Thermochemical Activity of Single- and Dual-Phase Oxide Compounds Based on Ceria, Ferrites, and Perovskites for Two-Step Synthetic Fuel Production.

This study focuses on the generation of solar thermochemical fuel (hydrogen, syngas) from CO2 and H2O molecules via two-step thermochemical cycles involving intermediate oxygen-carrier redox materials. Different classes of redox-active compounds based on ferrite, fluorite, and perovskite oxide structures are investigated, including their synthesis and characterization associated with experimental performance assessment in two-step redox cycles. Their redox activity is investigated by focusing on their ability to perform the splitting of CO2 during thermochemical cycles while quantifying fuel yields, production rates, and performance stability. The shaping of materials as reticulated foam structures is then evaluated to highlight the effect of morphology on reactivity. A series of single-phase materials including spinel ferrite, fluorite, and perovskite formulations are first investigated and compared to state-of-the-art materials. NiFe2O4 foam exhibits a CO2-splitting activity similar to its powder analog after reduction at 1400 °C, surpassing the performance of ceria but with much slower oxidation kinetics. On the other hand, although identified as high-performing materials in other studies, Ce0.9Fe0.1O2, Ca0.5Ce0.5MnO3, Ce0.2Sr1.8MnO4, and Sm0.6Ca0.4Mn0.8Al0.2O3 are not found to be attractive candidates in this work (compared with La0.5Sr0.5Mn0.9Mg0.1O3). In the second part, characterizations and performance evaluation of dual-phase materials (ceria/ferrite and ceria/perovskite composites) are performed and compared to single-phase materials to assess a potential synergistic effect on fuel production. The ceria/ferrite composite does not provide any enhanced redox activity. In contrast, ceria/perovskite dual-phase compounds in the form of powders and foams are found to enhance the CO2-splitting performance compared to ceria.

A Review of Oxygen Carrier Materials and Related Thermochemical Redox Processes for Concentrating Solar Thermal Applications.

Redox materials have been investigated for various thermochemical processing applications including solar fuel production (hydrogen, syngas), ammonia synthesis, thermochemical energy storage, and air separation/oxygen pumping, while involving concentrated solar energy as the high-temperature process heat source for solid-gas reactions. Accordingly, these materials can be processed in two-step redox cycles for thermochemical fuel production from H2O and CO2 splitting. In such cycles, the metal oxide is first thermally reduced when heated under concentrated solar energy. Then, the reduced material is re-oxidized with either H2O or CO2 to produce H2 or CO. The mixture forms syngas that can be used for the synthesis of various hydrocarbon fuels. An alternative process involves redox systems of metal oxides/nitrides for ammonia synthesis from N2 and H2O based on chemical looping cycles. A metal nitride reacts with steam to form ammonia and the corresponding metal oxide. The latter is then recycled in a nitridation reaction with N2 and a reducer. In another process, redox systems can be processed in reversible endothermal/exothermal reactions for solar thermochemical energy storage at high temperature. The reduction corresponds to the heat charge while the reverse oxidation with air leads to the heat discharge for supplying process heat to a downstream process. Similar reversible redox reactions can finally be used for oxygen separation from air, which results in separate flows of O2 and N2 that can be both valorized, or thermochemical oxygen pumping to absorb residual oxygen. This review deals with the different redox materials involving stoichiometric or non-stoichiometric materials applied to solar fuel production (H2, syngas, ammonia), thermochemical energy storage, and thermochemical air separation or gas purification. The most relevant chemical looping reactions and the best performing materials acting as the oxygen carriers are identified and described, as well as the chemical reactors suitable for solar energy absorption, conversion, and storage.

Continuous solar-driven gasification of oil palm agricultural bio waste for high-quality syngas production.

Empty fruit bunch (EFB) from oil palm is a solid agricultural bio-waste obtained from the edible oil process. Continuous solar-driven gasification of EFB offers a bright carbon-neutral avenue to convert both EFB bio-waste and renewable solar energy into sustainable and clean syngas. High-temperature concentrated solar heat is used to provide the reaction enthalpy, and therefore biomass waste feedstock is entirely dedicated to produce hydrogen and carbon monoxide (syngas). Solar energy is stored as a high-quality syngas and can be easily transported as a convertible and dispatchable chemical form. In this study, the performance of continuous steam gasification of EFB, fully powered by concentrated solar heat, was experimentally investigated in a solar gasification reactor. Experiments were carried out with continuous EFB biomass injection to evaluate the influence of temperature (1100-1300 °C) and biomass feeding rate (0.5-1.8 g/min). As a result, syngas yields and reactor performance were substantially enhanced by rising the EFB feeding rate and gasification temperature. An optimal EFB biomass feeding rate enabling maximum gasification performance was found to be 1.4 g/min at 1300 °C and 1.0 g/min at 1200 °C. Carbon conversion approaching 97%, energy upgrade factor of 1.38, and solar-to-fuel energy conversion efficiency up to 20% were demonstrated. Finally, the maximum syngas yield was found to be 81.1 mmol/gdry biomass at 1300 °C (with H2 and CO as the main constituents), closely approaching the maximum theoretical expected value reached at thermodynamic equilibrium (85.2 mmol/gdry biomass). Combining concentrated solar energy and biomass waste gasification was shown to be a promising and sustainable pathway toward waste valorization into carbon-neutral solar fuels.

