diesel) for fuel cells as well as reforming of CO2

12

are reactions that interest our research group as model reactions in the design of the

micro-channelled reactors with high flow rates and good selectivities.

Supercritical CO2 extraction of peat and northern plants is a project that has been

going on for some years. Reactions, especially catalytic reactions in supercritical

conditions (e.g. pericyclic organic reactions) are under careful consideration to be

among the future research areas in our group. A new start has also been taken in the

separation and purification (reactive absorption) as well as catalytic utilisation of CO2

as a starting material in special and bulk chemicals production. The use of

membranes and catalytic membranes is also one field that will be started in due

course.

Our Laboratory, Laboratory of Mass and Heat Transfer, is responsible for the courses

given in mass and heat transfer, fluid dynamics, separation processes as well as

multiphase separations. We also give post-graduate and under-graduate courses on

environmental catalysis, industrial catalysis, green chemistry and research

methodology, and participate in the education of industrial ecology and recycling, and

air pollution control engineering. Chemical engineering, especially heterogeneous

catalysis and environmental engineering are the main areas in research.

_______________________

Literature:

Anastas, P.T., Bartlett, L.B., Kirchhoff, M.M. and Williamson, T.C. The role of catalysis in the

design, development, and implementation of green chemistry. Catalysis Today 55, 2000, p. 11-

22.

13

Solid Phase Synthesis and Screening of New Modular Ligands for Transition Metal Catalysis

Hans-Günther Schmalz

Institut für Organische Chemie der Universität zu Köln Greinstrasse 4, D-50939 Köln, Germany

schmalz@uni-koeln.de _____________________________

In order to speed up the process of catalyst development, modular ligand

architectures are highly desirable, because they may even allow to exploit the

techniques of "combinatorial chemistry" to the search for new homogeneous

(single site) metal complex catalysts. In order to tackle this goal, methods are

needed which allow for the solid phase synthesis of libraries of organic ligands and

their respective metal complexes. While solid phase peptide chemistry has been

used by a number of groups to synthesize libraries of modular ligands, the solid

phase synthesis of modular non-peptidic ligand systems suited for the

complexation of low valent transition still remains a major challenge.[1]

We have now developed a modular approach to a new class of structurally diverse

bidentate chelate ligands.[2] The methodology opens an access to a broad variety of

new chiral and achiral transition metal complexes and is generally suited for the

(automated) solid phase synthesis of combinatorial libraries.

L2

L1M

O

OBr

OTHP

O

The presentation will focus on concepts, on specific technological challenges and

will disclose some recent promissing results obtained in this laboratory.

________________________ [1] B. Jandeleit, D. J. Schaefer, T. S. Powers, H. W. Turner, W. H. Weinberg, Angew. Chem. 1999, 111, 2648. [2] R. Kranich, K. Eis, O. Geis, S. Mühle, J. W. Bats, H.-G. Schmalz, Chem. Eur. J. 2000, 6, 2874-2894.

14

Application of High Throughput Experimentation, Parallel Testing and Combinatorial Techniques to Catalysis in

Support of Sustainability

Claude de Bellefon Laboratoire de Génie des Procédés Catalytiques, CNRS

F-69616 Villeurbanne Cdb@lgpc.cpe.fr

The discovery of new catalysts has always been a subtle balance between the trail &

error methodology, the structure-activity approach and serendipity (let’s call it intuition

or luck…). Thus the sequential steps of catalyst discovery were catalyst preparation,

catalyst testing, analysis of both the results of the catalytic test and of the catalyst

structure, and knowledge upgrading (Scheme a). At this stage the catalyst under

investigation could be selected. All the knowledge accumulated for years in catalyst

selection has and is still used to help designing new and better catalysts. This

structure-activity, structure-selectivity approach has proved very powerful in catalysis

and a faster “knowledge feeding” would be useful. High throughput catalyst screening

experiments are aimed to fulfil this requirement. Parallel (combinatorial)

synthesis and testing of catalysts has been proposed as an efficient tool (Scheme b).

Use of these new tools is believed to drive to:

- Improve the competitiveness of the European Chemicals Industry by enabling

them to bring entirely new processes to market far quicker than currently, with

optimised catalysts, chemistries and production.

Catalyst testing

Test analysis

Catalyst synthesis

Knowledge upgrading

Choice of the catalyst

(a)

Catalyst

s library

Tests

Knowledge upgrading

Test analysis

Choice of the catalyst

(b)

15

- Improve the efficiency of academic research by setting new routine tools for

experimental investigations in catalysis thus allowing more room for imaginative

work.

The lecture will review the state-of-the-art and the actors in the field of high throughput

screening of homogeneous and heterogeneous catalysts, i.e. gas-solid, gas-liquid-

solid, gas-liquid, liquid-liquid and last but not least, monophasic liquid processes.

Emphasise will be put on the many problems raised by each of the elementary unit

operations (catalyst library synthesis, testing, analysis, data mining…) required in the

application of the “combinatorial catalysis” approach as described in scheme b.

Selected examples from recent research reports will be presented.

16

Mesoporous and Macroporous Silicas with Ordered Pore Structures as Supports

Peter Behrens

Institut für Anorganische Chemie, Universität Hannover Callinstrasse 9, D-30167 Hannover, Germany

E-mail: Peter.Behrens@mbox.acb.uni-hannover.de _________________________________________________

Amorphous silicas are usually prepared via a sol-gel process which yields polysilicic

acids (SiO2-x(OH)2x) via a polycondensation process. Such materials are well known

as supports in heterogeneous catalysis and as separation media in chromatography.

When the sol-gel process is carried out in the presence of suitable templates, porous

materials with highly ordered pore structures can be formed. When, for example,

surfactants are present, mesostructured materials are formed with structures

resembling lyotropic phases. Upon removal of the surfactant molecules (for example

by calcination), mesoporous materials are formed with pore sizes between 2 and 20

nm. In a similar way, larger templates (e.g. latex spheres) or self-assembling

systems (emulsions) may be used to produce macropores (> 50 nm) or hierarchical

(micro-/mesoporous) pore systems.

In these materials, the pores have an ordered arrangement. The surface areas

are usually very high (up to 1500 m2g-1), as are the pore volumes (typically 1 mL g-1).

The surface exhibits silanol groups which allow a variety of chemical modifications.

Despite the high surface areas, the materials are thermally very stable, but they may

suffer from steam and aqueous solutions, especially when these are strongly basic.

Chemical modifications (pore wall thickening, hydrophobization, silanization) however

can considerably stabilize the silica framework. Such porous materials have been

prepared as films, spheres and have been grown on various supports. Together with

the high chemical variability and the high surface areas these materials may therefore

be suited as basis for supported reagents and catalysts.

17

The Functionalization of Oxides by Transition Metal Complexes

Michel Che

UMR 7609 Réactivité de surface, Université Pierre et Marie Curie (Paris VI) 4 Place Jussieu – Case 178, 75252 Paris Cedex 05, France

E-mail: che@ccr.jussieu.fr _______________________________________________

In recent years, major advances have been made in physical techniques [1]

particularly for the in situ characterization of solid materials [2]. A molecular approach

based on the combined deployment of such techniques, stable isotopes, and

transition metal elements has been developed and applied to the study of the

functionalization of solid oxides particularly toward transition metal complexes in

aqueous media [3]. It becomes then possible to describe in molecular terms the

interaction of the transition metal complex with the oxide and to reveal the nature of its

surface.

It will be shown that the oxide via its surface can play several roles toward the

transition metal complex: simple container, condenser plane, receptor, ligand,

reactant and finally solid solvent. In each case, elementary processes are involved

which correspond to various disciplines of chemistry [4-8], the concepts of which can

be applied to the reactivity of solid oxides, thus giving a stronger conceptual

framework to the field.

This type of study is related to important fields such as catalysis, environmental

protection, surface coatings. The models which can be derived from such studies

can also provide the basis of further theoretical calculations.

References: 1. Catalyst Characterization: Physical Techniques for Solid Materials, B. Imelik and J.C. Védrine, eds, Plenum Press, New York, 1994. 2. Catalyst Characterization under Reaction Conditions, Topics Catal., 8 (1999) 1-140. 3. K. Dyrek and M. Che, Chem. Rev., 97 (1997) 305. 4. J.-F. Lambert, M. Hoogland, M. Che, J. Phys. Chem. B 101, 10347-10355 (1997). 5. X. Carrier, J.F. Lambert and M. Che, J. Am. Chem. Soc., 119 (1997) 10137. 6. P. Burattin, M. Che and C. Louis, J. Phys. Chem. B, 102 (1998) 2722. 7. B. Shelimov, J. F. Lambert, M. Che, B. Didillon, J. Am. Chem. Soc. 121, (1999) 545-

556. 8. M. Che, Stud. Surf. Sci. Catal., 75A (1993) 31; 130A (2000) 115.

