Among the various water splitting processes, the thermo-electrochemical Hybrid Sulfur (HyS) is one of the most appealing cycles. It has only fluid reactants and is comprised of only two global reaction steps: a low temperature electrochemical exothermic section, operating at temperatures on the order of 100 °C, and a high temperature endothermic thermal section operating at max temperatures of about 800 °C. In the electrochemical section SO2 and H2O are combined to produce electrochemically H2 at the electrolyzer cathode and H2SO4 at the electrolyzer anode. Sulfuric acid is recycled inside the plant, concentrated and decomposed, in the high temperature thermal section, into SO2, O2 and H2O.
The endothermic decomposition of sulfuric acid takes place in two main reactions:
H2SO4 → SO3 + H2O (1)
SO3 → SO2 + 0.5 O2 (2)
The required thermal power is provided by external source and by internal heat recovery from the SO2-O2 stream product of the decomposition reactions.
Solar driven HyS process is being studied by the Greenway Energy and the University of South Carolina within the DOE HydroGEN program (part of the DOE Energy Material Network initiative) [1], partnering with the Idaho National Laboratory, the Savannah River National Laboratory and the National Renewable Energy Laboratory. The project focuses on the high temperature sulfuric acid decomposition section. One of the main tasks of the project is to develop and fabricate an effective and low cost high temperature solar reactor for the decomposition of the sulfuric acid into sulfur dioxide. Previous work was carried out within the DOE-NHI Initiative and resulted in identifying a reactor concept based on the bayonet heat exchanger as the baseline reactor configuration [2]. The bayonet reactor was tested both from a modeling point of view and from an experimental point of view, demonstrating the potential to achieve almost the reaction equilibrium conditions. At temperatures of about 800 °C and pressures of 14 bar, an SO2 production of approximately 19 mol fraction % was achieved, which is essentially the equilibrium value at the same operating conditions [3,2]. However, a solar driven bayonet concept presents several drawbacks, mainly relative to the need for an additional intermediate heat exchanger to transfer the solar power to the reactive sulfur mixture. The removal of the intermediate solar heat exchanger will result in increased energetic and exergetic efficiencies and decreased capital and operating costs.
A novel reactor concept is proposed, described and discussed, based on a direct solar heated cavity receiver system. It realizes the solar driven sulfuric acid decomposition and internal heat recovery in a single unit, directly heated by the incident solar radiation without the presence of any intermediate heat transfer fluid. The reactor includes catalytic structures to decompose H2SO4 and foamed structures in the internal heat recovery channels to increase the overall thermal conductivity. A reactor unit, made of SiC material, and directly heated from solar radiation has preliminarily been demonstrated from a modeling point of view. A detailed transport phenomena model was developed using Finite-Volume approach and run in STAR-CCM+. The kinetics parameters reported in Reference [3] were adopted for the current simulations. Results showed excellent conversion rates and reduced temperature gradients and pressure drops inside the device, achieving better performance than the bayonet configuration. The cavity receiver-reactor also allows: (1) efficient internal heat recovery from the decomposition products and (2) connections with the metallic interfaced HyS equipment (e.g. tubing, valves, etc.) at low temperatures. Results obtained from a first conceptual scale up analysis of the reactor concept also demonstrated the actual feasibility for integration in both centralized and distributed solar tower based plants.
References
[1] https://www.h2awsm.org/ (Accessed February 2018).
[2] Moore, R. et al. Integrated Boiler, Superheater, and Decomposer for Sulphuric Acid Decomposition. Sandia Corp., US Patent No. 7645437 B1, 2010
[3] Corgnale, C. et al. Int J Hydrogen Energy 42(32), 2017, 20463-72.