Final Report Summary - NOVACAM (NOVel cheap and Abundant Materials for catalytic biomass conversion)
Executive Summary:
The NOVACAM project (as one of three Critical Raw Materials projects) was part of NMP - Nanoscience, Nanotechnologies, Materials and New production Technologies - Coordinated call EU - Japan 2013 Programme of the EU Commission.
NOVACAM was a joint EU-Japanese project with the goal to develop novel technology to enable the substitution of critical metals in industrial catalysts. Industrial use of biomass feedstock is at an early stage and presents an opportunity to develop the next generation of catalysts that is based on abundant elements. Catalysts are one of the six major uses of critical metals. Many industrial heterogeneous catalysts have been developed empirically, such that the role of critical metals in affecting catalyst performance is not clearly understood yet.
The overarching objective of the project was to construct an innovative science base of novel catalytic technologies to enable the conversion of lignocellulosic biomass to useful and valuable organic chemicals, polymers, and transportation and heating fuels. The underlying science was developing and demonstrating new principles for achieving excellent catalytic properties by control and manipulation of the composition and structure of solid catalysts made from abundant materials. NOVACAM aimed to develop innovative catalysts by applying a “catalysis by design” approach, integrating the complete chain of knowledge from fundamental research to proof of concept.
NOVACAM developed catalysts using non-critical elements for the conversion of biomass to chemicals and fuels and targets to establish a solid basis for knowledge-based catalytic technology involving cheap and abundant elements. The focus was on lignocellulosic biomass as it will be possible to supply chemicals without adversely impacting land and other resources which are needed for food production. Specifically, NOVACAM used a “catalysis by design” approach to formulate the requirements for inorganic catalyst systems to speed up different steps relevant to upgrading of biomass. These nanoscale insights were then used to develop novel catalysts based on abundant elements and validated in three proofs of concept studies at laboratory scale to convert cellulose/sugar feedstock into fuels and chemicals. In this way, the extensive knowledge base acquired in catalysis research has been employed to design novel inorganic catalytic systems.
NOVACAM brings together seven academic partners: Eindhoven University of Technology (The Netherlands), Kanagawa University (Japan), Cardiff University (United Kingdom), Instituto Technologia Quimica (Spain), Hokkaido University (Japan), Tokyo Institute of Technology (Japan) and Chiba University (Japan), who combine excellence in catalysis research with a long-standing tradition in mission-driven research in collaboration with industry. Knowledge Transfer Network is UK’s innovation network and responsible for dissemination, exploitation and training within the NOVACAM consortium.
The project outcomes are derived from the complementary expertise in the field of innovative catalyst research between the academic partners. With the coordinated cooperation, the two consortia shared the same goals, building on each other’s expertise through exchange of academic personnel and joint project meetings, conferences and webinars. Especially, the exchange of young researchers such as PhD students, postdocs and young staff members has a positive effect on their development.
NOVACAM led to a high level of scientific output: more than 30 papers were published in peer-reviewed scientific publications, many of which were joint between EU or Japanese groups and several joint EU-Japanese. The number of conference contributions is higher than 50; participation in these conferences proved to be important to enhance the contact between the project partners. The project has also led to 6 PhD theses, 3 at the EU and 3 at the Japanese side.
Project Context and Objectives:
Raw materials are fundamental to Europe’s economy and they are essential to our quality of life. Critical raw materials refer to materials of high economic importance to the EU combined with a high risk associated with their supply. Catalysts are one of the six major uses of critical metals that are produced as byproducts of mining of primary metals, e.g. platinum group metals and lanthanides. The critical elements are widely used in many types of catalytic processes in petrochemical production and downstream conversion to high value products: in many cases they are also the default option for biomass conversion.
NOVACAM was an EU-funded FP7-NMP project with the goal to develop novel technology to enable the substitution of critical metals in industrial catalysts. Industrial use of biomass feedstock is at an early stage and presents an opportunity to develop the next generation of catalysts that is based on abundant elements. Catalysts are one of the six major uses of critical metals that are produced as byproducts of mining of primary metals, e.g. platinum group metals and lanthanides. Many industrial heterogeneous catalysts have been developed empirically, such that the role of these critical metals in affecting catalyst performance is not clearly understood yet.
The overarching objective of the project was therefore to construct an innovative science base of novel catalytic technologies to enable the conversion of lignocellulosic biomass to useful and valuable organic chemicals, polymers, and transportation and heating fuels. The novel catalytic technologies would completely eliminate the use of critical raw materials for these processes, and would have low environmental impacts. The underlying science was developed and demonstrated new principles for achieving excellent catalytic properties by control and manipulation of the composition and structure of solid catalysts made from abundant materials. With this, NOVACAM aimed to develop innovative catalysts by applying a “catalysis by design” approach, integrating the complete chain of knowledge from fundamental research to proof of concept.
The project was carried out with a partner consortium in Japan with complementary expertise in the field of innovative catalyst research.
The EU Consortium
In order to achieve the above objectives, the NOVACAM consortium involved three academic partners, namely TUE – EU coordinator (Eindhoven University of Technology, The Netherlands), CU (Cardiff University, United Kingdom) and CSIC - ITQ (Agencia Estatal Consejo Superior De Investigaciones Cientificas - Instituto Technologia Quimica, Spain), who combine excellence in catalysis research with a long-standing tradition in mission-driven research in collaboration with industry. TUE has extensive experience in mechanistic studies in heterogeneous catalysis involving quantum-chemical studies. CU brings in expertise in the field of catalyst synthesis targeted at chemical conversion processes. ITQ has broad expertise in heterogeneous catalysis of biomass conversion. KTN (Knowledge Transfer Network) is UK’s innovation network, bringing together business, entrepreneurs, academics and funders. Within NOVACAM, KTN was responsible for dissemination, exploitation and training within the NOVACAM consortium. KTN is very well connected into the EU community dealing with issues of sustainability including critical raw materials replacement.
The work in the consortium was closely interconnected to and coordinated with a Japanese consortium of academic groups led by Kanagawa University. The work at the Japanese side was funded by the Japanese Science and Technology Agency. With the coordinated cooperation, the two consortia shared the same goals, build on each other’s expertise through exchange of academic personnel and joint project meetings.
NOVACAM addressed the development of novel technology to enable the substitution of critical metals in catalysts. The project aimed to develop catalysts using non-critical elements for the conversion of biomass to chemicals and fuels. NOVACAM targeted to establish a solid basis for knowledge based catalytic technology involving cheap and abundant elements. While biomass in all its forms is potentially available as a renewable feedstock for chemicals, we focued in this project on the use of lignocellulose. Potentially, this can be converted into a whole range of existing useful chemicals and fuels, and also into new and different chemicals as better alternatives. It has the great benefit that starting from lignocellulose it will be possible to supply chemicals without adversely impacting land and other resources which are needed for food production.
NOVACAM develops catalysts using non-critical elements for the conversion of biomass to chemicals and fuels and targets to establish a solid basis for knowledge-based catalytic technology involving cheap and abundant elements.
The main objectives of the project were (i) to understand by a “catalysis by design” approach the requirements for inorganic catalyst systems to speed up elementary reaction steps and valorise biomass with a focus on conversion of cellulose into fuels and chemicals; (ii) using these nanoscale insights to develop novel catalysts based on abundant elements for the conversion of biomass and (iii) to develop three proof of concept studies at laboratory scale to convert cellulose/sugar feedstock into fuels and chemicals - specific attention will be paid to catalyst robustness. In this way, the extensive knowledge base acquired in catalysis research has been employed to design novel inorganic catalytic systems.
The work in NOVACAM was organized in two technical work packages (WP1 & WP2), complemented by two work packages dedicated to dissemination, exploitation and training (WP3) and to project management (WP4). The work related to dissemination was undertaken in WP3. The webpage, templates, dissemination material and press releases were provided. One training workshop with external participants and the final conference were organized. The specific activities will be described in the appropriate chapters of this report. Within WP4 all activities related to management and co-ordination were combined. Reports and deliverables were submitted in time, according to the revised schedule reflecting the amendment process. Project meetings and management committee meetings were organized, all issues dealing with payment and distribution were successfully fulfilled. The communication and everyday work kept the project smoothly running and supported effective and prosperous research and co-operation.
The total duration of the project was 42 months. The work plan was structured around developing the basic chemistry that underlies proof of concepts. The basic chemistry was addressed in the first two years of the project in work package 1, the proof of concepts was gaining attention in the last 24 months of the project in work package 2.
The work programme was organized on the basis of discussions between the European and Japanese academic scientists, the Industrial Advisory Committee and KTN on the essential knowledge, methods and tools to implement a new vision on rational catalyst design aimed at complete removal of critical elements. The objectives were defined to aim for a breakthrough progress in catalytic biomass conversion based on recent advances of knowledge in fundamental research, but within the boundaries of economic competitiveness and a vision compatible with industry. An essential aspect here was to combine a bottom-up approach in catalyst design with insights from modern catalysis research, which imply the use of state of the art tools. The overall strategy for the project was to begin with research on fundamental chemistries, followed by a three proofs of concept projects which take the new knowledge forward and develop it in an integrated context.
General structure of the work programme of the NOVACAM project
In agreement with the call text, the work by the consortium was separated from that of the Japanese consortium in that different classes of materials (EU: metal nanoparticles and zeolites; Japan: metal nanoparticles and base metal oxides) were investigated in line with the expertises of the two teams. However, to foster collaborative efforts, the EU and Japanese consortia have jointly decided on the work packages. This implies that the tasks at the EU and Japanese sides were similar, except some generic tasks (T1.4 - Novel chemistry in molten salts, T2.4 - Techno-economic evaluation and all tasks in WP3 - Dissemination, Exploitation and Training). A similar WP4 at the Japanese side covered financial and administrative management of the Japanese consortium. The cooperation between the two consortia was therefore considered one of the joint goals, joint meetings and exchange of young scientists who carried out characterisation and activity testing of the specific materials developed in each of the consortia.
WP1: Fundamental Chemistry of Catalytic Biomass Conversion eliminating critical metals
1) To develop novel catalytic chemistry for the basic reaction steps needed for upgrading cellulose/sugars including hydrogenation-dehydrogenation, decarboxylation, dehydration and isomerisation based on inorganic catalyst systems totally eliminating the use of non-critical metals.
2) To synthesise non-critical metal (oxide) clusters and nanoparticles on (porous) supports by sol immobilisation, chemical vapor deposition and precipitation concepts.
3) To synthesise structured catalysts, e.g. zeolites, nanostructured or with novel pore topologies and functionalised with well-defined isolated reaction sites and also metal oxides with metal cations in well-defined reaction environments.
4) To characterise in detail the active reaction centers by advanced microscopic and spectroscopic tools.
5) To undertake catalytic testing of novel non-critical metal (NCM) catalysts using biomass model compounds.
6) To develop fundamental knowledge on catalytic mechanism using catalysts for biomass conversion by theoretical modeling studies.
7) To explore the use of novel NCM catalysts in molten salt solvents.
WP2: Proof of concept: Catalytic Biomass Valorisation using Non-Critical Metals Catalysts
1) Translate outcomes of WP1 (novel NCM catalysts) into proofs of concept for biomass valorisation at the laboratory scale.
2) Evaluation of single- and multi-step approaches for the depolymerisation, decarboxylation and transfer hydrogenation of cellulose/glucose to γ-valerolactone using novel NCM catalysts.
3) Evaluation of single- or multi-step approaches for the valorisation of glucose into lactic acid and ethanol using novel NCM catalysts.
4) Evaluation of NCM catalysts for aqueous phase reforming of glycerol and glucose.
5) Use all of the results obtained in objectives 2-4 and those of WP1 to make a techno-economic feasibility analysis of the proof of concept against benchmark systems.
WP3: Dissemination, Exploitation and Training
1) To maximise the impact of the project through wide dissemination of the results of the project and its achievements to audiences within the chemical industry, the scientific community and the wider community interested in the substitution of critical raw materials.
2) To help increase uptake of the technology to improve competitiveness and sustainability within EU industry, reduce dependence on imports of scarce materials and maximise EU competitiveness.
WP4: Financial and administrative management
1) The objective is to realize a coherent and efficient project management. Specific objectives are to (i) ensure that objectives are met, schedules maintained, and budgets honored, and (ii) foster and boost interrelations between teams, exchange of knowledge and information between teams involved in the different approaches.
2) To improve the functionality of the project by managing specific objectives, the two functions of coordination and project management have been separated. This WP includes constant monitoring of the project management to improve its effectiveness.
