Opening

• Michael Tatoulian (Chimie ParisTech)

Room: Amphi Friedel

Moving from black to green: Development of biorefinery processes and products in Norway

• Karin Øyaas (Paper and Fibre Research Institute (PFI))

Room: Amphi Friedel Norway has significant forestry resources and ever since the late 18th century pulp and paper production has been central to the on-shore national value creation, ensuring activities along the whole forest based value chain. In 1969 oil was discovered on the Norwegian continental shelf, and since the early 1970s the expanding oil industry has ensured long-term wealth and welfare to the Norwegian society. During recent decades, however, increasing environmental concern has shifted the focus of research and innovation to strengthen the development of novel, environmentally benign processes and products based on biomass. Paper and Fibre Research Institute (PFI) is a central stakeholder focusing on research and development of new processing schemes and products based on green biomass resources. PFI is an independent research institute and has performed research on biomass conversion ever since its establishment in 1923. Since 2004 PFI has been part of the Swedish INNVENTIA group, an internationally leading concern in biomass conversion/biorefining. Today PFI’s research is centered around 4 focus areas: • Fibre and paper • Biorefinery and bioenergy • Biocomposites • Nanocellulose and carbohydrate polymers The presentation will give examples of PFI’s research activities within all these areas. In 2013-2014 PFI initiated and coordinated the establishment of the central national infrastructure project NorBioLab (Norwegian Biorefinery Laboratory), funded by the Norwegian Government through the Research Council of Norway. NorBioLab is a national infrastructure for biorefining, accessible to national and international stakeholders for the development of processes for the sustainable conversion of land and marine biomass to novel, environmentally benign biochemicals, biomaterials and bioenergy products. NorBioLab is headed by PFI and gathers central Norwegian stakeholders in the biomass conversion area, including The Norwegian Univ. of Science and Technology (NTNU), The Norwegian Univ. of Life Sciences (NMBU) and SINTEF. By uniting existing knowledge and infrastructures as well as supporting the establishment of novel research tools, NorBioLab shall allow for internationally leading research on new, innovative biorefinery processes. Acknowledgement We gratefully acknowledge the Research Council of Norway (Grant no. FORINFRA 226247/F50) for financial support of NorBioLab.

Biorefineries: The Central Role of Catalysis

• Frank Dumeignil

Room: Amphi Friedel The development and implementation of biorefinery processes is of the upmost importance to meet the vision towards a sustainable economy based on bio-resources [1,2]. In this context, catalysis, either enzymatic, heterogeneous or homogeneous is playing a major role like this is already the case in a ‘conventional’ refinery based on the treatment and the conversion of petro-resources. Nevertheless, contrary to petro-resources of which the nature and composition variations are ‘relatively’ limited, under the term ‘bio-resource’ or ‘biomass’ are gathered compounds of very different natures, namely cellulose, hemicellulose, oils, lignin and so on… Thus, a complete set of specific technologies must be developed in order to convert each fraction as smartly as possible. This implies, among others, the elaboration of a lot of processes based on catalysis. These latter constitute core technologies that will be implemented in the so-called ‘biorefineries’. Within this frame, the present author coordinated the elaboration and the development of the EuroBioRef concept 'EUROpean multilevel integrated BIOREFinery design for sustainable biomass processing' (www.eurobioref.org), as a 'large-scale' European project (2010-2014). EuroBioRef is a new highly integrated, diversified and sustainable concept, which involves all the biomass sector stakeholders. The potential of all the fractions issued from the various types of biomass is used to yield a value-added as high as possible in a sustainable and economical way. The overall efficiency of this approach is a vast improvement to the existing situation and considers options such as: Production and use of a high diversity of sustainable biomass adapted for European regions / Production and use of high specific energy bio-aviation fuels (42 MJ/kg) / Production of multiple products (chemicals, polymers, materials) in a flexible and optimized way that takes advantage of the differences in biomass components and intermediates / Improvement of the cost efficiency by as much as 30 per cent through improved reaction and separation effectiveness, reduced capital investments, improved plant and feedstock flexibility and reduction of production time and logistics / Reduction by 30 per cent of the required energy / Zero waste production and reduction of feedstock consumption. The EuroBioRef novel concept will be presented, after a general introduction on biomass, biorefineries and catalysis of which the central and key role will be discussed. Then, the next important developments for the next decade concerning catalysis for biorefineries will be presented. First, a new high throughput approach for catalysts developments materialized by the REALCAT platform [3] will be described, and then, the new concept of hybrid catalysis [4-6], integrating in one-pot chemo- and bio-catalysis, taking advantage of both technologies by creating synergies, will be presented. References 1) ‘Biorefinery: From Biomass to Chemicals and Fuels’, Edité par M. Aresta / A. Dibenedetto / F. Dumeignil, de Gruyter, ISBN 978-3-11-026023-6 (2012). 2) ‘BIOREFINERIES – An Introduction’, Edité par M. Aresta / A. Dibenedetto / F. Dumeignil, de Gruyter, ISBN 978-3-11-033153-0 (2015). 3) F. Dumeignil, L. Montagne, R. Froidevaux, S. Heyte, S. Paul. Chapitre 9 de ‘Modern Applications of High Throughput R&D in Heterogeneous Catalysis’, Bentham Science Publishers, Alfred Hagemeyer and Anthony F. Volpe, Jr. (Eds), p324-337 (2014). 4) F. Dumeignil, Public Service Review: European Union 2011, 22, 528. 5) M. Guehl, S. Desset, D. Delcroix, N. Lopes Ferreira, F. Dumeignil, FR15/50.532 Patent filed by IFPEN-UCCS (2014). 6) F. Dumeignil F., Chem. Ing. Tech. 2014, 86(9), 1496.

