Single layered hollow NiO-NiS catalyst with large specific surface area and highly efficient visible-light-driven carbon dioxide conversion.

A sea urchin-shaped, single-layer, and hollow NiO-NiS photocatalyst with a large surface area was designed for carbon dioxide (CO2) conversion in this study. A d-glucose polymeric hollow frame was fabricated using a d-glucose monomer, and NiO particles were stably grown on it using the hydrothermal method to form a hollow NiO surface. The d-glucose frame was removed by heat treatment to create hollowed NiO; hollowed NiO-NiS (h-NiO-NiS) was subsequently obtained through ion exchange between the O ions in NiO and S ions in the sulfur powder. Additionally, we attempted to determine the correlation among the surface area of the h-NiO-NiS catalyst, CO2 gas adsorption capacity, and catalyst performance. The surface area of the h-NiO-NiS catalyst was ten times larger than that of the nanometer-sized NiO-NiS (n-NiO-NiS, 21.2 m2 g-1) catalyst. The CO2 photocatalytic conversion performance of the hollowed catalyst was approximately seven times larger than that of the nanosized catalyst. As the amount of ion-exchanged S increased, methane selectivity increased, and optimal methane production was obtained when the weight ratio of NiO and sulfur powder was 1 : 4. Using temperature-programmed desorption (TPD) analyses of CO2 and H2O, the adsorption of water molecules on the Ni-S surface and that of CO2 gas on the Ni-O surface during CO2 conversion reaction were confirmed. The h-NiO-NiS catalyst facilitated an effective charge separation through a well-developed interfacial transition between the linked NiS and NiO, and resulted in increased CO2 photoreduction performance under sunlight.

Characteristics of fractionated drop-in liquid fuel of plastic wastes from a commercial pyrolysis plant.

Pyrolysis is a waste conversion technology to solve an increasing plastic waste issue worldwide. Waste plastic pyrolysis fuel from a commercial-scale pyrolysis plant (10 ton/day) was comprehensively investigated using distillation methods by separating the crude pyrolysis fuel to isolate the diesel-like pyrolysis fuel fraction (C9-C25 for fraction 2 + fraction 3, middle distillate). Other fractions were C5-C10 for the light distillate (fraction 1), and >C25 for the heavy distillate (fraction 4). The relationship between the fuel boiling point and liquid vapor temperature were found for designing a scaled-up oil separation process. The diesel grade pyrolysis fuel fraction comprised approximately 70-80% of the crude pyrolysis fuel, wherein it had values of 43-45 MJ/kg, 1-6 cSt, and 12-42 mgKOH/goil. Meanwhile, the elemental ratios of the crude pyrolysis oil improved to 0.1 for O/C and 1.9 for H/C after separation, close to petroleum fuels (0.0 O/C and 1.95 H/C). The highest relative chemical composition was the olefins (46% in fraction 1 and 41% in fraction 2), whereas the paraffin was approximately 15-20% in the light fraction. Finally, the potential CO2 reduction for the plastic waste-to-energy process was evaluated, revealing that a total of 0.26 tCO2/tonwaste of emissions could be avoided during the waste plastic pyrolysis process.

Improvement of Oxygen Mobility with the Formation of Defects in the Crystal Structure of Red Mud as an Oxygen Carrier for Chemical Looping Combustion.

Fe2O3 is the major component of red mud, which is a by-produced after eluting aluminum from bauxite in the Bayer process, and can be used as an oxygen carrier. On the other hand, red mud is unsuitable for using oxygen in the crystal lattice because of its low surface area. In this study the red-mud sample was sulfidated at high temperatures to improve the lattice oxygen mobility by forming lattice defects in the iron oxide crystals. To form crystal defects on red mud, iron oxide was converted to iron sulfide with hydrogen sulfide, and then re-oxidized by air to remove the sulfur components. In these processes, it was possible to generate defects could be generated in the crystal structure. Crystal defects are formed by the difference in the molar volume of oxygen and sulfur bound to the metal in the oxidation-sulfidation process. The surface area of the defective red mud increased from approximately 25.9 m2/g to 122.1 m2/g, and the pore volume increased from 0.1714cc/g to 0.2803 cc/g. In addition, the formation of crystal defects increased the oxygen transfer capacity of red mud from 1.75% to 2.25% at 15 vol.% hydrogen. This means that the amount of oxygen transported during the reduction process could be enhanced approximately 1.29 fold.

Oxygen Transfer Capacity of Pseudobrookite Particles Derived from Ilmenite Mineral (x wt.%CuO/y wt.%red Mud-z wt.%ilmenite).

