ANR Project DIRECTSYNBIOFUEL (2015-2019)
" Engineering of hierarchical metal-zeolite nanocomposites for direct synthesis high-octane gasoline from biosyngas "
The objectives of this project include:
-the preparation of uniform metal nanoparticles of controlled size and composition;
-the preparation of hierarchical zeolite crystals containing cavities and macropores of the desired size;
-nanocasting of metallic nanoparticles in the secondary porous system of zeolite;
-encapsulation of metallic nanoparticles in zeolite mesocavities by a secondary growth of the zeolite structure.
The novelty of this project is related to the development of new synthesis strategies for the preparation of metal-zeolite nanocomposites. Microporous, mesoporous or macroporous crystalline supports serve as a matrix for metallic nanoparticles, as the steric restrictions offered by zeolite cages limit the size of clusters and thus allow control effective metal scattering. Nanoparticle encapsulation in cages can interfere with cluster interactions with acid sites and increase stability. The regularity and uniform distribution of metal clusters in a zeolite matrix results in a significant increase in selectivity and lead to higher yields of branched hydrocarbons. In the final catalysts, zeolite is used to house metal nanoparticles for Fischer-Tropsch synthesis, while hydrocracking and hydrocarbon isomerization occurs in micro, meso - and macropores.
Effective control of catalyst morphology has led to significant improvements in the diffusional properties of zeolite. Several methods of preparing metal-zeolite nanocomposites and encapsulation of metal nanoparticles in zeolite have been developed. These new catalysts dismantled a greatly improved performance in the synthesis of petrol-type hydrocarbons during the Fischer-Tropsch synthesis
12 articles were published in reputable catalysis or generalist journals, 21 guest lectures and oral presentations at international conferences were given.
The DirectSynBioFuel project is a fundamental research project coordinated by the Unité de catalyse et chimie du solide (UCCS, UMR 8181 CNRS) in Villeneuve d'Ascq. It combines the Laboratory Catalyse Spectrochemistry (LCS) in Caen. The project began in January 2016 and lasted 36 months. It received ANR assistance of 329,680 euros at an overall cost of around 1,456,707 euros.
CAPES-COFECUB Project (2014-2017)
" Development of new technologies for obtaining high value products through catalytic transformation of mineral coal or biomass"
The development of new technologies for the production of fuels other than those based on petroleum is a great challenge. In this scenario, the search for alternatives that could provide synthetic fuels from renewable resources or from other fossil raw material with increased known reserves is a main issue. This requirement can be found in the XTL (X = Gas, Coal or Biomass) technology, because it allows the production of clean liquid fuels and fine chemicals by converting synthesis gas obtained from mineral coal, biomass and natural gas through the Fischer-Tropsch (FT) synthesis. A major advance recently found for this technology is the addition of organic compounds during the synthesis of catalysts, since it influences the mechanisms of active metal precursor decomposition, nucleation and crystal growth of metal oxide species, leading to the enhancement of metal dispersion. Notwithstanding the enhancement in the catalytic performance, results for FT catalysts modified with organic compounds are still scarce. In addition to the modification of traditional FT-catalysts, the development of novel technology that could enhance the global process by reducing steps for the XTL technology is another main target to be aimed. In this context, the present work focused on understanding the influence of different organic compounds added during the preparation of catalysts over their structure and catalytic properties mainly for FT. A comprehensive investigation was required to set the best compositions for the materials and operating variables considering deactivation issues and the different designs available for these technologies. This project had special interest for the south region of Brazil, because it has large reserves of mineral coal and solid residues to be managed that could be explored through these optimized processes. The project included several internship stages and periodic short-time missions. The project provided novel results to be shared through more than 10 joint papers at top level journals and numerous communications at congresses and, most of all, the formation of qualified human resources by changing ideas and knowledge by members of both institutions. During these 4 years of collaboration, 7 sandwich theses have been prepared by UFRGS students and one thesis from the University of Lille. These exchanges provided important scientific knowledge and greatly contributed to academic training, the discovery of another culture also greatly contributed to the personal and professional development of these students
ANR Project CATSYN-BIOFUEL (2013-2016)
" Hybrid hierarchical catalytic structures for synthesis of biofuels "
The goal of this project is to provide fundamental knowledge on the main parameters that determine the productivity of the direct synthesis of dimethyl ether from biosyngas.
