Heterogeneous thermochemical decomposition of a semi-transparent particle under direct irradiation

Transient heat and mass transfer in a non-uniform emitting, absorbing and anisotropically scattering medium inside a semi-transparent, optically large and chemically reacting particle directly exposed to an external source of high-flux radiation is analyzed numerically. Thermal decomposition of calcium carbonate is selected as the model chemical reaction. The unsteady mass and energy equations are solved numerically using the finite volume technique and the explicit Euler time-integration scheme. Radiative transport is modeled using the Rosseland diffusion approximation and the Monte Carlo ray tracing method. Direct irradiation and internal radiative transfer in the particle are highly favorable for particle heating and the decomposition reaction, decreasing the total reaction time by a factor of 15, as compared to the case with external and internal radiation neglected in the analysis. In the latter case, the temperatures at the particle center and the particle surface increase monotonically to 1406 and 1417 K for the reacting particle, and 1428 and 1432 K for the non-reacting particle, respectively, after 179 s—the total reaction time of the reacting particle. With radiation included in the analysis, the surface temperatures of both reacting and non-reacting particle increase from the initial 300 to 1300 K in less than 2 s, and at the same rate until the onset of the endothermic chemical reaction at t=1.1 s. The surface temperature of the reacting particle increases further up to 2000 K after 12 s, when the whole particle is calcined. Weak dependence of the temperature, the overall reaction extent, and the total reaction time on the CaO grain size is observed in spite of strong dependence of the radiative properties of porous CaO on the CaO grain size.     

Transient thermal behaviour of a cylindrical wood particle during devolatilization in a bubbling fluidized bed

This work proposes a transient heat transfer model to predict the thermal behaviour of wood in a heated bed of sand fluidized with nitrogen. The 2-D model in cylindrical coordinates considers wood anisotropy, variable fuel properties, fuel particle shrinkage, and heat generation due to drying and devolatilization. The influence of initial fuel moisture content, thermal diffusivity, particle geometry, shrinkage, external heat transfer coefficient, chemical reaction kinetics and heats of reaction on temperature rise is presented. The cylindrical wood particles chosen for the study have length (l) = 20 mm, diameter (d) = 4 mm and l = 50 mm and d = 10 mm, both having an aspect ratio (l/d) of 5. The bed temperature is 1123 K. The model prediction is validated using measurements obtained from literature. The temperature rise in the wood particle is found to be sensitive to changes in the moisture content and thermal diffusivity and heat of reaction (in larger particles) while it is less sensitive to the external heat transfer coefficient and chemical kinetics. Also shrinkage is found to have a compensating effect and it does not have any significant influence on the temperature rise. Beyond an aspect ratio of three, the wood particle behaves as a 1-D cylinder.     

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.     

Controllable and SDA-free synthesis of sub-micrometer sized zeolite ZSM-5. Part 2: Influence of sodium ions and ageing of the reaction mixture on the chemical composition, crystallinity and particulate properties of the products

In this work, the influences of excess amount of sodium ions and the way/duration of ageing of the reaction mixture (hydrogel) on structural, particulate, morphological and chemical properties of the crystalline end products obtained by hydrothermal treatment (heating at 483 K for 2 h) of the TPA-free reaction mixture: 1.0Al₂O₃/100SiO₂/xNa₂O/4000H₂O/yNa₂SO₄ (0.4 ? (x + y) ? 100) seeded by silicalite-1 nanocrystals (260 nm, 4 wt.% of silica in gel mixture), was investigated by different characterization methods such as, powder X-ray diffraction (XRD), scanning-electron microscopy (SEM), particle size distribution (PSD) measuring by laser light scattering (LLS) and X-ray fluorescence (XRF). The obtained results showed that addition of sodium sulfate in low-alkaline reaction mixture enhances the aggregation of the particles of colloidal silica and formation of gel by the action of sulfate oxy-anions while in high-alkaline reaction mixtures the condensation process takes place on the surface of the crystalline end products. Excess amount of sodium ions do not increase the crystallization rate thus showing that the rate-determining factor is concentration of “free” low-molecular weight silicate species, determined by the alkalinity of system. On the other hand, addition of sodium sulfate considerably reduces the formation of crystal aggregates, by combined chemical and electrical interactions. Ageing of the reaction mixture (hydrogel) mainly influences the particle size distribution of the crystalline end products, which is explained by the change in the relative rates of crystal growth and crystal aggregation with the time of ageing. However, hydrogel ageing does not affect the size and number of crystals in the crystalline end product, showing that the growth precursor particles form during hydrothermal treatment of the reaction mixture and not during its room-temperature ageing.     

