Periodic Reporting for period 1 - SHERLOHCK (SUSTAINABLE AND COST-EFFICIENT CATALYST FOR HYDROGEN AND ENERGY STORAGE APPLICATIONS BASED ON LIQUID ORGANIC HYDROGEN CARRIERS : ECONOMIC VIABILITY FOR MARKET UPTAKE)
Reporting period: 2021-01-01 to 2022-06-30
Liquid Organic Hydrogen Carriers (LOHC), consisting on a reversible transformation catalytically activated of a pair of stable liquid organic molecules integrated on hydrogenation/dehydrogenation cycles, are attractive due to their ability to store safely large amounts of hydrogen (up to 7 %wt or 2.300 KWh/ton) during long time and to release pure hydrogen on demand. The proof of concept and some commercial solutions exists but still suffers from high cost and energy needed to facilitate catalytic reactions.
In order to reduce the system cost for LOHC technology to 3 €/Kg for large scale applications SherLOHCk project targets the joint developments consisting on :i) highly active and selective catalyst with partial/total substitution of PGM and thermo-conductive catalyst support to reduce the energy intensity during loading/unloading processes: ii) novel catalytic system architecture ranging from the catalyst to the heat exchanger to minimize the internal heat loss and to increase space-time-yield and iii) novel catalyst testing, system validation and demonstration in demo unit (>10 kW, >200h); to drastically improve their technical performances and energy storage efficiency of LOHCs:
The combination of the materials’ challenges, the catalyst system and their related energy storage capabilities will constitute the core of a catalyst system for LOHC, that will be validated first at a lab scale, then in a demo unit > 10kW. As a whole they will enable the reduction of Energy intensity during loading/unloading processes, a higher efficiency and increased lifetime. Technological, economical and societal bottlenecks are considered to determine the economic viability, balance of energy and the environmental footprint of novel catalyst synthesis route.
Scale-up of the obtained solutions will be carried out together with technology comparison with other hydrogen logistic concepts based on Life Cycle Analysis (LCA) and Total Cost of Ownership (TCO) considerations to finally improve economic viability of the LOHC technology.
In order to reduce the system cost for LOHC technology to 3 €/Kg for large scale applications SherLOHCk project targets the joint developments consisting on :i) highly active and selective catalyst with partial/total substitution of PGM and thermo-conductive catalyst support to reduce the energy intensity during loading/unloading processes: ii) novel catalytic system architecture ranging from the catalyst to the heat exchanger to minimize the internal heat loss and to increase space-time-yield and iii) novel catalyst testing, system validation and demonstration in demo unit (>10 kW, >200h); to drastically improve their technical performances and energy storage efficiency of LOHCs:
The combination of the materials’ challenges, the catalyst system and their related energy storage capabilities will constitute the core of a catalyst system for LOHC, that will be validated first at a lab scale, then in a demo unit > 10kW. As a whole they will enable the reduction of Energy intensity during loading/unloading processes, a higher efficiency and increased lifetime. Technological, economical and societal bottlenecks are considered to determine the economic viability, balance of energy and the environmental footprint of novel catalyst synthesis route.
Scale-up of the obtained solutions will be carried out together with technology comparison with other hydrogen logistic concepts based on Life Cycle Analysis (LCA) and Total Cost of Ownership (TCO) considerations to finally improve economic viability of the LOHC technology.
During the period M1-M18 work has been performed as initially defined in the work program. Requirements have been defined for the hydrogenation & dehydrogenation catalyst, LOHC type & quality, hydrogen quality, testing routine, and energy consumption, to be compatible with all the objectives of the project. This first work has allowed laying the foundation for the whole project. BT (benzyl toluene) was chosen as the reference molecule and Pt-based catalysts from Clariant were selected as catalysts' benchmark.
