Deliverables

Deliverable 1: Development of novel low impact environmental methodologies for the valorisation of hemicellulose/xylan and lignin as derived from lignocellulose pretreatment or fractionation. Focus will also be placed on pretreatment/fractionation methods, since they determine the nature and capabilities of the side streams that are produced.

The deliverables of the Action are directly related to the respective objectives.
Collaborative research work was conducted (and continues after the end of the Action) on the topics of biomass pretreatment and (bio)catalytic valorization of hemicellulose and lignin streams, either in the form of “wastes/by-products” or as selectively isolated/recovered fractions.
Several methodologies have been developed and further optimized within the frame of the Action, and this can be justified by the published results in high impact referred journals as well as presentations in the Workshops and meetings (please see relevant places in the Action website: http://www.fp1306.com). Some of them have the potential of reaching an industrial production scale, but this needs further verification and can be the subject of dedicated R&D funded projects or confidential contracts between academia and industry. Still, the output and results generated by the collaborative work within this Action has certainly advanced the potential technologies one step further.
For the shake of completeness, examples of the studied/optimized methods are described below (with more details given above in the respective Objectives).


Pretreatment/Fractionation:
A variety of mechanical, physical and chemical pretreatment methods, and combinations thereof, have been studied/optimized utilizing the knowledge that was available within the Action, as well as the specific expertise of the various collaborating groups. Specific examples of selective pretreatment/fractionation methods, as also described above in more detail in the respective Objective, include:

  • - Hydrothermal (HWE, hot water extraction) pretreatment of biomass for selective removal of hemicellulose
  • - Steam explosion pretreatment of biomass (in comparison to HWE)
  • - Organosolv and hybrid organosolv steam explosion pretreatment of selective fractionation (recovery of lignin)
  • - “Lignin-first approach” which combines the features of an organosolv process with those of reductive catalytic fractionation by the simultaneous use of an appropriate catalyst at the stage of organosolv (pre)treatment
  • - Physicochemical pretreatment and fractionation of birch outer bark for the valorization of ‘oleochemicals’ and the additional ‘active’ ingredients

With regard to the down-stream valorization of hemicellulose and lignin, the following catalytic processes have been studied and developed/optimized (more details are given in the respective Objectives above):

  • - Novel efficient dehydration of biomass using alternative catalytic technologies towards a green avenue for the production of furfural
  • - High-throughput screening of heterogeneous hydrogenation catalysts for the conversion of furfural to bio-based fuel components (2-MF, 2-MTHF) – minimization of H2 use via catalytic transfer hydrogenation
  • - Catalytic condensation of furans – ketones and hydrodeoxygenation of derived condensates for fuel production
  • - Catalytic valorization of levulinic acid: Green synthesis of γ-valerolactone (GVL) via methyl levulinate hydrogenation
  • - Valorization of lignin by catalytic hydrogenation/hydrogenolysis in liquid phase systems by the use of hydrogen donor solvents (transfer hydrogenation)
  • - Catalytic pyrolysis of various lignin streams towards upgraded bio-oil for fuels or high value aromatics and alkyl-phenols for polymer production
  • - Nano-engineered photocatalysts and respective process schemes for lignin-based model molecules upgrading
  • - Engineering Enzymatic Specificity of Ligninolytic Enzymes
  • - Production of polymers and carbon Fibers from technical lignins

For all studied processes and reactions, focus has been placed on the improvement of known catalyst types or the development of new catalytic formulations, with tailored properties (i.e. zeolites, metal (nano)oxides, carbon-based catalysts, etc.). In addition, alternative reaction media/solvents and reactors have been utilized (such as microwave batch and continuous flow systems).
Techno-economic assessment and Life cycle analysis (LCA) of various processes has been considered, emphasizing on the production of aromatics and phenols via catalytic fast pyrolysis of lignin.

Deliverable 2: Production of transportation fuels, high value-added chemicals and related products from alkali & kraft lignin originating from lignin containing pulping waste liquors.