18

Development of Polymer/Carrier Composites for Chemical

Processes

Ulrich Kunz Institut für Chemische Verfahrenstechnik, Technischen Universität Clausthal

Leibnizstr. 17, D-38678 Clausthal-Zellerfeld, Germany Tel.: +49-(0)5323-72 2181, Fax: +49-(0)5323-72 2182, email: kunz@icvt.tu-clausthal.de

_______________________

The starting point of our polymer/carrier composite preparation was the development

of catalytic packings for reactive distillation columns. This process is used for

equilibrium limited processes during which one of the products is removed

continuously from the reaction mixture to shift the equilibrium composition and to drive

the reaction to high conversion rates. Such a process requires packings which are

suitable as distillation columns packings and simultaneously have catalytic activity.

State of the art is to wrap commercial ion exchange resins into wire nets or glass

fibre sheets and to form distillation structures from these materials. As an alternative

approach we developed composite materials consisting of inorganic carriers and

polymers in the shape of Raschig-rings.

The preparation of polymer/carrier composites is done by the use of megaporous

Raschig-rings made of glass and the polymerisation of crosslinked resins inside the

pore volume of the carrier materials. Various polymerization processes were

evaluated, finally precipitation polymerisation (dispersion polymerisation) was chosen

to prepare small interconnected polymer particles of styrene, crosslinked with

divinylbenzene inside the pore volume of Raschig-rings. After sulfonation with

chlorosulfonic acid catalysts well suited for acid catalysed reactions were obtained.

Characterisation was done by capacity measurements and by scanning electron

microscopy. The size of the polymer particles (micrometer range) is much smaller

than the size of classical resin beads ( millimetre range). The catalysts were tested in

etherification and esterification reactions in reactive distillation processes as well as

in chromatographic reactors.

As an extension to the acid composites we developed basic materials which can be

used as basic catalysts or for attachment of functional ions as reactants for organic

synthesis. Based on this technology monolithic polymer/carrier materials were

developed which can be used for other processes where chemical reaction coupled

with simultaneous separation occurs, offering new opportunities for the improvement

of chemical processes.

19

Dendritic Polymers as High-loading Supports for Synthesis

and Catalysis

Rainer Haag Freiburger Materialforschungszentrum und Institut für Makromolekulare Chemie, Albert-

Ludwigs-Universität, Stefan-Meier-Straße 21, 79104 Freiburg, Germany E-mail: haag@fmf.uni-freiburg.de

____________________________________________

During the past decade the usage of polymeric supports has become increasingly

important, especially for automated synthesis and combinatorial chemistry. So far

solid phase supports i.e. cross-linked polystyrene beads were primarily used for this

application. However, low concentration of functional groups (< 1.5 mmol/g) and

heterogenic reaction conditions are the major disadvantages of solid phase supports.

In addition the development of special linker systems is necessary. More recently,

dendrimers and hyperbranched polymers have been discussed as high-loading

soluble supports in organic synthesis.[1] Hyperbranched polyglycerol is a new highly

branched, multifunctional polyether support, which can be prepared in kilogram

quantities.[2] In contrast to other polymeric supports polyglycerol is easy available in

just one reaction step and allows high loading capacities up to 4 mmol/g (1,2-diols).

Due to its chemically stable polyether backbone it is well suited as support for organic

synthesis. For example carbonyl compounds can be supported without any additional

linker on the 'built-in' 1,2-diols, then chemical modified and finally cleaved in high

yields.[3] Also, this high-loading polymers can be used as support for reagents and

catalysts in homogeneous as well as in heterogeneous systems.

[1] R. Haag, Chem. Eur. J. 2001, 7, 327. [2] A. Sunder, R. Mülhaupt, R. Haag, H. Frey, Adv. Mater. 2000, 12, 235. [3] R. Haag, A. Sunder, A. Hebel, S. Roller, J. Combinatorial Chem. 2001, in press.

O

O

O

O

ORO

ORO

O

O

RO O

OR

O

OHHO

OH

OHO

OHOH

HO OH

O

OO

RO

OOH

OHHO

HO

core

R = H R = Me R = Et R = R =

O OHOH

OO

O

H,RR'

H,R R'

O

H,R R*

O

OR OR

H2O

H+

H+

-H2O1) selektive soupling of the substrate

2) working up e.g. ultrafiltration

4) cleavage of the product5) polymer recycling

3) chemical transformationen

PG PG

20

The Use of Nanostructured Supports in Catalysis

Marc J. Ledoux

Ecole Européenne de Chimie, Polymères et Matériaux de Strasbourg / Université Louis Pasteur Director of the L.M.S.P.C; Laboratoire des Matériaux, Surfaces et Procédés pour la Catalyse

UMR 7515 du C.N.R.S., 25, rue Becquerel, 67087-STRASBOURG Cedex 2, France Phone: +33-(0)-685-726 183 or +33-(0)-390-242 633, Fax: +33-(0)-390-242 674,

E-mail: ledoux@cournot.u-strasbg.fr ___________________________________

Since their discovery at the begining of the last decade carbon nanotubes have

received increasing interest both from the fundamental and the industrial point of view.

Carbon nanotubes can exhibit peculiar properties when they are used as catalyst

supports. Recently, the synthesis of medium surface area silicon carbide nanotubes

with different diameters was achieved in our laboratory. The aim of the presentation is

to report the preparation and characterization of these materials and their use as

catalyst supports for different reactions such as selective oxidation of hydrogen

sulfide into elemental sulfur or liquid-phase hydrogenation of cinnamaldehyde.

Catalysts supported on silicon carbide nanotubes exhibit a superior catalytic

performance for both reactions, compared to those obtained on more conventional

catalysts. Other reactions in fine chemistry where carbon nanotubes and nanofifers

have been tested will also be discussed.

Finally new concepts for catalysis including 1) the role of the support on the crystallin

shape of the active phase, 2) the probable importance of confinement at nano-

dimension level (higher than molecular dimension like in zeolites or mesoporous mat)

and 3) the exploitation of these phenomena in microreactors, will be open for

discussion.

21

Supercritical Fluid Processing for Chemistry in Support of

Sustainability

Francois Cansell UPR9048 Institut de chimie de la matière condenseé de Bordeaux (ICMCB), Centre nationale de

la recherche scientifique, 87, Av du Dr. A. Schweitzer, 33608 Pessac Cedex, France Phone: +33-(0)5-56 84 26 73, Fax: +33-(0)5-5684 66 34,

E-mail: cansell@icmcb.u-bordeaux.fr __________________________________________________

Supercritical fluids exhibit a range of unusual properties that can be exploited for new reactions

which are qualitatively different from those involving classical chemistry. The main interest of

supercritical fluids as reaction media relies on their continuously adjustable properties from gas

to liquid with small pressure and temperature variations. The main interest of supercritical fluids

processing, for chemistry in support of sustainability, are the lower waste production, the volatile

organic compound emission reduction and the energy supply reduction.

After giving a brief introduction to these fluids we describe both their use in inorganic chemistry

and in waste-waters management.

Concerning inorganic chemistry, the presentation of a new method, developed in our laboratory,

for the preparation of fine grained materials is presented. The chemical transformation of metallic

precursors inside a supercritical fluid is a new route for obtaining fine grained homogeneous

powders of materials such as metals, oxides, nitrides. Experimental results and simulations of

our process show that it is possible to continuously adjust the particle sizes as function of the

operating conditions. We present also an other application of this process related to the

elaboration of structured fine grained material as core-shell structures.

Concerning waste-waters management, the environmental regulation and the increasing waste-

water disposal cost, in France and more generally in industrial countries, lead to a new concept

for complete destruction of both toxic substances and sludges. Thus, hydrothermal oxidation of

wastes is developed as an alternative technique in order to limit the toxic end-products

formation, the waste volume and the energy supply. Hydrothermal oxidation processes allow a

“cold combustion” without energy supply due to the high exothermic reaction of oxidation and

without toxic end-products. CO2 obtained as end-product (under pressure) can be easily

collected and used for further specific industrial applications. Moreover hydrothermal waste

water treatment processes must be developed as a function of the effluent type with different

reactor types which can operate in continuous conditions with tubular or vessel reactor. We

present different tools, developed in our laboratory for the scale-up of these processes, which

permit to determined the kinetic parameters, the reaction enthalpy and the temperature profiles

in reactors . These tools are presented in bases of real wastes.