In the society of the future, biomass will become one of the main resources of the renewable energy production of food, feed, and chemical products. This project aims to provide a basic understanding of the main parameters governing productivity in dimethyl ether in its direct synthesis from synthesis gas from biomass. This fundamental understanding is then used for the design of new efficient hybrid hierarchical catalytic structures, as well as for the intensification of catalytic processes with increased productivity. The specific objectives of this project are the following:
-Design of new hydrides bifunctional catalysts with three levels of porosity (micro-, meso - and macro-).
- Optimization of heat transfer using a ceramic matrix with a high thermal conductivity;
- Improved catalyst stability, in particular in the presence of sulphur and other impurities biosyngas.
The research program is performed by 4 research teams that have complementary expertise in the design of new materials and catalytic processes.
Our method is based on nano-, micro- and macroscopic engineering of the catalyst structure and catalytic reactor. The catalysts were characterized using a combination of techniques: nuclear magnetic resonance, x-ray diffraction, Raman and infra-red spectroscopies, X-ray photoelectron spectroscopy, electron paramagnetic resonance, operando X-ray absorption, temperature-programmed reduction, and high resolution electron tomography imaging techniques, coupled with chemical analysis techniques. Dimethyl ether synthesis was performed in a milli-bed fixed reactor operating under pressure. In-depth characterization and catalytic tests helped to elucidate the relationship between catalytic performance for synthesis of dimethyl ether and chemical composition, crystal structure, acidity, micro, meso - and macroporosites and the size of metal and zeolite nanoparticles
New hybrid catalysts for direct synthesis of dimethyl ether from syngas was developed using ZSM-5 zeolites and copper nanoparticles. The preparation of these catalysts was founded on a better understanding of the mechanisms of formation of hierarchical zeolites. Catalytic performance was attributed to metal copper sites and zeolite acidity. The small size zeolite crystals enhanced the catalytic activity. Sintering and migration of copper were predominant mechanisms of catalyst deactivation. The catalyst stability and DME productivity have been improved by the neutralization of acid sites on the surface of the zeolite with tetraethyl orthosilicate. The intensification of direct DME synthesis by the use of reactors with microstructural and macroscopic catalyst shaping on the silicon carbide matrix were performed with the ultimate goal the development of a new active catalytic system. New development of hierarchical zeolite ZSM-5 with nanorods microstructure decorated silicon carbide composites.
7 articles were published in high-impact scientific journals, 7 invited lectures and 9 oral presentations were given at symposia and congresses. A PhD thesis was defended. An international workshop was organized during the project.
The CATSYN-BIOFUEL project is a fundamental research project coordinated by Dr. Andrei Khodakov. It associated the Unité de catalyse et de chimie du solide (UCCS, Villeneuve d’Ascq), Laboratoire Catalyse et Spectroscopies (LCS, Caen), Institut de chimie et procédés pour l’énergie, l’environnement et la santé (ICPEES, Strasbourg) and Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS, Strasbourg). The project started in February 2013 and lasted for 36 months. The ANR funding was €495 032 € for a global cost of € 1 658 006.
ANR Project OLSYNCAT (2012-2015)
" Novel Catalytic Materials and Intensified Processes for Olefin Synthesis from Syngas Produced from Biomass or Coal "
Development of novel catalytic materials based on the promoted metal sulphides and metal carbides, mesoporous materials and carbon nanotubes for syngas conversion to olefins. Design of novel process for olefin synthesis from H2/CO using milli- and micro-structured reactors
The goal of this proposal is to enhance the selectivity of C2-C4 olefin synthesis from syngas generated from biomass and coal using novel catalytic materials and novel intensified processes. The originality of this proposal also relates to the fact that novel catalytic materials and reactors are optimized for olefin synthesis using syngas produced from gasification of biomass and coal which contains sulphur and other impurities. These impurities are harmful for the performance of conventional Fischer-Tropsch catalysts.
The research program will be performed by two teams in France and China who will work complementarily on valorisation of syngas produced from biomass and coal.
Our method involves controlled synthesis of novel catalytic materials, searching for structure catalytic performance correlation and intensification of catalytic processes. Catalyst characterisation was conducted using a combination of techniques: XRD, Raman, IR spectroscopy, XPS, magnetic measurements, Mossbauer spectroscopy, Temperature programmed Reduction, Transmission and Scanning Electron Microscopies. The Fischer-Tropsch synthesis was conducted in both a single milli-fixed bed reactor and in a high-throughput unit equipped with 16 parallel milli-fixed-bed reactors.
