Structure of coke powder heat-treated with boron

Coal tar pitch-based coke powder with a fine mosaic texture was heat-treated with various concentrations of boron powder at 2900°C. Increasing the boron amount led to smaller d₀₀₂ and larger d₁₁₀, and made the original fine texture coarser. Some small particles showed specific structures of polyhedrons, of which surfaces are 002 planes of graphite lattice, after heat treatment with boron. The size of the polyhedron increased with boron content. Boron concentration was lower at the surface than at the inner portions of particles for a powder heat-treated with a higher amount of boron, while it depended less on the depth for that heat-treated with a lower amount of boron. The formation mechanism of the polyhedron particle is discussed.     

Mechanistic investigations of single-walled carbon nanotube synthesis by ferrocene vapor decomposition in carbon monoxide

The single-walled carbon nanotubes (SWCNTs) were synthesized by the carbon monoxide disproportionation reaction on Fe catalyst particles formed by ferrocene vapor decomposition in a laminar flow aerosol (floating catalyst) reactor. On the basis of in situ sampling of the product collected at different locations in the reactor, kinetics of the SWCNT growth and catalyst particle crystallinity were studied. Catalyst particles captured before SWCNT nucleation as well as inactive particles were determined to have cementite (Fe₃C) phase, while particles with γ- and α-Fe phases were found to be embedded in the SCWNTs. The growth rate in the temperature range from 804 to 915 °C was respectively varied from 0.67 to 2.7 μm/s. The growth rate constant can be described by an Arrhenius dependence with an activation energy of E_a = 1.39 eV, which was attributed to the carbon diffusion in solid iron particles. CNT growth termination was explained by solid-liquid phase transition in the catalyst particles. A high temperature gradient in the reactor was found to not have any effect on the diameter during the SWCNT growth and as a result on the chirality of the growing SWCNTs.     

Reactive infiltration processing (RIP) of ultra high temperature ceramics (UHTC) into porous C/C composite tubes

A novel reactive infiltration processing (RIP) technique was employed to infiltrate porous carbon fibre reinforced carbon (C/C) composite hollow tubes with ultra high temperature ceramic (UHTC) particles such as ZrB₂. The C/C composite tubes had initial porosity of ∼60% with a bimodal (10 μm and 100 μm) pore size distribution. A slurry with 40-50% ZrB₂ solid loading particles was used to infiltrate the C/C tubes. Our approach combines in situ ZrB₂ formation with coating of fine ZrB₂ particles on carbon fibre surfaces by a reactive processing method. A Zr and B containing diphasic gel was first prepared using inorganic-organic hybrid precursors of zirconium oxychloride (ZrOCl₂·8H₂O), boric acid, and phenolic resin as sources of zirconia, boron oxide, and carbon, respectively. Then commercially available ZrB₂ powder was added to this diphasic gel and milled for 6 h. The resultant hybrid slurry was vacuum infiltrated into the porous hollow C/C tubes. The infiltrated tubes were dried and fired for 3 h at 1400 °C in flowing Ar atmosphere to form and coat ZrB₂ on the carbon fibres in situ by carbothermal reaction. Microstructural observation of infiltrated porous C/C composites revealed carbon fibres coating with fine nanosized (∼100 nm) ZrB₂ particles infiltrated to a depth exceeding 2 mm. Ultra high temperature ablation testing for 60 s at 2190 °C suggested formation of ZrO₂ around the inner bore of the downstream surface.     

Magnetic properties of carbon nano-particles produced by a pulsed arc submerged in ethanol

Carbon powder was produced by a pulsed arc ignited between two carbon electrodes submerged in ethanol, and was comprised of both micro- and nano-particles. The measured magnetic properties of the mixed “raw” powder at 20 and 300 K were: saturation magnetization M_s ∼ 0.90-0.93 emu/g, residual magnetization M_r = 0.022 and 0.018 emu/g, and coercive force H_c = 11 and 8 Oe, respectively. The data lead to conclusion that the powder consisted of ferromagnetic particles with a critical temperature much higher than 300 K. Magnetic particles in solution were separated by means of bio-ferrography. It was found that the magnetically separated particles included chains of ∼30-50 nm diameter spheres, and nanotubes and nanorods with lengths of 50-250 nm and diameters of 20-30 nm. In contrast, the residual particles which passed through the bio-ferrograph consisted of 1 μm and larger micro-particles, and nano-particles without any definite shape.     