The minerals have a somewhat slower than other transition metals at critical reduction rates in their ability to deliver oxygen. Thus, single minerals alone do not exhibit a higher oxygen transfer capacity than metal oxide oxygen carriers. In this study, we try to solve the problem of single mineral ilmenite (FeTiO3) by combining it with Fe-based red mud and Cu oxide. When the ilmenite was used without calcination, the CH4-CO/air redox cycle showed rapid decayed. However, when ilmenite was calcined, the CH4-CO/air redox cycle became stable, and the oxygen transfer rate increased to 4.2%. This is because the FeTiO3 structure was converted to the pseudobrookite (Fe2TiO5) structure through the calcination process. That is, the Fe2+ ion in the ilmenite structure was converted into an Fe3+ ion. When 30 wt.% of red mud was added to the Fe ion, it reacted with the rutile-type titania mixed with pseudobrookite-typed Fe2TiO5, producing an almost perfect pseudobrookite crystal. This resulted in a slight increase in the capacity of oxygen transfer to 4.9%. When 15 wt.% of Cu oxide was added, the oxygen transfer capacity increased to 6.0%. This performance was indicated by the cyclic voltammetry curve that remained constant even after 200 cycles. Here, we argue that if low-cost minerals as a base material are used in appropriate amounts, the production of a lowest-cost oxygen carrier can be achieved.

Ni Substitution Effect on the Fe Position of Spinel Fe2MnO4 Particles for Chemical Looping Combustion.

The purpose of this study was to use a spinel structure to improve the performance and stability of chemical looping combustion processes. The oxygen carrier employed was Fe2MnO4, in which Ni was substituted at the Fe sites. Fe2-xNixMnO4 spinel particles were successfully synthesized by a sol-gel method. The obtained particles were characterized by X-ray diffraction (XRD), scanning electron microscopy, and CH4-/CO-temperature programmed desorption experiments. The XRD analysis confirmed that all the synthesized particles presented spinel structure. The performance of the particles was evaluated in redox cycle experiments under H2/air and CH4/air at 850 °C using a thermogravimetric analyzer. The Ni-substituted particles exhibited a higher performance than Fe2Mn1, being Fe1Ni1Mn1 the sample with the highest oxygen transfer capacity (19.68 wt% in H2/air and 15.90 wt% in CH4/air).

Effect of Manganese Oxide over Cu-Mn-Based Oxygen Carriers for Chemical Looping Combustion.

This study examined the effects of Mn on Cu-Mn-based mixed metal oxides used as oxygen transfer particles in the chemical looping combustion process. Chemical looping combustion of fuel is induced by the oxygen contained in the metal oxide. The oxidation reaction of the metal oxide particles reduced in the fuel reactor occurs in the air reactor. The metal oxide, which allows oxygen transfer, circulates between the fuel reactor to air reactor and supplies oxygen in the fuel reactor. Both reactors are operated at high temperatures (>850 °C) and the heat of reaction is recovered to produce electricity and heat. Oxygen carriers must have high thermal stability, high oxygen capacity, and rapid transfer rate, and should have a high attrition resistance because they are used in a circulating fluidized bed reactor. Cu exhibits high oxygen transfer rates, but it cannot be used for chemical looping combustion under high temperature conditions because of its low thermal stability. In this study, Mn was mixed to improve the thermal stability of the Cu component and the effect of these was investigated. This study examined copper metal oxide and the stability of Cu according to the temperature that the spinel structure had been synthesized. As a result, the spinel structure was well maintained in the oxidation-reduction cyclic-repeated tests and the migration of Cu was not severe. The spinel structure had high durability. Overall, Mn inhibits the migration of Cu because it forms a spinel structure with Cu.

Enhancement of CO2 sorption uptake on hydrotalcite by impregnation with K2CO3.

The awareness of symptoms of global warming and its seriousness urges the development of technologies to reduce greenhouse gas emissions. Carbon dioxide (CO(2)) is a representative greenhouse gas, and numerous methods to capture and storage CO(2) have been considered. Recently, the technology to remove high-temperature CO(2) by sorption has received lots of attention. In this study, hydrotalcite, which has been known to have CO(2) sorption capability at high temperature, was impregnated with K(2)CO(3) to enhance CO(2) sorption uptake, and the mechanism of CO(2) sorption enhancement on K(2)CO(3)-promoted hydrotalcite was investigated. Thermogravimetric analysis was used to measure equilibrium CO(2) sorption uptake and to estimate CO(2) sorption kinetics. The analyses based on N(2) gas physisorption, X-ray diffractometry, Fourier transform infrared spectrometry, Raman spectrometry, transmission electron microscopy, scanning electron microscopy, and energy dispersive X-ray spectroscopy were carried out to elucidate the characteristics of sorbents and the mechanism of enhanced CO(2) sorption. The equilibrium CO(2) sorption uptake on hydrotalcite could be increased up to 10 times by impregnation with K(2)CO(3), and there was an optimal amount of K(2)CO(3) for a maximum equilibrium CO(2) sorption uptake. In the K(2)CO(3)-promoted hydrotalcite, K(2)CO(3) was incorporated without changing the structure of hydrotalcite and it was thermally stabilized, resulting in the enhanced equilibrium CO(2) sorption uptake and fast CO(2) sorption kinetics.