Switchable Ionic Liquids in Biorefining: from fractionation and pretreatment to catalysis and nanocellulose

• Jyri-Pekka Mikkola

Room: Amphi Friedel For centuries the Nordic countries have been relying on their natural resources, particularly forest, to make value-added products exported throughout the world and, at the same time, helping the societies to create wealth, job opportunities and social welfare. The global changes taking place today have gradually rendered these industries less competitive and profitable upon increasing competition from, particularly, Asia and South America when the consumption of such bulk products like paper and pulp have declined in the western word. The rise of the digital era, i.e. increasing use of electronic information and documentation, has meant that the volumes needed are in the decline in the developed world whereas the developing world still has room for growth in these products. Consequently, the industry has been forced to adapt and change, moving a lot of production capacity to there were the demand is. At the same time, increasing efforts are made to transform and trim the production in the original ‘homeland’ mills partly towards new, more innovative and more sophisticated products but also ‘back-to-basics’ i.e. packaging solutions based on cellulose. Moreover, importantly, there is a strong incentive and drive to move towards production of various value-added, modern biorefining solutions covering the areas of bio-based energy, transportation and chemical commodities. To meet the future challenges we have been developing an entirely new concept for biorefining utilizing ‘switchable’ ionic liquids (SILs) to fractionate biomass to its constituents while still to a large extent retaining their native structure [1-11]. Further, the very same SIL technology can be used for CO2 or other acid gas capture and mitigation, productions of superior nanocellulose, as a medium of catalytic reactions including both bio- and supported heterogeneous catalysis as well as pre-processing/pretreatment and detoxification of biomass for e.g. fermentation processes. References: 1. I.Anugwom, P.Virtanen, P.Mäki-Arvela, J-P Mikkola, Switchable Ionic Liquids (SILs) based on glycerol and acid gases, RSC Advances 2011, 1, 452-457, doi:10.1039/C1RA00154J 2. I. Anugwom, P.Mäki-Arvela, P. Virtanen, S.Willför, R.Sjöholm, J.-P. Mikkola, Selective Extraction of Hemicelluloses from Spruce using Switchable Ionic Liquids, Carb.Polym. 87, 3, 2012, 2005-2011; doi:10.1016/j.carbpol.2011.10.006 3. I.Anugwom, P.Mäki-Arvela, P.Virtanen, S.Willför, P.Damlin, M.Hedenström, J.-P. Mikkola, Treating birch wood with a switchable 1,8-diazabicyclo-[5.4.0]-undec-7-ene-glycerol carbonate ionic liquid, Holzforschung, 2012, 66,809-815, DOI: 10.1515/hf-2011-0226 4. Ikenna Anugwom, Eta, V., Virtanen, P., Mäki-Arvela, P., Hedenström, M., Hummel, M., Sixta, H., Mikkola, J.-P New Alkanol Amine - Organic Superbase derived Switchable Ionic Liquids (SILs) as a Delignification Solvent for Birch (B. Pendula), ChemSusChem, 2014, 7, 1170-1176, 10.1002/cssc.201300773 5. Anugwom, I, Eta, V., Mäki-Arvela P., Virtanen, P., Lahtinen, M., Mikkola J.-P., The effect of Switchable Ionic Liquid (SIL) treatment on the composition and crystallinity of Birch Chips (Betula Pendula) using a novel alkanol amine-organic superbase-derived SIL, Green Process and Synthesis 2014, 3,2, 147-154, eISSN: 2191-9550, DOI: 10.1515/gps-2013-0108 6. Anugwom, I, Eta, V.,Mäki-Arvela, P., Virtanen, P., Hedenström M., Ma, Y., Hummel, M., Sixta, H., Mikkola J.-P., Towards optimal selective fractionation for Nordic woody biomass using Novel Amine–Organic Superbase derived Switchable Ionic Liquids (SILs), Biomass & Bioenergy, 2014, 70, 373-381, DOI: 10.1016/j.biombioe.2014.08.005 6. Eta, V., Anugwom I., Virtanen P., Mäki-arvela P., Mikkola J-P, Enhanced mass transfer upon switchable ionic liquid mediated wood fractionation, Industrial Crops and Products 55 (2014) 109–115 7. E. Salminen, P. Mäki-Arvela, P. Virtanen, J. Wärnå, T. Salmi and J.