Periodic Reporting for period 1 - CatGTP (Interdisciplinary concepts for one-step CATalytic hydrodeoxygenation of crude Glycerol-To-bioPropylene)
Reporting period: 2021-05-03 to 2023-05-02
This MSCA project, named as “CatGTP-Interdisciplinary concepts for one-step CATalytic hydrodeoxygenation of crude Glycerol-To-bioPropylene”, was implemented at “Unité de catalyse et Chimie du solide - UCCS” of the University of Lille (ULille; France). The CatGTP project was looking at developing efficient conversion routes for crude bioglycerol, which a by-product of world-scale biodiesel industry. Herein, major advances both in terms of fundamental catalysis and process optimization of one-step hydrodeoxygenation (HDO) of bioglycerol-to-propylene (GTP) were achieved to: i) provide new mechanistic and kinetic insights on GTP catalysis, and ii) improve the efficiency of GTP route by determining the conditions affecting the process operability and catalysts performance, which are challenging in hydrothermal media.
The data collected in the first part of CatGTP project concerns two model reactions: glycerol-to-propylene (GTP) and ethanol-to-ethylene (ET-to-ETY). The idea was to provide new insights on how occurs the elimination of hydroxyl -OH group from two similar oxygenated molecules. Doing so, HDO biomass-derived molecules, which can involve concomitant dehydration, deoxygenation, hydrogenation over redox, metals and acid systems, could actually be better understood. The main findings concern how to successfully: i) get high loadings of highly reactive sub-2 nm Mo particles onto silicas for single-step HDO of glycerol at; H2-pressure ≤50 bars and temperature ≤ 400ºC, and ii) re-modulate the population of acid-sites and their strength on Al-rich MFI zeolites with high density of H+ for selective dehydration of ethanol at temperature ≤ 225ºC. Thus, highly efficient catalysts (Mo@SBA-15 and acidic ZSM-5 zeolites), were developed to provide high yields in GTP (up to 81%) and ET-to-ETY (up to 92%), respectively. The adopted actions allowed to identify the main deactivations causes for HDO catalysts working in H2O-rich medium.
The second part of CatGTP gave new insights about the most efficient GTP strategies (i.e. high-temperature routes, multi-steps/tandem reactions or single-step HDO) for converting bioglycerol in propylene. These data were collected using various criteria such as process configuration, severity of conditions, sustainability, and propylene/CO2 production. They are discussed as a function of the thermodynamic and operating conditions. Further, high-speed tests were combined with design of experiments to high propylene (> 70%) yield, which were not reported so far for such process, at optimal conditions (T ~ 367°C, velocity ~9,5 h-1 and H2/glycerol ratio ~59).
All the collected data in this MSCA project, which focus on the upgrading of crude bioglycerol by-product and bioethanol excess, to value-added biopropylene and bioethylene, respectively, are highly important for The EU’s society, because they are serving as bases for: i) building a connecting bridge between the biorefinery and polyolefin industries, and ii) complying with global targets for future carbon neutrality set by 2050.
The data collected in the first part of CatGTP project concerns two model reactions: glycerol-to-propylene (GTP) and ethanol-to-ethylene (ET-to-ETY). The idea was to provide new insights on how occurs the elimination of hydroxyl -OH group from two similar oxygenated molecules. Doing so, HDO biomass-derived molecules, which can involve concomitant dehydration, deoxygenation, hydrogenation over redox, metals and acid systems, could actually be better understood. The main findings concern how to successfully: i) get high loadings of highly reactive sub-2 nm Mo particles onto silicas for single-step HDO of glycerol at; H2-pressure ≤50 bars and temperature ≤ 400ºC, and ii) re-modulate the population of acid-sites and their strength on Al-rich MFI zeolites with high density of H+ for selective dehydration of ethanol at temperature ≤ 225ºC. Thus, highly efficient catalysts (Mo@SBA-15 and acidic ZSM-5 zeolites), were developed to provide high yields in GTP (up to 81%) and ET-to-ETY (up to 92%), respectively. The adopted actions allowed to identify the main deactivations causes for HDO catalysts working in H2O-rich medium.
The second part of CatGTP gave new insights about the most efficient GTP strategies (i.e. high-temperature routes, multi-steps/tandem reactions or single-step HDO) for converting bioglycerol in propylene. These data were collected using various criteria such as process configuration, severity of conditions, sustainability, and propylene/CO2 production. They are discussed as a function of the thermodynamic and operating conditions. Further, high-speed tests were combined with design of experiments to high propylene (> 70%) yield, which were not reported so far for such process, at optimal conditions (T ~ 367°C, velocity ~9,5 h-1 and H2/glycerol ratio ~59).
All the collected data in this MSCA project, which focus on the upgrading of crude bioglycerol by-product and bioethanol excess, to value-added biopropylene and bioethylene, respectively, are highly important for The EU’s society, because they are serving as bases for: i) building a connecting bridge between the biorefinery and polyolefin industries, and ii) complying with global targets for future carbon neutrality set by 2050.
The CatGTP’s activities was conducted by the researcher via two WP1 and WP2, which included 4 new Trainings (TR1-4), 2 Transferable skills (TS1-2) and 5 transfer knowledges (TF1-5). The researcher implemented these tasks in close collaboration with in-house researchers at the hot lab-UCCS and with others from external centers. The high quality of the advances achieved reflect the stimulating learning environment at the host and the quality of the collaboration established.