This deliverable is directly related to the above discussed Objective on the valorization of pulp and paper industry side streams, with alkali & kraft lignin being a major one. As described in that Objective the utilization of kraft and alkaline lignin comprised one of the most important aspects of the Action. The valorization of lignin as feedstock towards phenolic and aromatic monomers or as raw material for the production of high added value products (biochar, fibers) or as additive in engineering polymers, was studied in the frame of the Action. Some representative activities resulting in publications, presentations and STSMs are described below (as also highlighted in the Objective above) and are also available in the Action website: http://www.fp1306.com.


- Presentations based on joint work, describing research activities on kraft lignin and pulp industry side streams valorization:
“Toward Carbon Fibers from Single Component Kraft Lignin Systems; optimization of Chain Extension Chemistry” Dimitris S. Argyropoulos, Hasan Sadeghifar, S. Sen and Shradha (2nd Joint WG1 & WG3 Meeting, SANA Malhoa, Lisbon, Portugal).
"Bioethanol production by simultaneous saccharification and fermentation of unbleached pulp and primary sludge from pulp mills" Cátia V.T. Mendes, 1st Annual Workshop (Belgrade, Feb. 2015).
"Upgrading of industrial kraft lignin by ultrafiltration", Olena Sevastyanova, 1st Annual Workshop (Belgrade, Feb. 2015).
"Design and Simulation of Biorefinery Processes from an Acid Sulfite Pulping Mill", Alberto Coz Fernandez, 1st Annual Workshop (Belgrade, Feb. 2015).
“Kraft lignin- and iron reinforced kraft lignin- based miHRcapsules; a novel potential drug delivery system” Elisavet D. Bartzoka, Heiko Lange, Claudia Crestini, 2nd Annual Workshop (Dubrovnik, Apr. 2016).
“Lignin depolymerization from Kraft black liquor by its depolymerization in different catalytic systems”, Javier Fernández-Rodríguez, Xabier Erdocia, Pedro Luis de Hoyos, Jalel Labidi, 2nd Annual Workshop (Dubrovnik, Apr. 2016).
“Recovery of byproducts from pulping”, Daniela Painer, 3rd Annual Workshop (Torremolinos, Mar. 2017).
"Synthesis of hybrid microspheres based on kraft lignin", Marta Goliszek, 3rd Annual Workshop (Torremolinos, Mar. 2017).
“About elemental and metal content of Estonian pulp wood”, J. Kers, M. Koel, A. Konist, M. Kulp, 4th Annual Workshop (Thessaloniki, Mar. 2018).
“Organosolv and kraft lignin as epoxy polymer bio-additive”, R. Kokoli, D. Giliopoulos, K. Karagiannidis, X. Pappa, A. Fotopoulos, P. Lazaridis, A. Margellou, K.S. Triantafyllidis, 4th Annual Workshop (Thessaloniki, Mar. 2018).


- Short Term Scientific Missions (STSMs) on this topic:
“Catalytic Hydrogenolysis of Kraft Lignin towards Phenolics and Hydrocarbons” Hue Tong Vu, PhD student from University of Leipzig (Home) to Aristotle University of Thessaloniki (Host)
“Enhacement of the reactivity of sulfite dissolving pulp by mechanical pre-treatment”, Carlos Arce PhD Student from Universidad de Cantabria to Politehnica University of Bucharest.


- Special issue dedicated to lignin: A special issue dedicated to lignin valorization was edited by two members of the Action: “Lignin Refining, Functionalization & Utilization”, in ACS Sustainable Chemistry & Engineering, Argyropoulos, D. S., & C. Crestini, Guest Editors, October 3, 2016 Volume 4, Issue 10 Pages 5089-5819, http://pubs.acs.org/toc/ascecg/4/10?ref=feature
Many papers in this issue have dealt with the characteristics and valorization potential of kraft and alkaline lignins. The Editorial of this issue, provided by the two Guest Editors, describes in the best way, the potential and weakness in the field of lignin utilization for the production of high added value products. (https://pubs.acs.org/doi/10.1021/acssuschemeng.6b02173)

Deliverable 3: Exploration of novel/advanced highly selective biomass conversion routes using new customized catalytic systems and energy-efficient downstream processes with diffusion of results.