On the spinel formation in Co1 − xO/Co2TiO4 composites via reactive sintering, exsolution and oxidation

The formation mechanism and microstructural development of the spinel phases in the Co_1 − xO/Co₂TiO₄ composites upon reactive sintering the Co_1 − xO and TiO₂ powders (9:1 molar ratio) at 1450 °C and during subsequent cooling in air were studied by X-ray diffraction and analytical electron microscopy. The Co₂TiO₄ spinel occurred as inter- and intragranular particles in the matrix of Ti-doped Co_1 − xO grains with a rock salt-type structure during reactive sintering. The submicron sized Co₂TiO₄ particles were able to detach from grain boundaries in order to reach an energetically favorable parallel orientation with respect to the host Co_1 − xO grains via a Brownian-type rotation/coalescence process. Upon cooling in air, secondary Co₂TiO₄ nanoparticles were precipitated and the Ti-doped Co_1 − xO host was partially oxidized as Co_3 − δO₄ spinel by rapid diffusion along the {1 1 1} and {1 0 0}-decorated interphase interface and the free surface of the composites.     

PM304 coating on a Ni-based superalloy rod for high temperature lubrication

PM304 coating on a Ni-based superalloy rod for high temperature lubrication has been prepared by high-energy ball milling and powder metallurgy techniques. The composition of the PM304 coating is the same as that of PS304 coating, but the microstructure is quite different. The microstructure of PM304 coating is fine and dense; the size of self-lubricating particles in the coating is very small. Self-lubricating Cr₂O₃ particles are about 100 nm, BaF₂/CaF₂ particles about 1 μm, Ag particles below 5 μm, while BaF₂/CaF₂ and Ag particles precipitated from NiCr matrix are less than 50 nm. The fine and dense microstructure results in increased tensile strength and crack growth resistance of PM304 coating. The mean tensile strength is about 46 MPa.     

Three-dimensional numerical simulation of a circulating fluidized bed reactor for multi-pollutant control

Circulating fluidized bed adsorber (CFBA) technology is regarded as a potentially effective method for simultaneously controlling emissions of sulfur dioxide, fine particulate matter, and trace heavy metals, such as mercury vapor. In order to analyze CFBA systems in detail, a gas mixture/solids mixture model based on the three-dimensional Navier-Stokes equations is developed for particle flow, agglomeration, physical and chemical adsorption in a circulating fluidized bed. The solids mixture consists of two solids, one with components of CaO and CaSO₄, and the other being an activated carbon. The gas mixture is composed of fine particulate matter (PM), sulfur dioxide, mercury vapor, oxygen and inert gas. Source terms representing fine particulate matter agglomeration onto sorbent particles, sulfur dioxide removal through chemical adsorption onto calcined lime, and mercury vapor removal through physical adsorption onto activated carbon are formulated and included into the model. The governing equations are solved using high-resolution upwind-differencing methods, combined with a time-derivative preconditioning method for efficient time-integration. Numerical simulations of bench-scale operation of a prototype CFBA reactor for multi-pollutant control are described.     

Prediction of thickness and fouling rate in pulsating flow heat exchangers,using FLUENT simulator

Heat exchangers are an important part of industrial processes as they handle a major portion of total energy consumption. Fouling could have serious impact on their performance and hence affect the economic performance of the process plant. The aim of this work was to simulate the crystallization fouling process in a heat exchanger by developing a C⁺⁺ program and adopting UDF functions through Fluent software; and hence evaluate all the given models and consequently implement the model which would best suit our particular case. The finding of this work would enable us to evaluate the thickness and fouling rate in the heat exchangers. Furthermore, the effect of pulsating flow on the crystallization fouling of calcium sulfate (CaSO₄) in the heat exchanger was also investigated, and the effect of operation of different amplitude of the oscillations (10–70) and frequencies (1.59–12.73 Hz) on the fouling of this compound was studied.     