22

The Application of Microwave Dielectric Heating in High-Speed Organic and Combinatorial Chemistry

C. Oliver Kappe Institute of Chemistry, Karl-Franzens-University Graz, Austria

oliver.kappe@uni-graz.at _______________________________________

Microwaves have truly revolutionized "chemistry" in the kitchen during the past three

decades. The rapid heating of foodstuffs in microwave ovens is nowadays used

routinely by a significant proportion of mankind. Other potential applications for this

heating method have been realized and scientists from different fields have applied

the rapid heating associated with microwave technology to a number of processes,

penetrating many chemical and allied disciplines. These include analytical chemistry

applications (sample preparation, digestion and extraction), applications to waste

treatment, polymer technology, ceramics, materials sciences, and biochemical

applications. Somewhat more recently (1986) the first pioneering reports on the use

of microwave heating to carry out synthetic organic transformations were published

independently by the groups of Gedye and Giguere/Majetich. It was soon realized that

performing organic synthesis under microwave irradiation has some significant

advantages as compared to classical heating techniques. Characteristically,

microwaves generate rapid intense heating of polar substances with significant

reductions in reaction times, cleaner reactions that are easier to work up, and in many

cases higher yields.

In this lecture the experiences of our group in the area of microwave-assisted organic

synthesis will be summarized. Emphasis will be given to microwave-assisted solid-

phase and combinatorial synthesis, the design of the different microwave reactors

used, and to the potential utilization of sub-critical water as solvent in microwave-

assisted reactions.

23

Ionic Liquids for Green Industrial Chemistry

K. R. Seddon School of Chemistry, The Queen's University of Belfast, Stranmillis Road,

Belfast BT9 5AG, Northern Ireland, E-mail: k.seddon@qub.ac.uk _______________________________________

The application of ionic liquids, which have no vapour pressure, to the chemical

industry (nuclear, petrochemical, commodity chemicals, fine chemicals, and

pharmaceuticals) will be discussed, with an emphasis being placed upon green

synthesis.

24

New Applications of Ionic Resins and Ionic Liquids in Organic Synthesis

Michel Vaultier*, Gilles Alcaraz,

UMR CNRS 6510, Institut de chimie de Rennes, Université de Rennes 1, Campus de Beaulieu, Avenue du Général Leclerc, 35042 Rennes Cedex, France. Tél. : 02 23 23 62 72. Fax : 02 23 23

69 55. E-mail : Michel.Vaultier@univ-rennes1.fr. __________________________________

Two topics will be presented :

1) The solid phase synthesis of macrocyclic systems involving a

transition metal catalyzed C-C bond formation is a current challenge investigated with

polymer-covalently bound precursors 1. To the best of our knowledge, only one

example describing the synthesis of a β-turn mimic via a Suzuki-Miyaura ring-closing

reaction has been reported 2. In this context, we developed a simple resin-capture

method to immobilize arylboronic acids species by reaction with macroporous

ammonium hydroxide-form Dowex ® Ion Exchangers resin (D-OH-) as BIV-

arylborates) 3. Efficient Suzuki-Miyaura coupling reactions could be achieved with

these immobilized arylhydroxyborates. Precursors containing both the arylboronic and

bromoaryl moieties necessary to perform the macrocyclisation reaction were built up

using an expedient multicomponent one pot synthesis. They were then efficiently

anchored on the resin and cyclised into biaryl macroheterocycles using Suzuki-

Miyaura coupling conditions.

2) Ionic liquids are salts that are liquid at low temperature which represent

a new class of solvents with ionic character 4. Ionic liquids have been almost

exclusively inves-tigated as solvents for transition metal catalysis. Switching from a

normal organic solvent to an ionic liquid can lead to novel and unusual chemical

reactivity. This opens up a vast field for future investigations into this new class of

solvents not only in catalytic applications but also in other fields such as solvent

effects in organic synthesis, physical chemistry, material science or extraction.

Results will be presented in transition metal catalyzed reactions and also targeting the

field of parallel synthesis.

1. A.V. Rama Rao,M.K. Gurjar, K.L. Reddy and A.S. Rao, Chem. Rev., 1995, 95, 2135. 2. (a) M. Hiroshige, J.R. Hauske and P. Zhou, J. Am. Chem. Soc., 1995, 117, 11590 ; (b) K.C.

Nicolaou, N. Winssinger, J. Pastor, S. Ninkovic, F. Sarabia, Y. He, D. Vourloumis, Z. Yang, T. Li, P. Glannakakou and E. Hamel, Nature, 1997, 387, 268 ; (c) K.C. Nicolaou, N. Winssinger, J. Pastor and F. Murphy, Angew. Chem. Int. Ed., 1998, 37, 2534.

3. V. Lobrégat, G. Alcaraz, H. Bienaymé and M. Vaultier, J. Chem. Soc., Chem. Commun, 2001, 817-818.

4. P. Wasserscheid and W. Keim, Angew. Chem. Int. Ed., 2000, 39, 3772-3789.

25

Microstructured Reactors: Novel approaches for Heterogeneous Catalytic Reactions

L. Kiwi-Minsker, A. Renken* Laboratory of Chemical Reaction Engineering,

Swiss Federal Institute of Technology, CH-1015 Lausanne E-mail: Albert.Renken@epfl.ch

________________________________________________ Microstructured reactors are mainly characterized by their very high surface to

volume ratio compared to traditional chemical reactors. Multichannel microreactors

having channel diameters in the order of ten to several hundred micrometers have

specific surface areas in the range of 10’000 to 50’000 m2/m3. This value is roughly

two orders of magnitude higher compared to conventional production vessels.

Due to the small reactor dimensions diffusion times are short and the influence of

mass transfer on the rate of reaction can be efficiently reduced. As the heat transfer

performance is greatly improved compared to conventional systems, higher reaction

temperatures are admissible leading to reduced reaction volumes and amount of

catalyst. Therefore, micro-structured reactors are especially predestinated for fast,

highly exothermic or endothermic chemical reactions. Although the flow in the

channels is laminar, a uniform radial concentration profile and consequently a narrow

residence time distribution is obtained. This allows to optimize the contact time in the

reactors and to avoid consecutive reactions. The main problem for the use of

microreactors in heterogeneous catalytic reactions is the introduction of catalytically

active micro-porous materials into the micro-reactor. The catalytic materials should

have a high activity/selectivity and mechanical stability under reaction conditions.

Therefore, the catalyst layer must be strongly anchored to the reactor wall.

In the present contribution a novel concept of a micro-reactor system will be

presented. It consists of a tube reactor of few millimeters in diameter filled by

catalytically active filaments placed in parallel to the tube walls. The arrangement

gives flow hydrodynamics similar to multichannel microreactors. The concept was

first studied for the non-oxidative hydrogenation of propane to propene.

26

Polymer-Assisted Solution Phase Synthesis with Novel

Flowthrough Reactors

Andreas Kirschning Institut für Organische Chemie, Universität Hannover, Schneiderberg 1B, 30167 Hannover,

Germany E-mail: andreas.kirschning@oci.uni-hannover.de

__________________________________________________________________

In the shadow of solid phase synthesis, the utilization of functional polymers as

reagents and catalysts have only recently gained increased interest for applications in

industrial laboratories.[1] Polymer-assisted solution-phase synthesis shows

advantages over Merrifield-type syntheses (SPOS). Indeed, these techniques are

much less demanding since polymer-supported reagents are used in only one

reaction and not every functional site needs to react. In this context, it has been

demonstrated in numerous examples that compared to solid phase synthesis the

time to develop new applications for polymer-supported reagents is much

shorter and highly simplified. Finally, the analytical monitoring of a reaction is

simplified and techniques like tlc-analysis known from classical solution phase

chemistry can be applied.

Furthermore, this method shows several advantages over the conventional solution

phase synthesis:

1. the ease of separation of the supported species from a reaction mixture

by filtration and washing.

2. the use of excess of reagent to force the reaction to completion without

causing workup problems.

3. reuse of the catalyst or of a supported reagent after regeneration.

4. their adaptability to continuous flow processes and hence use in

automated synthesis.

5. the reduced toxicity and odor of supported species compared with low

molecular weight species.

6. chemical differences, such as prolonged activity or altered selectivity of a

catalyst in supported form compared with its soluble analogue.

27

Scheme 1

AA A BB

A-B

Solid-phase synthesis on a polymer support (SPOS)

D

A

Polymer-assisted synthesis in solution using polymer-bound reagents or catalysts

B

E

C

linker

TThhee ttrruuee jjuussttiiffiiccaattiioonn ffoorr uussiinngg ssoolliidd ssuuppppoorrttss iinn oorrggaanniicc ssyynntthheessiiss iiss aauuttoommaattiioonn..

