CO2-gasification of a lignite coal in the presence of an iron-based oxygen carrier for chemical-looping combustion

Chemical-looping combustion (CLC) has the inherent property of separating the product CO2 from flue gases. Instead of air, it uses an oxygen carrier, usually in the form of a metal oxide, to provide oxygen for combustion. All techniques so far proposed for chemical looping with solid fuels involve initially the gasification of the solid fuel in order for the gaseous products to react with the oxygen carrier. Here, the rates of gasification of coal were compared when gasification was undertaken in a fluidised bed of either (i) an active Fe-based oxygen carrier used for chemical looping or (ii) inert sand. This enabled an examination of the ability of chemical looping materials to enhance the rate of gasification of solid fuels. Batch gasification and chemical-looping combustion experiments with a German lignite and its char are reported, using an electrically-heated fluidised bed reactor at temperatures from 1073 to 1223 K. The fluidising gas was CO2 in nitrogen. The kinetics of the gasification were found to be significantly faster in the presence of the oxygen carrier, especially at temperatures above 1123 K. A numerical model was developed to account for external and internal mass transfer and for the effect of the looping agent. The model also included the effects of the evolution of the pore structure at different conversions. The presence of Fe2O3 led to an increase in the rate of gasification because of the rapid oxidation of CO by the oxygen carrier to CO2. This resulted in the removal of CO and maintained a higher mole fraction of CO2 in the mixture of gas around the particle of char, i.e. within the mass transfer boundary layer surrounding the particle. This effect was most prominent at about 20% conversion when (i) the surface area for reaction was at its maximum and (ii) because of the accompanying increase in porosity and pore size, intraparticle resistance to gas mass transfer within the particle of char had fallen, compared with that in the initial particle. Excellent agreement was observed between the rates predicted by the numerical model and those observed experimentally. ©2013 Elsevier Ltd. All rights reserved.

The production of separate streams of pure hydrogen and carbon dioxide from coal via an iron-oxide redox cycle

A chemical looping process using the redox reactions of iron oxide has been used to produce separate streams of pure H2 and CO2 from a solid fuel. An iron oxide carrier prepared using a mechanical mixing technique and comprised of 100wt.% Fe2O3 was used. It was demonstrated that hydrogen can be produced from three representative coals - a Russian bituminous, a German lignite and a UK sub-bituminous coal. Depending on the fuel, pure H2 with [CO] ≲50vol.ppm can be obtained from the proposed process. The cyclic stability of the iron oxide carrier was not adversely affected by contaminants found in syngas which are gaseous above 273K. Stable quantities of H2 were produced over five cycles for all three coals investigated. Independent of the fuel, SO2 was not formed during the oxidation with steam, i.e. the produced H2 was not contaminated with SO2. Since oxidation with air removes contaminants and generates useful heat and pure N2 for purging, it should be included in the operating cycle. Overall, it was demonstrated that the proposed process may be an attractive approach to upgrade crude syngas produced by the gasification of low-rank coals to pure H2, representing a substantial increase in calorific value, whilst simultaneous capturing CO2, a greenhouse gas. © 2010 Elsevier B.V.

Kinetics of the chemical looping oxidation of H2 by a co-precipitated mixture of CuO and Al2O3

Chemical-looping combustion (CLC) has the inherent property of separating CO2 from flue gases. Instead of air, it uses an oxygen-carrier, usually in the form of a metal oxide, to provide oxygen for combustion. When used for the combustion of gaseous fuels, such as natural gas, or synthesis gas from the gasification of coal, the technique gives a stream of CO2 which, on an industrial scale, would be sufficiently pure for geological sequestration. An important issue is the form of the metal oxide, since it must retain its reactivity through many cycles of complete reduction and oxidation. Here, we report on the rates of oxidation of one constituent of synthesis gas, H2, by co-precipitated mixtures of CuO+Al2O3 using a laboratory-scale fluidised bed. To minimise the influence of external mass transfer, and also of errors in the measurement of [H2], particles sized to 355-500μm were used at low [H2], with the temperature ranging from 450 to 900°C. Under such conditions, the reaction was slow enough for meaningful measurements of the intrinsic kinetics to be made. The reaction was found to be first order with respect to H2. Above ∼800°C, the reaction of CuO was fast and conformed to the shrinking core mechanism, proceeding via the intermediate, Cu2O, in: 2CuO+H2→Cu2O+H2O, ΔH1073 K0=- 116.8 kJ/mol; Cu2O+H2→2Cu+H2O, ΔH1073 K0-80.9 kJ/mol. After oxidation of the products Cu and Cu2O back to CuO, the kinetics in subsequent cycles of chemical looping oxidation of H2 could be approximated by those in the first. Interestingly, the carrier was found to react at temperatures as low as 300°C. The influence of the number of cycles of reduction and oxidation is explored. Comparisons are drawn with previous work using reduction by CO. Finally, these results indicate that the kinetics of reaction of the oxygen carrier with gasifier synthesis gases is very much faster than rates of gasification of the original fuel. © 2010 The Institution of Chemical Engineers.

Noncatalytic chemical vapor deposition of graphene on high-temperature substrates for transparent electrodes

A noncatalytic chemical vapor deposition mechanism is proposed, where high precursor concentration, long deposition time, high temperature, and flat substrate are needed to grow large-area nanocrystalline graphene using hydrocarbon pyrolysis. The graphene is scalable, uniform, and with controlled thickness. It can be deposited on virtually any nonmetallic substrate that withstands ∼1000 °C. For typical examples, graphene grown directly on quartz and sapphire shows transmittance and conductivity similar to exfoliated or metal-catalyzed graphene, as evidenced by transmission spectroscopy and transport measurements. Raman spectroscopy confirms the sp 2-C structure. The model and results demonstrate a promising transfer-free technique for transparent electrode production. © 2012 American Institute of Physics.