-P. Mikkola, Kinetics upon isomerization of alpha and beta-pinene oxides over Supported Ionic Liquid Catalysts (SILCAs), Industrial & Engineering Chemistry Research, 2014, 53 (52), 20107–20115, DOI:10.1021/ie503999z 8. E. Salminen, L.Rujana, P. Mäki-Arvela, P. Virtanen, T. Salmi, J.-P. Mikkola, Biomass to value added chemicals: Isomerisation of β-pinene oxide over supported ionic liquid catalysts (SILCAs) containing Lewis acids, Cat. Tod. 2015, 257, 2, 318-321, DOI: 10.1016/j.cattod.2014.05.024 9. Venkata Prabhakar Soudham, Dilip Govind Raut, Ikenna Anugwom, Tomas Brandberg, Christer Larsson, Jyri-Pekka Mikkola, Coupled Enzymatic Hydrolysis and Ethanol Fermentation: Ionic Liquid Pretreatment for Enhanced Yields, Biotechnol Biofuels., 2015, 8:135, DOI 10.1186/s13068-015-0310-3 10. Valerie Eta & Jyri-Pekka Mikkola, Deconstruction of Nordic Hardwood in Switchable Ionic Liquids and Acylation of the Dissolved Cellulose, Carb. Polym. 2016, 136, 459-465, dx.doi.org/10.1016/j.carbpol.2015.09.058 11. Per Rogne, Tobias Sparrman, Ikenna Anugwom, Jyri-Pekka Mikkola, Magnus Wolf-Watz, Real-time 31P NMR shows that a hydrated switchable ionic liquid is compatible with enzymatic catalysis, ChemSusChem 2015, dx.doi.org/10.1002/cssc.201501104 (in press)

Second-generation biofuels and bio-products: an overview of recent projects at IFPEN

• Nadège Charon

Room: Amphi Friedel Second-generation biofuels produced from lignocellulosic biomass (forest residues, straw, high yield crops,…) are now one of the main technological options for reducing the climatic impacts imposed by fuels used in transportation. Two main types of process are used to convert lignocellulosic biomass into biofuels: biochemical and thermochemical processes. Today the main product from the biochemical route is known as ‘cellulosic ethanol’, produced from hydrolysis of polysaccharides and fermentation of extracted sugars. In the thermochemical processes, the initial structure of lignocellulosic solid matrix is broken down by gasification (BtL process) to produce a synthesis gas which can be converted by Fischer-Tropsch synthesis, after purification, into very high quality biodiesel and biokerosene. Bio-liquids can be also produced from other thermal treatments such as fast pyrolysis or hydroconversion. The choice of biomass valorization process depends on the characteristics of the input biomass, its availability and the type of output fuel required. Production of bio-based chemical intermediates using lignocellulosic resources is another major topic issue to deal with, in response to the need to find sustainable alternative sourcing channels for petrochemical intermediates (ethylene, propylene, etc.). A real opportunity exists to further develop a new chemical industry based on processing non-food biomass. Lignocellulosic transformation in biofuels or platform biomolecules is performed by multi-steps processes and involves complex chemical reaction pathways. The resulting aqueous or organic solutions are composed of a large diversity of oxygenated compounds (i.e. alcohols, sugars, carboxylic acids, carbonyls and phenols) whose characterization is essential to assist conversion reactions. Relevant analytical methodologies based on sample pretreatment and complementary chromatographic techniques are required to provide a detailed description of the chemical composition of these oxygenated matrices. This presentation provides an overview of some recent projects and studies in which IFP Energies nouvelles is involved to produce 2G biofuels and bio-products. A special attention will be paid on the products quality from a technical point of view, showing that analytical characterization of biomass derived liquids is a key point to get a better knowledge of their chemical composition and in this way to contribute on developing new processes for biomass transformation.