CCuurrrreenntt ssttrraatteeggiieess ooff aauuttoommaattiioonn aarree bbaasseedd oonn tthhee ttrraaddiittiioonn ooff ““EErrlleennmmeeyyeerr””.. IInn

ffaacctt,, rreeaaccttiioonnss aarree ppeerrffoommeedd iinn ffllaasskkss,, ccaannss oorr mmiinniiaattuurree vviiaallss iinn tthhee bbaattcchh mmooddee..

IInn tthhiiss rreeppoorrtt aa nnoovveell mmiiccrroorreeaaccttoorr iiss pprreesseenntteedd wwhhiicchh iiss ccoonnssttrruucctteedd aass aa ffllooww--

tthhrroouugghh ssyysstteemm.. HHeennccee,, tthhiiss tteecchhnniiqquuee aalllloowwss ttoo ppeerrffoorrmm ssyynntthheessiiss iinn ssoolluuttiioonn

wwiitthhoouutt tthhee nneeeedd ffoorr wwoorrkkuupp pprroocceedduurreess lliikkee eexxttrraaccttiioonn oorr ffiillttrraattiioonn.. IInn

aaddddiittiioonn,, aannaallyyssiiss ooff tthhee pprroodduuccttss aanndd bbiioollooggiiccaall ssccrreeeenniinngg ccaann bbee iinnccoorrppoorraatteedd

iinnttoo tthhee ssyysstteemm.. TThhee rreeaaccttoorr ssyysstteemm ccoonnssiissttss ooff aa ““hhaarrddwwaarree““ wwhhiicchh iiss tthhee

ccoolluummnn iittsseellff.. IItt ccoonnttaaiinnss aa cchheemmiiccaall ””ssooffttwwaarree”” wwhhiicchh iiss aa ppoorroouuss,, mmoonnoolliitthhiicc

ggllaassss//ppoollyymmeerr ccoommppoossiittee.. TThhiiss ccoommppoossiittee iiss llooaaddeedd wwiitthh cchheemmiiccaall ffuunnccttiioonnaalliittiieess

lliikkee iimmmmoobbiilliizzeedd rreeaaggeennttss oorr ccaattaallyyssttss.. AAtt tthhee eennddss ooff tthhee ccoolluummnn ttwwoo HHPPLLCC--

ccoonnnneeccttoorrss aarree iinntteeggrraatteedd wwhhiicchh aallllooww ttoo iinnccoorrppoorraattee tthhee rreeaaccttoorr iinn aa

ccoonnvveennttiioonnaall HHPPLLCC--ssyysstteemm..

SScchheemmee 22

TThhiiss PPAASSSSffllooww--ccoonncceepptt[[22]] ((PPoollyymmeerr AAssssiisstteedd SSoolluuttiioonn--pphhaassee SSyynntthheessiiss;;

fflloowwtthhrroouugghh mmooddee)) ccoommbbiinneess tthhee ddeessiiggnn ooff aa mmiinniiaattuurree rreeaaccttoorr wwiitthh cchheemmiiccaall

ffuunnccttiioonnaalliittyy iinn oonnee uunniitt ffoorr tthhee ffiirrsstt ttiimmee aanndd hheennccee aalllloowwss ttoo ppeerrffoorrmm ffllooww--

tthhrroouugghh pprroocceesssseess iinn ccoonnvveennttiioonnaall llaabboorraattoorriieess..

TThhee ggllaassss//ppoollyymmeerr ccoommppoossiittee hhaass vvaarriioouuss ffeeaattuurreess wwhhiicchh mmaakkeess iitt iiddeeaallllyy ssuuiitteedd

ffoorr uussee iinn ppoollyymmeerr--aassssiisstteedd ssoolluuttiioonn--pphhaassee ssyynntthheessiiss::

28

-- IItt iiss sseett uupp ooff aa ccoonnttiinnuuoouuss ppoollyymmeerriicc pphhaassee ((iinntteerrccoonnnneecctteedd bbeeaaddss 11--1100

µµmm)) wwiitthh tthhee aabbiilliittyy ttoo ffoorrmm ggeellss iinn oorrggaanniicc ssoollvveennttss.. PPhhyyssiiccaall ddeessttrruuccttiioonn

ooff tthhee ppoollyymmeerr iiss aavvooiiddeedd..

TThhee ggllaassss bbooddyy hhaass

-- llaarrggee ppoorreess ((ddiissoorrddeerreedd mmiiccrroocchhaannnneellss;; ssiizzee 1100--110000 µµmm)) wwhhiicchh lleeaaddss ttoo

-- ffoorrcceedd ccoonnvveeccttiivvee ffllooww ooff tthhee ssoolluuttiioonn aalloonngg tthhee ppoollyymmeerriicc mmaattrriixx

wwiitthhoouutt

-- llaarrggee pprreessssuurree bbuuiilltt--uupp ((55 mmLL ffllooww // 1188 bbaarr))..

TThhee rreeaaccttoorr iiss ddeessiiggnneedd iinn aa wwaayy,,

-- tthhaatt oonnllyy ggllaassss,, ffuunnccttiioonnaalliizzeedd ppoollyymmeerr,, tteefflloonn oorr PPEEEEKK ggeett iinn ccoonnttaacctt

wwiitthh tthhee oorrggaanniicc ssoollvveenntt

-- tthhaatt aabboouutt oonnee mmmmooll ooff pprroodduucctt ccaann bbee pprreeppaarreedd wwiitthh oonnee ””rreeaaccttoorr

ffiilllliinngg”” aanndd

-- tthhaatt tthhee rreeaaccttoorr ccaann bbee rreeggeenneerraatteedd aafftteerr uussee iinn aa ssttrraaiigghhttffoorrwwaarrdd aanndd

ssiimmppllee wwaayy ((aanniioonniicc eexxcchhaannggee rreessiinnss aarree pprreeffeerrrreedd aass ppoollyymmeerriicc mmaattiicceess))..

TThheessee rreeaaccttoorrss aarree tthhee ssttaarrttiinngg ppooiinntt ffoorr tthhee aauuttoommaattiioonn oodd ssoolluuttiioonn pphhaassee

ssyynntthheessiiss wwhhiicchh iiss wweellll ssuuiitteedd ffoorr mmuullttiisstteepp ssyynntthheessiiss iinn ssoolluuttiioonn ((SScchheemmee 33)).. TToo

aacchhiieevvee tthhiiss ggooaall tthhee lloonnggtteerrmm eexxppeerriieenncceess ffrroomm tthhee HHPPLLCC--tteecchhnnoollooggyy ccaann bbee

eexxppllooiitteedd.. IInn tthhiiss rreessppeecctt,, ccoonnvveennttiioonnaall ppuummppss,, vvaallvveess,, ttuubbeess,, ddeetteeccttoorrss aanndd

ssooffttwwaarree aarree aallrreeaaddyy aavvaaiillaabbllee..

SScchheemmee 33 LC-pump

polymericscavenger

addition of starting material

polymericreagents or catalysts

productchromatographicpurification bioassay

mass spectrometer

AAnnootthheerr uusseess ooff tthheessee rreeaaccttoorrss iiss ppaarraalllliizzaattiioonn tthhuuss uuppssccaalliinngg ooff rreeaaccttiioonnss ((KKgg

ssccaallee)) aapppplliiccaabbllee iinn pphhaarrmmaacceeuuttiiccaall iinndduussttrryy..

______________________________________

[1] Selected reviews on polymer-assisted syntheses in solution: (a) Kirschning, A.; Monenschein, H.; Wittenberg, R.; Angew. Chem. Int. Ed. Engl. 2001, 40, 650-679. (b) Kirschning, A.; Monenschein, H.; Wittenberg, R.; Chem. Eur. J. 2000, 6, 4445-4450. (c) Drewry, D. H.; Coe, D. M.; Poon, S., Med. Res. Rev. 1999, 19, 97-148. [2] Kirschning, A.; Altwicker, C.; Dräger, G.; Harders, J.; Hoffmann, N.; Hoffmann, U.; Schönfeld, H.; Solodenko, W.; Kunz, U., Angew. Chem. Int. Ed. Engl. 2001, 40, 3995-3998.

29

Microstructures for SMART Reactors :

Precision Performance in Industrial Production

Michael Matlosz*, Sabine Rode, Jean–Marc Commenge

Laboratoire des Sciences du Génie Chimique ENSIC–Nancy, CNRS–INPL

F–54001 Nancy, France, Phone: +33-(0)383-17 52 57, Fax: +33-(0)383-32 29 75 E-mail: michael.matlosz@ensic.inpl-nancy.fr

____________________________________________________

The increasing availability of low–cost microstructured components and

devices over the last three decades has led to revolutionary advances in electrical,

optical and mechanical systems, and the recent extension of microtechnology to

chemical and biological applications is at the heart of economic development in an

ever larger number of industrial sectors. For the process engineer, the advent of

microstructured unit operation and reaction modules has provided new possibilities

for industrial innovation that may ultimately lead to significant changes not only in the

processes themselves but also in the way in which process technologies are

conceived, designed and developed. On the basis of recent advances in the use of

microstructured components for process miniaturization and process intensification,

the present communication seeks to define future directions for process engineering

in terms of “smart reactors”, a new generation of highly integrated, adaptive and

“intelligent” devices for precision performance in chemical production.