This deliverable is related to the Objective that refers to the development of novel, highly efficient and stable catalytic systems, suitable for use in biomass conversion process. As described in the above respective Objective, the activities of the Action have specifically addressed this topic, considering the peculiarities of lignocellulosic feedstocks and the minimization of energy use so that that final bio-products exhibit a positive carbon balance.

Specific cases-studies that have contributed to this deliverable are:

  • - The development of mechano-chemical methods for the preparation of stable supported (nano)metal catalysts. Representative example include the preparation of Ni and other metals supported in zeolites and carbons for lignin depolymerization reactions, the synthesis of biogenic silica-based catalysts, etc.
  • - The development of hydrothermally stable zirconia, alumina and silica-alumina based (i.e. mesoporous materials, zeolites, etc.) by various synthetic methods.
  • - The study of leaching of (nano)metals and surface reactive groups, both in batch as well as in continuous flow reaction systems.
  • - The encapsulation of enzymes in silica or other solids towards the development of more sustainable and economically viable processes.

Furthermore, specific activities that refer to the minimization of energy consumption and environmental impact are:

  • - Catalytic transfer hydrogenation methods, where hydrogen donor solvents and reaction media are being utilized for the total or partial replacement of H2 that is usually required for hydrogenation processes. Lignin hydrogenolysis and lignin bio-oil hydrodeoxygenation, furfural hydrogenation to furanics, etc. are representative examples.
  • - The utilization of photocatalysis, sono-chemical and microwave systems, to replace high energy conventional heating reactors have been widely explored both in carbohydrate conversion (i.e. xylose dehydration to furfural, selective oxidation, etc.) and in lignin valorization (selective oxidation of aromatics/phenolics, etc.).

Representative publications, presentations, projects, etc. that justify the accomplishment of the above are (more information is available on the Action’s website):
"Mechanochemical preparationof zeolite-based catalysts for depolymerisation of lignin", Jelena Milovanovic, 1st Annual Workshop (Belgrade, Feb. 2015).
“Integrated Mechanochemical Approach for the Synthesis of Biogenic Silica-based catalyst from rice husk waste”, Ana Franco, 2nd Annual Workshop (Dubrovnik, Apr. 2016).
“Study on the pyrolysis products of two different hardwood lignins in the presence of NiO contained-zeolites”, Jelena Milovanović, Rafael Luque, Roman Tschentscher, Antonio A. Romero, Hangkong Li, Kaimin Shih, Nevenka Rajić, Biomass and Bioenergy 103 (2017) 29. https://www.sciencedirect.com/science/article/pii/S0961953417301629
“Mechanochemistry: towards sustainable design of advanced nanomaterials for electrochemical energy storage and catalytic applications” Mario J. Muñoz Batista, Daily Rodríguez-Padrón, Alain Rafael Puente Santiago, and Rafael Luque, ACS Sustainable Chem. Eng., Just Accepted Manuscript, 2018, DOI: 10.1021/acssuschemeng.8b01716
“2018 Winners of the ACS Sustainable Chemistry & Engineering Lectureship Awards”, Rafael Luque (University of Cordoba):, honored for his work on mechanochemical, solventless synthesis of nanomaterials for heterogeneously catalyzed applications and flow processes, and his work on converting biomass to valuable chemical.
“Design and fabrication of TiO2/lignocellulosic carbon materials:relevance of low-temperature sonocrystallization to photocatalytic performance”. J.C. Colmenares, P. Lisowski, O.Masek, W. Lisowski, D. Lisovytskiy, J. Grzonka, K, Kurzydłowski, ChemCatChem, 2018. https://onlinelibrary.wiley.com/doi/abs/10.1002/cctc.201800604
“Mild ultrasound-assisted synthesis of TiO2 supported on magnetic nanocomposites for selective photo-oxidation of benzyl alcohol”, Juan C. Colmenares, Weiyi Ouyang, Manuel Ojeda, Ewelina Kuna, Olga Chernyayeva, Dmytro Lisovytskiy, Sudipta De, Rafael Luque, Alina M. Balu, Applied Catalysis B: Environmental, 183 (2016) 107–112, http://www.sciencedirect.com/science/article/pii/S0926337315302150
“Application of sulfonated carbon-based catalyst for the furfural production from D-xylose and xylan in a microwave-assisted biphasic reaction”. Y. Wang, F. Delbecq, W. Kwapinski, C. Len. Mol. Catal. 2017, 438, 167-172. http://dx.doi.org/10.1016/j.mcat.2017.05.031.
“Milovanovic, J.; Rajic, N.; Romero, A. A.; Li, H.; Shih, K.; Tschentscher, R.; Luque, R. Insights into the Microwave-Assisted Mild Deconstruction of Lignin Feedstocks Using NiO Containing ZSM-5 Zeolites. ACS Sustainable Chem. Eng. 2016, 4, 4305−4313.
http://pubs.acs.org/doi/abs/10.1021/acssuschemeng.6b00825
“COSMIC: European Training Network for continuous sonication and microwave reactors” H2020 funded joint project (see list below).
“Batch vs continuous flow performance of supported mono- and bimetallic nickel catalysts for catalytic transfer hydrogenation of furfural in isopropanol”. Y. Wang, P. Prinsen, K.S. Triantafyllidis, S.A. Karakoulia, A. Yepez, C. Len, R. Luque. ChemCatChem. 2018, accepted.