Project Results:
Green synthesis of value-added chemicals from biomass has received widespread attention in recent years due to the availability of wood or agricultural residues as renewable feedstocks and an increase in CO2 emissions associated with the consumption of fossil fuels. Lignocellulose, the main component of abundant biomass resources, consists mainly of cellulose (35-50%), hemicellulose (20-35%), and lignin (10-25%). A variety of hydrothermal, chemocatalytic, and biological techniques have been proposed for the depolymerization of cellulose and hemicellulose into constituents such as glucose, xylose, and arabinose. However, as for chemocatalytic processes, single reaction-single catalyst systems on the basis of high catalytic performance noble metals and rare elements, that have been widely employed in the petrochemical process, cannot simply turn in biomass conversion reactions because the essence of the biomass conversion is a complicated multi-step reaction process like cascade reaction and domino reaction. In addition, the biomass reactants often contains water or the biomass reactions form water, so that catalysts for the reactions have to be highly water tolerant, which is not so common in the petrochemical process. Therefore, it is extremely important to establish multifunctional solid-state catalyst by combination of abundant elements in order to make biomass conversion a simple, easy, and low cost reaction process. In other words, the recent demand of biomass utilization as chemicals and fuels promotes the development of novel cheap and abundant catalysts, which is the main target and challenge of NOVACAM project. NOVACAM is intended with the goal of the use of lignocellulose important as biomass resources by catalytic process of plural non-rare elements. Achieved reactions by uniform artificial catalysts that are deployed structurally and that many functions are accommodated will be beyond the creature fermentation of biomass. This approach of catalytic element shift from critical elements to non-critical ones is with conjugations from abiotic oil resources to the biologic resources use.
Interactive collaboration among more than two of non-precious elements either in metal oxide form or in metallic form in well-organized state in terms of material structures is a key catalytic material synthesis concept for introducing multi-functional catalytic properties in solid-state materials in this project. For example, unit synthesis using metal oxide clusters for creating high-dimensionally structured complex metal oxides, oxide surface elemental complication on oxide surface by photo-induced functionalization, week oxide-oxide interaction in a form of amorphous complex oxide, and bimetallic formation on oxide surface are employed. These approaches are realized and strengthened by fundamental characterization and supported by theoretical calculation.
The highlights of the NOVACAM project were:
• To understand, by a “catalysis by design” approach, the requirements for inorganic catalyst systems to accelerate the elementary reaction steps needed to depolymerize, deoxygenate, isomerise and couple biomass constituents with a focus on cellulose conversion into fuels and chemicals
• To develop based on these nanoscale insights novel functional materials composed of cheap and abundant elements for the catalytic upgrading of biomass
• To develop three proofs of concepts at the laboratory scale to upgrade cellulose/sugar feedstocks to fuels and chemicals using catalysts based on non-critical elements with specific attention for catalyst robustness
The catalysis by design approach we have been employed to address these challenging and exciting objectives will integrate the complete chain of knowledge from fundamental concepts (theoretical studies of reaction mechanism and in-situ spectroscopic studies), via advanced synthesis protocols involving self-assembly approaches to complete laboratory proof of concept. In this way, the extensive knowledge base acquired in the last decades in catalysis research including tools and techniques have been employed to design novel inorganic catalytic systems.
The research work programme in NOVACAM was divided in two phases. In the first phase covering the first half of the project, fundamental studies were been employed to study the mechanistic and active site requirements for the underlying chemistry to valorise biomass. NOVACAM focused on transformations by highly selective catalysts in order to retain as much of the functionalities which nature has built into the final product molecules. To this purpose, modern tools such as advanced materials characterisation, quantum-chemical modeling of the surface reaction processes and modern synthesis approaches were been employed.
The second phase of the project covered the use of these insights to develop three proofs of concept at the laboratory scale: Given its size and the goal to arrive at proof of concept on the laboratory scale, we were focused on the valorisation of cellulose and carbohydrates, which are the dominant part of lignocellulosic (2nd generation) biomass. We envisaged at this time of writing the application that the three systems will be as follows:
• The valeric platform – this work comprises the development of novel catalytic routes from cellulose to γ-valerolactone, which is a platform for the production of transportation fuels. The objective was to replace state of the art precious metal based catalysts by cheaper metals and to decrease the number of steps in the upgrading process of cellulose by introducing novel chemistry.
• Chemocatalytic glycolysis – to replace the conventional acid-catalyzed cellulose depolymerization and glucose dehydration approaches and the more promising ones using a critical (and toxic) metal as chromium, novel approaches based on cheap metal oxides and well-defined Lewis acid sites in nanostrucured porous zeolites will be the target. The target product was lactic acid, the monomer for the biodegradable polymer PLA, and a possible intermediate to useful chemicals such as acrylic acids. A high risk, high reward task has been to develop decarboxylation chemistry (lactic acid to ethanol), by which a synthetic chemocatalytic glycolysis route would become available which can potentially replace the slow enzymatic process and create a possibility for the direct ethanol synthesis from cellulosic biomass.
• Aqueous phase reforming – This process produces hydrogen from biomass-derived oxygenated compounds such as glycerol and sugars. It is unique in that the reforming is done in the liquid phase, so there is no need to vaporize water representing energy savings and the possibility to convert sugars. The state of the art catalysts are precious metal nanoparticles. In this project, we targeted their replacement by cheaper metals, whose chemical state and nanoparticle size will be optimized to maximize hydrogen production.
The outcomes of the project are a combination of new knowledge in the catalysis domain and proof of concepts in which lignocellulosic biomass is converted into valuable products by novel processes that do not rely on noble metals.
Through the intensive collaboration between EU and Japanese partners and the “Catalysis by Design” approach, new chemistry has been developed in the area of biomass upgrading. The gained insights are currently being explored in a proof of concept setting concerning three principle routes:
1. Upgrading of cellulose to γ-valerolactone (GVL) by novel non-noble catalysts
a. Identification of non-critical metal catalysts based on Cu, Fe and Ni and combinations thereof for the vapor or liquid phase hydrogenation of levulinic acid to GVL.
b. Exploration of support effects on non-critical metal catalysts to boost the activity in levulinic acid hydrogenation.
2. Upgrading of sugars to platform molecules
a. Novel catalytic chemistry has been developed for the conversion of cellulose and glucose into platform chemicals. New catalytic materials include phosphated titania, cheap bulk oxides and tailored Lewis-acid base compounds. The mechanism of the underlying chemistry was resolved by a combination of quantum-chemical calculations and in situ spectroscopy.
b. Novel crystal structured metal oxide catalysts with molecular nanowire form and with porosity have been developed on the basis of group V and VI elements.
c. A new catalyst for the oxidative dehydrogenation of lactic acid has been developed.
3. Aqueous phase reforming for hydrogen generation
a. The catalytic activity of doped graphenes has been evaluated for the aqueous phase reforming of glycerol, being the B-doped G the most active catalyst in the series.
Main outcomes
The scientific work of NOVACAM was divided in 2 work packages and for each work package different tasks were formulated. The main result within these work packages and tasks are summarized as follow:
WP1: Fundamental chemistry of catalytic biomass conversion eliminating critical metals was dedicated to the development of novel catalysts by rational design approaches to address the basic reaction steps needed to convert biomass in an efficient manner. Key requirement was to avoid critical metals. The performance of the novel designed catalytic materials were been evaluated in relevant test reactions. All academic partners in the EU and Japanese consortia were been involved in WP1. The (EU) Beneficiaries focused on first row transition metals in combination with Lewis acid functionalised porous zeolites. The (Japanese) Partners were been working mainly on base metal oxide, consistent with their expertise in this area. Specific tasks were formulated around the basic chemistry for catalytic biomass conversion. Since we employed a modern “catalysis by design” approach, the basic concepts in the various tasks were similar.
The collaborative efforts arised in a bottom-up approach through the academic researchers with the coordinators at the EU and Japanese side facilitating and safeguarding exchange expertise through joint meetings, telecons and exchange of personnel and samples.
Task 1.1: Hydrogenation chemistry
Prepare NCM catalysts for the hydrogenation/dehydrogenation of biomass feedstock. Precious group metal replacement candidates are Co, Ni, Fe and Cu. Techniques will be developed to optimise the surface morphology, particle size and metal-support interaction for each of the target reactions. Use of techniques such as sol-immobilisation and chemical vapor deposition, optimisation of stabilisation and reducing agents. The test reaction for (transfer) hydrogenation is succinic acid hydrogenation (with formic acid).
• TiO2-supported Ni-Re and Fe-Re catalysts are identified as promising catalyst systems for the reductive transformations of biomass-derived carboxylic acids and in particular for levulinic acid hydrogenation to γ-valerolactone.
• γ-valerolactone can be obtained from levulinic acid with yields of >90% in water with Ni:Re/TiO2 catalyst at a temperature as low as 130 °C in water.
• Silica-supported Cu-Ni bimetallic catalysts with a Cu/Ni weight ratio of 3/7 exhibit excellent catalytic activity in vapor-phase hydrogenation of levulinic acid (LA) into GVL. A GVL yield in excess of 98% with a productivity of 6.48 kgGVL kgcat.-1 h-1 was achieved at WHSV of 6.60 h-1.
• Vapor-phase hydrogenolysis of GVL into 1,4-pentanediol was optimally carried out with a Cu-ZnO catalyst calcined at 500 oC.
Task 1.2: Decarboxylation chemistry
Development of novel chemistry for the decarboxylation of biomass constituents. Explore the use of small NCM oxide clusters or cations in functionalised zeolites. Synthesis and evaluation of delaminated zeolites or nanostructured zeolites. Test reactions involve the decarboxylation of levulinic acid into 2-butanone and decarboxylation of sugars.
• New chemical pathways for decarboxylation of lactic acid discovered.
• TiO2-supported transition metal photocatalysts allow a strong enhancement of the decarboxylation rate by promoting the concert decarboxylation and dehydrogenation of the substrate resulting in acetaldehyde as the main product.
• A record-high lactic acid decarboxylation activity is obtained with the noble metal-based Pt/TiO2 catalyst.
• An alternative highly active NCM-type Ni/TiO2 photocatalyst is identified.
• Photocatalytic decarboxylative acceptorless dehydrogenation can be used to develop new sustainable routes for low-temperature oxidative coupling of lactic acid with H2 as the major useful by-product.
• A highly active and selective MoO3/TiO2 catalyst made of non-critical elements for lactic acid oxidative dehydrogenation is developed.
• The highest selectivity of about 90% to pyruvic acid at 50% lactic acid conversion can be obtained with 1%Mo catalyst.
• In the absence of external oxidant a transfer hydrogenolysis process to produce propionic and pyruvic acids in equimolar amounts can be carried out with these catalysts.
Task 1.3: Isomerization/Dehydration chemistry
Development of heterogeneous Lewis acid catalysts based on NCM consisting of Lewis acid cations embedded in zeolites. Exploration of large pore zeolites and/or delaminated zeolites. Modification of surfaces to control Lewis and Brønsted acidity. In-situ spectroscopy to evaluate surface acidic properties. Use of nanostructured zeolites for higher accessibility. Test reactions are the isomerisation of glucose to fructose, the direct dehydration of glucose to 5-hydroxymethylfurfural and the conversion of 1,3-dihydroxyacetone to lactic acid.
• Based on a methodology involving building units, self-assembly of Mo-O or W-O octahedra with SeIV, TeIV or PIII formed hexagonal-shaped [XY6O21] (X = P, Se, Te, and Y = Mo, W) units which connect each other though X-O-X bond to grow infinite chains, inorganic molecular wires was achieved. These highly stable nanowires display high activity in biomass hydrolysis to convert cellulose into hexoses. Combined with Sn-W-Se oxide, promising results in the conversion of cellulose to levulinic acid were achieved.
• Porous niobium and tantalum oxyfluorides were synthesized, rendering suitable acidic materials for the catalytic conversion of cellulose and 1,3-DHA. Characterization shows that these materials contain not only Brønsted acid sites but also water tolerant Lewis acid properties, enabling conversion of cellulose into lactic acid.
• A novel YNbO4 catalyst was introduced involving a Lewis acid-base pair able to convert glucose to lactic acid in water. This catalyst system is also active for the conversion of glucose to HMF.
• High phosphate-loaded TiO2 catalyst was developed for dehydration of glucose to HMF. High activity, selectivity and robustness was achieved, rendering this one of the most promising materials in the consortium. Quantum-chemical calculations allowed identifying a novel highly favorable reaction mechanism involving cooperation between Lewis acid and Brønsted base sites for the direct glucose to fructose dehydration is identified for TiO2-based catalysts. These efforts confirm that bare TiO2 adsorbs a large amount of glucose, so that intermolecular reactions between adsorbed glucose molecules or between adsorbed glucose molecules and 3-deoxyglucosone are enhanced, resulting in low HMF selectivity. Phosphate-immobilization on TiO2 decreases these intermolecular side reactions by decreasing the surface glucose concentration, which increases the HMF selectivity.
• Bulk tungsten oxide was identified as another promising catalyst with combined Brønsted and Lewis acidity. Transition metal doping guided by quantum-chemical calculations proved to be a promising strategy towards new oxide-based catalysts for sugar isomerization. The formation of oxygen vacancies on the tungstite surface can substantially enhance its reactivity and open a new reaction channel involving a one-step glucose isomerization to fructose
• Advanced ab initio molecular dynamics simulations confirms the strong promoting role of cooperative action between the Lewis and Brønsted acidic centers in Sn-zeolite catalysts for the selective glucose to fructose isomerization reaction. In situ NMR confirmed theoretical predictions on the crucial role of competitive adsorption between solvents and carbohydrate substrates on the activity of zeolite-based systems. In combination with DFT modeling, a promising mixed solvent system is identified for glucose conversion over Sn-Beta catalyst.