Hydration of tricalcium aluminate in the presence of various amounts of calcium sulphite hemihydrate: Conductivity tests

Hydration of calcium aluminate C₃A (3CaO·Al₂O₃) in the presence of calcium sulphite hemihydrate (CaSO₃·0.5H₂O), with the molar ratio of substrates close to 1, produces the C₃A·CaSO₃·11H₂O calcium monosulphite aluminate phase. Small amounts of calcium sulphite added to calcium aluminate (the ratio of CaSO₃·0.5H₂O / C₃A equalling 0 : 1) change the rate of C₃A hydration and influence the whole reaction. Reaction processes for various ratios of the C₃A-CaSO₃·0.5H₂O mixture were examined in pure distilled water with a considerable amount of liquid W / S = 38-50 (constant W / C₃A). Processes in the liquid phase were monitored with conductivity equipment, and the XRD analysis was used to identify the phases precipitated during the examined reactions.     

Characterisation of flow and heat transfer patterns in low aspect ratio packed beds by a 3D network-of-voids model

Using an illustrative sphere packing assembly, it is demonstrated that flow structure and wall heat transfer patterns in low aspect ratio fixed bed reactors are more realistically modelled by properly accounting for the discrete void fraction variations. A 3D network-of-voids (NoV) model has been devised to characterise and examine the discrete flow and heat transfer phenomena in a low aspect ratio packed bed with d_t/d_p = 1.93. The model as formulated is deliberately designed to be not too complicated so as not to place severe demands on computational resources. Hence, the model can potentially easily be applied to simulate the typically large sets of tubes (often comprising more than 10,000) in the case of industrial multi-tubular reactors, where every tube is different due to the random insertion of the packing particles. Because of its simplicity, the model offers an opportunity of coupling the individual catalyst pellet level transport with the complex interstitial flows at the reactor scale. Illustrative studies of this NoV model on a random packed bed of spheres predict large variations of discrete in-void angular velocities and consequently wall heat transfer coefficients within a single tube. The wide variations of wall heat transfer coefficients imply that the different angular sections of the tube will transfer heat at radically different rates resulting in potentially large temperature differences in different segments of the tube. This may possibly result in local temperature runaway and/or hot spot development leading to several potentially unanticipated consequences for safety and integrity of the tube and hence the reactor. The NoV model predictions of the overall pressure drop behaviour are shown to be consistent with the quantitative and qualitative features of correlations available in the literature.     

An experimental study of sulphate transformation during pyrolysis of an Australian lignite

The transformation of sulphate minerals during pyrolysis of an Australian lignite has been studied using pure sulphates (CaSO₄, FeSO₄ and Fe₂(SO₄)₃), a high mineral (HM) lignite sample and a low mineral (LM) lignite sample collected from different locations of the same deposit, and samples of acid-washed LM doped with sulphates (CaSO₄+ LM and FeSO₄+ LM), respectively. Thermogravimetric analysis and fixed-bed reactor techniques were used for the pyrolysis experimentation and the lignite samples and their chars were analysed using FTIR and XRD. The TGA experiments showed that CaSO₄ decomposes between 1400 and 1700 K in nitrogen and a 50/50 N₂/CO₂ mixture, while in air CaSO₄ decomposes between 1500 and 1700 K. Using a TGA-MS it was found that only a small fraction of CaSO₄ in CaSO₄+ LM decomposed at 653 K, releasing SO₂. CaSO₄ was still observed in the char recovered at 1073 K as confirmed by the FTIR and XRD analysis. FeSO₄·7H₂O released the bound water below 543 K and the remaining FeSO₄ decomposed between 813 and 953 K. FeSO₄ in FeSO₄+ LM decomposed at 500 K to release SO₂. The inherent sulphates in HM were dominated by iron sulphates which started to decompose and release SO₂ at around 500 K and all sulphate had been decomposed at 1073 K. It was observed that during the fixed-bed pyrolysis at 1073 K in nitrogen, approximately 36% of the total sulphur in the CaSO₄+ LM decomposed, 88% of the total sulphur in the FeSO₄+ LM decomposed and around 76% of the total sulphur in HM decomposed. It was also confirmed that FeSO₄+ LM produced more volatile sulphur than CaSO₄+ LM during pyrolysis.     

