Paul Lichty

Efficient generation of H2 by splitting water with an isothermal redox cycle.

Isothermal Water Splitting Solar concentrators can create extremely high temperatures that can drive chemical reactions, including the thermal splitting of water to provide hydrogen. A metal oxide catalyst is needed that is usually cycled between hotter conditions where it is reduced and cooler conditions where it is reoxidized by water. This cycling can limit catalyst lifetime, which can be costly. Muhich et al. (p. 540; see the Perspective by Roeb and Sattler) developed an approach that allowed the redox cycle to be driven isothermally, using pressure swings. A thermal process for generating H2 from water uses pressure changes to recycle between catalyst redox states. [Also see Perspective by Roeb and Sattler] Solar thermal water-splitting (STWS) cycles have long been recognized as a desirable means of generating hydrogen gas (H2) from water and sunlight. Two-step, metal oxide–based STWS cycles generate H2 by sequential high-temperature reduction and water reoxidation of a metal oxide. The temperature swings between reduction and oxidation steps long thought necessary for STWS have stifled STWS’s overall efficiency because of thermal and time losses that occur during the frequent heating and cooling of the metal oxide. We show that these temperature swings are unnecessary and that isothermal water splitting (ITWS) at 1350°C using the “hercynite cycle” exhibits H2 production capacity >3 and >12 times that of hercynite and ceria, respectively, per mass of active material when reduced at 1350°C and reoxidized at 1000°C.

Rapid High Temperature Solar Thermal Biomass Gasification in a Prototype Cavity Reactor

High temperature biomass gasification has been performed in a prototype concentrated solar reactor. Gasification of biomass at high temperatures has many advantages compared with historical methods of producing fuels. Enhancements in overall conversion, product composition ratios, and tar reduction are achievable at temperatures greater than 1000°C. Furthermore, the utilization of concentrated solar energy to drive these reactions eliminates the need to consume a portion of the product stream for heating and some of the solar energy is stored as chemical energy in the product stream. Experiments to determine the effects of temperature, gas flow rate, and feed type were conducted at the high flux solar furnace at the National Renewable Energy Laboratory, Golden, CO. These experiments were conducted in a reflective cavity multitube prototype reactor. Biomass type was found to be the only significant factor within a 95% confidence interval. Biomass conversion as high as 68% was achieved on sun. Construction and design considerations of the prototype reactor are discussed as well as initial performance results.

Solar-thermal Water Splitting Using the Sodium Manganese Oxide Process & Preliminary H2A Analysis

There are three primary reactions in the sodium manganese oxide high temperature water splitting cycle. In the first reaction, Mn2O3 is decomposed to MnO at 1,500°C and 50 psig. This reaction occurs in a high temperature solar reactor and has a heat of reaction of 173,212 J/mol. Hydrogen is produced in the next step of this cycle. This step occurs at 700°C and 1 atm in the presence of sodium hydroxide. Finally, water is added in the hydrolysis step, which removes NaOH and regenerates the original reactant, Mn2O3. The high temperature solar-driven step for decomposing Mn2O3 to MnO can be carried out to high conversion without major complication in an inert environment. The second step to produce H2 in the presence of sodium hydroxide is also straightforward and can be completed. The third step, the low temperature step to recover the sodium hydroxide is the most difficult. The amount of energy required to essentially distill water to recover sodium hydroxide is prohibitive and too costly. Methods must be found for lower cost recovery. This report provides information on the use of ZnO as an additive to improve the recovery of sodium hydroxide.