• Niobium oxide supported on modified carbon nanotubes can convert glucose into succinic acid or lactic acid with high selectivity at high conversion. The fine balance between Brønsted and Lewis acid sites is crucial to achieve the optimal catalysts.
Task 1.4: Novel chemistry in molten salts
Evaluation of catalytic performance of NCM catalysts developed in tasks 1.1-1.3 in molten salts and other solvents as a possible reaction medium facilitating the depolymerisation of cellulose. Development of heterogeneous Lewis acid catalysts based on NCM, mostly Lewis acid cations embedded in zeolites. Evaluation of hydrogenation properties in solvent. In-situ spectroscopy to evaluate surface acidic properties. Use of nanostructured zeolites for higher accessibility. Test reactions are the isomerisation of glucose to fructose, the direct dehydration of glucose to 5 hydroxymethylfurfural and the conversion of 1,3-dihydroxyacetone to lactic acid.
• The initial experiments on glucose conversion in molten salts have identified substantial drawbacks of these systems. At the mid-term assessment (M24), it was decided to discontinue this research line due to the low yields obtained in the molten salts. Preliminary experiments with noble metals indicate that the high chloride content blocks the active sites.
• The personnel efforts have been shifted to carry out sugar isomerization in continuous flow (WP2).
WP2: Proof of concept: Catalytic Biomass Valorisation using Non-Critical Metals Catalysts addressed three biomass conversion routes, all of industrial importance and interest in biorefinery concepts (million tons production), and which demonstrate the potential – the catalytic performance and robustness - of the concepts for the development of novel catalyst systems with completely eliminated critical element content for catalytic biomass conversion. An essential step in this phase is a benchmark against the state of the art systems. At this stage, attention has been paid to possible scale up issues and integration with other steps, fine-tuning of catalyst synthesis parameters based on these results and characterisation studies of catalysts at work to identify possible negative aspects as low performance or fast deactivation. Part of the activities in WP2 was also dedicated to techno-economical analysis of the results obtained, because we consider this as an integral part of the evaluation of the potential of the novel solutions developed. At the time of writing the application three potential proofs of concept projects have been identified which meet the criteria for demonstrating the potential of the new approaches (i) direct production of γ-valerolactone (gVL) from cellulose; (2) a chemocatalytic route to lactic acid or even ethanol and (3) aqueous phase reforming of biomass constituents. In all cases the catalysts will contain no critical metals.
Task 2.1 – The valeric platform
Investigate the performance of NCM catalysts for the combined isomerisation, dehydration, decarboxylation and transfer hydrogenation of glucose to γ-valerolactone; evaluate the effect of reaction conditions on catalyst activity, stability and regenerability; evaluate performance when cellulose is the starting reactant. Compare the results (in terms of productivity, selectivity, operation conditions, kinetics and stability) with those obtained using conventional catalyst technology (best practice).
• Low-temperature process for levulinic acid hydrogenation employing Ni:Re(2:1)/TiO2 catalyst is developed.
• Substantial recyclability of Ni:Re(2:1)/TiO2 is demonstrated.
• A synergy between Ni and Re components in the bimetallic catalyst is revealed.
Task 2.2 – Synthetic glycolysis
Investigate the performance of novel NCM catalysts for the conversion of glucose to lactic acid and the subsequent decarboxylation to ethanol. Explore the use of NCM metal oxide or Lewis acid functionalised zeolites for the combined depolymerisation of (hemi)cellulose in molten ZnCl2-hydrate and subsequent conversion of the sugars to lactic acid/ethanol.
• Sn-Beta zeolite deactivates rapidly in the course of glucose retro-aldolization. Our results suggest that the deactivation is caused by the oligomerization of the highly reactive fructose intermediate at the outer part of the zeolite crystals. Separation of the isomerization and retro-aldolization steps is desirable for the glucose to methyl lactate conversion process.
• Deactivation of Sn-Beta upon glucose conversion in water is due to both the accumulation of oligomeric byproducts in the zeolite pores and structural decomposition of the siliceous framework. The latter effect results in a long-term catalyst deactivation. By carrying out the reaction in ethanol/water mixed solvent medium, both effects can be largely suppressed resulting in a prolonged stability of the zeolite catalysts under continuous flow conditions.
• Ru/TiO2 catalyst is highly efficient for the selective conversion of lactic acid to 1,2-propanediol under relatively mild conditions.
• A superior catalytic system for lactic acid dehydrogenation based on non-noble metal MoO3/TiO2 oxides is discovered. The stable catalytic performance of this system in flow under oxidative and non-oxidative conditions is demonstrated.
• Depolymerization of cellulose has been achieved with high glucose yields in methanol.
• Modified graphenes having acid groups and magnetic iron nanoparticles have been used as recoverable catalysts for starch depolymerisation.
Task 2.3 – Aqueous phase reforming
Performance testing of NCM nanoparticulate catalysts in the aqueous phase reforming of glycerol and carbohydrates. Kinetic studies of the product distribution as a function of nanoscale properties of the nanoparticulate catalysts (size, morphology, support functionalities) as well as catalyst stability. Development of structure-performance relations for NCM catalysts based on particle size and metal type. Exploration of mixed NCM nanoparticulate catalysts.
• The catalytic activity of doped graphenes has been evaluated for the aqueous phase reforming of glycerol, being the B-doped G the most active catalyst in the series.
Task 2.4 – Techno-economic evaluation
First techno-economic analysis of the concepts explored in NOVACAM. Input to these studies is the outcome of Tasks 2.1-2.3 in terms of productivity and selectivity and the most likely process layout and best practice literature data. Issues like energy management and its impact on investment and the impact of feedstock price (e.g. renewable biomass against crude oil) will also be taken into account.
• The economics of a process for glucose conversion to 5-HMF by P/TiO2 were positively evaluated. Preliminary economic calculations indicate that optimized P/TiO2 is able to obtain 5-HMF from glucose in a biphasic system with above 60% selectivity showing that the process can be scaled up. Predictions are pricing below 1 €/kg which makes the process attractive.
• Friedel-Crafts alkylation of hydroxymethylfurfural by toluene, followed by hydrogenative deoxygenation renders a hydrocarbon that is suitable to be combined with the gasoil fraction in the refining process.
Twenty-nine (29) project deliverables were completed (10 – WP1, 4 – WP2, 6 – WP3, 9 – WP4) during the project lifetime from September 2013 to February 2017. The Midterm assessment (MTA) of NOVACAM was programmed at the end of the 2nd year. This MTA (D4.8) was a major decision point, because it has been the formal point where the Consortium decided how to proceed in the second period, by identifying promising catalyst systems and reformulating the approaches in the second period based on the chemistry developed in the first period. The consortium discussed the progress towards the objectives extensively and critically assessed the most promising results on the basis of quality, novelty and potential to contribute to the development of non-critical element based catalysts. In the second phase of NOVACAM a two-pronged approach were been pursued consisting of work on the underlying chemistry to be carried out in WP1 and work towards the proofs of concepts which will be part of WP2. Based on the progress in WP1 and the initial results pertaining to WP2, it was decided that all three subtasks in WP2 will be pursued. Nevertheless, most attention was to be given to tasks 2.1 and 2.2 because task 2.3 was least promising and, in principle, a supply of hydrogen might be derived from other feedstock as well. Work in task 2.3 has been postponed until promising results are obtained in WP1 (D4.8).
The main outcomes from the deliverables are presented below:
D1.1 Interim report on novel NCM catalyst(s) for hydrogenation (August 2015) task leader: CU
This deliverable presents the interim results on NCM catalysts for hydrogenation. The focus was the development of hydrogenation catalysts for the conversion of levulinic acid (LA) to γ-valerolactone (GVL). The previous work showed that Cu-ZrO2 catalysts prepared by co-precipitation and oxalate gel precipitation were found to be active catalysts for LA hydrogenation. The addition of Ni to the Cu-ZrO2 in order to enhance the activity was also investigated. These catalysts were synthesized using the oxalate gel precipitation method.
D1.2 Interim report on novel NCM catalyst(s) for transfer hydrogenation (August 2015) task leader: CU
The deliverable presents the results on various oxide catalysts that have been prepared and tested for the transfer hydrogenation reaction. The catalysts were prepared by hydrothermal, mechanothermal and oxalate gel precipitation methods.
D1.3 Interim report on novel NCM catalyst(s) for decarboxylation (August 2015) task leader: TU/e
This deliverable summarises the interim results of our work on theoretical DFT calculations that have been undertaken to understand the reaction mechanism. Two possible routes were indicated and the theoretical model suggested that the reaction mechanism involves the formation of a keto carboxylic intermediates (route a) should be the one kinetically preferred. In view of the novel and very promising results on the direct lactic acid photodecarboxylation obtained with the TiO2-supported catalysts and unsatisfactory results obtained with alternative support materials, the former system was chosen as the main research object. With this system we could demonstrate the possibility of highly selective sugar decarboxylation (‘synthetic glycolysis’). The utility of this reaction for the development of novel acceptorless dehydrogenative coupling processes has also been demonstrated.
D1.4 Interim report on novel NCM catalyst(s) for dehydration/isomerisation (August 2015) task leader: CSIC
This deliverable presents the interim results on NCM catalysts for dehydration/isomerization. Among the metal oxides that have been screened as isomerisation catalysts those that have showed high catalytic activity and were the most promising leads for further development in this area are ZrO2, CeO2 and WO3. These three oxides are based on abundant and non-critical metals and were been useful to develop WP2 with the proof of concept of an industrial process.
Complementary theoretical and experimental study performed suggested that the nanostructuring or the increase of the pore size of the zeolite matrix may not result in the expected increase of catalytic performance of Sn-zeolite glucose conversion catalyst. Our study identified alternative oxide-based systems that can promote glucose activation following the mechanism analogous to that realized in the zeolite as well as in the enzymatic catalysis. These systems were being studied systematically by computational methods.
D1.5 Interim report on potential of NCM catalyst(s) to operate in molten salts (August 2015) task leader: TU/e
The initial results showed that glucose can be completely oxidized as CO2 is formed. The best performing system was the one with a Pt co-catalyst. The problem here was the poisoning of the metal catalyst as evident from the data that compare the reaction in water and molten salt hydrate. Although this concept may have potential, we concluded that this is well outside the scope of NOVACAM and this part of the research was discontinued.
D1.6 Report on novel NCM catalyst(s) for hydrogenation (August 2016) task leader: CU
This deliverable present the final results on NCM catalysts for hydrogenation. Cu/Ni/ZrO2 catalyst was found to be better than Cu/ZrO2 catalyst for LA conversion into GVL. Grinding the catalysts (both Cu and Ni based) resulted in an enhancement in the activity, and a significant increase in BET surface area was observed. An attempt has been made to decrease the amount of Cu in Cu/ZrO2 catalyst system and initial results are very promising. Solvent screening has shown that MeOH was more efficient solvent system for an increased catalyst activity and stability for Cu/ZrO2 catalyst system. pH studies will be performed on the catalytic reactions scurried out in different solvents.
D1.7 Report on novel NCM catalyst(s) for transfer hydrogenation (August 2016) task leader: CU
This deliverable summarises the final results on catalysts for transfer hydrogenation. For transfer hydrogenation of methyllevulinate Cu/ZrO2 catalyst prepared by the oxalate gel method showed a high activity for GVL production using MeOH as a sacrificial hydrogen donor. By-products in terms of gases were observed in this reaction. Reduction of the reaction temperature decreased the amount of gaseous by-products produced during the reaction. Quantitative NMR of the post reaction effluents is required in order to assess the mechanistic details. The addition of small quantities of H2O increased the GVL selectivity which suggests that undesirable by-products may be formed from the reduced intermediate species.
In the work related with process design various catalysts have been tested in order to understand the dehydration of glucose into ML. Brønsted acidity seems to be a required factor for the reaction. Strength of the acid determines selectivity towards desired products, however a fine balance needs to be tuned. The activity of the catalyst is significantly affected by choice of metal oxide support. The current focus is determining the reaction mechanism and limit the formation of humins. Utilising a sacrificial secondary alcohol to inhibit the aldol polymerisation route can be an option.
D1.8 Final report on novel NCM catalyst(s) for decarboxylation (August 2016) task leader: TU/e
New chemical pathways for decarboxylation of lactic acid discovered. TiO2-supported transition metal photocatalysts allow a strong enhancement of the decarboxylation rate by promoting the concert decarboxylation and dehydrogenation of the substrate resulting in acetaldehyde as the main product. A record-high lactic acid decarboxylation activity is obtained with the noble metal-based Pt/TiO2 catalyst. An alternative highly active NCM-type Ni/TiO2 photocatalyst is identified. Photocatalytic decarboxylative acceptorless dehydrogenation can be used to develop new sustainable routes for low-temperature oxidative coupling of lactic acid with H2 as the major useful by-product. A highly active and selective MoO3/TiO2 catalyst made of non-critical elements for lactic acid oxidative dehydrogenation is developed. The highest selectivity of about 90% to pyruvic acid at 50% lactic acid conversion can be obtained with 1%Mo catalyst. In the absence of external oxidant a transfer hydrogenolysis process to produce propionic and pyruvic acids in equimolar amounts can be carried out with these catalysts.
