S.A. Phadke
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4 records found
1
Valorization of Hydrogen Peroxide for Sodium Percarbonate and Hydrogen Coproduction via Alkaline Water Electrolysis
Conceptual Process Design and Techno-Economic Evaluation
The recent interest in the production of green hydrogen through water electrolysis is hampered by its high cost when compared to steam methane reforming. To overcome this disadvantage, some studies explore replacing oxygen production with hydrogen peroxide at the anode, which has a higher value. Existing electrocatalysis research primarily focuses on hydrogen peroxide synthesis, neglecting process design and separation. Additionally, hydrogen peroxide’s thermodynamic instability in alkaline conditions and the existence of other ions make the separation difficult. This paper proposes a novel concept for the paired water electrolysis process that can be used to improve green hydrogen production economics through valuable chemical coproductions. Valorizing hydrogen peroxide to sodium percarbonate as the final product was chosen to address hydrogen peroxide separation challenges. An electrolyzer stack of 2 MW was chosen, incorporating a recirculating structure, and a boron-doped diamond anode to enhance the hydrogen peroxide production as the base case. According to the techno-economic analysis, for a 2 MW electrolyzer stack, capital expenditure was calculated as 64.5 M€, operational expenses as 21.6 M€, and revenue was calculated as 2.5 M€, resulting in a negative cash flow of −19.1 M€. Results revealed that the process can be profitable (breakeven point) at a capacity of approximately 308 electrolyzer stacks, which is 616 MW in capacity. A sensitivity analysis was conducted to determine how cost drivers including electricity price, anode price, Faradaic efficiency, price of the products and tax subsidy affect the breakeven point. A breakeven point of 60 electrolyzer stacks (120 MW) was found with a 100% increase in the sodium percarbonate sale price. In comparison, a theoretical 100% Faradaic efficiency in the anode material would result in a breakeven point of 38 electrolyzer stacks (76 MW). Even a more realistic 75% Faradaic efficiency leads to a breakeven plant size of 75 stacks (150 MW). Further, multiple two-parameter sensitivity analyses were conducted to assess the relations between Faradaic efficiency, sodium percarbonate sale price and anode material price. For instance, if sodium percarbonate price increases by 100% and Faradaic efficiency increases to 75%, the breakeven capacity drops down to 13 stacks (26 MW). Despite facing economic challenges for the proposed process design based on available technologies, the techno-economic analysis highlights key targets for future works. It also provides valuable insights into the economic feasibility of simultaneously producing hydrogen and sodium percarbonate through water electrolysis, indicating promising potential for the future.
The anodic co-production of hydrogen peroxide (H2O2) during alkaline water electrolysis has gained interest as a sustainable alternative for anthraquinone oxidation. However, electrochemical H2O2 production is often studied with idealized laboratory setups to determine the H2O2 formation kinetics. In this work, we perform the reaction with industrially relevant operating principles using a flow cell with separately recirculating anolyte and catholyte. We then fit the data to an analytical model that we derive based on mole balances that accounts for anodic generation, anodic oxidation, and bulk disproportionation of H2O2, as well as electrolyte volumes and electrode surface area. We performed experiments at 100, 200, and 300 mA cm-2 to derive values for the reaction system. At 200 mA cm-2, we found a generation rate of 0.037 mmol min-1 cm-2 (FEH2O2 = 59%) and an anodic decomposition rate constant of 0.304 cm min-1, with a bulk disproportionation rate constant of 1.85 × 10-3 min-1. We successfully applied our model to two sources in literature to derive values for their systems as well. In all cases, the contribution of anodic oxidation of H2O2 was found to be the larger loss mechanism in comparison to bulk disproportionation. Using the analytical model, we show that decreasing the reservoir volume is a simple way to increase the H2O2 concentration over time. Further refinement of the model can be achieved through the use of mass transfer relationships based on electrolyzer geometries to describe the anodic oxidation of H2O2 in the mole balance equations.
Traps in the spotlight
How traps affect the charge carrier dynamics in Cs2AgBiBr6 perovskite
Suitable optoelectronic properties of lead halide perovskites make these materials interesting semiconductors for many applications. Toxic lead can be substituted by combining monovalent and trivalent cations, such as in Cs2AgBiBr6. However, efficiencies of Cs2AgBiBr6-based photovoltaics are still modest. To elucidate the loss mechanisms, in this report, we investigate charge dynamics in Cs2AgBiBr6 films by double-pulse excitation time-resolved microwave conductivity (DPE-TRMC). By exciting the sample with two laser pulses with identical wavelengths, we found a clear photoconductance enhancement induced by the second pulse even 30 μs after the first laser pulse. Modeling the DPE-TRMC results, complemented by photoluminescence and transient absorption, we reveal the presence of deep emissive electron traps, while shallow hole trapping is responsible for the long-lived transient absorption signals. These long-lived carriers offer interesting possibilities for X-ray detectors or photocatalysis. The DPE-TRMC methodology offers unique insight into the times involved in charge trapping and depopulation in Cs2AgBiBr6.