Deliverable 4: Short Scientific Missions (exchanges) of young researchers, Workshops and Training Schools and joint publications in the focus areas.

A Table containing figures, statistics and indicators regarding the extent of networking and the fulfillment of policies targeted by COST on Inclusiveness Target Countries (ITCs), Early Career Investigators (ECIs)/ Young Researchers, and gender balance, is available on the Action website http://www.fp1306.com/about.

An overview of the implemented activities is presented below:


    • a. STSMs: Fifty one (51) Short Term Scientific Missions (STSMs) of young researchers have been implemented during the whole period of the Action, with almost 100% being ECIs or PhD students, 24% coming from ITCs, and an almost equal male/female distribution http://www.fp1306.com/stsms.
    • b. Workshops/Conferences: Four (4) international Workshops (annual workshops of the Action) with a total of 360 participants (23% from ITCs, 29% being ECIs/PhD students, 57%/43% male/female), including plenary and keynote lectures by renowned experts in the field, oral and flash presentations as well as posters. http://www.fp1306.com/meetings.
    • c. Working Group meetings: Nine (9) WG meetings have been implemented in total, from one separate meeting for WGs 1, 2, 3, two separate meetings for WG4, and two joint WG1+WG2 and WG1+WG3 meetings. Total participants 160, with 25% being from ITCs, 21% being ECIs and PhD students, and 52%/48% male/female balance http://www.fp1306.com/meetings.
    • d. Training Schools: Two (2) Training Schools. The first on the topic of “Green Chemistry in the framework of lignocellulosic biorefineries" which took place in parallel with the 3rd International Symposium on Green Chemistry. The trainees were 39 young researchers and the courses were delivered by 14 experts in the field. As a “highlight” of the School was the round table discussions of the trainees with the experts, including experts from industry (i.e. Shell company). The second Training School was on the topic of “Catalysis Research for Biomass Utilization in Modern Biorefineries” and was held at the University of Leipzig with 27 trainees and 8 expert trainers, while a field trip to the Infrastructure in Leuna and Visit of the Fraunhofer Center for Chemical-Biotechnological Processes complemented the exciting lecture program. Detailed information about the Training Schools are provided on the Actions website http://www.fp1306.com/training.
    • e. Joint publications and presentations:
      - In the WG meetings, the Annual Workshops of the Action and other conferences that the Action members participated, there were more than 100 joint presentations (oral/poster). For example, during the 4th Annual Workshop of the Action (Thessaloniki, March 12-14, 2018), there were 50 joint presentations with affiliations from 2 or more countries and 15 presentations acknowledging the contribution and support from STSMs. http://www.fp1306.com/meetings.
      - The joint publications with at least 2 members from 2 different countries in refereed journals were more than 40. In addition to joint publications between the members, work initiated by exchanging of knowledge and open information within the Action, have also inspired new activities with relevant results coming out from the member groups, leading also to high quality publications of the individual groups (the most relevant being more than 50). http://www.fp1306.com/dissemination

