Synergies between Direct Air Capture Technologies and Solar Thermochemical Cycles in the Production of Methanol

Methanol is an example of a valuable chemical that can be produced from water and carbon dioxide through a chemical process that is fully powered by concentrated solar thermal energy and involves three steps: direct air capture (DAC), thermochemical splitting and methanol synthesis. In the present work, we consider the whole value chain from the harvesting of raw materials to the final product. We also identify synergies between the aforementioned steps and collect them in five possible scenarios aimed to reduce the specific energy consumption. To assess the scenarios, we combined data from low and high temperature DAC with an Aspen Plus® model of a plant that includes water and carbon dioxide splitting units via thermochemical cycles (TCC), CO/CO2 separation, storage and methanol synthesis. We paid special attention to the energy required for the generation of low oxygen partial pressures in the reduction step of the TCC, as well as the overall water consumption. Results show that suggested synergies, in particular, co-generation, are effective and can lead to solar-to-fuel efficiencies up to 10.2% (compared to the 8.8% baseline). In addition, we appoint vacuum as the most adequate strategy for obtaining low oxygen partial pressures.

A Novel Method for the Preparation of Fibrous CeO2–ZrO2–Y2O3 Compacts for Thermochemical Cycles

Zirconium-Yttrium-co-doped ceria (Ce0.85Zr0.13Y0.02O1.99) compacts consisting of fibers with diameters in the range of 8–10 µm have been successfully prepared by direct infiltration of commercial YSZ fibers with a cerium oxide matrix and subsequent sintering. The resulting chemically homogeneous fiber-compacts are sinter-resistant up to 1923 K and retain a high porosity of around 58 vol% and a permeability of 1.6–3.3 × 10−10 m² at a pressure gradient of 100–500 kPa. The fiber-compacts show a high potential for the application in thermochemical redox cycling due its fast redox kinetics. The first evaluation of redox kinetics shows that the relaxation time of oxidation is five times faster than that of dense samples of the same composition. The improved gas exchange due to the high porosity also allows higher reduction rates, which enable higher hydrogen yields in thermochemical water-splitting redox cycles. The presented cost-effective fiber-compact preparation method is considered very promising for manufacturing large-scale functional components for solar-thermal high-temperature reactors.

A Dual Reactor for Isothermal Thermochemical Cycles of H2O/CO2 Co-Splitting Using La0.3Sr0.7Co0.7Fe0.3O3 as an Oxygen Carrier

Catalytic performance of La0.3Sr0.7Co0.7Fe0.3O3 (LSCF3773 or LSCF) catalyst for syngas production via two step thermochemical cycles of H2O and CO2 co-splitting was investigated. Oxygen storage capacity (OSC) was found to depend on reduction temperature, rather than the oxidation temperature. The highest oxygen vacancy (Δδ) was achieved when the reduction and oxidation temperature were both fixed at 900 °C with the feed ratio (H2O to CO2) of 3 to 1, with an increasing amount of CO2 in the feed mixture. CO productivity reached its plateau at high ratios of H2O to CO2 (1:1, 1:2, and 1:2.5), while the total productivities were reduced with the same ratios. This indicated the existence of a CO2 blockage, which was the result of either high Ea of CO2 dissociation or high Ea of CO desorption, resulting in the loss in active species. From the results, it can be concluded that H2O and CO2 splitting reactions were competitive reactions. Ea of H2O and CO2 splitting was estimated at 31.01 kJ/mol and 48.05 kJ/mol, respectively, which agreed with the results obtained from the experimentation of the effect of the oxidation temperature. A dual-reactors system was applied to provide a continuous product stream, where the operation mode was switched between the reduction and oxidation step. The isothermal thermochemical cycles process, where the reduction and oxidation were performed at the same temperature, was also carried out in order to increase the overall efficiency of the process. The optimal time for the reduction and oxidation step was found to be 30 min for each step, giving total productivity of the syngas mixture at 28,000 μmol/g, approximately.

Thermodynamic Analysis of Hydrogen Production by a Thermochemical Cycle Based on Magnesium-Chlorine

Most thermochemical cycles require complex thermal processes at very high temperatures, which restrict the production and the use of hydrogen on a large scale. Recently, thermochemical cycles producing hydrogen at relatively low temperatures have been developed in order to be competitive with other kinds of energies, especially those of fossil origin. The low temperatures required by those cycles allow them to work with heats recovered by thermal, nuclear and solar power plants. In this work, a new thermochemical cycle is proposed. This cycle uses the chemical elements Magnesium-Chlorine (Mg-Cl) to dissociate the water molecule. The configuration consists of three chemical reactions or three physical steps and uses mainly thermal energy to achieve its objectives. The highest temperature of the process is that of the production of hydrochloric acid, HCl, estimated between 350-450℃. A thermodynamic analysis was performed according to the first and second laws by using Engineering Equation Solver (EES) software and the efficiency of the proposed cycle was found to be 12.7%. In order to improve the efficiency of this cycle and make it more competitive, an electro-thermochemical version should be studied.

Air separation via two-step solar thermochemical cycles based on SrFeO3−δ and (Ba,La)0.15Sr0.85FeO3−δ perovskite reduction/oxidation reactions to produce N2: rate limiting mechanism(s) determination

Two-step solar thermochemical cycles based on reversible reactions of SrFeO3−δ and (Ba,La)0.15Sr0.85FeO3−δ perovskites were considered for air separation.