D1.9 Report on novel NCM catalyst(s) for dehydration/isomerisation (August 2016) task leader: CSIC
Theory predicts transition metal doping as a promising strategy towards new oxide-based catalysts for sugar isomerization. The formation of oxygen vacancies on the tungstite surface can substantially enhance its reactivity and open a new reaction channel involving a one-step glucose isomerization to fructose. A new highly favorable reaction mechanism involving a cooperation between Lewis acid and Brønsted base sites for the direct glucose to fructose dehydration is identified for TiO2-based catalysts.
Advanced ab initio molecular dynamics simulations confirms the strong promoting role of cooperative action between the Lewis and Brønsted acidic centers in Sn-zeolite catalysts for the selective glucose to fructose isomerization reaction. In situ NMR study confirms our earlier theoretical predictions on the crucial role of competitive adsorption between solvents and carbohydrate substrates on the activity of zeolite-based systems. In combination with DFT modeling, a promising mixed solvent system is identified for glucose conversion over Sn-Beta catalyst. Niobium oxide supported on modified carbon nanotubes can convert glucose into succinic acid or lactic acid with high selectivity at high conversion. The fine balance between Brønsted and Lewis acid sites is crucial to achieve the optimal catalysts. The present of magnetic nanoparticles makes easy the recovery and reuse of the supported niobia catalyst.
D1.10 Report on potential of NCM catalyst(s) to operate in molten salts (August 2016) task leader: TU/e
At the mid-term assessment (M24), it was decided to discontinue this research line due to the low yields obtained in the molten salts. Preliminary experiments with noble metals indicate that the high chloride content blocks the active sites. The personnel efforts have been shifted to carry out sugar isomerization in continuous flow (WP2).
D2.1 Report on proof of concept for the valeric platform (February 2017) task leader: CSIC
Updated focus of the task during midterm assessment:
- Improve supported Ni/Co/Cu catalysts
- Compare liquid vs. gas phase
- Screening in flow reactors to assess stability
- Solvent exploration, e.g. use gVL as solvent
D2.2 Report on proof of concept for synthetic glycolysis (February 2017) task leader: TU/e
Updated focus of the task during midterm assessment: the project partners decided to focus the work in this task on:
- routes from glucose to lactic acid (avoiding 5-HMF) supported by computational studies
- photodecarboxylation of lactic acid as a base for coupling chemistry
- lactic acid dehydrogenation to pyruvic acid
- lactic acid hydrogenation to 1,2-propanediol
- catalyst stability in flow reactors (Sn-Beta), influence of solvents
D2.3 Report on proof of concept for aqueous phase reforming (February 2017) task leader: CU
During midterm assessment, the project partners decided to focus the work in this task on:
- Understand Ni-Re/TiO2 system, explore use of other Ni promoters (CSIC)
- Explore use of cellulose dissolved in ZnCl2-hydrate as feed for APR
D2.4 Final techno-economic analysis (February 2017) task leader: TU/e
In this deliverable, the preliminary economic calculations for optimized P/TiO2 to obtain 5-HMF from glucose in a biphasic system are presented showing that the process can be scaled up. Predictions are pricing below 1 €/kg which makes the process attractive. Also Friedel-Crafts alkylation of hydroxymethylfurfural by toluene is suitable to be combined with the gasoil fraction in the refining process.
D3.1 Project website: Project website (November 2013) task leader: KTN
In this deliverable an operational website www.novacam.eu has been established.
The NOVACAM website was the main portal and communication channel for the dissemination of NOVACAM project results. The website disseminated to the scientific community, both to alert other researchers to the project research findings and potential businesses who might be interesting in commercialising the technology developed.
D3.2 Initial promotional materials (October 2013) task leader: KTN
The deliverable presented the initial promotional materials including logo, press release and project brochure.
The NOVACAM logo was developed. The logo had a scientific feel to indicate the technical nature of the project and features a zeolite structure, a key material to be used in the project. A press release to announce the launch of NOVACAM was published on 2nd September 2013 on CORDIS wire. A project leaflet has been designed.
D3.3: Final Exploitation Strategy (February 2017) task leader: KTN
Management of Exploitation Strategy was an ongoing activity throughout the project to work with project partners to identify likely exploitable results, formulate exploitation opportunities and develop exploitation strategy. As the main deliverable, this Final Exploitation Strategy report sets out the exploitation measures put in place at the beginning of the project and enacted during the course of the project as well as setting out future plans for exploiting project results. This deliverable illustrates the framework needed to identify NOVACAM results, establish ownership and detail how the result can and will be exploited.
D3.4: Professional Training event (February 2017) task leader: TU/e
Two workshop were organized during the lifetime of the project (one in Europe, one in Japan). The deliverable presents the European training event.
A training programme was devised for the young researchers working on the project. The programme was based on the principles of the Marie Curie Initial Training Networks and covered both training in science and in a range of other skills. The training programme is composed of two main activities: webinars and a winter school. The NOVACAM Winter School on ‘’Green Catalysis by Design’’ was held on 22 February 2017 at The University of Padova, Padova, Italy.
D3.5: Final Project Conference (February 2017) task leader: KTN
This deliverable describes the final project conference. A final project conference has been organised in the EU at the end of the project and included invited speakers from Japan. The event will target participants with the influence to act to implement the projects findings from across industry and academia. Members of relevant EU and Japanese networks related to the substitution of critical raw materials and the manufacture of bio-based products were been invited to attend. The conference featured NOVACAM speakers to communicate the results and recommendations of the project.
The NOVACAM final project conference - marketed publically as “Green Catalysis By Design Scientific Meeting” - was held on Thursday 23rd February at the University of Padova, Italy.
D3.6 Publishable compendium on training webinars (August 2016) task leader: CU
A training programme was devised for the young researchers working on the project. A series of webinars will develop and broaden their research competences. By month 36, the webinar series were completed.
This deliverable presents the details of all the webinars: they have been collated into one place and recordings of all webinars are available via the project website: http://novacam.eu/category/news-events/webinars/
D4.1 D4.2 D4.3 D4.4 D4.5 D4.6 D4.7 task leader: TU/e
These deliverables present the minutes of all EU and joint EU-Japan meetings.
D4.8 Minutes Midterm Assessment with motivations of revisions (August 2015) task leader: TU/e
The MTA reports on the progress of the research and the Beneficiary’s plans for the proofs of concept phase were been submitted before month 24. The project coordinator organized a MTA meeting with all Beneficiaries and the Commission’s representative. The purpose of this meeting was to report on the progress to date and to redefine (if necessary) the Project Programme for the remaining part of the contract. During Midterm assessment meeting the project has been discussed in depth. Particularly, the progress, weakness and strengths of each of the three reactivity lines were discussed to focus the project on the more promising activities.
D4.9: Final report on project management including actions and results for coordination to Japanese consortium (February 2017) task leader: TU/e
This deliverable presents the main outcome of the NOVACAM project. One major outcome of the project is the intensification of scientific bonds between the European and Japanese catalysis communities. This has been fostered through the direct interaction within the project, but has also led to broader collaboration between the two communities via joint conferences, student exchanges and sabbatical leaves. Finally, the project has had major impact on young researchers, who obtained their PhD degree on the basis of the NOVACAM work.
Potential Impact:
Exploitation of results
Management of exploitation was an ongoing activity throughout the project, identifying likely exploitable results, formulate exploitation opportunities and develop an exploitation strategy. The objective was to maximize the impact of the project through wide adoption of its results and achievements within the chemical industry and scientific community. To achieve this aim a clear methodology of how to treat new innovations to provide competitive advantage to the end user partners must be established and followed in detail for each identified development. Where the potential for commercial gain is noted the route to implementation requires assessment for risk and mitigation processes put in place to ensure maximum benefit.
Project partners were encouraged to publish non-commercially sensitive project results in high impact academic journals and to present oral presentations and posters at scientific conferences and meetings. In order to ensure that commercially exploitable results were protected, any external dissemination of this kind requires approval from the consortium. The aim of this approval process is to support this activity whilst protecting commercially sensitive results. Once a project result has been identified as potentially exploitable, an exploitation plan for that result will be developed. An exploitable result is defined as “achieved or expected output coming from work performed on the project which has commercial significance and can be exploited as a stand-alone product, process, service etc.” The exploitation plan is developed jointly by partners by assessing local best experiences.
Certain project results were evaluated for their potential commercial interest and protection of intellectual property though patent was considered. However, to date all project results are still at the experimental stage and further research would be required before they would be of commercial interest. The most interesting results of the NOVACAM project from a commercial exploitation perspective are detailed in Table 1.
The NOVACAM project put in place from the beginning robust processes to collectively decide how project results should be taken forward. The processes were followed and allowed for appropriate treatment of project results. The research conducted by NOVACAM consortium partners has delivered substantial advances in the understanding of catalytic processes and progress towards the goal of critical raw material free catalysts. ITQ has submitted two patent applications in the field of catalytic biomass conversion, concerning novel routes that enable the co-processing of biomass with conventional fossil feedstock. Whilst more results show early promise and were considered for patenting, ultimately due to the experimental nature of project results, the most appropriate mechanism for disseminating these results has been through the open literature allowing for exploitation of results through and the required further development via the wider scientific and industrial community. The consortium will continue to work with industrial collaborators towards this goal.
Summary of most potentially commercially relevant NOVACAM project results
Result: Hydrogenation of levulinic acid to γ-valerolactone using a Mn-ZrO2 catalyst.
Market opportunity: Potential bio-based fuel or solvent derived from cheap feedstocks replacing fossil fuel-based supply chains.
Further research required towards commercialization: Current activity of critical raw material free catalysts does not yet match traditional catalysts. To be commercially deployed, materials need to be recovered for reuse.
Result: The use of a gradient pH method to control the co-precipitation of Cu and Zr in the materials preparation method.
Result: Hydrogenation of levulinic acid to γ-valerolactone using a Fe-Re catalyst.
Market opportunity: Potential bio-based fuel or solvent derived from cheap feedstocks replacing fossil fuel-based supply chains.
Further research required towards commercialization: Although Fe is cheap substitute for the most active Ru catalytic metal used for this reaction, Re is also an expensive metal.
Result: Photodecarboxylation of lactic acid using titania-supported transition metals
Market opportunity: Part of a chemocatalytic route from sugars to ethanol/acetaldehyde that can replace sugar to ethanol fermentation
Further research required towards commercialization: Reaction rates need to be increased.
The objective of NOVACAM to develop abundant element-based innovative solid-state catalysts for biomass utilization was well accomplished by discoveries of new crystalline oxide materials, Lewis acid-base generation in complex oxides, and bimetallic species on oxide surfaces. Overall, the consortium has demonstrated the success of the “catalysis by design” approach in the field of biomass conversion, as evident from the development of novel catalytic sites based on nanoscale insights gained through combined theoretical and experimental characterization. All of the newly synthesized catalysts revealed high catalytic performance for various biomass-derived materials conversion to desired products. Some of the most promising materials still depend on elements that are not abundant in order to achieve high activity. Next to high activity also stability is an issue when precious group metals are replaced by more reactive first-row transition metals. A highlight is the development of a high-loading phosphorous modified TiO2 – completely based on abundant elements - showing high catalytic performance in the conversion of glucose to 5-hydroxymethylfurfural. Several other leads have been identified such as the potency of cheap bulk oxides when properly promoted and molecular metal oxide wires as a new solid-state acid catalyst.
Another major outcome of the project is the intensification of scientific bonds between the European and Japanese catalysis communities. This has been fostered through the direct interaction within the project, but has also led to broader collaboration between the two communities via joint conferences, student exchanges and sabbatical leaves. Finally, the project has had major impact on young researchers, who obtained their PhD degree on the basis of the NOVACAM work.
The NOVACAM project was fruitfully done with various new solid-state materials having multi-functional catalytic properties that were found very suitable for promoting the cellulose or glucose conversion in water to desired product in high selectivity. The key of the success was the evolution of synthetic methodology for making functional catalytic materials.
Synergy
Whilst some of the researcher on both sides were already acquainted, only through the research cooperation it become possible to collaborate and explore the apparent synergy in expertise. The exchange of young researchers proved to be instrumental to achieve the goal of new catalyst development based on nanoscale insight. As all partners were active in participating in international conferences and also actively contributed to organize dissemination activities (conferences, symposia, webinars) in which also other researchers at the EU and Japanese side were involved, the project was very effective in bringing together the EU and Japanese catalysis communities.
Altogether, this project allowed building a strong consortium with considerable synergy in expertise towards idea generation and identifying novel catalysts and their impact on biomass conversion. The impact will be lasting as further collaborations are underway.
Potential impact
Reducing European industry’s reliance on imported critical raw materials to improve competitiveness, sustainability and to reduce risk is a key European policy objective. Development of critical raw material-free catalysts would make a significant contribution to this objective, particularly given the underpinning role played by catalysts in chemical supply chains. The NOVACAM project has delivered substantial advances in the understanding of catalytic processes and progress towards the goal of critical raw material free catalysts.