A catalyst design through DFT (Density Functional Theory) predictive analysis has led to reducing the use of PGM catalysts. Calculations were applied to the dehydrogenation of methylcyclohexane (to toluene) as a reference molecule, BT being too complex for such calculation. The calculated overall dehydrogenation energies for the various considered alloys showed that alloys such as Co, Co3Pt, SnPt, Sn3Pt2, Sn2Pt, and Sn4Pt could be potential low Pt-based catalytic materials. Then catalyst materials have been synthesized and tested on a lab scale. Some Pt-X (X=Fe, Zn, Co, Cu) catalysts supported on alumina outperform the benchmark catalyst in activity. For Pt-Co, with a cobalt content of 0.5 wt.% achieved almost the same dehydrogenation activity and selectivity as the catalysts with 1 wt.% Pt but reducing half the amount of this noble metal. PGM-free catalyst show very low activity. Furthermore, through experiments with model substances simulating by-product formation, it was also possible to gain better insights into the dehydrogenation reaction and catalyst deactivation. Further promising results were obtained for the first catalyst reactivation procedures by oxidative regeneration with synthetic air executed in batch operation.
In parallel, to explore the advantages of structured heat-exchangers reactors combined with improved catalysts, models and simulations were performed to support the choice of possible reactor geometries, in particular, to define suitable heat conductive reactor structures. These results indicate that for both reactions, foam structure, catalyst activity, mass, and operating conditions are first-order parameters. First 3D monolith structures have been prepared to integrate catalysts materials.
A communication and dissemination plan was developed at the beginning of the project. The communication activities carried out are integrated with the Project website (https://sherlohck.eu/) diffusion of activities on two social platforms: LinkedIn (https://www.linkedin.com/in/sherlohck/?originalSubdomain=es) and Twitter (https://twitter.com/SherlohckProj) and participation to promotional events (Conferences, workshops, Newsletters, and press releases).
A catalyst design through DFT (Density Functional Theory) predictive analysis has led to reducing the use of PGM catalysts. Calculations were applied to the dehydrogenation of methylcyclohexane (to toluene) as a reference molecule, BT being too complex for such calculation. The calculated overall dehydrogenation energies for the various considered alloys showed that alloys such as Co, Co3Pt, SnPt, Sn3Pt2, Sn2Pt, and Sn4Pt could be potential low Pt-based catalytic materials. Then catalyst materials have been synthesized and tested on a lab scale. Some Pt-X (X=Fe, Zn, Co, Cu) catalysts supported on alumina outperform the benchmark catalyst in activity. For Pt-Co, with a cobalt content of 0.5 wt.% achieved almost the same dehydrogenation activity and selectivity as the catalysts with 1 wt.% Pt but reducing half the amount of this noble metal. PGM-free catalyst show very low activity. Furthermore, through experiments with model substances simulating by-product formation, it was also possible to gain better insights into the dehydrogenation reaction and catalyst deactivation. Further promising results were obtained for the first catalyst reactivation procedures by oxidative regeneration with synthetic air executed in batch operation.
In parallel, to explore the advantages of structured heat-exchangers reactors combined with improved catalysts, models and simulations were performed to support the choice of possible reactor geometries, in particular, to define suitable heat conductive reactor structures. These results indicate that for both reactions, foam structure, catalyst activity, mass, and operating conditions are first-order parameters. First 3D monolith structures have been prepared to integrate catalysts materials.
A communication and dissemination plan was developed at the beginning of the project. The communication activities carried out are integrated with the Project website (https://sherlohck.eu/) diffusion of activities on two social platforms: LinkedIn (https://www.linkedin.com/in/sherlohck/?originalSubdomain=es) and Twitter (https://twitter.com/SherlohckProj) and participation to promotional events (Conferences, workshops, Newsletters, and press releases).
The screening and evaluation of the catalysts is an ongoing task, but their integration and study in thermal conductive support will be one of the main expected results. To confirm promising developed catalysts, experimental evaluation of the catalyst lifetime and maintenance in continuous operation (>200h) in a demo unit (>10 kW) will also be considered since these validations are the only way to outperform the catalyst benchmark regarding catalyst productivity, selectivity, and stability to have a significant impact on the economic viability for the market uptake of the LOHC technology.