Project main results: We have developed different sulphide and carbide catalysts supported by metal oxide and carbon materials and processes for synthesis of olefins in the presence of sulphur in syngas. The catalytic performance was improved by using different supports and promotion. These designed catalysts have shown improved stability in the presence of biomass and coal derived syngas. New active and selective catalysts for carbon dioxide hydrogenation to higher hydrocarbons were also developed as a part of this project.
Scientific production and patents since the beginning of the project: 13 papers were published in high impact journals, 13 presentations were given at the international congresses and symposiums. Two PhD theses were defended. An international symposium was organised during the project.
The OLSYNCAT project is a fundamental research project coordinated by Dr Andrei Khodakov in France and by Prof. Ye Wang in China. It associated the Unité de catalyse et de chimie du solide and State Key Laboratory of Physical Chemistry of Solid surfaces. The project started on February 2012 and lasted 36 months. ANR grant amounted to 179 677 € and NSFC grant amounted to 1 000 000 RMB.
ADEME PROJECT GAYA (2010-2017)
" Technical, economic, environmental and societal validity of the thermochemical production of gaseous biofuels (methane) "
The Gaya project was launched in 2010 at the initiative of 11 partners from the industrial, institutional and academic world, in France and in Europe. It is a research and development project that aims to validate innovative technological choices and applications of biomethane from dry biomass, biomethane mainly from lignocellulosic materials (wood, straw, etc.).
Gaya has become in four years an emblematic project to meet the challenges of energy transition and energy mix. At government level, a bill is underway on this subject. Renewable energies are of course one of the pillars.
Gaya a collaborative project that brings together 11 cutting-edge partners. The project is managed by ENGIE. Its funding, provided by ENGIE and ADEME, through investments for the future, and its partners, has been validated by the European Union.
But what is Gaya? This is the name of a project that covers several dimensions. Gaya is a cutting-edge technological platform (in 2013, the foundation stone was laid and the launch of works is effective today); a new green gas; a method of methanation; one ambition: to be a component of the energy mix; and finally an organization. The project aims to establish a new organized biomethane sector and to ensure its viability and development.
The construction of the Gaya platform is based on a technological challenge. Its purpose is to allow the production of a so-called 2nd generation green gas, transportable in current networks or directly usable for CNG vehicles, with an innovative production process, methanation, and from residues such as wood , straw, etc.
The platform is now an experimental model pilot for future biomethane production plants that could be launched from 2020. This green gas will be economical and ecological. Its expected overall yield is greater than 60%. Few processes reach this level of efficiency, which justifies the economic aspect of the green gas produced.
To carry out this project, a budget of € 47 million was planned at the launch of the project, including € 19 million in grants from the ADEME.
The Gaya platform is under construction in Saint-Fons, south of Lyon, in the Valley of Chemistry.
The Gaya platform is built in Saint-Fons on land belonging to Greater Lyon. This is the first flagship project to redevelop this industrial space with an international focus. The GAYA project is collaborating with the Institute of Excellence on Low Carbon Energy, IDEEL on the development of the factory of the future.
" Operando study in temperature and pressure of the conversion of syngas loaded with typical impurities derived from biomass to methane and higher hydrocarbons. "
This project addresses crucial technological problems related to the utilisation of synthesis gas derived from biomass gasification (biosyngas: mixture of CO, CO2, H2 and impurities), thus pertaining to the wider societal agendas dealing with global warming and local production of cheap and sustainable fuels and chemicals. A major barrier in the commercialisation of biomass gasification is the presence of bio-impurities such as NH3, HCl, H2S and tars in the gas products that are detrimental to downstream processes.
Two important downstream processes are the conversion of syngas to (i) methane and light hydrocarbons (Substitute Natural Gas, SNG) and (ii) higher hydrocarbons (Fischer-Tropsch synthesis, FT). The exact role and effects of biomass-derived impurities on the catalysts used for these reactions were poorly known and this project has investigated these fundamental aspects using a set of model poisons: e.g. NH3, H2S, trichloroethylene and toluene. The operating conditions were adapted to the possibilities of the operando techniques used for investigating ageing mechanisms.
All reference and operando tests were carried out under simulated reaction conditions of temperature and pressure up to 300 °C and from atmospheric pressure to 4 bar. The comparison of the reaction rate and product selectivity at the exit of the spectroscopic cells ensured that meaningful data were collected. This work resulted in a better understanding of the effect of the bio-poisons on typical syngas conversion catalysts, which helped rationalising future catalyst and process designs (which was not done here).
