Small-scale and flexible green ammonia production technology
Ammonia has been responsible for feeding population growth in the 20th century through synthetic fertilizer, and is poised to become the preferred energy storage medium for a society powered by renewable electricity in the 21st century. However, conventional brown ammonia production through the Haber-Bosch process is optimized for utilization of centralized and steady energy supply from fossil-fuels. When shifting to distributed and intermittent energy supply through wind and solar energy, a re-optimization is required for a low-capital and flexible green ammonia production processes. This thesis re-designs and Haber-Bosch process by targeting the integration of reaction and separation in a single process vessel at low pressures, thereby achieving the simplification and down-scaling of the high pressure recycle loop of the Haber-Bosch process. Materials are developed for this purpose, the feasibility of integration is demonstrated, and mathematical modeling is utilized for assessing the application of the single-vessel process to a range of renewable energy sources in comparison to competing ammonia production processes. Herein, a catalyst with low-temperature (< 350°C) and high-conversion (i.e. near equilibrium) activity is developed using ruthenium nanoparticles as the active metal supported on ceria and promoted with cesium to mitigate hydrogen and ammonia inhibition, respectively. This catalyst is compared to commercial iron-based catalyst from the perspective of the final application. Concurrently, a high-temperature (> 300°C) manganese chloride absorbent is developed that resists decomposition and is stable when supported on silica. These catalyst and absorbent are integrated in a layered reactor configuration to demonstrate the feasibility of the integrated process by exceeding single-pass reaction equilibrium. Mathematical modelling of ammonia production processes illustrates that at small-scales (< 1 t day-1) the single-vessel process is optimal compared to the Haber-Bosch process due to its modular design. In addition, it can achieve simpler ramping because the Haber-Bosch process is constrained by heat-integration in the recycle loop and the potential for runaway reaction. For final application, the pairing of ammonia production processes with examples of intermittent solar and wind sources demonstrates that the flexibility of the production process is essential when considering non-ideal sources of energy with a long-term (e.g. seasonal) oscillations. Flexible ammonia production also expands the economic usage of ammonia as an energy storage vector from the seasonal to the weekly time-scale, with advantage compared to batteries or hydrogen. The work of this thesis provides a framework for advancing the electrification of the chemical industry given the novel constrains of intermittent and distributed renewable energy. A systems level approach is applied from the ground up, starting from material design and progressing to optimized process design and application.
ammonia, catalysis, absorption, reaction engineering, renewable energy
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