DOE OSTI2023
Ammonia (NH 3 ) is an energy-dense chemical and a vital component of fertilizer. In addition, it is a carbon-neutral liquid fuel and a potential candidate for thermochemical energy storage for high-temperature concentrating solar power (CSP). Currently, NH 3 synthesis occurs via the Haber-Bosch process, which requires high pressures (15-25 MPa) and medium to high temperatures (400-500 °C). N 2 and H 2 are essential feedstocks for this NH 3 production process. H 2 is generally derived from methane via steam reforming; N 2 is sourced from air, after oxygen removal via combustion of hydrocarbons. Both processes consume hydrocarbons, resulting in the release of CO 2 . In addition, hydrocarbon fuels are burned to produce the heat and mechanical energy required to perform the NH 3 reaction, further increasing CO 2 emissions. Overall, the production of ammonia via the Haber-Bosch (H-B) process is responsible for up to 1.4% of the world’s carbon emissions. The development of a renewable pathway to NH 3 synthesis, which utilizes concentrated solar irradiation as a process heat instead of fossil fuels and operates under low or ambient pressure, will result in a decrease (or elimination) of greenhouse gas emissions as well as avoid the cost, complexity, and safety issues inherent in high-pressure processes. Most current efforts to “green” ammonia production involve either electrolysis or simply replacing the energy source for H-B with renewable electricity, but otherwise leaving the process intact. The effort proposed here would create a new paradigm for the synthesis of NH 3 utilizing solar-thermal heat, water, and air as feedstocks, providing a truly green method of production. The overall objective of the STAP (Solar Thermal Ammonia Production) project was to develop a solar thermochemical looping technology to produce and store nitrogen (N 2 ) from air for the subsequent production of ammonia (NH 3 ) via an advanced two-stage process. The goal is a cost-effective and energy efficient technology for the renewable N 2 production and synthesis of NH 3 from H 2 (produced from H 2 O) and air using solar-thermal energy from concentrating sunlight, under pressures an order of magnitude lower than H-B NH 3 production. Our process involves two looping cycles, which do not require catalysts and can be recycled. Over the course of the STAP project, we (1) developed and deeply characterized oxide materials for N 2 separation; (2) developed a method for the synthesis of metal nitrides, producing a series of quaternary compounds that have been heretofore unreported; (3) modeled, designed, and fabricated bench-scale tube and on-sun reactors for the N 2 production step and demonstrated the ability to separate N 2 over multiple cycles in the tube reactor; (4) designed and fabricated a bench-scale Ammonia Synthesis Reactor (ASR) and demonstrated the proof of concept of NH 3 synthesis via a novel looping process using metal nitrides over multiple cycles; and (5) completed a systems- and technoeconomic analysis showing the feasibility of ammonia production on a larger scale via the STAP process. The development of renewable, low-cost NH 3 will be of great interest to the chemicals industry, particularly agricultural sectors. The CSP industry should be both an important customer and potential end-user of this technology, as it affords the capability of synthesizing a promising thermochemical storage material on-site. Since the NH 3 synthesis step also requires H 2 , there will exist a symbiotic relationship between this technology and solar-thermochemical water-splitting applications. Green ammonia synthesis will result in the decarbonization of a hydrocarbon-intensive industry, helping to meet the Administration goal of industrial decarbonization by 2050. The resulting decrease in CO 2 and related pollutants will improve health and well-being of society, particularly for those living in the vicinity of commercial production plants.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