Radiative transfer in a solar chemical reactor for the co-production of hydrogen and carbon by thermal decomposition of methane

Radiation heat transfer in a solar chemical reactor for the co-production of hydrogen and carbon by thermal decomposition of CH₄ is analyzed by the Monte Carlo ray-tracing method. The solar chemical reactor features a vortex flow of CH₄ confined to a cavity and laden with carbon particles that serve simultaneously as radiant absorbers and nucleation sites for the heterogeneous decomposition reaction. The reactor is treated as a 3D non-isothermal non-gray absorbing-emitting-scattering gas/particle suspension directly exposed to concentrated solar irradiation. The analysis includes coupling to conduction/convection heat transfer and chemical kinetics. Calculated temperature distribution and chemical conversion are compared with the experimentally measured values obtained with a 5 kW prototype reactor tested in a solar furnace.     

Multi-period design of heat exchanger networks

Heat exchanger networks are an integral part of chemical processes as they recover available heat and reduce utility consumption, thereby improving the overall economics of an industrial plant. This paper focuses on heat exchanger network design for multi-period operation wherein the operating conditions of a process may vary with time. A typical example is the hydrotreating process in petroleum refineries where the operators increase reactor temperature to compensate for catalyst deactivation. Superstructure based multi-period models for heat exchanger network design have been proposed previously employing deterministic optimisation algorithms, e.g. (0005 and 0180). Stochastic optimisation algorithms have also been applied for the design of flexible heat exchanger networks recently (0110 and 0115). The present work develops an optimisation approach using simulated annealing for design of heat exchanger networks for multi-period operation. A comparison of the new optimisation approach with previous deterministic optimisation based design approaches is presented to illustrate the utilisation of simulated annealing in design of optimal heat exchanger network configurations for multi-period operation.     

Surface-to-bed heat transfer in fluidised beds of fine particles

This work reports experimental results on the heat transfer between a fluidised bed of fine particles and a submerged surface. Experiments have been carried out using different bed materials (polymers, ballotini, corundum, carborundum and quartz sand) with Archimedes number between 2 and 50. Dry air at ambient pressure and temperature has been used as fluidising gas. Three different exchange surfaces, namely a sphere and two cylinders with different base diameter and same height, have been used.Experimental results show that the heat transfer coefficient increases with particle Archimedes number and is almost independent from particle thermal conductivity for K_p/K_g > 30. Finally, the comparison of heat transfer coefficient for the different surfaces shows that the effect of the surface geometry may account for a 30% variation in the heat transfer coefficient, with higher differences occurring for coarser particles.     

Electrochemical performance of pyrolytic carbon-coated natural graphite spheres

Natural graphite (NG) spheres were coated by pyrolytic carbon from the thermal decomposition of C₂H₂/Ar at 950 °C in a fluidized bed reactor. Scanning electron microscopy and secondary electron focused ion beam (FIB) images clearly showed that a pyrolytic carbon layer with a thickness of ∼250 nm was uniformly deposited on the surface of the NG spheres. Electrochemical performance measurements for the original and coated NG spheres as anode materials of a lithium-ion battery indicated that the first coulombic efficiency and cyclability were significantly improved in the coated sample. The reasons for this were investigated by analyzing structural characteristics, specific surface area, pore size distribution, and solid electrolyte interphase (SEI) film. Using a FIB workstation, we demonstrated, by cross-section imaging of a coated NG sphere that had experienced five electrochemical cycles, that the SEI film formed on the non-graphitic pyrolytic carbon surface became thinner (60-150 nm) and more uniform in composition compared with that on the surface of uncoated NG spheres; and the formation of an “internal SEI film” inside the NG spheres was also remarkably suppressed due to the uniform coating of pyrolytic carbon.     

Synthesis of twisted carbon fibres comprised of four intertwined helical strands

NiSO₄/Al₂O₃ was reacted with H₂ and C₂H₂ in a fluidised-bed reactor at 650 °C to form Ni/Al₂O₃ and H₂S. The Ni catalyst became coated with a moderately graphitised (0.6 I_D/I_G ratio) carbonaceous product containing twisted carbon fibres, 200-500 nm in diameter and up to 27 μm in length. The fibres are comprised of four intertwined helical strands and are a unique carbon morphology. Their growth pattern and surface morphology is attributed to differing carbon extrusion speeds from the faces of the polycrystalline Ni catalyst particles that have been modified by H₂S.     