List of Websites:
www.novacam.eu
The NOVACAM project (as one of three Critical Raw Materials projects) was part of NMP - Nanoscience, Nanotechnologies, Materials and New production Technologies - Coordinated call EU - Japan 2013 Programme of the EU Commission.
NOVACAM was a joint EU-Japanese project with the goal to develop novel technology to enable the substitution of critical metals in industrial catalysts. Industrial use of biomass feedstock is at an early stage and presents an opportunity to develop the next generation of catalysts that is based on abundant elements. Catalysts are one of the six major uses of critical metals. Many industrial heterogeneous catalysts have been developed empirically, such that the role of critical metals in affecting catalyst performance is not clearly understood yet.
The overarching objective of the project was to construct an innovative science base of novel catalytic technologies to enable the conversion of lignocellulosic biomass to useful and valuable organic chemicals, polymers, and transportation and heating fuels. The underlying science was developing and demonstrating new principles for achieving excellent catalytic properties by control and manipulation of the composition and structure of solid catalysts made from abundant materials. NOVACAM aimed to develop innovative catalysts by applying a “catalysis by design” approach, integrating the complete chain of knowledge from fundamental research to proof of concept.
NOVACAM developed catalysts using non-critical elements for the conversion of biomass to chemicals and fuels and targets to establish a solid basis for knowledge-based catalytic technology involving cheap and abundant elements. The focus was on lignocellulosic biomass as it will be possible to supply chemicals without adversely impacting land and other resources which are needed for food production. Specifically, NOVACAM used a “catalysis by design” approach to formulate the requirements for inorganic catalyst systems to speed up different steps relevant to upgrading of biomass. These nanoscale insights were then used to develop novel catalysts based on abundant elements and validated in three proofs of concept studies at laboratory scale to convert cellulose/sugar feedstock into fuels and chemicals. In this way, the extensive knowledge base acquired in catalysis research has been employed to design novel inorganic catalytic systems.
NOVACAM brings together seven academic partners: Eindhoven University of Technology (The Netherlands), Kanagawa University (Japan), Cardiff University (United Kingdom), Instituto Technologia Quimica (Spain), Hokkaido University (Japan), Tokyo Institute of Technology (Japan) and Chiba University (Japan), who combine excellence in catalysis research with a long-standing tradition in mission-driven research in collaboration with industry. Knowledge Transfer Network is UK’s innovation network and responsible for dissemination, exploitation and training within the NOVACAM consortium.
The project outcomes are derived from the complementary expertise in the field of innovative catalyst research between the academic partners. With the coordinated cooperation, the two consortia shared the same goals, building on each other’s expertise through exchange of academic personnel and joint project meetings, conferences and webinars. Especially, the exchange of young researchers such as PhD students, postdocs and young staff members has a positive effect on their development.
NOVACAM led to a high level of scientific output: more than 30 papers were published in peer-reviewed scientific publications, many of which were joint between EU or Japanese groups and several joint EU-Japanese. The number of conference contributions is higher than 50; participation in these conferences proved to be important to enhance the contact between the project partners. The project has also led to 6 PhD theses, 3 at the EU and 3 at the Japanese side.
Project Context and Objectives:
Raw materials are fundamental to Europe’s economy and they are essential to our quality of life. Critical raw materials refer to materials of high economic importance to the EU combined with a high risk associated with their supply. Catalysts are one of the six major uses of critical metals that are produced as byproducts of mining of primary metals, e.g. platinum group metals and lanthanides. The critical elements are widely used in many types of catalytic processes in petrochemical production and downstream conversion to high value products: in many cases they are also the default option for biomass conversion.
NOVACAM was an EU-funded FP7-NMP project with the goal to develop novel technology to enable the substitution of critical metals in industrial catalysts. Industrial use of biomass feedstock is at an early stage and presents an opportunity to develop the next generation of catalysts that is based on abundant elements. Catalysts are one of the six major uses of critical metals that are produced as byproducts of mining of primary metals, e.g. platinum group metals and lanthanides. Many industrial heterogeneous catalysts have been developed empirically, such that the role of these critical metals in affecting catalyst performance is not clearly understood yet.
The overarching objective of the project was therefore to construct an innovative science base of novel catalytic technologies to enable the conversion of lignocellulosic biomass to useful and valuable organic chemicals, polymers, and transportation and heating fuels. The novel catalytic technologies would completely eliminate the use of critical raw materials for these processes, and would have low environmental impacts. The underlying science was developed and demonstrated new principles for achieving excellent catalytic properties by control and manipulation of the composition and structure of solid catalysts made from abundant materials. With this, NOVACAM aimed to develop innovative catalysts by applying a “catalysis by design” approach, integrating the complete chain of knowledge from fundamental research to proof of concept.
The project was carried out with a partner consortium in Japan with complementary expertise in the field of innovative catalyst research.
The EU Consortium
In order to achieve the above objectives, the NOVACAM consortium involved three academic partners, namely TUE – EU coordinator (Eindhoven University of Technology, The Netherlands), CU (Cardiff University, United Kingdom) and CSIC - ITQ (Agencia Estatal Consejo Superior De Investigaciones Cientificas - Instituto Technologia Quimica, Spain), who combine excellence in catalysis research with a long-standing tradition in mission-driven research in collaboration with industry. TUE has extensive experience in mechanistic studies in heterogeneous catalysis involving quantum-chemical studies. CU brings in expertise in the field of catalyst synthesis targeted at chemical conversion processes. ITQ has broad expertise in heterogeneous catalysis of biomass conversion. KTN (Knowledge Transfer Network) is UK’s innovation network, bringing together business, entrepreneurs, academics and funders. Within NOVACAM, KTN was responsible for dissemination, exploitation and training within the NOVACAM consortium. KTN is very well connected into the EU community dealing with issues of sustainability including critical raw materials replacement.
The work in the consortium was closely interconnected to and coordinated with a Japanese consortium of academic groups led by Kanagawa University. The work at the Japanese side was funded by the Japanese Science and Technology Agency. With the coordinated cooperation, the two consortia shared the same goals, build on each other’s expertise through exchange of academic personnel and joint project meetings.
NOVACAM addressed the development of novel technology to enable the substitution of critical metals in catalysts. The project aimed to develop catalysts using non-critical elements for the conversion of biomass to chemicals and fuels. NOVACAM targeted to establish a solid basis for knowledge based catalytic technology involving cheap and abundant elements. While biomass in all its forms is potentially available as a renewable feedstock for chemicals, we focued in this project on the use of lignocellulose. Potentially, this can be converted into a whole range of existing useful chemicals and fuels, and also into new and different chemicals as better alternatives. It has the great benefit that starting from lignocellulose it will be possible to supply chemicals without adversely impacting land and other resources which are needed for food production.
NOVACAM develops catalysts using non-critical elements for the conversion of biomass to chemicals and fuels and targets to establish a solid basis for knowledge-based catalytic technology involving cheap and abundant elements.
The main objectives of the project were (i) to understand by a “catalysis by design” approach the requirements for inorganic catalyst systems to speed up elementary reaction steps and valorise biomass with a focus on conversion of cellulose into fuels and chemicals; (ii) using these nanoscale insights to develop novel catalysts based on abundant elements for the conversion of biomass and (iii) to develop three proof of concept studies at laboratory scale to convert cellulose/sugar feedstock into fuels and chemicals - specific attention will be paid to catalyst robustness. In this way, the extensive knowledge base acquired in catalysis research has been employed to design novel inorganic catalytic systems.
The work in NOVACAM was organized in two technical work packages (WP1 & WP2), complemented by two work packages dedicated to dissemination, exploitation and training (WP3) and to project management (WP4). The work related to dissemination was undertaken in WP3. The webpage, templates, dissemination material and press releases were provided. One training workshop with external participants and the final conference were organized. The specific activities will be described in the appropriate chapters of this report. Within WP4 all activities related to management and co-ordination were combined. Reports and deliverables were submitted in time, according to the revised schedule reflecting the amendment process. Project meetings and management committee meetings were organized, all issues dealing with payment and distribution were successfully fulfilled. The communication and everyday work kept the project smoothly running and supported effective and prosperous research and co-operation.
The total duration of the project was 42 months. The work plan was structured around developing the basic chemistry that underlies proof of concepts. The basic chemistry was addressed in the first two years of the project in work package 1, the proof of concepts was gaining attention in the last 24 months of the project in work package 2.
The work programme was organized on the basis of discussions between the European and Japanese academic scientists, the Industrial Advisory Committee and KTN on the essential knowledge, methods and tools to implement a new vision on rational catalyst design aimed at complete removal of critical elements. The objectives were defined to aim for a breakthrough progress in catalytic biomass conversion based on recent advances of knowledge in fundamental research, but within the boundaries of economic competitiveness and a vision compatible with industry. An essential aspect here was to combine a bottom-up approach in catalyst design with insights from modern catalysis research, which imply the use of state of the art tools. The overall strategy for the project was to begin with research on fundamental chemistries, followed by a three proofs of concept projects which take the new knowledge forward and develop it in an integrated context.
General structure of the work programme of the NOVACAM project
In agreement with the call text, the work by the consortium was separated from that of the Japanese consortium in that different classes of materials (EU: metal nanoparticles and zeolites; Japan: metal nanoparticles and base metal oxides) were investigated in line with the expertises of the two teams. However, to foster collaborative efforts, the EU and Japanese consortia have jointly decided on the work packages. This implies that the tasks at the EU and Japanese sides were similar, except some generic tasks (T1.4 - Novel chemistry in molten salts, T2.4 - Techno-economic evaluation and all tasks in WP3 - Dissemination, Exploitation and Training). A similar WP4 at the Japanese side covered financial and administrative management of the Japanese consortium. The cooperation between the two consortia was therefore considered one of the joint goals, joint meetings and exchange of young scientists who carried out characterisation and activity testing of the specific materials developed in each of the consortia.
WP1: Fundamental Chemistry of Catalytic Biomass Conversion eliminating critical metals
1) To develop novel catalytic chemistry for the basic reaction steps needed for upgrading cellulose/sugars including hydrogenation-dehydrogenation, decarboxylation, dehydration and isomerisation based on inorganic catalyst systems totally eliminating the use of non-critical metals.
2) To synthesise non-critical metal (oxide) clusters and nanoparticles on (porous) supports by sol immobilisation, chemical vapor deposition and precipitation concepts.
3) To synthesise structured catalysts, e.g. zeolites, nanostructured or with novel pore topologies and functionalised with well-defined isolated reaction sites and also metal oxides with metal cations in well-defined reaction environments.
4) To characterise in detail the active reaction centers by advanced microscopic and spectroscopic tools.
5) To undertake catalytic testing of novel non-critical metal (NCM) catalysts using biomass model compounds.
6) To develop fundamental knowledge on catalytic mechanism using catalysts for biomass conversion by theoretical modeling studies.
7) To explore the use of novel NCM catalysts in molten salt solvents.
WP2: Proof of concept: Catalytic Biomass Valorisation using Non-Critical Metals Catalysts
1) Translate outcomes of WP1 (novel NCM catalysts) into proofs of concept for biomass valorisation at the laboratory scale.
2) Evaluation of single- and multi-step approaches for the depolymerisation, decarboxylation and transfer hydrogenation of cellulose/glucose to γ-valerolactone using novel NCM catalysts.
3) Evaluation of single- or multi-step approaches for the valorisation of glucose into lactic acid and ethanol using novel NCM catalysts.
4) Evaluation of NCM catalysts for aqueous phase reforming of glycerol and glucose.
5) Use all of the results obtained in objectives 2-4 and those of WP1 to make a techno-economic feasibility analysis of the proof of concept against benchmark systems.
WP3: Dissemination, Exploitation and Training
1) To maximise the impact of the project through wide dissemination of the results of the project and its achievements to audiences within the chemical industry, the scientific community and the wider community interested in the substitution of critical raw materials.
2) To help increase uptake of the technology to improve competitiveness and sustainability within EU industry, reduce dependence on imports of scarce materials and maximise EU competitiveness.
WP4: Financial and administrative management
1) The objective is to realize a coherent and efficient project management. Specific objectives are to (i) ensure that objectives are met, schedules maintained, and budgets honored, and (ii) foster and boost interrelations between teams, exchange of knowledge and information between teams involved in the different approaches.
2) To improve the functionality of the project by managing specific objectives, the two functions of coordination and project management have been separated. This WP includes constant monitoring of the project management to improve its effectiveness.