Biocatalytic enzyme processes for CO2 conversion and lignin modification

• Anne S. Meyer

Room: Amphi Friedel Global anthropogenic carbon dioxide (CO2) emissions recently reached a record high level of 35.7 billion tons per year. An agreement to achieve zero net greenhouse gas emissions and pursue efforts to limit the temperature increase to 1.5 °C during the 21st century was negotiated recently at the 2015 United Nations Climate Change Conference, COP 21, in Paris, France. Enzyme catalysis (biocatalysis) may offer new solutions to help lower CO2 emissions by removing the CO2 and actually use CO2 as a carbon substrate for production of chemicals: A designed biocatalytic cascade system based on reverse enzymatic catalysis by formate dehydrogenase (EC 1.2.1.2), formaldehyde dehydrogenase (EC 1.2.1.46), and alcohol dehydrogenase (EC 1.1.1.1) can convert CO2 to methanol (CH3OH) via formation of formic acid (HCOOH) and formaldehyde (HCHO) during equimolar cofactor oxidation of NADH to NAD+. This reaction is appealing because it represents a double gain: 1. Reduction of CO2 and 2. An alternative production route to fossil oil derived chemicals. The talk will present the efficiency of different immobilized enzyme systems and reaction designs that have been explored for optimizing this sequential enzymatic conversion of CO2 to CH3OH, and present data we have obtained at DTU from enzymes immobilized in membranes [1]. The talk will also highlight some recent important learnings we have achieved in relation to enzymatic modification of lignin, a lignocellulosic biomass conversion residue, and notably address how laccase enzymes (EC 1.10.3.2) work to oxidize phenolic substrates using oxygen and whether laccases can really act upon lignin [2]. References 1) Luo et al. Cascade catalysis in membranes with enzyme immobilization for multi-enzymatic conversion of CO2 to methanol, New Biotechnol. 2015, 32, 319–327. 2) Munk et al. Can laccases catalyze bond cleavage in lignin? Biotechnol Adv 2015, 33, 13–24. Acknowledgement: Financial support from The Technical University of Denmark, The BioValue Program, and the B21st Program (Innovation Fund, Denmark) are gratefully acknowledged.

From different biomass to new macromolecular architectures, based on aliphatic-aromatic polyurethanes

• Luc Averous

Room: Amphi Friedel

Low-temperature transformation of biomass: challenge for chemical reaction engineering

