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FP7

NOVACAM Report Summary

Project ID: 604319
Funded under: FP7-NMP
Country: Netherlands

Periodic Report Summary 2 - NOVACAM (NOVel cheap and Abundant Materials for catalytic biomass conversion)

Project Context and Objectives:
NOVACAM is 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 is 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 will develop and demonstrate 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 aims 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 is carried out with a partner consortium in Japan with complementary expertise in the field of innovative catalyst research.
The Consortium
In order to achieve the above objectives, the NOVACAM consortium involves 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 is 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 is closely interconnected to and coordinated with a Japanese consortium of academic groups led by Hokkaido University. The work at the Japanese side is funded by the Japanese Science and Technology Agency. With the coordinated cooperation, the two consortia share the same goals, build on each other’s expertise through exchange of academic personnel and joint project meetings.

Motivation 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 addresses the development of novel technology to enable the substitution of critical metals in catalysts. The project will aim to develop catalysts using non-critical elements for the conversion of biomass to chemicals and fuels. NOVACAM targets 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 focus 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.
The main objectives of the project are (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 will be employed to design novel inorganic catalytic systems.

Project Results:
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:
Upgrading of cellulose to γ-valerolactone by novel non-noble catalysts
- A Cu-based catalyst for levulinic acid hydrogenation were identified as an alternative to noble metal based hydrogenation catalysts. The performance of this catalyst with respect to dispersion, support and preparation is being optimized. The reaction mechanism on Cu and zirconia-supported Cu catalyst has been explored by quantum-chemical calculations.
- TiO2-suppoerted Ni-Re and Fe-Re catalysts were 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.

Upgrading of sugars to platform molecules
- A novel route for the conversion of glucose to ethanol has been identified. Its innovative nature is the combination of a Lewis acidic zeolite catalyst for the retro-aldol reaction of glucose to lactic acid. Lactic acid is then decarboxylated under benign conditions by a titania-based Pt catalyst. The energy is provided by the sun. An alternative highly active non-critical metal Ni/TiO2 photocatalyst is identified as a suitable substitute for Pt/TiO2. The mechanism of this complex chemistry has been resolved by a combination of quantum-chemical calculations and in situ spectroscopy.
- 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.
- The dehydration of glucose to 5-HMF via the initial isomerization of glucose to fructose was investigated by computational chemistry. A conceptual framework was developed highlighting the cooperative nature of Lewis acidic reaction centers that occur in heterogeneous catalysts (e.g., zeolites), homogeneous catalysts (e.g., Cr in ionic liquids) and enzymes. Following the consortium’s “Catalysis by Design” ambition, these insights guide the synthesis of novel mixed oxide systems based on abundant elements for sugar conversion.

- Based on these insights, a computational study gained insight into the effectiveness of several novel chemical approaches towards glucose dehydration developed in NOVACAM:

- Tungstites are active Lewis acid catalysts which can isomerize glucose to fructose. Combining them with a small amount of protic acids yields high 5-HMF yield. Computational modelling has predicted that doping tungstate with different cations improves reaction rate and selectivity. This has been confirmed by experiments.
- The mechanism of glucose dehydration on phosphated titania has been explored by quantum-chemical calculations. These efforts confirm that glucose dehydration without isomerization to fructose is possible. This opens possibilities for new chemistry for glucose valorization.
- 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 presence of magnetic nanoparticles makes easy the recovery and reuse of the supported niobia catalyst.

Aqueous phase reforming for hydrogen generation
- 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.
- Oriented Pt films on graphene show unprecedented performance in aqueous phase reforming of glycerol.

Potential Impact:
The work in NOVACAM is organized in two technical work packages, complemented by two work packages dedicated to dissemination, exploitation and training and to project management. The total duration of the project is 42 months. The work plan is structured around developing the basic chemistry that underlies proof of concepts. The basic chemistry is addressed in the first two years of the project in work package 1, the proof of concepts is gaining attention in the last 24 months of the project in work package 2.
The outcomes of the project will be 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. Specifically, we expect to
• 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 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 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

- Identification of non-critical metal catalysts based on Cu, Fe and Ni for the hydrogenation of levulinic acid to GVL. A zirconia-supported Cu nanoparticle catalyst was optimized with respect to dispersion, support and preparation and the reaction mechanism was understood by quantum-chemical calculations. Titania-supported Ni-Re and Fe-Re catalysts are able to hydrogenate levulinic acid to GVL in >90% yield in water with a Ni:Re/TiO2 catalyst at a temperature as low as 130 °C.

2. Upgrading of sugars to platform molecules

- A novel route for the conversion of glucose to ethanol has been developed. The chemistry is based on a Lewis acidic zeolite catalyst for the retro-aldol reaction of glucose to lactic acid. Lactic acid is decarboxylated using a titania-based Pt catalyst using energy provided by the sun. Ni/TiO2 is a viable alternative non-critical metal photocatalyst. The mechanism of the underlying chemistry was resolved by a combination of quantum-chemical calculations and in situ spectroscopy.
- A highly active and selective MoO3/TiO2 catalyst made of non-critical elements for oxidative dehydrogenation of lactic has been developed. Pyruvic acid yield has been optimized in terms of Mo dispersion.
- Dehydration of glucose to 5-HMF has been thoroughly investigated by computational chemistry. Derived from this novel chemistry has been explored:
- Tungstites are active Lewis acid catalysts which can isomerize glucose to fructose.
- The mechanism of glucose dehydration on phosphated titania has been explored by quantum-chemical calculations.
- 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.
- 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 presence of magnetic nanoparticles makes easy the recovery and reuse of the supported niobia catalyst.

3. Aqueous phase reforming for hydrogen generation

- 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.
- Oriented Pt films on graphene show unprecedented performance in aqueous phase reforming of glycerol.

List of Websites:
www.novacam.eu

Contact

Laurent Nelissen, (Managing director)
Tel.: +31 40 2473000
E-mail
Record Number: 192699 / Last updated on: 2016-12-16
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