A prospective life cycle assessment of global ammonia decarbonisation scenarios.

A prospective life cycle assessment was performed for global ammonia production across 26 regions from 2020 to 2050. The analysis was based on the IEA Ammonia Roadmap and IMAGE electricity scenarios model for three climate scenarios related to a mean surface temperature increase of 3.5 °C, 2.0 °C, and 1.5 °C by 2100. Combining these models with a global perspective and new life cycle inventories improves ammonia's robustness, quality, and applicability in prospective life cycle assessments. It reveals that complete decarbonisation of the ammonia industry by 2050 is unlikely from a life cycle perspective because of residual emissions in the supply chain, even in the most ambitious scenario. However, strong policies in the 1.5 °C scenario could significantly reduce climate impacts by up to 70% per kilogram of ammonia. The cumulative greenhouse gas emissions from the ammonia supply chain between 2020 and 2050 are estimated at 24, 21, and 15 gigatonnes CO2-equivalent for the 3.5 °C, 2.0 °C, and 1.5 °C scenarios, respectively. The paper examines challenges in achieving these scenarios, noting that electrolysis-based (yellow) ammonia, contingent on electricity decarbonisation, offers a cleaner production pathway. However, achieving significant GHG reductions is complex, requiring advancements in technologies with lower readiness, like carbon capture and storage and methane pyrolysis. The study also discusses limitations such as the need to reduce urea demand, potential growth in ammonia as a fuel, reliance on CO2 transport and storage, expansion of renewable energy, raw material scarcity, and the longevity of existing plants. It highlights potential shifts in environmental impacts, such as increased land, metal, and mineral use in scenarios with growing renewable electricity and bioenergy with carbon capture and storage.

Electrochemical Reduction of CO2 to Oxalic Acid: Experiments, Process Modeling, and Economics.

We performed H-cell and flow cell experiments to study the electrochemical reduction of CO2 to oxalic acid (OA) on a lead (Pb) cathode in various nonaqueous solvents. The effects of anolyte, catholyte, supporting electrolyte, temperature, water content, and cathode potential on the Faraday efficiency (FE), current density (CD), and product concentration were investigated. We show that a high FE for OA can be achieved (up to 90%) at a cathode potential of -2.5 V vs Ag/AgCl but at relatively low CDs (10-20 mA/cm2). The FE of OA decreases significantly with increasing water content of the catholyte, which causes byproduct formation (e.g., formate, glycolic acid, and glyoxylic acid). A process design and techno-economic evaluation of the electrochemical conversion of CO2 to OA is presented. The results show that the electrochemical route for OA production can compete with the fossil-fuel based route for the base case scenario (CD of 100 mA/cm2, OA FE of 80%, cell voltage of 4 V, electrolyzer CAPEX of $20000/m2, electricity price of $30/MWh, and OA price of $1000/ton). A sensitivity analysis shows that the market price of OA has a huge influence on the economics. A market price of at least $700/ton is required to have a positive net present value and a payback time of less than 10 years. The performance and economics of the process can be further improved by increasing the CD and FE of OA by using gas diffusion electrodes and eliminating water from the cathode, lowering the cell voltage by increasing the conductivity of the electrolyte solutions, and developing better OA separation methods.

On the Potential of Gallium- and Indium-Based Liquid Metal Membranes for Hydrogen Separation.

The concept of liquid metal membranes for hydrogen separation, based on gallium or indium, was recently introduced as an alternative to conventional palladium-based membranes. The potential of this class of gas separation materials was mainly attributed to the promise of higher hydrogen diffusivity. The postulated improvements are only beneficial to the flux if diffusion through the membrane is the rate-determining step in the permeation sequence. Whilst this is a valid assumption for hydrogen transport through palladium-based membranes, the relatively low adsorption energy of hydrogen on both liquid metals suggests that other phenomena may be relevant. In the current study, a microkinetic modeling approach is used to enable simulations based on a five-step permeation mechanism. The calculation results show that for the liquid metal membranes, the flux is limited by the dissociative adsorption over a large temperature range, and that the membrane flux is expected to be orders of magnitude lower compared to the membrane flux through pure palladium membranes. Even when accounting for the lower cost of the liquid metals compared to palladium, the latter still outperforms both gallium and indium in all realistic scenarios, in part due to the practical difficulties associated with making liquid metal thin films.

Simulating the reactions of CO2 in aqueous monoethanolamine solution by reaction ensemble Monte Carlo using the continuous fractional component method.

Molecular simulations were used to compute the equilibrium concentrations of the different species in CO2/monoethanolamine solutions for different CO2 loadings. Simulations were performed in the Reaction Ensemble using the continuous fractional component Monte Carlo method at temperatures of 293, 333, and 353 K. The resulting computed equilibrium concentrations are in excellent agreement with experimental data. The effect of different reaction pathways was investigated. For a complete understanding of the equilibrium speciation, it is essential to take all elementary reactions into account because considering only the overall reaction of CO2 with MEA is insufficient. The effects of electrostatics and intermolecular van der Waals interactions were also studied, clearly showing that solvation of reactants and products is essential for the reaction. The Reaction Ensemble Monte Carlo using the continuous fractional component method opens the possibility of investigating the effects of the solvent on CO2 chemisorption by eliminating the need to study different reaction pathways and concentrate only on the thermodynamics of the system.