Project Results:
Green synthesis of value-added chemicals from biomass has received widespread attention in recent years due to the availability of wood or agricultural residues as renewable feedstocks and an increase in CO2 emissions associated with the consumption of fossil fuels. Lignocellulose, the main component of abundant biomass resources, consists mainly of cellulose (35-50%), hemicellulose (20-35%), and lignin (10-25%). A variety of hydrothermal, chemocatalytic, and biological techniques have been proposed for the depolymerization of cellulose and hemicellulose into constituents such as glucose, xylose, and arabinose. However, as for chemocatalytic processes, single reaction-single catalyst systems on the basis of high catalytic performance noble metals and rare elements, that have been widely employed in the petrochemical process, cannot simply turn in biomass conversion reactions because the essence of the biomass conversion is a complicated multi-step reaction process like cascade reaction and domino reaction. In addition, the biomass reactants often contains water or the biomass reactions form water, so that catalysts for the reactions have to be highly water tolerant, which is not so common in the petrochemical process. Therefore, it is extremely important to establish multifunctional solid-state catalyst by combination of abundant elements in order to make biomass conversion a simple, easy, and low cost reaction process. In other words, the recent demand of biomass utilization as chemicals and fuels promotes the development of novel cheap and abundant catalysts, which is the main target and challenge of NOVACAM project. NOVACAM is intended with the goal of the use of lignocellulose important as biomass resources by catalytic process of plural non-rare elements. Achieved reactions by uniform artificial catalysts that are deployed structurally and that many functions are accommodated will be beyond the creature fermentation of biomass. This approach of catalytic element shift from critical elements to non-critical ones is with conjugations from abiotic oil resources to the biologic resources use.
Interactive collaboration among more than two of non-precious elements either in metal oxide form or in metallic form in well-organized state in terms of material structures is a key catalytic material synthesis concept for introducing multi-functional catalytic properties in solid-state materials in this project. For example, unit synthesis using metal oxide clusters for creating high-dimensionally structured complex metal oxides, oxide surface elemental complication on oxide surface by photo-induced functionalization, week oxide-oxide interaction in a form of amorphous complex oxide, and bimetallic formation on oxide surface are employed. These approaches are realized and strengthened by fundamental characterization and supported by theoretical calculation.
The highlights of the NOVACAM project were:
• To understand, by a “catalysis by design” approach, the requirements for inorganic catalyst systems to accelerate the elementary reaction steps needed to depolymerize, deoxygenate, isomerise and couple biomass constituents with a focus on cellulose conversion into fuels and chemicals
• To develop based on these nanoscale insights novel functional materials composed of cheap and abundant elements for the catalytic upgrading of biomass
• To develop three proofs of concepts at the laboratory scale to upgrade cellulose/sugar feedstocks to fuels and chemicals using catalysts based on non-critical elements with specific attention for catalyst robustness
The catalysis by design approach we have been employed to address these challenging and exciting objectives will integrate the complete chain of knowledge from fundamental concepts (theoretical studies of reaction mechanism and in-situ spectroscopic studies), via advanced synthesis protocols involving self-assembly approaches to complete laboratory proof of concept. In this way, the extensive knowledge base acquired in the last decades in catalysis research including tools and techniques have been employed to design novel inorganic catalytic systems.
The research work programme in NOVACAM was divided in two phases. In the first phase covering the first half of the project, fundamental studies were been employed to study the mechanistic and active site requirements for the underlying chemistry to valorise biomass. NOVACAM focused on transformations by highly selective catalysts in order to retain as much of the functionalities which nature has built into the final product molecules. To this purpose, modern tools such as advanced materials characterisation, quantum-chemical modeling of the surface reaction processes and modern synthesis approaches were been employed.
The second phase of the project covered the use of these insights to develop three proofs of concept at the laboratory scale: Given its size and the goal to arrive at proof of concept on the laboratory scale, we were focused on the valorisation of cellulose and carbohydrates, which are the dominant part of lignocellulosic (2nd generation) biomass. We envisaged at this time of writing the application that the three systems will be as follows:
• The valeric platform – this work comprises the development of novel catalytic routes from cellulose to γ-valerolactone, which is a platform for the production of transportation fuels. The objective was to replace state of the art precious metal based catalysts by cheaper metals and to decrease the number of steps in the upgrading process of cellulose by introducing novel chemistry.
• Chemocatalytic glycolysis – to replace the conventional acid-catalyzed cellulose depolymerization and glucose dehydration approaches and the more promising ones using a critical (and toxic) metal as chromium, novel approaches based on cheap metal oxides and well-defined Lewis acid sites in nanostrucured porous zeolites will be the target. The target product was lactic acid, the monomer for the biodegradable polymer PLA, and a possible intermediate to useful chemicals such as acrylic acids. A high risk, high reward task has been to develop decarboxylation chemistry (lactic acid to ethanol), by which a synthetic chemocatalytic glycolysis route would become available which can potentially replace the slow enzymatic process and create a possibility for the direct ethanol synthesis from cellulosic biomass.
• Aqueous phase reforming – This process produces hydrogen from biomass-derived oxygenated compounds such as glycerol and sugars. It is unique in that the reforming is done in the liquid phase, so there is no need to vaporize water representing energy savings and the possibility to convert sugars. The state of the art catalysts are precious metal nanoparticles. In this project, we targeted their replacement by cheaper metals, whose chemical state and nanoparticle size will be optimized to maximize hydrogen production.
The outcomes of the project are a combination of new knowledge in the catalysis domain and proof of concepts in which lignocellulosic biomass is converted into valuable products by novel processes that do not rely on noble metals.
Through the intensive collaboration between EU and Japanese partners and the “Catalysis by Design” approach, new chemistry has been developed in the area of biomass upgrading. The gained insights are currently being explored in a proof of concept setting concerning three principle routes:
1. Upgrading of cellulose to γ-valerolactone (GVL) by novel non-noble catalysts
a. Identification of non-critical metal catalysts based on Cu, Fe and Ni and combinations thereof for the vapor or liquid phase hydrogenation of levulinic acid to GVL.
b. Exploration of support effects on non-critical metal catalysts to boost the activity in levulinic acid hydrogenation.
2. Upgrading of sugars to platform molecules
a. Novel catalytic chemistry has been developed for the conversion of cellulose and glucose into platform chemicals. New catalytic materials include phosphated titania, cheap bulk oxides and tailored Lewis-acid base compounds. The mechanism of the underlying chemistry was resolved by a combination of quantum-chemical calculations and in situ spectroscopy.
b. Novel crystal structured metal oxide catalysts with molecular nanowire form and with porosity have been developed on the basis of group V and VI elements.
c. A new catalyst for the oxidative dehydrogenation of lactic acid has been developed.
3. Aqueous phase reforming for hydrogen generation
a. The catalytic activity of doped graphenes has been evaluated for the aqueous phase reforming of glycerol, being the B-doped G the most active catalyst in the series.
Main outcomes
The scientific work of NOVACAM was divided in 2 work packages and for each work package different tasks were formulated. The main result within these work packages and tasks are summarized as follow:
WP1: Fundamental chemistry of catalytic biomass conversion eliminating critical metals was dedicated to the development of novel catalysts by rational design approaches to address the basic reaction steps needed to convert biomass in an efficient manner. Key requirement was to avoid critical metals. The performance of the novel designed catalytic materials were been evaluated in relevant test reactions. All academic partners in the EU and Japanese consortia were been involved in WP1. The (EU) Beneficiaries focused on first row transition metals in combination with Lewis acid functionalised porous zeolites. The (Japanese) Partners were been working mainly on base metal oxide, consistent with their expertise in this area. Specific tasks were formulated around the basic chemistry for catalytic biomass conversion. Since we employed a modern “catalysis by design” approach, the basic concepts in the various tasks were similar.
The collaborative efforts arised in a bottom-up approach through the academic researchers with the coordinators at the EU and Japanese side facilitating and safeguarding exchange expertise through joint meetings, telecons and exchange of personnel and samples.
Task 1.1: Hydrogenation chemistry
Prepare NCM catalysts for the hydrogenation/dehydrogenation of biomass feedstock. Precious group metal replacement candidates are Co, Ni, Fe and Cu. Techniques will be developed to optimise the surface morphology, particle size and metal-support interaction for each of the target reactions. Use of techniques such as sol-immobilisation and chemical vapor deposition, optimisation of stabilisation and reducing agents. The test reaction for (transfer) hydrogenation is succinic acid hydrogenation (with formic acid).
• TiO2-supported Ni-Re and Fe-Re catalysts are identified as promising catalyst systems for the reductive transformations of biomass-derived carboxylic acids and in particular for levulinic acid hydrogenation to γ-valerolactone.
• γ-valerolactone can be obtained from levulinic acid with yields of >90% in water with Ni:Re/TiO2 catalyst at a temperature as low as 130 °C in water.
• Silica-supported Cu-Ni bimetallic catalysts with a Cu/Ni weight ratio of 3/7 exhibit excellent catalytic activity in vapor-phase hydrogenation of levulinic acid (LA) into GVL. A GVL yield in excess of 98% with a productivity of 6.48 kgGVL kgcat.-1 h-1 was achieved at WHSV of 6.60 h-1.
• Vapor-phase hydrogenolysis of GVL into 1,4-pentanediol was optimally carried out with a Cu-ZnO catalyst calcined at 500 oC.
Task 1.2: Decarboxylation chemistry
Development of novel chemistry for the decarboxylation of biomass constituents. Explore the use of small NCM oxide clusters or cations in functionalised zeolites. Synthesis and evaluation of delaminated zeolites or nanostructured zeolites. Test reactions involve the decarboxylation of levulinic acid into 2-butanone and decarboxylation of sugars.
• New chemical pathways for decarboxylation of lactic acid discovered.
• TiO2-supported transition metal photocatalysts allow a strong enhancement of the decarboxylation rate by promoting the concert decarboxylation and dehydrogenation of the substrate resulting in acetaldehyde as the main product.
• A record-high lactic acid decarboxylation activity is obtained with the noble metal-based Pt/TiO2 catalyst.
• An alternative highly active NCM-type Ni/TiO2 photocatalyst is identified.
• Photocatalytic decarboxylative acceptorless dehydrogenation can be used to develop new sustainable routes for low-temperature oxidative coupling of lactic acid with H2 as the major useful by-product.
• A highly active and selective MoO3/TiO2 catalyst made of non-critical elements for lactic acid oxidative dehydrogenation is developed.
• The highest selectivity of about 90% to pyruvic acid at 50% lactic acid conversion can be obtained with 1%Mo catalyst.
• In the absence of external oxidant a transfer hydrogenolysis process to produce propionic and pyruvic acids in equimolar amounts can be carried out with these catalysts.
Task 1.3: Isomerization/Dehydration chemistry
Development of heterogeneous Lewis acid catalysts based on NCM consisting of Lewis acid cations embedded in zeolites. Exploration of large pore zeolites and/or delaminated zeolites. Modification of surfaces to control Lewis and Brønsted acidity. In-situ spectroscopy to evaluate surface acidic properties. Use of nanostructured zeolites for higher accessibility. Test reactions are the isomerisation of glucose to fructose, the direct dehydration of glucose to 5-hydroxymethylfurfural and the conversion of 1,3-dihydroxyacetone to lactic acid.
• Based on a methodology involving building units, self-assembly of Mo-O or W-O octahedra with SeIV, TeIV or PIII formed hexagonal-shaped [XY6O21] (X = P, Se, Te, and Y = Mo, W) units which connect each other though X-O-X bond to grow infinite chains, inorganic molecular wires was achieved. These highly stable nanowires display high activity in biomass hydrolysis to convert cellulose into hexoses. Combined with Sn-W-Se oxide, promising results in the conversion of cellulose to levulinic acid were achieved.
• Porous niobium and tantalum oxyfluorides were synthesized, rendering suitable acidic materials for the catalytic conversion of cellulose and 1,3-DHA. Characterization shows that these materials contain not only Brønsted acid sites but also water tolerant Lewis acid properties, enabling conversion of cellulose into lactic acid.
• A novel YNbO4 catalyst was introduced involving a Lewis acid-base pair able to convert glucose to lactic acid in water. This catalyst system is also active for the conversion of glucose to HMF.
• High phosphate-loaded TiO2 catalyst was developed for dehydration of glucose to HMF. High activity, selectivity and robustness was achieved, rendering this one of the most promising materials in the consortium. Quantum-chemical calculations allowed identifying a novel highly favorable reaction mechanism involving cooperation between Lewis acid and Brønsted base sites for the direct glucose to fructose dehydration is identified for TiO2-based catalysts. These efforts confirm that bare TiO2 adsorbs a large amount of glucose, so that intermolecular reactions between adsorbed glucose molecules or between adsorbed glucose molecules and 3-deoxyglucosone are enhanced, resulting in low HMF selectivity. Phosphate-immobilization on TiO2 decreases these intermolecular side reactions by decreasing the surface glucose concentration, which increases the HMF selectivity.
• Bulk tungsten oxide was identified as another promising catalyst with combined Brønsted and Lewis acidity. Transition metal doping guided by quantum-chemical calculations proved to be a promising strategy towards new oxide-based catalysts for sugar isomerization. The formation of oxygen vacancies on the tungstite surface can substantially enhance its reactivity and open a new reaction channel involving a one-step glucose isomerization to fructose
• Advanced ab initio molecular dynamics simulations confirms the strong promoting role of cooperative action between the Lewis and Brønsted acidic centers in Sn-zeolite catalysts for the selective glucose to fructose isomerization reaction. In situ NMR confirmed theoretical predictions on the crucial role of competitive adsorption between solvents and carbohydrate substrates on the activity of zeolite-based systems. In combination with DFT modeling, a promising mixed solvent system is identified for glucose conversion over Sn-Beta catalyst.
