Carbothermal Reduction Of ZnO Research Articles

Exploring Enhanced Hydrolytic Dehydrogenation of Ammonia Borane with Porous Graphene-Supported Platinum Catalysts.

Graphene is a good support for immobilizing catalysts, due to its large theoretical specific surface area and high electric conductivity. Solid chemical converted graphene, in a form with multiple layers, decreases the practical specific surface area. Building pores in graphene can increase specific surface area and provide anchor sites for catalysts. In this study, we have prepared porous graphene (PG) via the process of equilibrium precipitation followed by carbothermal reduction of ZnO. During the equilibrium precipitation process, hydrolyzed N,N-dimethylformamide sluggishly generates hydroxyl groups which transform Zn2+ into amorphous ZnO nanodots anchored on reduced graphene oxide. After carbothermal reduction of zinc oxide, micropores are formed in PG. When the Zn2+ feeding amount is 0.12 mmol, the average size of the Pt nanoparticles on PG in the catalyst is 7.25 nm. The resulting Pt/PG exhibited the highest turnover frequency of 511.6 min-1 for ammonia borane hydrolysis, which is 2.43 times that for Pt on graphene without the addition of Zn2+. Therefore, PG treated via equilibrium precipitation and subsequent carbothermal reduction can serve as an effective support for the catalytic hydrolysis of ammonia borane.

Solar metallurgical process for high-purity Zn and syngas production using carbon or biomass feedstock in a flexible thermochemical reactor

Co-production of high-purity Zn and syngas via carbothermal reduction of ZnO was performed in a directly-irradiated concentrated solar reactor, thereby converting and storing intermittent sunlight into high-value chemical fuels and commodities. On-sun experiments were carried out by varying operating parameters including solid carbonaceous feedstocks (either solid carbon or beech wood biomass) in batch and continuous modes at 950–1350 °C, demonstrating solar reactor flexibility and robustness. Decreasing pressure (150–400 hPa) promoted both ZnO reduction rate and net ZnO conversion above 78%, thus enhancing Zn production yield. Nevertheless, CO selectivity decreased because of rising CO2 due to the residence time decrease. A remarkable increase in gas production rates/yields, CO selectivity, and reaction extent was highlighted when increasing temperature during continuous pellets reactant injection. Furthermore, utilizing wood biomass as a sustainable green reducer was proved to be an attractive choice to produce both metallic Zn and high-quality syngas in a single process consisting of biomass gasification with solid ZnO. Zn content exceeding 90 wt% was demonstrated for both batch and continuous tests, unveiling high reactor performance for the metallurgical process. The energy content of the feedstock was upgraded by the solar power input (maximum energy upgrade factor up to 1.2), and the maximum solar-to-fuel energy conversion efficiency up to ∼ 6% was achieved with continuous reactant injection. The high-purity Zn can be further used to produce fuel via CO2-splitting in a complete and fast reaction.

A packed‐bed solar reactor for the carbothermal zinc production – dynamic modelling and experimental validation

Integration of concentrated solar energy into the pyrometallurgical Zn production process as clean source of high‐temperature process heat could significantly reduce fossil fuels consumption and its concomitant CO2 emissions. The solar‐driven carbothermal reduction of ZnO is investigated using a 10‐kWth solar reactor featuring two cavities, the upper one serving as the solar absorber and the lower one containing a packed‐bed of ZnO and beech charcoal as the biogenic reducing agent. Experimentation in a high‐flux solar simulator is carried out under radiative fluxes of 2300–2890 suns, yielding a peak solar‐to‐chemical energy conversion efficiency of 18.4%. The reactor performance under variable operating conditions is analyzed via a dynamic numerical model coupling heat transfer with chemical kinetics. The model is validated by comparison to the experimental data obtained with the 10‐kWth packed‐bed solar reactor and further applied to predict the effect of incorporating semi‐continuous feeding of reactants on the process efficiency. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4586–4594, 2016

On the Development of a Zinc Vapor Condensation Process for the Solar Carbothermal Reduction of Zinc Oxide