Smaller : process miniaturization

The strong impetus for the development of “microreactors” (i. e.,

microstructures for chemical and biological applications) results from the clear

advantages of miniaturization in many application areas where only very small

quantities of chemical and biological substances are available or desirable. Portable

energy sources, such as fuel cells for personal computers, and small–scale analysis

systems, such as those required for combinatorial chemistry or medical diagnosis,

are typical examples of current industrial applications of microtechnology in this area.

Distributed and delocalized production of toxic or hazardous chemical intermediates

with miniplant technology is another area in which microstructured components play a

major role [1], and applications abound in many other areas including artificial organs,

high throughput screening and “lab on a chip”. A recent review of the major

developments in the field of microchemical systems can be found in [2]. In all of

30

these application areas, microstructured devices and systems are advantageous in

large part simply because they are smaller.

Better : process intensification

The movement of microfabrication methods from silicon–based technology

into plastics, glasses, ceramics and metals has enabled the use of microstructured

components in applications involving a large variety of aggressive and corrosive

process fluids, and under highly demanding operating conditions. Furthermore,

process engineers have realized that the advantages of microstructured components

are not limited to simple miniaturization, and a number of highly promising

applications involving moderate and, in some cases, even large quantities of matter

and / or energy have begun to emerge in the rapidly growing field of process

intensification [3]. For process intensification, microstructures are not simply

employed to make devices smaller, but rather to make them better.

Compact macro–devices containing engineered microstructures with

characteristic dimensions on the order of typical momentum–, heat– and mass–

transfer boundary layers can provide significant gains in performance, even for

existing technologies, in many industrial and domestic applications. There is little

doubt, therefore, that microtechnology will continue to play a major role in process

intensification, leading not only to more compact but also to more economically

efficient and reliable process devices.

In chemical process applications, a number of encouraging results have

already been reported on the pilot scale for improvement of existing industrial designs

by simple addition of microstructured components such as microstructured static

mixers [4] or microstructured heat exchangers [5] upstream of traditional chemical

reactors.

The specific topological features of micromachined static mixers generate

substantial decreases in mixing times by reducing diffusion lengths through intimate

contact of fluid streams, while at the same time maintaining laminar flow conditions

and avoiding turbulence. Efficient rapid mixing under laminar flow conditions in

microstructured devices not only provides considerable reduction in energy

consumption, but the precise control of local micromixing and fluid contacting that can

be obtained with the devices can be extremely effective for maintaining narrow weight

and size distributions in many polymerization, emulsion and precipitation processes.

A number of specifically designed microstructured demonstration units has

been reported in the literature for targeted applications. A microstructured gas–liquid

31

reactor with integrated heat exchange (Figure 1), for example, has been developed for

direct fluorination of aromatics [6], a reaction pathway that is impossible to employ

safely with conventional designs. A key feature in this regard is the ability of

microstructured heat exchangers to provide a particularly short thermal diffusion

length (rapid removal of reaction heat) while at the same time avoiding contact

between the process and heat–transfer fluids. In these applications, not only is the

small scale an advantage, but also the specific topological features of micromachined

objects can be of interest, as illustrated by recent studies of nanostructured surface

treatments for catalyst supports on the walls of accurately machined microchannels

[7]. Numerous possibilities for performing reactions in highly unusual operating

regimes (for example, with explosive reactant mixtures [8, 9] or with periodic

modulation of inlet composition [10]) have also been proposed.

In all of these areas, the development of relevant demonstration devices for

experimental study, combined with theoretical analyses to determine reliable design

rules and evaluation criteria, is an urgent necessity and should be actively pursued.

Figure 1. Process intensification. Microstructured gas–liquid reactor for direct

fluorination of aromatics. (Source : IMM–Mainz)

The existence of these new technologies suggests strongly that traditional

concepts in chemical process engineering will need to be re–examined carefully in

the next few years, and that new process design concepts are likely to emerge. In

32

some cases, the validity of traditional chemical engineering scaling laws may need to

be re–evaluated [11], and the nature of scale–up itself may change.

The concept of "numbering up", for example, inspired by analogy with

integrated circuit technology and discussed by many workers [12], seeks to replace

traditional "scale–up" by a new approach involving "assembly" of a large number of

elementary "micro"–modules to create a large–scale "macro"–device. As pointed out

by Jensen [13], few efforts at real numbering up have been attempted, suggesting that

the necessary assembly may constitute in itself a serious limitation. In this regard,

research efforts concerning assembly of microreactor units into larger–scale devices

(Figure 2) should offer insight into the nature of the difficulties likely to be encountered.

In fact, although direct application of numbering up by a simple “LEGO”

approach is unlikely to be directly operable, the concept of numbering up as a

paradigm for process design has inspired much recent research. Rather than

breaking down (or “deconstructing”) a macrodevice into discrete microelements for

analysis (traditional chemical engineering), a radically different approach involves

building up (or “constructing”) the macrodevice from elementary micro–scale building

blocks for optimal performance. The appropriate design rules for such multi–scale

devices, as well as the methods for "scale interconnection" that will be required for

their construction, pose challenging theoretical questions that need to be addressed

and investigated.

Figure 2. Numbering–up assembly. Macroreactor device constructed by assembly of

microstructured building blocks. (Source : MTL-–MIT)

33

For the simplest case, scale–interconnection rules can be taken to be scale–

independent. Macro–devices built up progressively from micro-scale components

under scale–independent rules present a fractal structure, and the Devil’s comb

(Figure 3) proposed by Villermaux et al. [14] is a two–dimensional example of such a

structure. When employed as a support for heterogeneous catalysis, the Devil’s

comb has been shown to exhibit particularly interesting properties of self–adaptability

in the presence of catalyst poisoning that may have potential application [15].

By generalizing the approach to scale–interconnection rules that may vary

from one scale to another, a new “constructal” theory for process optimization is

under development that may lead to radically different process design methods and

may even change the way processes are conceived and developed in the future [16].

Figure 3. Multi–scale microstructured device. The Devil’s comb, a two–dimensional

fractal structure as catalyst support. (Source : LSGC–Nancy)

Smarter : process innovation

Innovative production methods are an essential factor in the pursuit of safe,

sustainable development for the chemical and process industries, and engineered

microstructures provide an extensive field of opportunity in this context for the

establishment of new, creative design concepts for the chemical plants of the future.

Extrapolation of recent developments suggests that new applications of

microstructured components in process engineering will involve not only

miniaturization and intensification, but also advanced process control and systems

design as well. This new generation of microstructured devices encourages true

34

process innovation, opening the way to completely novel synthesis routes, unexplored

operating regimes and dynamic operation. Microstructured reactors in the future will

not only be “smaller” and “better”, but also smarter as well.

Whereas current developments involving microstructured components for

chemical production are essentially "passive" in nature, further conceptual advances

will require a more "active" approach involving not only geometrical microstructures

but also interactions between sensors, transmitters and actuators distributed in the

structures. Application of these ideas suggests future directions for process

development in chemical and biological reactors that go beyond "intense" or

"compact" operation to include "intelligent" or "adaptive" aspects as well. Jacques

Villermaux, in his address to the World Congress on Chemical Engineering in 1996

[17], proposed that increased efficiency, productivity and selectivity could be obtained

through "intelligent operation and multi–scale control," an approach that he coined

"Smart Chemical Engineering". "Smart" design would involve assemblies of

structured, modular components and precise computer control based on information

transfer between distributed arrays of local sensors and actuators.

Local, distributed process control is a key feature of "smart" reactors, and the

multisectioned fixed bed electrochemical design described in [18] is an example of a

demonstration device based on this approach (Figure 4). When combined with

periodic operation, as suggested for example for "raster pulse electrolysis" [19],

microstructured devices constitute totally new possibilities for innovative chemical

synthesis. With this approach, one can envision a "programmable" reactor unit

mounted directly onto a printed circuit board and providing optimal spatial and

temporal profiles in reaction conditions that adjust automatically to the desired

synthesis. Local process control is naturally not limited to electrochemically

activated processes. Analogous systems involving optical fiber networks for

photochemical reactions or distributed Peltier elements for thermally activated

processes are also conceivable and deserve investigation.

35

Figure 4. “Programmable” reactor with localized process control. Comparison of a

traditional packed–bed electrochemical reactor and a microsectioned design.