• Niobium oxide supported on modified carbon nanotubes can convert glucose into succinic acid or lactic acid with high selectivity at high conversion. The fine balance between Brønsted and Lewis acid sites is crucial to achieve the optimal catalysts.
Task 1.4: Novel chemistry in molten salts
Evaluation of catalytic performance of NCM catalysts developed in tasks 1.1-1.3 in molten salts and other solvents as a possible reaction medium facilitating the depolymerisation of cellulose. Development of heterogeneous Lewis acid catalysts based on NCM, mostly Lewis acid cations embedded in zeolites. Evaluation of hydrogenation properties in solvent. In-situ spectroscopy to evaluate surface acidic properties. Use of nanostructured zeolites for higher accessibility. Test reactions are the isomerisation of glucose to fructose, the direct dehydration of glucose to 5 hydroxymethylfurfural and the conversion of 1,3-dihydroxyacetone to lactic acid.
• The initial experiments on glucose conversion in molten salts have identified substantial drawbacks of these systems. At the mid-term assessment (M24), it was decided to discontinue this research line due to the low yields obtained in the molten salts. Preliminary experiments with noble metals indicate that the high chloride content blocks the active sites.
• The personnel efforts have been shifted to carry out sugar isomerization in continuous flow (WP2).
WP2: Proof of concept: Catalytic Biomass Valorisation using Non-Critical Metals Catalysts addressed three biomass conversion routes, all of industrial importance and interest in biorefinery concepts (million tons production), and which demonstrate the potential – the catalytic performance and robustness - of the concepts for the development of novel catalyst systems with completely eliminated critical element content for catalytic biomass conversion. An essential step in this phase is a benchmark against the state of the art systems. At this stage, attention has been paid to possible scale up issues and integration with other steps, fine-tuning of catalyst synthesis parameters based on these results and characterisation studies of catalysts at work to identify possible negative aspects as low performance or fast deactivation. Part of the activities in WP2 was also dedicated to techno-economical analysis of the results obtained, because we consider this as an integral part of the evaluation of the potential of the novel solutions developed. At the time of writing the application three potential proofs of concept projects have been identified which meet the criteria for demonstrating the potential of the new approaches (i) direct production of γ-valerolactone (gVL) from cellulose; (2) a chemocatalytic route to lactic acid or even ethanol and (3) aqueous phase reforming of biomass constituents. In all cases the catalysts will contain no critical metals.
Task 2.1 – The valeric platform
Investigate the performance of NCM catalysts for the combined isomerisation, dehydration, decarboxylation and transfer hydrogenation of glucose to γ-valerolactone; evaluate the effect of reaction conditions on catalyst activity, stability and regenerability; evaluate performance when cellulose is the starting reactant. Compare the results (in terms of productivity, selectivity, operation conditions, kinetics and stability) with those obtained using conventional catalyst technology (best practice).
• Low-temperature process for levulinic acid hydrogenation employing Ni:Re(2:1)/TiO2 catalyst is developed.
• Substantial recyclability of Ni:Re(2:1)/TiO2 is demonstrated.
• A synergy between Ni and Re components in the bimetallic catalyst is revealed.
Task 2.2 – Synthetic glycolysis
Investigate the performance of novel NCM catalysts for the conversion of glucose to lactic acid and the subsequent decarboxylation to ethanol. Explore the use of NCM metal oxide or Lewis acid functionalised zeolites for the combined depolymerisation of (hemi)cellulose in molten ZnCl2-hydrate and subsequent conversion of the sugars to lactic acid/ethanol.
• Sn-Beta zeolite deactivates rapidly in the course of glucose retro-aldolization. Our results suggest that the deactivation is caused by the oligomerization of the highly reactive fructose intermediate at the outer part of the zeolite crystals. Separation of the isomerization and retro-aldolization steps is desirable for the glucose to methyl lactate conversion process.
• Deactivation of Sn-Beta upon glucose conversion in water is due to both the accumulation of oligomeric byproducts in the zeolite pores and structural decomposition of the siliceous framework. The latter effect results in a long-term catalyst deactivation. By carrying out the reaction in ethanol/water mixed solvent medium, both effects can be largely suppressed resulting in a prolonged stability of the zeolite catalysts under continuous flow conditions.
• Ru/TiO2 catalyst is highly efficient for the selective conversion of lactic acid to 1,2-propanediol under relatively mild conditions.
• A superior catalytic system for lactic acid dehydrogenation based on non-noble metal MoO3/TiO2 oxides is discovered. The stable catalytic performance of this system in flow under oxidative and non-oxidative conditions is demonstrated.
• Depolymerization of cellulose has been achieved with high glucose yields in methanol.
• Modified graphenes having acid groups and magnetic iron nanoparticles have been used as recoverable catalysts for starch depolymerisation.
Task 2.3 – Aqueous phase reforming
Performance testing of NCM nanoparticulate catalysts in the aqueous phase reforming of glycerol and carbohydrates. Kinetic studies of the product distribution as a function of nanoscale properties of the nanoparticulate catalysts (size, morphology, support functionalities) as well as catalyst stability. Development of structure-performance relations for NCM catalysts based on particle size and metal type. Exploration of mixed NCM nanoparticulate catalysts.
• The catalytic activity of doped graphenes has been evaluated for the aqueous phase reforming of glycerol, being the B-doped G the most active catalyst in the series.
Task 2.4 – Techno-economic evaluation
First techno-economic analysis of the concepts explored in NOVACAM. Input to these studies is the outcome of Tasks 2.1-2.3 in terms of productivity and selectivity and the most likely process layout and best practice literature data. Issues like energy management and its impact on investment and the impact of feedstock price (e.g. renewable biomass against crude oil) will also be taken into account.
• The economics of a process for glucose conversion to 5-HMF by P/TiO2 were positively evaluated. Preliminary economic calculations indicate that optimized P/TiO2 is able to obtain 5-HMF from glucose in a biphasic system with above 60% selectivity showing that the process can be scaled up. Predictions are pricing below 1 €/kg which makes the process attractive.
• Friedel-Crafts alkylation of hydroxymethylfurfural by toluene, followed by hydrogenative deoxygenation renders a hydrocarbon that is suitable to be combined with the gasoil fraction in the refining process.
Twenty-nine (29) project deliverables were completed (10 – WP1, 4 – WP2, 6 – WP3, 9 – WP4) during the project lifetime from September 2013 to February 2017. The Midterm assessment (MTA) of NOVACAM was programmed at the end of the 2nd year. This MTA (D4.8) was a major decision point, because it has been the formal point where the Consortium decided how to proceed in the second period, by identifying promising catalyst systems and reformulating the approaches in the second period based on the chemistry developed in the first period. The consortium discussed the progress towards the objectives extensively and critically assessed the most promising results on the basis of quality, novelty and potential to contribute to the development of non-critical element based catalysts. In the second phase of NOVACAM a two-pronged approach were been pursued consisting of work on the underlying chemistry to be carried out in WP1 and work towards the proofs of concepts which will be part of WP2. Based on the progress in WP1 and the initial results pertaining to WP2, it was decided that all three subtasks in WP2 will be pursued. Nevertheless, most attention was to be given to tasks 2.1 and 2.2 because task 2.3 was least promising and, in principle, a supply of hydrogen might be derived from other feedstock as well. Work in task 2.3 has been postponed until promising results are obtained in WP1 (D4.8).
The main outcomes from the deliverables are presented below:
D1.1 Interim report on novel NCM catalyst(s) for hydrogenation (August 2015) task leader: CU
This deliverable presents the interim results on NCM catalysts for hydrogenation. The focus was the development of hydrogenation catalysts for the conversion of levulinic acid (LA) to γ-valerolactone (GVL). The previous work showed that Cu-ZrO2 catalysts prepared by co-precipitation and oxalate gel precipitation were found to be active catalysts for LA hydrogenation. The addition of Ni to the Cu-ZrO2 in order to enhance the activity was also investigated. These catalysts were synthesized using the oxalate gel precipitation method.
D1.2 Interim report on novel NCM catalyst(s) for transfer hydrogenation (August 2015) task leader: CU
The deliverable presents the results on various oxide catalysts that have been prepared and tested for the transfer hydrogenation reaction. The catalysts were prepared by hydrothermal, mechanothermal and oxalate gel precipitation methods.
D1.3 Interim report on novel NCM catalyst(s) for decarboxylation (August 2015) task leader: TU/e
This deliverable summarises the interim results of our work on theoretical DFT calculations that have been undertaken to understand the reaction mechanism. Two possible routes were indicated and the theoretical model suggested that the reaction mechanism involves the formation of a keto carboxylic intermediates (route a) should be the one kinetically preferred. In view of the novel and very promising results on the direct lactic acid photodecarboxylation obtained with the TiO2-supported catalysts and unsatisfactory results obtained with alternative support materials, the former system was chosen as the main research object. With this system we could demonstrate the possibility of highly selective sugar decarboxylation (‘synthetic glycolysis’). The utility of this reaction for the development of novel acceptorless dehydrogenative coupling processes has also been demonstrated.
D1.4 Interim report on novel NCM catalyst(s) for dehydration/isomerisation (August 2015) task leader: CSIC
This deliverable presents the interim results on NCM catalysts for dehydration/isomerization. Among the metal oxides that have been screened as isomerisation catalysts those that have showed high catalytic activity and were the most promising leads for further development in this area are ZrO2, CeO2 and WO3. These three oxides are based on abundant and non-critical metals and were been useful to develop WP2 with the proof of concept of an industrial process.
Complementary theoretical and experimental study performed suggested that the nanostructuring or the increase of the pore size of the zeolite matrix may not result in the expected increase of catalytic performance of Sn-zeolite glucose conversion catalyst. Our study identified alternative oxide-based systems that can promote glucose activation following the mechanism analogous to that realized in the zeolite as well as in the enzymatic catalysis. These systems were being studied systematically by computational methods.
D1.5 Interim report on potential of NCM catalyst(s) to operate in molten salts (August 2015) task leader: TU/e
The initial results showed that glucose can be completely oxidized as CO2 is formed. The best performing system was the one with a Pt co-catalyst. The problem here was the poisoning of the metal catalyst as evident from the data that compare the reaction in water and molten salt hydrate. Although this concept may have potential, we concluded that this is well outside the scope of NOVACAM and this part of the research was discontinued.
D1.6 Report on novel NCM catalyst(s) for hydrogenation (August 2016) task leader: CU
This deliverable present the final results on NCM catalysts for hydrogenation. Cu/Ni/ZrO2 catalyst was found to be better than Cu/ZrO2 catalyst for LA conversion into GVL. Grinding the catalysts (both Cu and Ni based) resulted in an enhancement in the activity, and a significant increase in BET surface area was observed. An attempt has been made to decrease the amount of Cu in Cu/ZrO2 catalyst system and initial results are very promising. Solvent screening has shown that MeOH was more efficient solvent system for an increased catalyst activity and stability for Cu/ZrO2 catalyst system. pH studies will be performed on the catalytic reactions scurried out in different solvents.
D1.7 Report on novel NCM catalyst(s) for transfer hydrogenation (August 2016) task leader: CU
This deliverable summarises the final results on catalysts for transfer hydrogenation. For transfer hydrogenation of methyllevulinate Cu/ZrO2 catalyst prepared by the oxalate gel method showed a high activity for GVL production using MeOH as a sacrificial hydrogen donor. By-products in terms of gases were observed in this reaction. Reduction of the reaction temperature decreased the amount of gaseous by-products produced during the reaction. Quantitative NMR of the post reaction effluents is required in order to assess the mechanistic details. The addition of small quantities of H2O increased the GVL selectivity which suggests that undesirable by-products may be formed from the reduced intermediate species.
In the work related with process design various catalysts have been tested in order to understand the dehydration of glucose into ML. Brønsted acidity seems to be a required factor for the reaction. Strength of the acid determines selectivity towards desired products, however a fine balance needs to be tuned. The activity of the catalyst is significantly affected by choice of metal oxide support. The current focus is determining the reaction mechanism and limit the formation of humins. Utilising a sacrificial secondary alcohol to inhibit the aldol polymerisation route can be an option.
D1.8 Final report on novel NCM catalyst(s) for decarboxylation (August 2016) task leader: TU/e
New chemical pathways for decarboxylation of lactic acid discovered. TiO2-supported transition metal photocatalysts allow a strong enhancement of the decarboxylation rate by promoting the concert decarboxylation and dehydrogenation of the substrate resulting in acetaldehyde as the main product. A record-high lactic acid decarboxylation activity is obtained with the noble metal-based Pt/TiO2 catalyst. An alternative highly active NCM-type Ni/TiO2 photocatalyst is identified. Photocatalytic decarboxylative acceptorless dehydrogenation can be used to develop new sustainable routes for low-temperature oxidative coupling of lactic acid with H2 as the major useful by-product. A highly active and selective MoO3/TiO2 catalyst made of non-critical elements for lactic acid oxidative dehydrogenation is developed. The highest selectivity of about 90% to pyruvic acid at 50% lactic acid conversion can be obtained with 1%Mo catalyst. In the absence of external oxidant a transfer hydrogenolysis process to produce propionic and pyruvic acids in equimolar amounts can be carried out with these catalysts.