The WP1 comprised two studies on GTP and on ET-to-ETY routes, that yielded 2 peer-review journal articles (published in open access in 2022 & 2023), and 4 oral presentation (in 2022 & 2023), and further 1 journal manuscript underway to be published in 2024. These advances were accomplished by exploring an interdisciplinary approach, which combines rational design of catalysts, well-chosen model reactions, and high-level labs-facilities like high-throughput experimentations, in-situ spectroscopies, high-resolution microscopies, etc. Within this project, a new PhD student is being supervised to prepare her PhD thesis, thus, ensuring the transfer of CatGTP's knowledges (TF5) beyond the implementation of the present MSCA action.
WP2 sought to demonstrate what the most efficient technology for converting crude bioglycerol to propylene. Extensive data on different GTP routes, including single-step HDO, are processed via design of experiments to be compared with those computed by ASPEN software. The whole of obtained data gave rise to 1 peer-reviewed articles published in open access (in 2023), 2 others oral presentation (in 2023), 2 other manuscripts underway to be published in 2024 and 1 divulgation mini-article for large audience. This WP2 included extensive manipulation on high-throughput experimentations (TR3) and additional training with new engineering concepts (TR4) and multi-management tasks (TS1-2). To transfer knowledge (TF1-5) various direct interactions with internal/external agents have been explored through collaboration, supervision and mentoring for early career researchers (1 post-doc on DFT calculations and 1 post-doc on dry reforming of methane). The researcher has been also appointed: Co-chair of “glycerine Innovation Session” at the 2023 AOCS Annual Meeting & Expo April 30–May 3, 2023, Denver, Colorado, USA, and he served as reviewer during this period for various articles from high-levels journals.
The WP1 comprised two studies on GTP and on ET-to-ETY routes, that yielded 2 peer-review journal articles (published in open access in 2022 & 2023), and 4 oral presentation (in 2022 & 2023), and further 1 journal manuscript underway to be published in 2024. These advances were accomplished by exploring an interdisciplinary approach, which combines rational design of catalysts, well-chosen model reactions, and high-level labs-facilities like high-throughput experimentations, in-situ spectroscopies, high-resolution microscopies, etc. Within this project, a new PhD student is being supervised to prepare her PhD thesis, thus, ensuring the transfer of CatGTP's knowledges (TF5) beyond the implementation of the present MSCA action.
WP2 sought to demonstrate what the most efficient technology for converting crude bioglycerol to propylene. Extensive data on different GTP routes, including single-step HDO, are processed via design of experiments to be compared with those computed by ASPEN software. The whole of obtained data gave rise to 1 peer-reviewed articles published in open access (in 2023), 2 others oral presentation (in 2023), 2 other manuscripts underway to be published in 2024 and 1 divulgation mini-article for large audience. This WP2 included extensive manipulation on high-throughput experimentations (TR3) and additional training with new engineering concepts (TR4) and multi-management tasks (TS1-2). To transfer knowledge (TF1-5) various direct interactions with internal/external agents have been explored through collaboration, supervision and mentoring for early career researchers (1 post-doc on DFT calculations and 1 post-doc on dry reforming of methane). The researcher has been also appointed: Co-chair of “glycerine Innovation Session” at the 2023 AOCS Annual Meeting & Expo April 30–May 3, 2023, Denver, Colorado, USA, and he served as reviewer during this period for various articles from high-levels journals.
CatGTP project has pushed the research frontiers on GTP and ET-to-ETY catalysis forward in numerous ways. For example, the rich mechanistic and engineering data published expect to enrich the future publications dealing with ET-to-ETY/GTP routes-related topics in the coming years, ensuring further advances beyond CatGTP project. Also, these progresses are of high interests for building a connecting bridge between the biorefinery and polyolefin industries, which would contribute to overcome the challenges related with the shortage of light olefins in EU. Seen the remarkable industrial/sustainability aspects of CatGTP’s actions, the disseminated results expect to generate an overarching socio-economic and environmental impacts on the EU society, thus, enhancing public perception of useful industries such as biorefineries and polyolefins.
On other side, CatGTP project allowed to train one fully independent researcher and is contributing to form another PhD student under stimulating scientific environment. The Researcher’s PhD student is generating important new data about the stability of HDO catalysts and operability of GTP process that will advance even more this technology. Working together, we are generating new advances that describe shortfalls in various GTP routes and illustrate what can be done to improve their efficiency. Sharing these knowledges with internal/external collaborators is boarding the research networks of the researcher. Through these interactions, the bases for successful collaborations between ULille and others other international centers are emerging to develop in the future new projects for training train new PhD students. Such opportunities are allow cultivating a broader human capacity to produce quality research in catalysis field and intra-European knowledge transfer in benefit of the European research area and industries.
On other side, CatGTP project allowed to train one fully independent researcher and is contributing to form another PhD student under stimulating scientific environment. The Researcher’s PhD student is generating important new data about the stability of HDO catalysts and operability of GTP process that will advance even more this technology. Working together, we are generating new advances that describe shortfalls in various GTP routes and illustrate what can be done to improve their efficiency. Sharing these knowledges with internal/external collaborators is boarding the research networks of the researcher. Through these interactions, the bases for successful collaborations between ULille and others other international centers are emerging to develop in the future new projects for training train new PhD students. Such opportunities are allow cultivating a broader human capacity to produce quality research in catalysis field and intra-European knowledge transfer in benefit of the European research area and industries.