(Source : LSGC–Nancy)

SMART reactors : Structured, Multiscale devices

for Advanced Reaction Technology

Recent reports on accelerated process development and concurrent

engineering have emphasized the importance of multiscale analysis and multilevel

approaches [20, 21]. SMART reactors, when viewed as a convenient acronym for

“Structured Multiscale devices for Advanced Reaction Technology”, build on these

considerations as the basis for innovative design methods in industrial production.

SMART designs are the result of increased interactions between structures (at the

micro–, meso– and macro–levels) and materials (including materials for sensors,

actuators and other functions), combined with localized process control (in space and

in time). Figure 5 summarizes the essential features of these new, highly adaptive

and efficient production systems.

36

AdvancedStructures

AdvancedMaterials

AdvancedProcess Control

multi-scalefinely defined

multifunctiontaylor-designed

locally targetedglobally optimized

SMARTREACTORS

Figure 5. The essential features of SMART reactor technology.

Although relatively easy to imagine in principle, true industrial development

and use of SMART reactor concepts must await further progress in theoretical and

experimental research, combined with corresponding advances in the

microfabrication methods required for their construction. Targeted laboratory and

pilot–scale demonstrator devices are an urgent necessity in this regard, along with

critical technico–economic analysis of potential practical applications. Despite the

difficulties, prospects and potential markets for SMART reactors are considerable,

and concerted research actions between industrial and academic institutions should

lead to rapid advances and significant perspectives for their development in the near

future.

__________

[1] R. S. Benson and J. W. Ponton, “Process Miniaturisation. A Route to Total Environmental Acceptability ?” Transactions of the Institution of Chemical Engineers, Part A, 71, 160–168 (1993). [2] K. F. Jensen, "Microchemical Systems : Status, Challenges and Opportunities," AIChE Journal, 45, 2051–2054 (October 1999). [3] A. I. Stankiewicz and J. A. Moulijn, “Process Intensification : Transforming Chemical Engineering,” Chemical Engineering Progress, 96, 22–34 (January 2000). [4] T. Bayer, D. Pysall and O. Wachsen, "Micromixing effects in continuous radical polymerization," Proceedings of the Third International Conference on Microreaction Technology (IMRET 3), Frankfurt/Main, Germany, April 19-21, Springer-Verlag, Berlin, 2000, pp. 165-170. [5] H. Heinichen, I. Leipprand and T. Bayer, "Using a micro heat exchanger as diagnostic tool for the process optimisation of a gas phase reaction," Proceedings of the World Micro-Technologies Congress, Expo 2000, Hanover, Germany, September 25-27, VDE-Verlag, Berlin, 2000, vol. 2, pp. 493-497. [6] V. Hessel, W. Ehrfeld, K. Golbig, V. Haverkamp, H. Löwe, M. Storz, Ch. Wille, A. E. Guber, K. Jähnisch and M. Baerns, "Gas/liquid microreactors for direct fluorination of aromatic compounds using elemental fluorine," Proceedings of the Third International Conference on Microreaction Technology (IMRET 3), Frankfurt/Main, Germany, April 19-21, Springer-Verlag, Berlin, 2000, pp. 526-540.

37

[7] G. Wießmeier and D. Hönicke, “Microfabricated components for heterogeneously catalysed reactions,” Journal of Micromechanics and Microengineering, 6, 285–289 (1996). [8] R. Srinivasan, I.–M. Hsing, P. E. Berger, K. F. Jensen, S. L. Firebaugh, M. A. Schmidt, M. P. Harold, J. J. Lerou and J. F. Ryley, “Micromachined reactors for Catalytic Partial Oxidation Reactions,” AIChE Journal, 43, 3059–3069 (1997). [9] U. Hagendorf, M. Janicke, F. Schüth, K. Schubert and M. Fichtner, “A Pt/Al2O3 coated microstructured reactor/heat exchanger for the controlled H2O2-reaction in the explosion regime”, in Process Miniaturization : Proceedings of the Second Int. Conf. on Microreaction Technology (IMRET 2), Editor : American Institute of Chemical Engineers (AIChE), 81–87 (1998). [10] A. Rouge, B. Spoetzl, K. Gebauer, R. Schenk and A. Renken", "Microchannel reactors for fast periodic operation : the catalytic dehydration of isopropanol,” Chemical Engineering Science, 56, 1419–1427 (2001). [11] A. R. Oroskar, K. Van den Busche and G. Towler, “Scale Up vs Numbering Up – Can miniaturization change the rules in chemical processing,”, Proceedings of the World Micro-Technologies Congress, Expo 2000, Hanover, Germany, September 25-27, VDE-Verlag, Berlin, 2000, vol. 1, pp. 385-392. [12] W. Ehrfeld, V. Hessel and H. Löwe, Microreactors : New technology for modern chemistry, Weinheim, Wiley–VCH (2000). [13] K.F. Jensen, “Microreaction engineering – is small better ?” Chemical Engineering Science, 56, 293–303 (2001). [14] J. Villermaux, D. Schweich and J. R. Authelin, “Le “Peigne du Diable”, un modèle d’interface fractale bidimensionnelle,” Comptes Rendus de l’Académie des Sciences de Paris, 304, série II, n° 8, 307–310 (1987). [15] P. Mougin, M. Pons and J. Villermaux, “Reaction and diffusion at an artificial fractal interface : evidence for a new diffusional regime,” Chemical Engineering Science, 51, 2293–2302 (1996). [16] A. Béjan and D. Tondeur, "Equipartition, optimal allocation and the constructal approach to predicting organization in nature," Revue Générale de Thermique, 37, 165–180 (1998). [17] J. Villermaux, "New Horizons in Chemical Engineering," Proceedings of the World Congress on Chemical Engineering, San Diego, California (USA), pp. 16–23 (1996). [18] C. Vallières and M. Matlosz, "A Multisectioned Porous Electrode for Synthesis of D–Arabinose," Journal of the Electrochemical Society, 146, 2933–2939 (August 1999). [19] M. Matlosz, "Electrochemical Engineering Analysis of Multisectioned Porous Electrodes," Journal of the Electrochemical Society, 142, 1915–1922 (June 1995). [20] O. Wörz, K. P. Jäckel, Th. Richter and A. Wolf, “Microreactors, a new efficient tool for optimum reactor design,” Chemical Engineering Science, 56, 1029-1033 (2001). [21] J. J. Lerou and K. M. Ng, “Chemical Reaction Engineering : A Multiscale Approach to a Multiobjective Task,” Chemical Engineering Science, 51, 1595–1614 (1996).

38

Structured Reactors, a Contribution to Process

Intensification

Jacob A. Moulijn*, A.I. Stankiewicz and Freek Kapteijn DelftChemTech, section Reactor and Catalysis Engineering, Technical University Delft, The Netherlands, E-mail: J.A.Moulijn@tnw.tudelft.nl

_________________________________

Process Intensification can dramatically change the ‘traditional’ chemical industry. It

can contribute to compact plants that are more safe, more energy-efficient and much

more selective. A drastic reduction in waste products can be the result. It is an

approach aiming at a revolution rather than an evolution.

The field of Process Intensification can be divided into two areas:

• Process-intensifying equipment

• Process-intensifying methods

The development of process-intensifying equipment includes the chemical reactor.

The reactor plays the major role in the chemical plant and in relation with Process

Intensification many promising developments are visible. A breakthrough form

structured catalysts and reactors. They give a freedom in design allowing on the one

hand high precision and on the other hand high volumetric rates. This makes them a

very promising building block for Process Intensification. By purpose structured

catalysts and reactors are mentioned together. In traditional packed bed reactors it is

convenient to see them as separate entities. In structured systems the difference

between the two vanishes.

Process-intensifying methods include multifunctional reactors. Very appealing are

catalytic distillation and membrane reactors. In the former case structured packings

are extensively studied and are found to be quite promising. The latter case is based

on membranes that also belong to the class of spatially structured systems.

The lecture will consist of a general discussion of Process Intensification and a more

specialized treatment of the most common type of structured reactor, viz., the

monolithic reactor. The emphasis will be on multi-phase systems.

Literature

I. Stankiewicz and J.A. Moulijn, ‘Process Intensification: Transforming Chemical Engineering’,

Chemical Engineering Progress, 2000, 96, 22-34

F. Kapteijn, J.J. Heiszwolf, T.A. Nijhuis and J.A. Moulijn, ‘Monoliths in multi-phase processes-

aspects and prospects’, CATTECH 1999, 3, 24-41

39

Integration of Biosynthesis and Organic Synthesis A New Future for Synthesis

Prof. Dr. Alle Bruggink Nijmegen University and DSM Research

Toernooiveld, 6525 ED Nijmegen, The Netherlands E-mail: Alle.Bruggink@dsm.com

_______________________________

Outline of a national research program

Motto: . Multi-step, (bio)-catalytic, organic syntheses.