Several operando spectroscopic cells (i.e. FTIR cells and a novel cell enabling magnetic measurements) were used to monitor the changes happening to the catalysts and draw structure-activity relationships. The combination of these complementary spectroscopic techniques allowed probing the surface and bulk of the catalysts. The FTIR analysis focussed on the detection of i) carbonyl species, main surface intermediates, which also characterise the nature and quantity of metal surface sites and ii) spectators adspecies, mostly related to the supports. The coupling of SSITKA and FTIR techniques allowed discriminating spectator species from potential surface intermediates.
A direct relationship between the rate of formation of methane and entre the surface concentration of adsorbed CO was observed. This observation demonstrate the relevance of the operando techniques consisting in the monitoring of catalytic surface at work. The effects of the two most potent poisons, sulfur and chlorine, were evidenced and structure-activity relationships were proposed. The project partners will suggest more resistant formulations based on these results.
Four publications are already published in international journals and several others are submitted. Two invited keynote lectures were given, two oral presentations and four posters were reported at international conferences. Several others communications are planned.
The BIOSYNGOP is a fundamental research project coordinated by Frederic Meunier from the IRCELYON laboratory of the CNRS and the University of Lyon. The project involves the laboratoire Catalyse et Spectrochimie of the ENSICAEN – University of Caen (Dr. Arnaud Travert) and the UCCS Laboratory from the University of Lille at Villeneuve d’Ascq (Dr Andrei Khodakov). The project started in novembre 2011 and lasted 42 months. The ANR funding was of 448 000 € for a total cost of 1 278 000 €
" European Multilevel Integrated Biorefinery Design for Sustainable Biomass Processing "
The EuroBioRef project coordinated by CNRS, France, has just been launched on the 1st of March 2010 for a 4 years duration. It is supported by a 23 M€'s funding from the EU's 7th Framework Program. EuroBioRef will deal with the entire process of transformation of biomass, from fields to final commercial products. It will involve 30 partners from 15 different countries into a highly collaborative work.
The development and implementation of bio-refinery processes is of crucial importance to build a bio-based economy. The EuroBioRef project will develop a new highly integrated and diversified concept including multiple feedstocks (non-edible), multiple processes (chemical, biochemical, thermochemical), and multiple products (aviation fuels and chemicals). The project has a specific aim to overcome the fragmentation in the biomass industry. As efficiency is the key to the bio-refinery processes, this implies to take decisive actions to facilitate better networking, coordination and cooperation among a wide variety of actors.
New synergies, cost efficiencies and improved methods will be achieved by involving the stakeholders at all levels: large and small (bio)chemical industries, academics and researchers from the whole biomass value chain, as well as European organisations. Large-scale research, testing, optimisation and demonstrations of processes in the production of a range of products design adapted to large- and small-scale production units, which will be easier to install in various European areas.
The overall efficiency of this approach will be a vast improvement of the existing situation, and will ensure the production of aviation fuels and multiple chemical products in a flexible and optimized way. It will also take advantage of the differences in biomass components and intermediates. The target is also to improve cost efficiency by as much as 30 per cent through improved reaction and separation effectiveness, reduced capital investments, improved plant and feedstock flexibility, and reduction of production time and logistics. Further, we expect to reduce by 30 per cent the energy used and produce zero waste. Raw material management will also mean that a reduction of feedstock consumption will be possible to the tune of at least 10 per cent.
The EuroBioRef concept achieves integration across the whole system from feedstock to product diversification and adapts to regional conditions, integrating into existing infrastructures, minimizing risks to investors. The flexible approach means widening bio-refinery implementation to the full geographical range of Europe, and offers opportunities to export bio-refinery technology packages to more local markets and feedstock hotspots.
The impact of the project in terms of environment, social and economic benefits is important and could give a serious advantage for European bio-industry. The techno-economic evaluation of the whole integrated biorefinery will be carried out. Moreover, the environmental life cycle assessment studies will be performed in line with the requirements of the International Reference Data System (ILCD) Handbook and the LCI data will be made available via the ILCD Data Network. The approach on social sustainability will be based on the recently developed UNEP guidelines for social life cycle assessment of products, allowing for the required modifications to meet the requirements of respective analysis on biorefinery chains.
The EuroBioRef project has the potential to re-energize biomass production, grow the industry, and achieve the original dream of biomass sustainability in the whole Europe.