Robocasting of 3D printed and sintered ceria scaffold structures with hierarchical porosity for solar thermochemical fuel production from the splitting of CO2.

We report the first ever robocast (additive manufacturing/3D printing) sintered ceria scaffolds, and explore their use for the production of renewable fuels via solar thermochemical fuel production (STFP, water and carbon dioxide splitting using concentrated solar energy). CeO2 catalyst scaffolds were fabricated as 50 mm diameter discs (struts and voids ∼500 µm), sintered at 1450 °C, with specific surface area of 1.58 m2 g-1. These scaffolds have hierarchical porosity, consisting of the macroporous scaffold structure combined with nanoscale porosity within the ceria struts, with mesopores <75 Å and an average pore size of ∼4 nm, and microporosity <2 nm with a microporous surface area of 0.29 m2 g-1. The ceria grains were ≤500 nm in diameter after sintering. STFP testing was carried out via thermogravimetric analysis (TGA) with reduction between 1050-1400 °C under argon, and oxidation at 1050 °C with 50% CO2, gave rapid CO production during oxidation, with high peak CO production rates (0.436 µmol g-1 s-1, 0.586 ml g-1 min-1), for total CO yield of 78 µmol g-1 (1.747 ml g-1). 90% CO was obtained after just 10 min of oxidation, comparing well to reticulated ceria foams, this CO production rate being an order of magnitude greater than that for ceria powders when tested at similar temperatures.

A Review of Solar Thermochemical CO2 Splitting Using Ceria-Based Ceramics With Designed Morphologies and Microstructures.

This review explores the advances in the synthesis of ceria materials with specific morphologies or porous macro- and microstructures for the solar-driven production of carbon monoxide (CO) from carbon dioxide (CO2). As the demand for renewable energy and fuels continues to grow, there is a great deal of interest in solar thermochemical fuel production (STFP), with the use of concentrated solar light to power the splitting of carbon dioxide. This can be achieved in a two-step cycle, involving the reduction of CeO2 at high temperatures, followed by oxidation at lower temperatures with CO2, splitting it to produce CO, driven by concentrated solar radiation obtained with concentrating solar technologies (CST) to provide the high reaction temperatures of typically up to 1,500°C. Since cerium oxide was first explored as a solar-driven redox material in 2006, and to specifically split CO2 in 2010, there has been an increasing interest in this material. The solar-to-fuel conversion efficiency is influenced by the material composition itself, but also by the material morphology that mostly determines the available surface area for solid/gas reactions (the material oxidation mechanism is mainly governed by surface reaction). The diffusion length and specific surface area affect, respectively, the reduction and oxidation steps. They both depend on the reactive material morphology that also substantially affects the reaction kinetics and heat and mass transport in the material. Accordingly, the main relevant options for materials shaping are summarized. We explore the effects of microstructure and porosity, and the exploitation of designed structures such as fibers, 3-DOM (three-dimensionally ordered macroporous) materials, reticulated and replicated foams, and the new area of biomimetic/biomorphous porous ceria redox materials produced from natural and sustainable templates such as wood or cork, also known as ecoceramics.

Kinetic rate laws of Cd, Pb, and Zn vaporization during municipal solid waste incineration.

The kinetic rate laws of heavy metal (HM) vaporization from municipal solid waste during its incineration were studied. Realistic artificial waste (RAW) samples spiked with Pb, Zn, and Cd were injected into a fluidized bed reactor. Metal vaporization wastracked by continuous measure ofthe above metals in exhaust gases. An inverse model of the reactor was used to calculate the metal vaporization rates from the concentration vs time profiles in the outlet gas. For each metal, experiments were carried out at several temperatures in order to determine the kinetic parameters and to obtain specific rate laws as functions of temperature. Temperature has a strong influence on the HM vaporization dynamics, especially on the vaporization kinetics profile. This phenomenon was attributed to internal diffusion control of the HM release. Two types of kinetic rate laws were established based on temperature: a fourth- or fifth-order polynomial rate law (r(x) = k0e(-E(A)/RT)p(x)) for temperatures lower than 740 degrees C and a first-order polynomial (r(x) = k0e(-E(A)/ RT(q-q(f) for temperatures higher than 740 degrees C.

Kinetics of heavy metal vaporization from model wastes in a fluidized bed.

Metal vaporization experiments were carried out in an atmospheric fluidized bed to study the influence of operating conditions on the extent of heavy metal (HM) release in fumes from municipal solid waste incinerators. Modelwastes spiked with compounds of Pb, Cd, and Zn were used. The parameters studied were temperature, treatment duration, matrix of the model waste (mineral and organic), HM initial speciation, and gas composition (N2, air, air + HCl, gas mixture simulating the incinerators). The extent of vaporization was measured by solid sample analysis and on-line analysis of the gaseous effluent, after customization of the ICP technique for gas analysis. The results indicate the metal vaporization rate is very high initially and then slows. The results with mineral matrices give the decreasing order of volatility Cd > Pb > Zn, but in industrial incinerators Zn volatilizes slightly more than Pb. Temperature (especially for porous alumina) and mineral matrix have a strong influence on the HM vaporization, but HCl concentration and HM initial speciation do not. The gas composition and the initial metal concentration are significant parameters. The matrix influence clearly denoted the mass transfer limitations in the vaporization process from mineral matrix.