Decentralised Ammonia production from Renewable Energy utilising novel sorption-enhanced plasma-catalytic Power-to-X technology

Project Information

DARE2X

Grant agreement ID: 101083905

DOI

10.3030/101083905

Project closed

EC signature date 2 September 2022

Start date 1 October 2022

End date 30 September 2025

Funded under

• Climate, Energy and Mobility

Total cost

€ 2 380 800,00

EU contribution

€ 2 380 800,00

Coordinated by

TEKNOLOGISK INSTITUT
Denmark

Periodic Reporting for period 1 - DARE2X (Decentralised Ammonia production from Renewable Energy utilising novel sorption-enhanced plasma-catalytic Power-to-X technology)

Reporting period: 2022-10-01 to 2024-03-31

Summary of the context and overall objectives of the project

The DARE2X project is proposing a disruptive approach to decarbonising ammonia (NH3) production: development of sorption-enhanced plasma-catalytic synthesis. NH3 is the chemical produced in the second highest quantities globally and is responsible for 1.8% of global CO2 emissions. Furthermore, its demand is expected to increase drastically in the coming decade through its huge promise as a green fuel. As a result, decarbonisation of NH3 production is an essential goal for decarbonisation of the EU economy by 2050. The timing is vital in starting the push for future production technologies for green NH3, to meet the expected increase in demand.

The main challenges for realising European green NH3 production is to transition away from fossil fuel-based, centralised Haber-Bosch facilities, to decentralised, dynamic systems that can be coupled directly to renewable electricity generators at or near the point of use. This does, however, require significant developments. DARE2X will overcome these barriers through the following game-changing solutions: (i) reactors utilising non-thermal plasma to drive NH3 synthesis; (ii) novel, more active catalysts using low-CRM materials, iii) stable and efficient NH3 sorption materials for in-situ NH3 separation. These innovations will be integrated into a single sorption-enhanced plasma-catalytic device that will be validated at TRL4. The economic, environmental and social feasibility will be assessed through LCA, LCC and a social acceptance study.

The DARE2X main objectives are listed below:
MAIN OBJECTIVE 1: Development of highly efficient catalysts and sorption materials, to provide means of converting renewable H2 into NH3 at ambient conditions, and effectively col-lect/separate NH3 while promoting a higher system efficiency, respectively.
MAIN OBJECTIVE 2: Development of a novel sorption-enhanced reactor using plasma-catalytic technology, with a scalable design. The integration of sorption materials will allow the im-mediate separation of the produced NH3. This single stage configuration will be evaluat-ed in comparison with the competitive efficiency levels of the industrial Haber-Bosch process. NH3 synthesis will have target operation conditions of 30 °C and 1-3 bar, powered directly by an electricity supply, and therefore compatible with green renewable sources.

The technical development in the project of catalyst, sorption materials and plasma reactors, are complemented by environmental, economical and social acceptance assessments. These assessments feed back into the technical development to take environmental, economic and social considerations into account when developing the technology.

Work performed from the beginning of the project to the end of the period covered by the report and main results achieved so far

Through meticulous computational analyses across multiple metals and the extrapolation of descriptors to encompass the entire periodic table, we have established a systematic framework for catalyst design. The following materials are predicted to perform best: Re, Fe, Mo, W, Ru, Os. This work continues for alloys and to include the support effect which experimentally has a large effect on activity.

Several catalysts have been synthesized and tested in the plasma reactor. Based on the computational screening and literature, catalyst materials based on Ru, Ni, Co, Pt, Cu was synthesized on different supports and tested in the plasma reactor. Ni and Co based catalyst showed the highest activity, but the effect of the support turned out to be more significant than the active metal for the catalyst activity. Catalyst supported on zeolites had much higher activities than catalyst supported on alumina and carbon. Our catalyst KPI was reached with a catalyst activity of >2100 μmolNH3·gcat.-1·h-1, in a lab-scale reactor system (1 bar, 30 °C, 16 W, 20 ml*min-1).

Different zeolites were tested for ammonia adsorption and characterized for physisorption and chemisorption. For this application the physisorption capacity is more important as we aim for a material that can adsorb/desorb without large temperature swings. The goal is to develop sorption materials that can be integrated into the reactor bed and also sorption material for a separate sorption unit that can separate the ammonia without condensation. For this purpose, the best performing sorption materials have been tested for both pressure and temperature swing adsorption where pressure swing would be the optional as the plasma reactor works at ambient conditions.

Plasma technology: A scalable coaxial dielectric barrier discharge (DBD) reactor was built for plasma-catalytic ammonia production. This was used for testing the catalytic materials developed in the project. Using the best catalyst it was possible to reach an NH3 yield of 2.4% at ambient conditions.

Progress beyond the state of the art and expected potential impact (including the socio-economic impact and the wider societal implications of the project so far)

Significant efforts were made in the first reporting period to develop new and improved catalyst materials tailored to operation in the non-thermal plasma-based reactor. The methodology used took these activities beyond state-of-the-art, with screening through DFT modelling to identify promising catalyst candidates, along with synthesis of the promising candidates and testing in a laboratory-scale plasma reactor to evaluate performance. This resulted in the identification of the best performing metals (both pure and alloys), in addition to elucidation of the strong support effect on overall activity described above, where the use of NH3 sorption materials as supports gave a strong activity boost.

The identification of the most effective sorption materials in the low-temperature region <100 °C is an improvement upon state-of-the-art in the field. Furthermore, considerations about how these sorption materials could be implemented in the prototype system were started, with the aim to identify the most efficient NH3 separation approach at low temperature and pressure. The impact of the sorption material development in DARE2X is to enable efficient NH3 separation also at lower concentrations and pressures, where state-of-the-art condensation would be far too inefficient. This is key for efficient NH3 plasma-catalytic synthesis.

A key DARE2X innovation beyond state-of-the-art is the combination of plasma catalysts and sorption materials into the same overall material. By sorbing produced NH3 already inside the plasma reactor, the reverse reaction of plasma-induced decomposition will be mitigated. As elaborated in the above points, supporting the active catalyst on sorption material results in the best steady-state activity. The dynamic operation of combined catalyst/sorption materials also including the sorption/desorption of NH3 is a key focus point for the second half of the project, and is expected to yield further performance enhancements.

The novel plasma reactor designed for NH3 synthesis described above goes beyond state-of-the-art, along with optimisation of operating parameters and reactor configuration. This work will continue throughout the integration and prototyping stage in the second half of the project.

Value chain of NH3 comparison between current fossil production and DARE2X concept. Current producti

DARE2X’ overall concept focusing on catalyst and sorption materials, as well as non-thermal plasma-c