Colloidal submicron-palladium particles stabilized with acetate

Palladium spherical particles 0.23 μm in diameter were synthesized by reducing palladium acetate with hydrazine in the presence of surfactant, with an aim of exhibiting both easy separation by filtration and easy dispersion for a catalyst. The particles in the suspension were sedimented slowly but not aggregated. The suspension showed voltammetric redox waves. The anodic wave was ascribed to the oxidation of Pd to Pd²⁺, whereas the cathodic one was to the reduction of the palladium acetate moiety to Pd. The current ratio of the anodic peak to the cathodic one 4:1, was close to the ratios by the partial chemical oxidation with permanganate and by the thermogravimetry, suggesting the composition of 80% palladium metal and 20% palladium acetate in the molar ratio. Heating the palladium particles at 300 °C yielded palladium metal. The decomposition proceeded to the first-order reaction with the activation energy of 40 kJ mol⁻¹. The particle catalyzed the reduction of methylene blue with hydrazine. The reaction rate was of the first-order with respect to methylene blue. The rate constant was proportional to the geometrical surface area of the palladium particle, suggesting a surface catalysis.     

Design and simulation of a solar chemical reactor for the thermal reduction of metal oxides: Case study of zinc oxide dissociation

A laboratory-scale solar reactor was designed and simulated for the thermal reduction of metal oxides involved in water-splitting thermochemical cycles for hydrogen production. This reactor features a cavity-receiver directly heated by concentrated solar energy, in which solid particles are continuously injected. A computational model was developed by coupling the fluid flow, heat and mass transfer, and the chemical reaction. The reactive particle-laden flow was simulated, accounting for a multiphase model (solid-gas flow). A discrete phase model based on a Lagrangian approach was developed. The kinetics of the chemical reaction was considered in the specific case of zinc oxide dissociation for which reliable data are available. The complete model predicts temperature and gas velocity distributions, species concentration profiles inside the reactor, particle trajectories and fates, and conversion rate assessing the reaction degree of completion. The reaction extent is highly dependent on temperature of the radiation-absorbing particles. Initial diameter of injected particles is also a key parameter because it determines the available surface area for a given particle mass feed rate. The higher the particle surface area, the higher the conversion rate. As a result, reaction completion can be achieved when particle temperature exceeds 2200 K for a initial particle diameter.     

Kinetic study of hydrogen sulfide absorption in aqueous chlorine solution

Hydrogen sulfide (H₂S) is currently removed from gaseous effluents by chemical scrubbing using water. Chlorine is a top-grade oxidant, reacting with H₂S with a fast kinetic rate and enhancing its mass transfer rate. To design, optimize and scale-up scrubbers, knowledge of the reaction kinetics and mechanism is requested. This study investigates the H₂S oxidation rate by reactive absorption in a mechanically agitated gas–liquid reactor. Mass transfer (gas and liquid sides mass transfer coefficients) and hydrodynamic (interfacial area) performances of the gas–liquid reactor were measured using appropriated physical or chemical absorption methods. The accuracy of these parameters was checked by modeling the H₂S absorption in water without oxidant. A sensitivity analysis confirmed the robustness of the model. Finally, reactive absorption of H₂S in chlorine solution for acidic or circumneutral pH allowed to investigate the kinetics of reaction. The overall oxidation mechanism could be described assuming that H₂S is oxidized irreversibly by both hypochlorite anion ClO⁻ (k = 6.75 × 10⁶ L mol⁻¹ s⁻¹) and hypochlorous acid ClOH (k = 1.62 × 10⁵ L mol⁻¹ s⁻¹).     

A carbon in molten carbonate anode model for a direct carbon fuel cell

The electrochemical oxidation of carbon at the anode of a direct carbon fuel cell (DCFC) includes charge transfer steps and chemical steps. A microstructural model of carbon particle is built, in which perfect graphene stacks are taken as the basic building blocks of carbon. A modified mechanism taking account of the irreversibility of the process and supposing that the electrochemical oxidation of carbon takes place only at the edges of the graphene sheets is proposed. A Tafel type overall rate equation is deduced along with expressions of exchange current density (j₀) and activation polarization (η_act). The performance of carbon black and graphite as the fuel of DCFC is examined. It has been found that j₀ is in the range of 0.10-6.12 mA cm⁻² at 923-1123 K and η_act is in the range of 0.024-0.28 V at 923-1123 K with current density in 10-120 mA cm⁻². Analysis of the j₀, η_act values and the product composition reveals that the charge transfer steps as well as the oxygen ion absorption steps are both important for the reaction rate. The activity of the carbon material with respect to atom location is introduced to the open circuit potential difference (OCP) calculation with Nernst equation.     

