The utilization of ammonia for hydrogen storage relies on the implementation of efficient decomposition techniques, and the membrane reactor, which allows simultaneous ammonia decomposition and hydrogen recovery, can be regarded as a promising technology. While Pd-based membranes show the highest performance for hydrogen separation, their applicability for NH3-sensitive applications, such as proton exchange membrane (PEM) fuel cells, demands relatively thick, and therefore expensive, membranes to meet the purity targets for hydrogen. To address this challenge, this study proposes a solution involving the utilization of a downstream hydrogen purification unit to remove residual ammonia, thereby enabling the use of less selective, therefore more cost-effective, membranes. Specifically, a carbon molecular sieve membrane was prepared on a tubular porous alumina support and tested for ammonia decomposition in a membrane reaction setup. Operating at 5 bar and temperatures ranging from 450 to 500 °C, NH3 conversion rates exceeding 90% were achieved, with conversion approaching thermodynamic equilibrium at temperatures above 475 °C. Simultaneously, the carbon membrane facilitated the recovery of hydrogen from ammonia, yielding recoveries of 8.2–9.8%. While the hydrogen produced at the permeate side of the reactor failed to meet the purity requirements for PEM fuel cell applications, the implementation of a downstream hydrogen purification unit comprising a fixed bed of zeolite 13X enabled the production of fuel cell-grade hydrogen. Despite performance far from being comparable with the ones achieved in the literature with Pd-based membranes, this study underscores the viability of carbon membranes for fuel cell-grade hydrogen production, showcasing their competitiveness in the field.
2 September 2024 in International Journal of Hydrogen Energy
Methane (CH4) is the second-largest contributor to climate change after carbon dioxide (CO2) and has a global warming potential about 72 times greater than CO2 over a 20-year timescale. A possible solution to mitigate CH4 emissions from diluted sources is direct removal of CH4 through tailored sorbents. In this work, ion-exchanged zeolites have been investigated, owing to their low cost, excellent chemical stability, and ease of production. The impact of barium, lithium, and nickel exchange was investigated, along with one, three, and five ion-exchange sequences. XRD analysis confirmed that the structure remained intact after ion exchange. However, nitrogen physisorption revealed that nickel- and barium-exchanged zeolites had reduced pore volume and surface area compared to the parent zeolite, possibly due to mesopore formation from lattice strain relaxation. ICP-OES and SEM-EDX confirmed the successful incorporation of metals into the zeolite. Finally, breakthrough experiments were carried out to assess the saturation capacity of the synthesized sample. The results demonstrated that the lithium-exchanged samples provided the highest saturation capacity, namely 1.58 ± 0.05 mmol g−1 for the Li-13X-3 and 1.76 ± 0.07 mmol g−1 for the Li-SAPO34-5 over 10 adsorption cycles. Furthermore, the stability of the Li-SAPO34-5 was confirmed over 100 adsorption cycles.