D1.9 Report on novel NCM catalyst(s) for dehydration/isomerisation (August 2016) task leader: CSIC
Theory predicts transition metal doping as a promising strategy towards new oxide-based catalysts for sugar isomerization. The formation of oxygen vacancies on the tungstite surface can substantially enhance its reactivity and open a new reaction channel involving a one-step glucose isomerization to fructose. A new highly favorable reaction mechanism involving a cooperation between Lewis acid and Brønsted base sites for the direct glucose to fructose dehydration is identified for TiO2-based catalysts.
Advanced ab initio molecular dynamics simulations confirms the strong promoting role of cooperative action between the Lewis and Brønsted acidic centers in Sn-zeolite catalysts for the selective glucose to fructose isomerization reaction. In situ NMR study confirms our earlier theoretical predictions on the crucial role of competitive adsorption between solvents and carbohydrate substrates on the activity of zeolite-based systems. In combination with DFT modeling, a promising mixed solvent system is identified for glucose conversion over Sn-Beta catalyst. Niobium oxide supported on modified carbon nanotubes can convert glucose into succinic acid or lactic acid with high selectivity at high conversion. The fine balance between Brønsted and Lewis acid sites is crucial to achieve the optimal catalysts. The present of magnetic nanoparticles makes easy the recovery and reuse of the supported niobia catalyst.
D1.10 Report on potential of NCM catalyst(s) to operate in molten salts (August 2016) task leader: TU/e
At the mid-term assessment (M24), it was decided to discontinue this research line due to the low yields obtained in the molten salts. Preliminary experiments with noble metals indicate that the high chloride content blocks the active sites. The personnel efforts have been shifted to carry out sugar isomerization in continuous flow (WP2).
D2.1 Report on proof of concept for the valeric platform (February 2017) task leader: CSIC
Updated focus of the task during midterm assessment:
- Improve supported Ni/Co/Cu catalysts
- Compare liquid vs. gas phase
- Screening in flow reactors to assess stability
- Solvent exploration, e.g. use gVL as solvent
D2.2 Report on proof of concept for synthetic glycolysis (February 2017) task leader: TU/e
Updated focus of the task during midterm assessment: the project partners decided to focus the work in this task on:
- routes from glucose to lactic acid (avoiding 5-HMF) supported by computational studies
- photodecarboxylation of lactic acid as a base for coupling chemistry
- lactic acid dehydrogenation to pyruvic acid
- lactic acid hydrogenation to 1,2-propanediol
- catalyst stability in flow reactors (Sn-Beta), influence of solvents
D2.3 Report on proof of concept for aqueous phase reforming (February 2017) task leader: CU
During midterm assessment, the project partners decided to focus the work in this task on:
- Understand Ni-Re/TiO2 system, explore use of other Ni promoters (CSIC)
- Explore use of cellulose dissolved in ZnCl2-hydrate as feed for APR
D2.4 Final techno-economic analysis (February 2017) task leader: TU/e
In this deliverable, the preliminary economic calculations for optimized P/TiO2 to obtain 5-HMF from glucose in a biphasic system are presented showing that the process can be scaled up. Predictions are pricing below 1 €/kg which makes the process attractive. Also Friedel-Crafts alkylation of hydroxymethylfurfural by toluene is suitable to be combined with the gasoil fraction in the refining process.
D3.1 Project website: Project website (November 2013) task leader: KTN
In this deliverable an operational website www.novacam.eu has been established.
The NOVACAM website was the main portal and communication channel for the dissemination of NOVACAM project results. The website disseminated to the scientific community, both to alert other researchers to the project research findings and potential businesses who might be interesting in commercialising the technology developed.
D3.2 Initial promotional materials (October 2013) task leader: KTN
The deliverable presented the initial promotional materials including logo, press release and project brochure.
The NOVACAM logo was developed. The logo had a scientific feel to indicate the technical nature of the project and features a zeolite structure, a key material to be used in the project. A press release to announce the launch of NOVACAM was published on 2nd September 2013 on CORDIS wire. A project leaflet has been designed.
D3.3: Final Exploitation Strategy (February 2017) task leader: KTN
Management of Exploitation Strategy was an ongoing activity throughout the project to work with project partners to identify likely exploitable results, formulate exploitation opportunities and develop exploitation strategy. As the main deliverable, this Final Exploitation Strategy report sets out the exploitation measures put in place at the beginning of the project and enacted during the course of the project as well as setting out future plans for exploiting project results. This deliverable illustrates the framework needed to identify NOVACAM results, establish ownership and detail how the result can and will be exploited.
D3.4: Professional Training event (February 2017) task leader: TU/e
Two workshop were organized during the lifetime of the project (one in Europe, one in Japan). The deliverable presents the European training event.
A training programme was devised for the young researchers working on the project. The programme was based on the principles of the Marie Curie Initial Training Networks and covered both training in science and in a range of other skills. The training programme is composed of two main activities: webinars and a winter school. The NOVACAM Winter School on ‘’Green Catalysis by Design’’ was held on 22 February 2017 at The University of Padova, Padova, Italy.
D3.5: Final Project Conference (February 2017) task leader: KTN
This deliverable describes the final project conference. A final project conference has been organised in the EU at the end of the project and included invited speakers from Japan. The event will target participants with the influence to act to implement the projects findings from across industry and academia. Members of relevant EU and Japanese networks related to the substitution of critical raw materials and the manufacture of bio-based products were been invited to attend. The conference featured NOVACAM speakers to communicate the results and recommendations of the project.
The NOVACAM final project conference - marketed publically as “Green Catalysis By Design Scientific Meeting” - was held on Thursday 23rd February at the University of Padova, Italy.
D3.6 Publishable compendium on training webinars (August 2016) task leader: CU
A training programme was devised for the young researchers working on the project. A series of webinars will develop and broaden their research competences. By month 36, the webinar series were completed.
This deliverable presents the details of all the webinars: they have been collated into one place and recordings of all webinars are available via the project website: http://novacam.eu/category/news-events/webinars/
D4.1 D4.2 D4.3 D4.4 D4.5 D4.6 D4.7 task leader: TU/e
These deliverables present the minutes of all EU and joint EU-Japan meetings.
D4.8 Minutes Midterm Assessment with motivations of revisions (August 2015) task leader: TU/e
The MTA reports on the progress of the research and the Beneficiary’s plans for the proofs of concept phase were been submitted before month 24. The project coordinator organized a MTA meeting with all Beneficiaries and the Commission’s representative. The purpose of this meeting was to report on the progress to date and to redefine (if necessary) the Project Programme for the remaining part of the contract. During Midterm assessment meeting the project has been discussed in depth. Particularly, the progress, weakness and strengths of each of the three reactivity lines were discussed to focus the project on the more promising activities.
D4.9: Final report on project management including actions and results for coordination to Japanese consortium (February 2017) task leader: TU/e
This deliverable presents the main outcome of the NOVACAM project. One major outcome of the project is the intensification of scientific bonds between the European and Japanese catalysis communities. This has been fostered through the direct interaction within the project, but has also led to broader collaboration between the two communities via joint conferences, student exchanges and sabbatical leaves. Finally, the project has had major impact on young researchers, who obtained their PhD degree on the basis of the NOVACAM work.
Potential Impact:
Exploitation of results
Management of exploitation was an ongoing activity throughout the project, identifying likely exploitable results, formulate exploitation opportunities and develop an exploitation strategy. The objective was to maximize the impact of the project through wide adoption of its results and achievements within the chemical industry and scientific community. To achieve this aim a clear methodology of how to treat new innovations to provide competitive advantage to the end user partners must be established and followed in detail for each identified development. Where the potential for commercial gain is noted the route to implementation requires assessment for risk and mitigation processes put in place to ensure maximum benefit.
Project partners were encouraged to publish non-commercially sensitive project results in high impact academic journals and to present oral presentations and posters at scientific conferences and meetings. In order to ensure that commercially exploitable results were protected, any external dissemination of this kind requires approval from the consortium. The aim of this approval process is to support this activity whilst protecting commercially sensitive results. Once a project result has been identified as potentially exploitable, an exploitation plan for that result will be developed. An exploitable result is defined as “achieved or expected output coming from work performed on the project which has commercial significance and can be exploited as a stand-alone product, process, service etc.” The exploitation plan is developed jointly by partners by assessing local best experiences.
Certain project results were evaluated for their potential commercial interest and protection of intellectual property though patent was considered. However, to date all project results are still at the experimental stage and further research would be required before they would be of commercial interest. The most interesting results of the NOVACAM project from a commercial exploitation perspective are detailed in Table 1.
The NOVACAM project put in place from the beginning robust processes to collectively decide how project results should be taken forward. The processes were followed and allowed for appropriate treatment of project results. The research conducted by NOVACAM consortium partners has delivered substantial advances in the understanding of catalytic processes and progress towards the goal of critical raw material free catalysts. ITQ has submitted two patent applications in the field of catalytic biomass conversion, concerning novel routes that enable the co-processing of biomass with conventional fossil feedstock. Whilst more results show early promise and were considered for patenting, ultimately due to the experimental nature of project results, the most appropriate mechanism for disseminating these results has been through the open literature allowing for exploitation of results through and the required further development via the wider scientific and industrial community. The consortium will continue to work with industrial collaborators towards this goal.
Summary of most potentially commercially relevant NOVACAM project results
Result: Hydrogenation of levulinic acid to γ-valerolactone using a Mn-ZrO2 catalyst.
Market opportunity: Potential bio-based fuel or solvent derived from cheap feedstocks replacing fossil fuel-based supply chains.
Further research required towards commercialization: Current activity of critical raw material free catalysts does not yet match traditional catalysts. To be commercially deployed, materials need to be recovered for reuse.
Result: The use of a gradient pH method to control the co-precipitation of Cu and Zr in the materials preparation method.
Result: Hydrogenation of levulinic acid to γ-valerolactone using a Fe-Re catalyst.
Market opportunity: Potential bio-based fuel or solvent derived from cheap feedstocks replacing fossil fuel-based supply chains.
Further research required towards commercialization: Although Fe is cheap substitute for the most active Ru catalytic metal used for this reaction, Re is also an expensive metal.
Result: Photodecarboxylation of lactic acid using titania-supported transition metals
Market opportunity: Part of a chemocatalytic route from sugars to ethanol/acetaldehyde that can replace sugar to ethanol fermentation
Further research required towards commercialization: Reaction rates need to be increased.
The objective of NOVACAM to develop abundant element-based innovative solid-state catalysts for biomass utilization was well accomplished by discoveries of new crystalline oxide materials, Lewis acid-base generation in complex oxides, and bimetallic species on oxide surfaces. Overall, the consortium has demonstrated the success of the “catalysis by design” approach in the field of biomass conversion, as evident from the development of novel catalytic sites based on nanoscale insights gained through combined theoretical and experimental characterization. All of the newly synthesized catalysts revealed high catalytic performance for various biomass-derived materials conversion to desired products. Some of the most promising materials still depend on elements that are not abundant in order to achieve high activity. Next to high activity also stability is an issue when precious group metals are replaced by more reactive first-row transition metals. A highlight is the development of a high-loading phosphorous modified TiO2 – completely based on abundant elements - showing high catalytic performance in the conversion of glucose to 5-hydroxymethylfurfural. Several other leads have been identified such as the potency of cheap bulk oxides when properly promoted and molecular metal oxide wires as a new solid-state acid catalyst.
Another major outcome of the project is the intensification of scientific bonds between the European and Japanese catalysis communities. This has been fostered through the direct interaction within the project, but has also led to broader collaboration between the two communities via joint conferences, student exchanges and sabbatical leaves. Finally, the project has had major impact on young researchers, who obtained their PhD degree on the basis of the NOVACAM work.
The NOVACAM project was fruitfully done with various new solid-state materials having multi-functional catalytic properties that were found very suitable for promoting the cellulose or glucose conversion in water to desired product in high selectivity. The key of the success was the evolution of synthetic methodology for making functional catalytic materials.
Synergy
Whilst some of the researcher on both sides were already acquainted, only through the research cooperation it become possible to collaborate and explore the apparent synergy in expertise. The exchange of young researchers proved to be instrumental to achieve the goal of new catalyst development based on nanoscale insight. As all partners were active in participating in international conferences and also actively contributed to organize dissemination activities (conferences, symposia, webinars) in which also other researchers at the EU and Japanese side were involved, the project was very effective in bringing together the EU and Japanese catalysis communities.
Altogether, this project allowed building a strong consortium with considerable synergy in expertise towards idea generation and identifying novel catalysts and their impact on biomass conversion. The impact will be lasting as further collaborations are underway.
Potential impact
Reducing European industry’s reliance on imported critical raw materials to improve competitiveness, sustainability and to reduce risk is a key European policy objective. Development of critical raw material-free catalysts would make a significant contribution to this objective, particularly given the underpinning role played by catalysts in chemical supply chains. The NOVACAM project has delivered substantial advances in the understanding of catalytic processes and progress towards the goal of critical raw material free catalysts.
List of Websites:
www.novacam.eu