Low partial pressure chemical vapor deposition of graphene on copper

A systematic study of the Cu-catalyzed chemical vapor deposition of graphene under extremely low partial pressure is carried out. A carbon precursor supply of just P CH4∼ 0.009 mbar during the deposition favors the formation of large-area uniform monolayer graphene verified by Raman spectra. A diluted HNO 3 solution is used to remove Cu before transferring graphene onto SiO 2/Si substrates or carbon grids. The graphene can be made suspended over a ∼12 μm distance, indicating its good mechanical properties. Electron transport measurements show the graphene sheet resistance of ∼0.6 kΩ/□ at zero gate voltage. The mobilities of electrons and holes are ∼1800 cm 2/Vs at 4.2 K and ∼1200 cm 2/Vs at room temperature. © 2011 IEEE.

The phase of iron catalyst nanoparticles during carbon nanotube growth

We study the Fe-catalyzed chemical vapor deposition of carbon nanotubes by complementary in situ grazing-incidence X-ray diffraction, in situ X-ray reflectivity, and environmental transmission electron microscopy. We find that typical oxide supported Fe catalyst films form widely varying mixtures of bcc and fcc phased Fe nanoparticles upon reduction, which we ascribe to variations in minor commonly present carbon contamination levels. Depending on the as-formed phase composition, different growth modes occur upon hydrocarbon exposure: For γ-rich Fe nanoparticle distributions, metallic Fe is the active catalyst phase, implying that carbide formation is not a prerequisite for nanotube growth. For α-rich catalyst mixtures, Fe3C formation more readily occurs and constitutes part of the nanotube growth process. We propose that this behavior can be rationalized in terms of kinetically accessible pathways, which we discuss in the context of the bulk iron-carbon phase diagram with the inclusion of phase equilibrium lines for metastable Fe3C. Our results indicate that kinetic effects dominate the complex catalyst phase evolution during realistic CNT growth recipes. © 2012 American Chemical Society.

Twin-free uniform epitaxial GaAs nanowires grown by a two-temperature process.

We demonstrate vertically aligned epitaxial GaAs nanowires of excellent crystallographic quality and optimal shape, grown by Au nanoparticle-catalyzed metalorganic chemical vapor deposition. This is achieved by a two-temperature growth procedure, consisting of a brief initial high-temperature growth step followed by prolonged growth at a lower temperature. The initial high-temperature step is essential for obtaining straight, vertically aligned epitaxial nanowires on the (111)B GaAs substrate. The lower temperature employed for subsequent growth imparts superior nanowire morphology and crystallographic quality by minimizing radial growth and eliminating twinning defects. Photoluminescence measurements confirm the excellent optical quality of these two-temperature grown nanowires. Two mechanisms are proposed to explain the success of this two-temperature growth process, one involving Au nanoparticle-GaAs interface conditions and the other involving melting-solidification temperature hysteresis of the Au-Ga nanoparticle alloy.

High purity GaAs nanowires free of planar defects: Growth and characterization

We investigate how to tailor the structural, crystallographic and optical properties of GaAs nanowires. Nanowires were grown by Au nanoparticle-catalyzed metalorganic chemical vapor deposition. A high arsine flow rate, that is, a high ratio of group V to group III precursors, imparts significant advantages. It dramatically reduces planar crystallographic defects and reduces intrinsic carbon dopant incorporation. Increasing V/III ratio further, however, instigates nanowire kinking and increases nanowire tapering. By choosing an intermediate V/III ratio we achieve uniform, vertically aligned GaAs nanowires, free of planar crystallographic defects, with excellent optical properties and high purity. These findings will greatly assist the development of future GaAs nanowire-based electronic and optoelectronic devices, and are expected to be more broadly relevant to the rational synthesis of other III-V nanowires. © 2008 WILEY-VCH Verlag GmbH & Co. KGaA.

Nature of heterointerfaces in GaAs/InAs and InAs/GaAs axial nanowire heterostructures

The structural and compositional characteristics of heterointerfaces of Au-catalyzed GaAs/InAs and InAs/GaAs axial nanowire heterostructures were comprehensively investigated by transmission electron microscopy. It has been found that the GaAs/InAs interface is not sharp and contains an InGaAs transition segment, and in contrast, the InAs/GaAs interface is atomically sharp. This difference in the nature of heterointerfaces can be attributed to the difference in the affinity of the group III elements with the catalyst material. © 2008 American Institute of Physics.

Twin plane re-entrant mechanism for catalytic nanowire growth.

A twin-plane based nanowire growth mechanism is established using Au catalyzed Ge nanowire growth as a model system. Video-rate lattice-resolved environmental transmission electron microscopy shows a convex, V-shaped liquid catalyst-nanowire growth interface for a ⟨112⟩ growth direction that is composed of two Ge {111} planes that meet at a twin boundary. Unlike bulk crystals, the nanowire geometry allows steady-state growth with a single twin boundary at the nanowire center. We suggest that the nucleation barrier at the twin-plane re-entrant groove is effectively reduced by the line energy, and hence the twin acts as a preferential nucleation site that dictates the lateral step flow cycle which constitutes nanowire growth.