In the conventional Imperial Smelting Process, the dominating pyrometallurgical zinc production process, zinc vapor is recovered from the furnace off-gas by absorption into an intense spray of molten lead droplets in a splash condenser, followed by separation of zinc from the Zn-Pb alloy upon cooling from 550°C to 450°C by taking advantage of the decrease in the solubility of zinc in lead at lower temperatures. The adaptation of this condenser technology into a solar-driven thermochemical plant using concentrated solar energy faces several drawbacks owing to its mechanical complications and the continuous recirculation of large quantities of lead. An alternative zinc condenser concept involving gas bubbling through a zinc liquid bath of the off-gas evolved from the carbothermal reduction of ZnO is thus proposed and numerically modeled for transient heat and mass transfer. Condensation of bubbles containing 53.5% of noncondensable gases yielded chemical conversions of Zn(g) to Zn(l) in the range of 95.6–99.8% for operation in the temperature range 500–650°C while conversions of Zn(g) to ZnO in the order of 10−6 were obtained, thus predicting successful suppression of Zn(g) reoxidation by CO2 and CO.

Bio-hydrogen production based on catalytic reforming of volatiles generated by cellulose pyrolysis: An integrated process for ZnO reduction and zinc nanostructures fabrication

Abstract The paper presents a process of cellulose thermal degradation with bio-hydrogen generation and zinc nanostructures synthesis. Production of zinc nanowires and zinc nanoflowers was performed by a novel processes based on cellulose pyrolysis, volatiles reforming and direct reduction of ZnO. The bio-hydrogen generated in situ promoted the ZnO reduction with Zn nanostructures formation by vapor–solid (VS) route. The cellulose and cellulose/ZnO samples were characterized by thermal analyses (TG/DTG/DTA) and the gases evolved were analyzed by FTIR spectroscopy (TG/FTIR). The hydrogen was detected by TPR (Temperature Programmed Reaction) tests. The results showed that in the presence of ZnO the cellulose thermal degradation produced larger amounts of H 2 when compared to pure cellulose. The process was also carried out in a tubular furnace with N 2 atmosphere, at temperatures up to 900 °C, and different heating rates. The nanostructures growth was catalyst-free, without pressure reduction, at temperatures lower than those required in the carbothermal reduction of ZnO with fossil carbon. The nanostructures were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) and transmission electron microscopy (TEM). The optical properties were investigated by photoluminescence (PL). One mechanism was presented in an attempt to explain the synthesis of zinc nanostructures that are crystalline, were obtained without significant re-oxidation and whose morphologies are dependent on the heating rates of the process. This route presents a potential use as an industrial process taking into account the simple operational conditions, the low costs of cellulose and the importance of bio-hydrogen and nanostructured zinc.

Zinc nanowires synthesized on a large scale by a simple carbothermal process

Metallic Zn nanowires have been synthesized by a new carbothermal reduction route in which ZnO and Eucalyptus sp. tar pitch were used as source materials. This simple practical procedure was capable of producing Zn nanowires in large quantities without reoxidation. This process was carried out in inert atmosphere, without vacuum or catalyst, at temperatures (800–900 °C) lower than those required in the carbothermal reduction of ZnO with graphite. A comparative study was performed using graphite that is traditionally used as a ZnO reducer, under the same experimental conditions, however, no reaction was observed. The new process involves the pyrolysis of biopitch to obtain a highly reactive coke and the reduction of ZnO with the release of Zn (v) for the growth of Zn (s) nanowires. The resulting Zn nanowires were characterized by X-ray diffractometry, energy-dispersive spectroscopy and scanning electron microscopy. Differential thermal analysis and thermogravimetric analysis coupled with infrared analysis techniques were used in an effort to understand the underlying mechanism and establish the best ratio biopitch/ZnO to be used. This paper presents the characterization of the as-synthesized nanowires and discusses the main reactions involved in their production.

Towards the Industrial Solar Carbothermal Production of Zinc

Based on the experimental results of a 300kW solar chemical pilot plant for the production of zinc by carbothermal reduction of ZnO, we performed a conceptual design of a 5MW demonstration plant and of a 30MW commercial plant. Zinc can be used as a fuel for zinc-air batteries and fuel cells, or it can be reacted with water to form high-purity hydrogen. In either case, the chemical product is ZnO, which in turn is solar recycled to zinc. The proposed thermochemical process provides an energy efficient route for the conversion, storage, and transportation of solar energy in the form of solar fuels.