• Tapio Salmi

Room: Amphi Friedel The global tendency towards the use of renewable sources is a big challenge not only for conceptual chemical technology, but to chemical engineering, too. We are shifting from relatively simple molecular structures appearing in crude oil and natural gas to the very complex ones in biomass. Molecules originating from biomass are, typically polyfunctional macromolecules. On the other hand, biomass is a well-organized entity, consisting mainly of cellulose, hemicelluloses and lignin. The sugar platform of a future biorefinery is based on bio-chemical conversion processes of biomass to sugar feedstocks, while the syngas, pyrolysis platform is based on thermo-chemical conversion processes of biomass to synthesis gas or pyrolysis oils for chemicals, materials and fuels. There are still several problems to be solved to make the mild-temperature sugar platform working in practice. One of the key issues is the catalyst development. In order to obtain platform chemicals from cellulose and hemicellulose, the glycosidic bonds should be broken by hydrolysis. Several catalysts have been proposed, such as homogeneous mineral and organic acids, heterogenized acid catalysts on carbon support, cation exchange resins as well as enzymes. The hydrolysis kinetics of polysaccharides in the presence of several catalysts is considered, along with kinetic modelling of autocatalytic phenomena appearing in the hydrolysis of polysaccharides. A new kinetic model for the hydrolysis kinetics has been developed, taking into account the differences in the reactivities of the glycosidic bonds in the polymer chain. From the mild-temperature hydrolysis process, valuable monomeric sugars are obtained: besides glucose, polyfunctional molecules, such as arabinose, galactose, mannose and xylose are obtained. These molecules can be used as such, or refined further, e.g. by hydrogenation, oxidation and isomerization. The process intensification approach starts with catalyst selection and optimization, kinetic studies, investigation of physical properties as well as mass and heat transfer phenomena. In general, it can be stated that the interaction of chemical reaction kinetics and internal mass transfer effects in the pores of solid catalysts plays a crucial role in the transformation of molecules from biomass. In many cases, catalyst deactivation interferes with kinetic and mass transfer phenomena. Several examples of the application of continuous structured reactors on the transformation of sugars to value-added molecules are shown in the lecture. The approach covers the following possible aspects: from the optimization of catalyst nanoparticles to the design of structured elements, kinetic and mass transfer studies, mathematical modelling of individual catalyst particles and continuous reactors. A general research strategy will be presented: from reaction kinetics to reactor design. Acknowledgement: Financial support from Academy of Finland is gratefully acknowledged.

Design of bio-based solvents

• Sophie Thiebaud-Roux (ENSIACET/INRA)

Room: Amphi Friedel The European consumption of solvents is significant, with about 6 million metric tons out of the 28 million tons worldwide consumed in 2012.[1] They are used in many applications such as the formulations of pesticides, inks, and paints, or for industrial cleaning, extraction / separation processes and syntheses. The depletion of fossil resources, stricter regulations and collective awareness for the environmental protection incite the development of alternatives to the use of petrochemical solvents. Therefore, the chemical industry shows a growing interest in designing bio-based solvents made from renewable raw materials and supposed to prevent hazards in the field of health, safety and environment. Two methodologies different from the trial and error approach, were developed to design these novel bioproducts. The first methodology, predictive, is based on the properties prediction thanks to various models [2] before the synthesis of the molecules. The reverse design is, in turn, an innovative methodology to design molecules of biosolvents through a virtual laboratory. Stages of generation of molecular structures and properties prediction are integrated in a computer-aided molecular design tool (CAMD) providing solutions that meet the outlined specifications. This tool is able to help the chemist to find out the optimal structures in agreement with defined specifications in terms of physico-chemical properties (Hansen solubility parameters, boiling point, melting point, vapor pressure, and flash point), toxicity and ecotoxicity. [3] These methodologies lead to identify a pool of candidate molecules derived from a bio-based building block that may act as a solvent for the target applications. Then, the relevance of these best candidates is checked with respect to their ability to be synthesized according to the green chemistry principles and their real performance in the target application. The feasibility of their syntheses is studied by retrosynthetic analyses. The reverse design approach is more rational and efficient to find the best molecules suitable for the application: it presents the advantages to generate time, energy and cost-savings. Only potentially interesting molecules (with predicted properties meeting the specifications) are synthesized and validated in application. References [1] IHS Chemical Global Solvents Report: Opportunities for Greener Solvents [2] M. Bergez-Lacoste, S. Thiebaud-Roux, P. De Caro, J.F. Fabre, V.Gerbaud, Z. Mouloungui, "From chemical platform molecules to new biosolvents: Design engineering as substitution methodology", Biofuels, Bioproducts & Biorefining 2014, 8, 438-451. [3] J. Heintz, J.P. Belaud, N. Pandyaa, M. Teles Dos Santosa, V. Gerbaud, Computer aided product design tool for sustainable product development, Computers and Chemical Engineering 2014, 71, 362–37

The role of pervaporation in biorefineries

• Riitta Keiski (Oulu University)

Room: Amphi Friedel

Welcome, registration, opening Room: Amphi Friedel

CNRS support tools for French-Nordic cooperation

• Chantal KHAN-MALEK (CNRS - DERCI)

Room: Amphi Friedel

Feedback from ANR projects

• Patrick Cognet (ANR / ENSIACET)

Room: Amphi Friedel

Presentation of 3BCAR

• Paul Colonna (INRA)

Room: Amphi Friedel

Face-to-face meetings & Coffee Room: Amphi Friedel