CRADA Final Report For CRADA NO. CR-12-006 [Operation and Testing of an SO<sub>2</sub>-depolarized Electrolyzer (SDE) for the Purpose of Hydrogen and Sulfuric Acid Production

Abstract

Over the past several years, Savannah River National Laboratory (SRNL) has led a team of collaborators under the Department of Energy’s (DOE) nuclear hydrogen production program to develop the Hybrid Sulfur (HyS) Process. HyS is a 2-step water-splitting process consisting of high temperature decomposition of sulfuric acid to generate SO2, followed by the electrolysis of aqueous SO2 to generate hydrogen and sulfuric acid. The latter is fed back into the high temperature reactor. SRNL designed and built an SO2-depolarized electrolyzer (SDE) and a test facility. Over 40 SDE’s were tested using different catalysts, membranes and other components. SRNL demonstrated that an SDE could be operated continuously for approximately 200 hours under certain conditions without buildup of sulfur at the SDE’s cathode, thus solving a key technical problem with SDE technology. Air Products and Chemicals, Inc. (APCI) is a major supplier of hydrogen production systems, and they have proprietary technology that could benefit from the SDE developed by SRNS, or some improved version thereof. However, to demonstrate that SRNL’s SDE is a truly viable approach to the electrolyzer design, continuous operation for far greater periods of time than 200 hours must be demonstrated, and the electrolyzer must be scaled up to greater hydrogen production capacities. SRNL and Air Products entered into a Cooperative Research and Development Agreement with the objective of demonstrating the effectiveness of the SDE for hydrogen and sulfuric acid production and to demonstrate long-term continuous operation so as to dramatically increase the confidence in the SDE design for commercial operation. SRNL prepared a detailed technical report documenting previous SDE development, including the current SDE design and operating conditions that led to the 200-hour sulfurfree testing. SRNL refurbished its single cell SDE test facility and qualified the equipment for continuous operation. A new membrane electrode assembly (MEA) was fabricated and installed in the single cell electrolyzer (60 cm2 active cell area). Shakedown testing was conducted, and several modifications were made to the test facility equipment. Seven different MEAs were used during testing. Beginning on May 20, 2013, SRNL was able to test the SDE continuously for 1200 hours, including 1000 hours under power to generate hydrogen at an average rate of 10.8 liters per hour. The SDE was not removed or repaired during the 50-day test and was successfully restarted after each shutdown. The test was intentionally stopped after 1200 hours (1000 hours of hydrogen production) due to funding constraints. Post-test examination of the MEA using Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Microanalysis (EDAX) showed no elemental sulfur deposits or sulfur layer inside the cell, thus successfully achieving the test goals. The results demonstrated that the SDE could be operated for extended periods without major performance degradation or the buildup of sulfur inside the MEA. Air Products conducted an assessment of the economic viability of the SDE based on the “as tested” design. The results indicated that the SDE faces significant economic obstacles in its current state. Further development and scale-up are necessary before the SDE is ready for commercialization.