H2 production by steam-quenching of Zn vapor in a hot-wall aerosol flow reactor

Hydrogen production by steam-hydrolysis of zinc is investigated as part of a two-step water-splitting thermochemical cycle based on ZnO/Zn redox reactions. The hydrolysis reactor consists of a hot-wall tube containing a flow of Zn(g) that is steam-quenched to co-produce H₂ and Zn/ZnO nanoparticles. The effects of the quenching gas flow rate and reactor wall temperature on the Zn-to-ZnO chemical conversion and particle yield are examined. Solid products are characterized by X-ray diffraction, N₂ adsorption, and SEM microscopy. Quench rates of 2-6×10⁴ K/s yielded conversions of up to 95% at the expense of low particle yield due to significant wall deposition with subsequent hydrolysis. Aerosol particles with hexagonal structure were formed by Zn evaporation-condensation containing low ZnO mass fraction. In contrast, operation at quench rates up to 10⁶ K/s led to increased particle yield but lower conversion. Filamentary and rod-like particles were formed with high ZnO content by surface reaction and coagulation.     

Kinetics of heterogeneous reactions of carbon and oxygen during combustion of porous carbon particles in oxygen

A model of combustion of a high-porosity carbon particle in oxygen is considered, which takes into account heterogeneous and homogeneous chemical reactions inside the particles and radiative heat transfer. The boundaries of the domain where the burning rate depends on the particle temperature are determined. The possibility of two combustion regimes is demonstrated: regime with a high burning rate, where the carbon-oxygen reaction proceeds in a layer adjacent to the particle surface, and regime with a low burning rate, where the reaction proceeds in the entire particle volume. In the regime with a high burning rate, the main product of the reaction between carbon and oxygen is carbon monoxide, whereas both carbon monoxide and carbon dioxide can be formed in the regime with a low burning rate. The kinetic equations of heterogeneous reactions C + O₂ = CO₂ and 2C + O₂ = 2CO are determined, which reveal the retarding effect of carbon monoxide and dioxide on the rates of these reactions. __________ Translated from Fizika Goreniya i Vzryva, Vol. 42, No. 3, pp. 11–22, May–June, 2006.     

Effect of crosslinking on the mobility of PDMS filled with polysilicate nanoparticles: Positron lifetime, rheology and NMR relaxation studies

We study the effect of adding trimethylsilyl-treated polysilicate nanoparticles (Rg ∼ 2.2 nm) to crosslinked poly(dimethylsiloxane) (PDMS) elastomers above the entanglement molecular weight. The results are compared to un-crosslinked PDMS of a similar molecular weight, reported in previous studies and filled with the same polysilicate nanoparticles.Three techniques are used and compared to assess the enhancement or reduction in mobility with addition of filler: positron annihilation lifetime spectroscopy (PALS), rheology and nuclear magnetic resonance (NMR) spin-spin relaxation (T₂) measurements. PALS measurements do not show any clear effect of the filler on the mobility of the chains, as assessed by the size of free volume holes, but reveal a net increase in free volume with temperature increase (from 30 °C to 60 °C). A reduction in the dynamic shear storage modulus (measured at 1 rad s⁻¹) is observed in the filled network relative to the unfilled polymer (from 63 kPa without filler to 44 kPa with 40 w/w% filler), attributed primarily to a partial inhibition of the chemical crosslinking reaction by the particles. The NMR relaxation measurements, instead, show a reinforcement of the polymer network with increasing addition of polysilicate particles, as revealed by the faster T₂ decays at higher filler loadings, caused by increasing polymer bridging and particle flocculation. Similar trends are observed at higher temperatures (up to 80 °C), with a higher overall mobility. The apparent disagreement between rheology and NMR stems from the fact that rheology reflects bulk mobility and is primarily sensitive to chemical crosslinks in the network, while NMR probes segmental dynamics, which are affected by the presence of particles.In un-crosslinked PDMS instead, both rheology and NMR show an initial increase in mobility at low filler content, followed by reinforcement with further particle addition. These results strongly suggest that entanglements and filler-induced packing disruption, rather than free volume, play a major role in polymer dynamics.     