. Simultaneous bond makings and/or cleavages.

. The end of protective group chemistry.

. Fermentation of a wide scope of natural and non-natural products.

New scientific challenges with great implications for synthetic chemistry are

developing rapidly, in particular in Life Sciences, Performance Materials and

Nanotechnology. Without a drastic and radical change in approach synthetic

chemistry can not be expected to deliver the required contributions, whereas the

timely availability of the desired molecules, employing sustainable processes in their

manufacturing, has to be at the basis of these new developments.

At the start of the chemical and pharmaceutical industry stoïchiometric synthetic

chemistry was sufficient to obtain the required molecules. With the increasing scale

and volume, in particular in the petrochemicals industry, chemo-catalysis was

required to reach efficient and economical processes. The increasing complexity and

functionality of the desired molecules, in particular in the pharmaceutical industry,

could be met through the introduction of bio-catalysis allowing mild reaction conditions

and subtle processes. However, bio-catalysis is often combined with traditional,

stoïchiometric chemistry to reach the desired synthesis goals. Translation of chemo-

catalysis from petrochemicals to a broader application in chemical and

pharmaceutical industry is still rather remote from maturity and, more importantly, will

not be sufficient to meet the present challenges. Moreover all our synthetic

methodology is still characterized by a ‘one-by-one’ approach; i.e. chemical bonds are

40

manipulated one by one, requiring several protecting groups for the remaining

functionalities and various activation mechanisms for the desired transformations.

Increased waste streams and laborious recycle loops are important drawbacks in

these developments, hampering a sustainable chemical industry for the future.

The fast developments in the industrial segments of Life Sciences, Performance

Materials and Nano-technology are causing an enormous increase in the demand for

increasingly complex molecules. Despite the great diversity of the present synthesis

tools, it is becoming increasingly difficult to synthesize these molecules, in particular

when combined with the demands for higher development speed and efficient,

sustainable processes. The limits of the present bio-/chemo catalytic synthesis

methodology are in sight.

Time has come to change strategy in synthetic chemistry. At short notice we have to

use the principles of molecular biology to guide our developments in synthesizing

molecules.

Not single enzymes or catalysts should govern our approach but complete cells or

other (rational) arrays of catalysts should steer the synthesis of the future, allowing

several transformations simultaneously. Low or no waste processes will come within

reach, whereas parallel and high-throughput experimentation programs will allow for

increased development speed combined with developing sustainable manufacturing

processes (‘the dream of one-time-right’).

This program aims at realizing the drastic and radical change in synthetic chemistry

by integrating the diversity of nowadays chemistry with the subtlety of modern

molecular biology. Biotechnology integrated into chemical synthesis will enable a new

future for synthesis meeting the molecular complexity and precision of modern

industries in health care and materials.

The presently proposed program has been formulated under the auspices of CW-

NWO by a committee of academic and industrial researchers.

41

Bio-Inspired Catalysis Increasing Sustainability

Andreas Liese

Research Centre Jülich, Institute of Biotechnology, D-52425 Jülich, Germany Tel.: ++49-2461-616044; Fax: ++49-2461-613870; email: a.liese@fz-juelich.de

________________________

E.J. Corey said: 'Nature is a wonderful chemist'. In nature the most complex chemical

molecules with a high number of stereochemical centers can be found. To synthesize

these molecules nature uses multicatalyst systems, consisting of biocatalysts,

macromolecular homogeneously soluble catalysts that are optimized to their specific

task. Bio-inspired catalysis means that principles from nature are transferred to the

classical in vitro synthesis of fine chemicals. Two principles will be discussed and

their transfer to chemical synthesis demonstrated:

1) application of multicatalyst systems

2) biocatalysts as homogeneously soluble macromolecular catalysts

1) The principle of the application of multicatalysts is transferred to the in vitro

enantioselective synthesis of diols starting from aldehydes. By coupling lyases with

oxidoreductases an efficient reaction system is designed to produce selectively all

four different diastereomers of phenylpropane-1,2-diol.

O

OHR

O

R

O

+BFD

OH

R OH

ADHNAD(P)H

To optimize such multicatalyst systems the special properties of each catalyst have

to be considered. The cofactor regeneration of NADPH could be carried out in situ

with a hydrogenase from Pyrococcus furiosus utilizing molecular hydrogen. By this

means a wasteless cofactor regeneration process is established.

42

2) The principle of biocatalysts as homogeneously soluble macromolecular

catalysts is transferred to chemical synthesis by designing and using a salen-based

homogeneously soluble polymer-enlarged catalyst (chemzyme) in chemical transfer

hydrogenation. The process characteristic values yielded with the chemzyme will be

compared to those of an alcohol dehydrogenase. By designing a continuously

operated stirred tank reactor the total turnover number of the chemzymes could be

increased significantly.

43

Functional Supports via Metathesis: Design, Synthesis and Applications

B. Mayr, M. Mayr, S. Lubbad, M. R. Buchmeiser*

Institute of Analytical Chemistry and Radiochemistry, University of Innsbruck Innrain 52 a, A-6020 Innsbruck

michael.r.buchmeiser@uibk.ac.at ____________________________________________

Metathesis-based polymerization techniques have been used for the tailor-made

synthesis of functionalized polymer supports. For these purposes, both ring-opening

metathesis polymerization (ROMP) and alkyne metathesis polymerization[1a] have

been combined with suspension[1, 2], precipitation polymerization as well as grafting

and coating techniques[3,3a]. The first part of this contribution will cover the synthesis

of such supports and their use in heterogeneous catalytic reactions such as Heck-[4],

Suzuki and Sonogashira-Hagihara couplings[5, 6]as well as atom-transfer radical

polymerization (ATRP)[7]. One important feature of the entire concept is that the

corresponding catalytic centers are not changed during polymerization. In due

consequence, a direct comparison with homogeneous analogues in terms of activity,

selectivity as well as stability may be conducted.

The second part will summarize recent results that have been obtained in the

metathesis-based synthesis of monolithic supports[8, 9,12]. Such supports are

designed to optimize catalytic activity by reducing transport phenomena, and offer

access to flow-through reactor-based reactions. Taking advantage of the “living”

catalytic sites, an“ in situ” functionalization may be accomplished by subsequently

grafting a variety of functional monomers onto the rod. Their design and use as

separation media for biomedical (protein or DNA separation[10]) as well as catalytic

applications (supported second generation Grubbs type catalysts[11]) will be

presented.

References: [1] M. R. Buchmeiser, N. Atzl, G. K. Bonn, J. Am. Chem. Soc. 1997, 119, 9166 [1a] M. R. Buchmeiser, Chem. Rev. 2000, 100, 1565

44

[2] F. Sinner, M. R. Buchmeiser, R. Tessadri, M. Mupa, K. Wurst, G. K. Bonn, J. Am. Chem. Soc. 1998, 120, 2790

[3] M. R. Buchmeiser, M. Mupa, G. Seeber, G. K. Bonn, Chem. Mater. 1999, 11, 1533 [3a] M. R. Buchmeiser, F. Sinner, M. Mupa, K. Wurst, Macromolecules 2000, 33, 32 [4] M. R. Buchmeiser, K. Wurst, J. Am. Chem. Soc. 1999, 121, 11101 [5] J. Silberg, T. Schareina, R. Kempe, K. Wurst, M. R. Buchmeiser, J. Organomet. Chem. 2000,

622, 6 [6] M. R. Buchmeiser, T. Schareina, R. Kempe, K. Wurst, J. Organomet. Chem. 2001, 634, 39 [7] R. Kröll, C. Eschbaumer, U. S. Schubert, M. R. Buchmeiser, K. Wurst, Macromol. Chem. Phys.