Heat transfer in a pulsed bubbling fluidized bed

Surface-to-bed heat transfer and pressure measurements were carried out in a 0.17 m ID pulsed bubbling fluidized bed with glass bead and silica sand particles having mean diameters ranging from 37 μm to 700 μm to investigate the effects of flow pulsation on heat transfer and bed hydrodynamics. A solenoid valve was used to supply pulsed air to the bed at 1 to 10 Hz. The bed surface was found to oscillate with the frequency of pulsation, the oscillation's amplitude decreasing with frequency. The standard deviation of the bed pressure drop in the pulsed bed was found to be larger than that in the conventional bed due to the acceleration force imposed by pulsation. For both Geldart B and A particles, high frequency pulsation (7, 10 Hz) enhances the heat transfer compared to continuous flow, the enhancement diminishing with superficial gas velocity and particle size. For Geldart B particles, the effect of pulsation on heat transfer ceases around U_o/U_mf = 3.5, whereas 24% improvement in heat transfer coefficient was obtained for 60 μm glass bead particles (Group A) at superficial gas velocities as high as U_o/U_mf = 27. Furthermore, in the fixed bed (U_o/U_mf < 1) for Geldart B particles, 1 Hz pulsation was found to be very effective resulting in two- to three-fold increase in heat transfer coefficient compared to continuous flow at the same superficial gas velocity. The flow pulsation loses its effect on heat transfer with increasing static bed height, i.e., when H_bed/D > 0.85.     

TEM and electron tomography studies of carbon nanospheres for lithium secondary batteries

The structure of carbon nanospheres of 100-200 nm diameter, which showed superior high-speed charge-discharge behavior as the negative electrode in a lithium ion battery, was investigated with XRD, SEM and TEM with an electron tomography attachment. Observation of carbon 0 0 2 lattice images, as well as electron diffraction patterns, illustrated that heterogeneous microtexture was formed as the polyhedronization of the particle proceeded with heat-treatment. The outside region of the particle heat-treated at 2800 °C has stacking structure of aromatic layers with some distribution of d₀₀₂, while the center region consisted of non-graphitic. Structure defects seemed to be concentrated along the ridgelines of the polyhedronized particles after heat-treatment. The electron tomography technique clarified the morphology of the graphitized particles, although the images should be understood with other crystallographic measurements. A slice image computed in the 3D-reconstruction process showed the inner texture of the graphitized particles more clearly than the conventional TEM bright-field image.     

Reactivity of a CaSO<Subscript>4</Subscript>-oxygen carrier in chemical-looping combustion of methane in a fixed bed reactor

Chemical-looping combustion (CLC) is a promising technology for the combustion of gas or solid fuel with efficient use of energy and inherent separation of CO₂. A reactivity study of CaSO₄ oxygen carrier in CLC of methane was conducted in a laboratory scale fixed bed reactor. The oxygen carrier particles were exposed in six cycles of alternating reduction methane and oxidation air. A majority of CH₄ reacted with CaSO₄ to form CO₂ and H₂O. The oxidation was incomplete, possibly due to the CaSO₄ product layer. The reactivity of CaSO₄ oxygen carrier increased for the initial cycles but slightly decreased after four cycles. The product gas yields of CO₂, CH₄, and CO with cycles were analyzed. Carbon deposition during the reduction period was confirmed with the combustible gas (CO+H₂) in the product gas and slight CO₂ formed during the early stage of oxidation. The mechanism of carbon deposition and effect was also discussed. SO₂ release behavior during reduction and oxidation was investigated, and the possible formation mechanism and mitigation method was discussed. The oxygen carrier conversion after the reduction decreased gradually in the cyclic test while it could not restore its oxygen capacity after the oxidation. The mass-based reaction rates during the reduction and oxidation also demonstrated the variation of reactivity of CaSO₄ oxygen carrier. XRD analysis illustrated the phase change of CaSO₄ oxygen carrier. CaS was the main reduction product, while a slight amount of CaO also formed in the cyclic test. ESEM analysis demonstrated the surface change of particles during the cyclic test. The reacted particles tested in the fixed bed reactor were not uniform in porosity. EDS analysis demonstrated the transfer of oxygen from CaSO₄ to fuel gas while leaving CaS as the dominant reduced product. The results show that CaSO₄ oxygen carrier may be an interesting candidate for oxygen carrier in CLC. This work was presented at the 7 ^th China-Korea Workshop on Clean Energy Technology held at Taiyuan, China, June 26–28, 2008.