Supercritical antisolvent precipitation from an emulsion: β-Carotene nanoparticle formation

Supercritical antisolvent precipitation of β-carotene from an oil-in-water emulsion in which the solute is dissolved in the droplets that confirm the dispersed phase has been studied, with the objective of producing particles with a mean particle size in the nanometer scale. The aim of the current research work was to confirm the possibility to control the particle size of the carotene + surfactant suspensions obtained with this process, with the initial drop size present in the emulsions. The final products were formed by particles with a mean size below 400 nm in suspension in an aqueous media, which was also the mean droplet size of the emulsion. This result suggests that produced particles are encapsulated in surfactant micelles. The final suspension was then lyophilized and observed by means of a scanning electron microscopy. In order to obtain a better comprehension of the process, a mass transfer model was developed. This model is based on previous observations of the evolution of the organic phase drop and the solute, obtained with a view cell.     

Biomass pyrolysis experiments in an analytical entrained flow reactor between 1073 K and 1273 K

Experiments are performed in an entrained flow reactor to better understand the kinetic processes involved in biomass pyrolysis under high temperatures (1073-1273 K) and fast heating condition (>500 K s⁻¹). The influence of the particle size (0.4 and 1.1 mm), of the temperature (1073-1273 K), of the presence of steam in the gas atmosphere (0 and 20 vol%) and of the residence time (between 0.7 and 3.5 s for gas) on conversion and selectivity is studied. Under these conditions, the particle size is the most crucial parameter that influences decomposition. For 1.1 mm particles, pyrolysis requires more than 0.5 s and heat transfer processes are limiting. For 0.4 mm particles, pyrolysis seems to be finished before 0.5 s. More than 70 wt% of gas is produced. Forty percent of the initial carbon is found in CO; less than 5% is found in CO₂. The hydrogen content is almost equally distributed among H₂, H₂O and light hydrocarbons (CH₄, C₂H₂, C₂H₄). Under these conditions, the evolution of the produced gas mixture is not very significant during the first few seconds, even if there seems to be some reactions between H₂, the C₂ and tars.     

RADIATIVE TRANSFER IN A SOLAR ABSORBING PARTICLE LADEN FLOW†

Solar central receivers which utilize solid thermal carriers such as sand or small refractory particles for direct absorption of concentrated solar radiation have been investigated at several laboratories. In the central receiver concept a field of tracking mirrors (heliostats) is used to focus solar energy onto a receiver mounted atop a tower. A possible receiver configuration is a cavity in which a falling sheet of solid particles is directly irradiated by the concentrated solar flux passing through the aperture. Regardless of the particular geometry, the radiative transfer within the falling particle curtain must be studied in order to determine the net radiative heating rate for the particles

A discrete ordinate radiative transfer model has been applied to study the radiative coupling within the falling particle curtain. The model determines how much energy is absorbed by the particles, how much is transmitted to the rear wall of the receiver, and determines the effects of particle scattering and thermal emission on the net radiation absorbed by the particles. The model accounts for the directional nature of the radiation field, particle scattering, and the wavelength dependence of the optical properties

The discrete ordinate model has been used to assess the influence of the pertinent radiation transfer parameters in determining the local and overall particle heating rates. The results of this study are discussed as well as the analysis.     

Computational modelling of the impact of particle size to the heat transfer coefficient between biomass particles and a fluidised bed

The fluid-particle interaction and the impact of different heat transfer conditions on pyrolysis of biomass inside a 150 g/h fluidised bed reactor are modelled. Two different size biomass particles (350 μm and 550 μm in diameter) are injected into the fluidised bed. The different biomass particle sizes result in different heat transfer conditions. This is due to the fact that the 350 μm diameter particle is smaller than the sand particles of the reactor (440 μm), while the 550 μm one is larger. The bed-to-particle heat transfer for both cases is calculated according to the literature. Conductive heat transfer is assumed for the larger biomass particle (550 μm) inside the bed, while biomass-sand contacts for the smaller biomass particle (350 μm) were considered unimportant. The Eulerian approach is used to model the bubbling behaviour of the sand, which is treated as a continuum. Biomass reaction kinetics is modelled according to the literature using a two-stage, semi-global model which takes into account secondary reactions. The particle motion inside the reactor is computed using drag laws, dependent on the local volume fraction of each phase. FLUENT 6.2 has been used as the modelling framework of the simulations with the whole pyrolysis model incorporated in the form of User Defined Function (UDF).     