2001, 202, 645 [8] F. Sinner, M. R. Buchmeiser, Angew. Chem. Int. Ed. 2000, 39, 1433 [9] F. Sinner, M. R. Buchmeiser, Macromolecules 2000, 33, 5777 [10] B. Mayr, R. Tessadri, E. Post, M. R. Buchmeiser, Anal. Chem. 2001, 73, 4071 [11] M. Mayr, B. Mayr, M. R. Buchmeiser, Angew. Chem. Int. Ed. 2001, 40, 3839 [12] M. R. Buchmeiser, Macromol. Rapid Commun. 2001, 22, 1081

45

List of Participants Prof. Dr. Chris Adams Director The Institute of Applied Catalysis Kings Buildings Smith Square London SW1P 3JJ, UK Phone: +44 –20-7963 6719 E-mail: chris.adams@iac.org.uk Participant

Prof. Dr. Peter Behrens Institut für Anorganische Chemie Callinstr. 9 30167 Hannover Germany Phone: +49-(0)511-762 3697 Fax: +49-(0)511-762 3006 E-mail: Peter.Behrens@mbox.acb.uni-hannover.de Participant

Prof. Dr. Claude de Bellefon Laboratoire de Génie des Procédés Catalytiques CPE Lyon, 43 bd 11 Novembre 1918 BP 2077 69626 Villeurbanne Cedex France Phone: +33-(0)4-72 43 17 57 Fax: +33-(0)4-72 43 16 73 E-mail: cdb@lobivia.cpe.fr Participant

Prof. Dr. Alle Bruggink Nijmegen University and DSM Research Toernooiveld 6525 ED Nijmegen The Netherlands Phone: Fax: E-mail: Alle.Bruggink@dsm.com Participant

Prof. Dr. M. R. Buchmeiser Arbeitskreis Makromolekulare Chemie Institut für Analytische Chemie und Radiochemie Universität Innsbruck Innrain 52a, A-6020 Innsbruck Austria Phone: +43-(0)512-507 5184 Fax: +43-(0)512-507 2677 E-mail: michael.r.buchmeiser@uibk.ac.at Participant

Prof. Dr. François Cansell UPR9048 Institut de chimie de la matière condenseé de Bordeaux (ICMCB) Centre nationale de la recherche scientifique 87, Av du Dr. A. Schweitzer 33608 Pessac Cedex France Phone: +33-(0)5-56 84 26 73 Fax: +33-(0)5-5684 66 34 E-mail: cansell@icmcb.u-bordeaux.fr Participant

Prof. Dr. Michel Che UMR 7609 Réactivité de surface Université Pierre et Marie Curie (Paris VI) 4 Place Jussieu – Case 178 75252 Paris Cedex 05 France Phone: +33-(0)1-44 27 5560 or +33-(0)1-44 27 2577 Fax: +33-(0)1-44 27 6033 E-mail: che@ccr.jussieu.fr Participant

Dr. Pierre Gallezot Universitè de Lyon 2, avenue Albert Einstein 69626 Villeurbanne Cedex France Phone: +33-(0)4-7244 5386 Fax: +33-(0)4-7244 5399 E-mail: pierre.gallezot@catalyse.univ-lyon1.fr Participant

Priv.-Doz. Dr. Rainer Haag Institut für Makromolekulare Chemie Universität Freiburg Stefan-Meier-Str. 31 D-79104 Freiburg Germany Phone: +49-(0)761-203 4756 Fax: +49-(0)761-203 4709 E-mail: haag@fmf.uni-freiburg.de Participant

46

Dr. Torsten Hotopp Deutsche Forschungsgemeinschaft Chemie und Verfahrenstechnik Kennedyallee 40 53175 Bonn Germany Phone: +49-(0)228-885 2736 Fax: +49-(0)228-885 2777 E-mail: torsten.hotopp@dfg.de CERC3 / DFG

Prof. Dr. C. O. Kappe Institut für Chemie Karl-Franzens-Universität Graz Heinrichstrasse 28 A-8010 Graz Austria Phone: +43-316-38 05 352 Fax: +43-316-38 09 840 E-mail: oliver.kappe@uni-graz.de Participant

Prof. Dr. Riitta L. Keiski Department of Process and Environmental Engineering University of Oulu P.O. Box 4300 FIN-90014 University of Oulu Finland Phone: +358-8-553 2348 Fax: +358-8-553 2304 E-mail: riitta.keiski@oulu.fi Participant

Prof. Dr. Andreas Kirschning Institut für Organische Chemie Schneiderberg 1B 30167 Hannover Germany Phone: +49-(0)511-762 4614 Fax: +49-(0)511-762 3010 E-mail: Andreas.Kirschning@aci.uni-hannover.de Participant / Organizer

Priv.-Doz. Dr. Ulrich Kunz Institut für Chemische Verfahrenstechnik TU Clausthal Leibnizstraße 17 D-38678 Clausthal-Zellerfeld Germany Phone: +49-(0)5323-72 2181 Fax: +49-(0)5323-72 2182 E-mail: kunz@icvt.tu-clausthal.de Participant

Prof. Dr. Marc J. Ledoux Ecole Européenne de Chimie, Polymères et Matériaux de Strasbourg Université Louis Pasteur Director of the L.M.S.P.C Laboratoire des Matériaux, Surfaces et Procédés pour la Catalyse UMR 7515 du C.N.R.S. 25, rue Becquerel 67087-Strasbourg Cedex 2 France Phone: +33-(0)-685-726 183 or +33-(0)-390-242 633 Fax: +33-(0)-390-242 674 E-mail: ledoux@cournot.u-strasbg.fr Participant

Priv,-Doz. Dr. Andreas Liese Institut für Biotechnologie Forschungszentrum Juelich GmbH 52425 Juelich Germany Phone: +49-(0)2461-61 6044 Fax: +49-(0)2461-61 3870 E-mail: a.liese@fz-juelich.de Participant

Prof. Dr. Michael Matlosz LSGC-ENSIC 1, rue Grandville BP 451 F-54001 Nancy France Phone: +33-(0)383-17 52 57 Fax: +33-(0)383-32 29 75 E-mail: michael.matlosz@ensic.inpl-nancy.fr Participant

Prof. Dr. Jacob Moulijn Dept. Chemical Technology P. O. Box 5045, 2600 GA Delft The Netherlands Phone: +31 15-2786725 FAX: +31 15-2784452 E-mail: J.A.Moulijn@tnw.tudelft.nl Participant

Prof. Dr. Albert Renken École Polytechnique Fédérale de Lausanne (EPFL) Institut de génie chimique (IGC) - Chimie Laboratoire de génie de la réaction chimique et électrochimique (LGRC) Switzerland Phone: +41-21-693 3181 Fax: +41-21-693 3190 E-mail: Albert.Renken@epfl.ch Participant

47

Prof. Dr. Marja-Liisa Riekkola Department of Chemistry P.O. Box 55 Fin-00014 University of Helsinki Finland Phone: 358-9-191 50268 Fax: 358-9-191 50253 E-mail: Marja-liisa.riekkola@helsinki.fi CERC3 CHAIR

Dr. Dana Schleyer Gesellschaft für Chemische Technik und Biotechnologie e. V. DECHEMA Theodor-Heuss-Allee 25 D-60486 Frankfurt am Main Germany Phone: +49-(0)69-75 64 452 Fax: +49-(0)69-75 64 117 E-mail: schleyer@dechema.de Observer DECHEMA

Prof. Hans-Günter Schmalz Universität zu Köln Institut für Organische Chemie Greinstr. 4 50939 Köln Germany Phone: +49-(0)221- 470 3063 Fax: +49-(0)221- 470 3064 E-mail: Schmalz@uni-koeln.de Participant

Dr. Karl-Heinz Schmidt Deutsche Forschungsgemeinschaft Chemistry and Process Engineering Kennedyallee 40 53175 Bonn Germany Phone: +49-(0)228-885 2318 Fax: +49-(0)228-885 2777 E-mail: karlheinz.schmidt@dfg.de CERC3 / DFG

Prof. Ken R. Seddon Chair of Inorganic Chemistry School of Chemistry The Queen's University of Belfast Stranmillis Road BELFAST BT9 5AG Northern Ireland Phone: +44-28-90335420 Fax: +44-28-90665297 E-mail: k.seddon@qub.ac.uk Participant

Prof. Dr. Joop Schoonman Laboratory of Inorganic Chemistry Delft Institute for Sustainable Energy Delft University of Technology Julianalaan 136 2628 BL Delft The Netherlands Phone : +31-15-278 2647 Fax: +31-15-278 8047 E-mail: J.Schoonman@tnw.tudelft.nl Participant

Prof. Dr. Michel Vaultier Directeur de Recherche C.N.R.S. Directeur de l'U.M.R. 6510 Université de Rennes 1 Campus de Beaulieu Bat 10 263 Avenue du Général Leclerc 35042 - Rennes Cedex France Phone: +33-(0)2-99 28 62 74 Fax: +33-(0)2-99 28 69 55 E-mail: michel.vaultier@univ-rennesl.fr Participant

Prof. Dr. C. Vinckier Department of Chemistry KULeuven Celestijnenlaan 200F 3001 Heverlee Belgium Phone: +32-16-327 376 Fax: +32-16-327 992 E-mail: Chris.Vinckier@chem.kuleuven.ac.be Participant

Prof. Dr. Dr. h.c. E. Winterfeldt Institut für Organische Chemie Universität Hannover Schneiderberg 1B 30167 Hannover Germany Phone: +49-(0)511-762 4649 Fax: +49-(0)511-762 3011 E-mail: winterfeldt@mbox.oci.uni-hannover.de CERC3 / Observer