Growth and characterisation of epitaxially ordered zinc aluminate domains on c-sapphire

Epitaxially ordered zinc aluminate domains with sub-micron dimensions are formed on bare c-sapphire substrates using a vapour phase method (with vapour generated by carbothermal reduction of ZnO) at various temperatures and growth durations. A zinc aluminate (ZnAl 2O 4) layer is formed by reaction of the source materials (Zn and O) with the substrate. We observe crystallites with a well-defined epitaxial relationship on the sapphire substrate in addition to polycrystalline material. The epitaxially oriented deposit displays the form of characteristically twinned (singly or multiply) grains of sub-micron dimensions with three variants, consistent with the c-sapphire substrate symmetry. Scanning electron microscopy and transmission electron microscopy studies show that the formation of these grains is associated with the presence of extended defects in the sapphire substrate. Epitaxially ordered grains formed at higher temperatures show a change in the nature of the twin boundaries and epitaxial relations as a function of growth time, attributed to the effects of annealing during growth.

A 300kW Solar Chemical Pilot Plant for the Carbothermic Production of Zinc

In the framework of the EU-project SOLZINC, a 300-kW solar chemical pilot plant for the production of zinc by carbothermic reduction of ZnO was experimentally demonstrated in a beam-down solar tower concentrating facility of Cassegrain optical configuration. The solar chemical reactor, featuring two cavities, of which the upper one is functioning as the solar absorber and the lower one as the reaction chamber containing a ZnO/C packed bed, was batch-operated in the 1300–1500 K range and yielded 50 kg/h of 95%-purity Zn. The measured energy conversion efficiency, i.e., the ratio of the reaction enthalpy change to the solar power input, was 30%. Zinc finds application as a fuel for Zn/air batteries and fuel cells, and can also react with water to form high-purity hydrogen. In either case, the chemical product is ZnO, which in turn is solar-recycled to Zn. The SOLZINC process provides an efficient thermochemical route for the storage and transportation of solar energy in the form of solar fuels.

Photocatalytic effect of ZnO on carbon gasification with CO2 for high temperature solar thermochemistry

A photocatalytic effect of ZnO on carbon gasification with CO2 was studied using a concentrated Xe beam to enhance the gasification rate in solar/chemical energy conversion process. The sample, activated carbon impregnated with ZnO (5 wt%), was heated at 873 K by a Xe beam irradiation with UV (<400 nm). The gasification rate at 873 K increased 2 folds in comparison with the Xe irradiation without UV, but, the difference of the rate of CO evolution decreased with the increasing temperature from 873 to 1073 K. The carbothermal reduction of ZnO (ZnO+C→Zn+CO) proceeded at above 950 K, which was demonstrated by XRD analysis and thermodynamic calculation. These results indicate that the photocatalytic effect of ZnO with the UV irradiation enhance the gasification rate of carbon at low temperature (873 K).

Carbothermal reduction of zinc ferrite

The carbothermal reduction of zinc ferrite was studied using X-ray diffractometer (XRD), wet chemical analysis, scanning electron microscope (SEM), surface area meter, and thermogravimetrical analysis (TGA) systems. Zinc ferrite was found to be decomposed to ZnO and Fe2O3 initially and carbothermal reduction of ZnO and Fe2O3 took place simultaneously. The results of the surface area measurement indicated that the surface area of the solid sample increased with reaction time. Pore volume and average pore diameter were found to increase, reach a maximum, and then decrease with reaction time. These results were explained by considering the escape of zinc vapor, the expansion of the iron oxide grain, and the sintering of the iron. A mechanism and a model were proposed to explain the reaction. The experimental results of the thermogravimetrical analysis indicated that the reaction rate can be increased by increasing either the argon flow rate or the reaction temperature. Furthermore, the reaction rate was found to increase with a decrease in either the sample height, the molar ratio of ZnFe2O4/C, the size of the carbon agglomerate, or the initial bulk density.