Inter-particle heat transfer in a riser of gas-solid turbulent flows

Effects of the particle-particle heat transfer in a gas-solid turbulent flow in a riser were evaluated. An Eulerian/Lagrangian four-way interaction formulation including the particle collisions in conjunction with the k − τ and the k_θ − τ_θ model equations were used in the numerical simulation. Inter-particles and particle-wall interactions were accounted for with an inelastic collision model, where the restitution coefficient was evaluated for each collision. The special case when the flow initially contains two groups of hot and cold particles was treated in details. Particular attention was given to the nature of heat transfer to particles due to inter-particle interactions. The results showed that the effect of particle-particle heat transfer was more significant for smaller sizes, lower flow Reynolds numbers, and for higher loading ratios. Solid thermal properties, however, did not have a noticeable effect on the inter-particle heat transfer. The simulation results indicates that although the heat transferred to each group of hot and cold particles was significant, the mean values of gas and particle temperatures and suspension heat transfer was insensitive to the inter-particle heat transfer.     

Coal devolatilization and char conversion under suspension fired conditions in O2/N2 and O2/CO2 atmospheres

The aim of the present investigation is to examine differences between O₂/N₂ and O₂/CO₂ atmospheres during devolatilization and char conversion of a bituminous coal at conditions covering temperatures between 1173 K and 1673 K and inlet oxygen concentrations between 5 and 28 vol.%. The experiments have been carried out in an electrically heated entrained flow reactor that is designed to simulate the conditions in a suspension fired boiler. Coal devolatilized in N₂ and CO₂ atmospheres provided similar results regarding char morphology, char N₂-BET surface area and volatile yield. This strongly indicates that a shift from air to oxy-fuel combustion does not influence the devolatilization process significantly. Char combustion experiments yielded similar char conversion profiles when N₂ was replaced with CO₂ under conditions where combustion was primarily controlled by chemical kinetics. When char was burned at 1573 K and 1673 K a faster conversion was found in N₂ suggesting that the lower molecular diffusion coefficient of O₂ in CO₂ lowers the char conversion rate when external mass transfer influences combustion. The reaction of char with CO₂ was not observed to have an influence on char conversion rates at the applied experimental conditions.     

De- and rehydration of Ca(OH)2 in a reactor with direct heat transfer for thermo-chemical heat storage. Part A: Experimental results

Heat storage technologies are used to improve energy efficiency of power plants and recovery of process heat. Storing thermal energy by reversible thermo-chemical reactions offers a promising option for high storage capacities especially at high temperatures. Due to its low material cost the use of the reversible reaction Ca(OH)₂ ? CaO + H₂O has been suggested. This paper reports on the thermal behavior of a reactor with direct heat transfer between the gaseous reactant and the solid material. Cycling stability is confirmed and the impact of the most significant parameters such as the maximum possible enthalpy difference of the heat transfer fluid between inlet and outlet, the heat transfer, the particle reaction rate and the mass transport is derived. In the test system the particle reaction rate could be identified as the main limiting parameter.     

A 1-D non-isothermal dynamic model for the thermal decomposition of a gibbsite particle

A 1-D mathematical model describing the thermal decomposition, or calcination, of a single gibbsite particle to alumina has been developed and validated against literature data. A dynamic, spatially distributed, mass and energy balance model enables the prediction of the evolution of chemical composition and temperature as a function of radial position inside a particle. In the thermal decomposition of gibbsite, water vapour is formed and the internal water vapour pressure plays a significant role in determining the rate of gibbsite dehydration. A thermal decomposition rate equation, developed by closely matching experimental data reported previously in the literature, assumes a reaction order of 1 with respect to gibbsite concentration, and an order of −1 with respect to water vapour pressure. Estimated values of the transformation kinetic parameters were k₀ = 2.5 × 10¹³ mol/(m³ s) for the pre-exponential factor, and E_a = 131 kJ/mol for the activation energy. Using these kinetic parameters, the gibbsite particle model is solved numerically to predict the evolution of the internal water vapour pressure, temperature and gibbsite concentration. The model prediction was shown to be very sensitive to the values of heat transfer coefficient, effective diffusivity, particle size and external pressure, but relatively less sensitive to the mass transfer coefficient and particle thermal conductivity. The predicted profile of the water vapour pressure inside the particle helps explain some phenomena observed in practice, including particle breakage and formation of a boehmite phase.