Screening of optimal dopants on cobalt-based ceramics for high-temperature thermochemical energy storage

To date, numerous dopants have been investigated to promote the initial heat storage performance or sintering resistance of Co₃O₄ for thermochemical energy storage. Owing to the different synthesis methods and heat storage test conditions, the performances of these materials are not comparable. In this work, nine dopants, including four unreported dopants, were systematically compared and screened under the same conditions. Results demonstrated that for five redox cycles, the Si- and Mg- doped sample had adverse effects on the conversion rate, and the others maintained the conversion rate above 0.95. Cu and Zr doping exhibited the highest re-oxidation rate values, and those of the others were lower than that of pure cobalt oxide. Moreover, except for Cu and Zr, all dopants adversely affected energy density. According to aforementioned heat storage properties, Cu-, Zr-doped samples, and pure cobalt oxide were subjected to 100 cycles for further comparison. The Cu-doped sample exhibited a higher re-oxidation rate and energy density, and the Zr-doped sample exhibited more stable cyclability. Finally, by doping Cu and Zr, the micromorphology evolution was more stable than that of pure oxide for multiple cycles, and X-ray photoelectron spectroscopy results revealed that the higher surface oxygen was the primary reason for the superior performance facilitated by Cu and Zr. The Cu- and Zr-modified cobalt oxides were the potential candidates for thermochemical energy storage.     

H2 production by thermochemical water splitting with reticulated porous structures of ceria-based mixed oxide materials

In this work, we present for the first time the preparation and evaluation of Ceria-based mixed oxides reticulated porous ceramic (RPC) structures for H₂ production by thermochemical water splitting. After appropriate screening of the powder materials, ceria-based materials modified with Co, Mn and Zr were discarded due to their low cyclability and/or hydrogen productivity, derived from segregation of active phases or sintering during the thermal reduction and reoxidation. Sponge replica method has been optimized to allow obtaining a Ce_0.9Fe_0.1O_y RPC sponge structure with an outstanding hydrogen production of 15 STPcm³/g_material·cycle at a maximum temperature of 1300 °C. This better performance, comparing to the powder, can be attributed to the open macroporosity of the reticulated porous structure which enhances both heat and mass transfer. The H₂ production is maintained along several consecutive cycles without loss of activity, reinforcing the favorable prospects for large-scale hydrogen production.     

Conversion of yeast by hydrothermal treatment under reducing conditions

In the work reported here, baker’s yeast (Saccharomyces cerevisiae) was used as feed for the production of liquid biofuels in a continuous one-step process under hydrothermal conditions in the presence of excess hydrogen and K₂CO₃. The yeast conversion experiments were performed in an up-flow reactor under near-critical water conditions (T 330–450 °C, p 20–32 MPa). The products consisted of three phases, an oil-like organic phase, a gaseous phase, and an aqueous phase. Higher concentrations of organic carbon in the process resulted in a higher product yield. The heating value of the organic phase was up to 38.6 MJ/kg. Liquefaction of yeast without any addition of K₂CO₃ also resulted in liquid oil, but the quality and the yield of the oil product were lower. A reaction temperature of 400 °C was found to be optimal for the oil yield and quality.     

Catalytic conversion of waste biomass by hydrothermal treatment

The purpose of the work presented here is the production of liquid biofuels from wet organic waste matter in a continuous one-step catalytic process under hydrothermal conditions. The catalytic reaction of wet organic matter at near-critical water conditions (T > 300 °C, p > 22.1 MPa) is used to produce a mixture of combustible organics which can be used as liquid biofuel. In order to achieve a good product quality in a continuous one-step process, two catalysts were applied, a homogeneous potassium carbonate catalyst and a heterogeneous ZrO₂ catalyst. In addition, the reaction mixture was recirculated. The continuous flow of concentrated waste biomass feed at low flow rates and recirculation of the hot reaction mixture were the most challenging obstacles to overcome. The scale of the plant (0.1 l reactor volume) allowed for a variation of the feed, reaction temperature, and recirculation rate in order to optimise the process conditions. Still, the product quantity obtained was sufficient to perform a analytical characterisation. The experimental results confirmed the feasibility of the process. Hydrothermal treatment of waste biomass, after dewatering, resulted in a biocrude oil of high calorific value.     

Thermodynamic and kinetic studies of NaBH4 regeneration by NaBO2–Mg–H2 ternary system at isothermal condition

NaBH₄ is a candidate for H₂ storage in solid phase. NaBH₄ hydrolysis readily produces H₂ gas and NaBO₂ which can regenerate NaBH₄ with pressurized hydrogen and the aid of a reducing agent like Magnesium above 500 °C. This paper deals with the NaBH₄ thermochemical regeneration from the NaBO₂–Mg–H₂ ternary system at isothermal temperatures between 558 and 634 °C and H₂ pressure in the range 2–31 bar. A simplified Langmuir adsorption model has been applied for the interpretation of the in-situ H₂ pressure variations. The applied model is zero-dimensional but provides a reasonable approach to identify the rate determining step and acquire relevant thermodynamic and kinetic parameters such as equilibrium constant (K_eq), Gibbs free energy (Δ_rG⁰) and reaction rate coefficients (k). The study provides an apparent activation energy and Gibbs free energy of this process of 29.2 kJ/mol and −76.9 kJ/mol, respectively.