      In addition to the publications to different journals, the Action organized/inspired three major Special Issues:
      - “Valorization of Lignocellulosic Biomass Side Streams for Sustainable Production of Chemicals, Materials & Fuels using Low Environmental Impact Technologies” Virtual Special Issue, in ChemCatChem (Wiley). Guest editors: Rafael Luque, Kostas Triantafyllidis http://onlinelibrary.wiley.com/journal/10.1002/(ISSN)1867-3899/homepage/2491_lignoval.html
      The main aim of this themed issue is to compile key contributions and advances from work carried out in the framework of the COST Action related to novel and innovative (bio)catalytic strategies for the valorization of lignocellulosic feedstocks and fractions (i.e. hemicelluloses, cellulose and/or lignin) and the design of catalytic materials for this purpose.
      Virtual Editorial: The challenge in biomass and lignocellulosics conversion lies in the development of novel catalytic formulations with tailored properties and increased stability, able to efficiently process such complex and recalcitrant feedstocks. https://onlinelibrary.wiley.com/doi/abs/10.1002/cctc.201600226

      - “Nano-(bio)catalysis in lignocellulosic biomass valorization”, Special Issue in Frontiers in Chemistry (Open Access), Guest editors: Rafael Luque, Christophe Len, Kostas Triantafyllidis https://www.frontiersin.org/research-topics/6419/nano-biocatalysis-in-lignocellulosic-biomass-valorization#overview
      About this Research Topic: The importance of understanding the deconstruction of biomass-derived feedstocks towards valuable chemicals, fuels and related added-value products lies in the fundamental and rational design of processes, catalytic systems and methodologies able to efficiently break down these recalcitrant feedstocks. Based on these premises, a number of different approaches have been reported in literature to valorize the main three different fractions of lignocellulosics (cellulose, hemicellulose and lignin) using a wide range of bio- nano- and photocatalyzed protocols. These have been mostly aimed towards the production of fuels and chemicals, with lignin and cellulose been the most attractive fractions to be valorized.
      Based on these premises and the relevance of the topic for biomass valorization and catalyst design based on fundamental understanding, the proposed article collection will deal with the broad topic of the design of nano- and biocatalytic systems for lignocellulosics valorization, with a particular emphasis on the valorization of hemicellulose and lignin side streams and related derived molecules.

      - “Lignin Refining, Functionalization & Utilization”, Special Issue in ACS Sustainable Chemistry & Engineering, Guest editors: Argyropoulos, D. S., & C. Crestini, October 3, 2016 Volume 4, Issue 10 Pages 5089-5819, http://pubs.acs.org/toc/ascecg/4/10?ref=feature
      About this Special Issue: The recent tremendous activity in lignin chemistry research shows that such molecular assemblies, when treated as a valuable chemical feedstock, become a material that can be used for the creation of polymeric materials, films, blends, rubber compounds, carbon fibers, drug delivery vehicles, etc. This is just to name a few of the possible applications enumerated in Lignin Refining, Functionalization, and Utilization.
      Editorial: D.S. Argyropoulos and C. Crestini https://pubs.acs.org/doi/10.1021/acssuschemeng.6b02173
    • f. Joint project proposals: More than 10 joint proposals have been submitted within the frame of H2020 or national/regional funding agencies with three of them being successful and are being implemented (see related list below). The proposals have engaged several groups from the Action as well as industrial members, as usually required in H2020 or other type proposals. As the Action has come to its end, and more collaboration and jointly developed processes have emerged, even more joint proposals are expected to arise in the future.
  • g. Other dissemination/ awareness activities (i.e. participation in conferences, non-technical documents, etc.): Some representative examples are:
    - One conference participation (dissemination grant by COST) of young researcher (female) presenting her research on the topics of the Action and advertising also the activities of the Action, on 3-7 May 2015, at La Rochelle, France, during the 3rd International Symposium on Green Chemistry (http://www.fp1306.com/dissemination)
    - The website of the Action: http://www.fp1306.com/
    - A general-audience article by the Chair of the Action, Prof. Rafael Luque on the European Energy Innovation platform/magazine presenting the scope, objectives and activities of the Action. http://www.europeanenergyinnovation.eu/OnlinePublication/Spring2017/mobile/index.html#p=57

 

 

eu