Study of an Energy Storage and Recovery Concept Based on the W/WO3 Redox Reaction: Part I. Kinetic Study and Modeling of the WO3 Reduction Process for Energy Storage

Energy storage and recovery using the redox reaction of tungsten/tungsten-oxide is proposed. The system will store energy as tungsten metal by reducing the tungsten oxide with hydrogen. Thereafter, steam will be used to reoxidize the metal and recover the hydrogen. The volumetric energy density of W for storing hydrogen by this process is 21 kWh/L based on the lower heating value (LHV) of hydrogen. The main objective of this investigation was to study the kinetics of the reduction process of tungsten oxide (WO₃) and determine the optimum parameters for rapid and complete reduction. Theoretical treatment of isothermal kinetics has been extended in the current work to the reduction of tungsten oxide in powder beds. Experiments were carried out using a thermogravimetric technique under isothermal conditions at different temperatures. The reaction at 1073 K (800 °C) was found to take place in the following sequence: WO₃ → WO_2.9 → WO_2.72 → WO₂ → W. Expressions for the last three reaction rate constants and activation energies have been calculated based on the fact that the intermediate reactions proceed as a front moving at a certain velocity while the first reaction occurs in the entire bulk of the oxide. The gas–solid reaction kinetics were modeled mathematically in terms of the process parameters. This model of the reduction has been found to be accurate for bed heights above 1.5 mm and hydrogen partial pressures greater than 3 pct, which is ideal for implementing the energy storage concept.     

Kinetics of the reaction between hydrogen sulfide and lime particles

The reaction between hydrogen sulfide and lime is important, among others, as a component reaction of the hydrogen reduction of metal sulfides in the presence of lime, and in the desulfurization of fossil fuels. The results of experiments on the kinetics of this reaction are presented in this paper. The experiments were carried out in the temperature range 873 to 1073 K, using a thermogravimetric analysis technique. A “pore blocking” model was found to fit the reaction rate, which was initially rapid and leveled off at less than the complete conversion. An activation energy of 76.1 kJ/mol (18.2 kcal/g-mole) was obtained. The reaction was first order with respect to hydrogen sulfide concentration in a gaseous mixture with hydrogen. A higher initial moisture content in the calcium oxide particles resulted in a considerably higher reaction rate. Formerly Graduate Student in the Department of Metallurgy and Metallurgical Engineering, University of Utah     

Hydrogen reduction of a Cu2O-WO3 mixture

In the present work, the reduction kinetics of Cu₂O-WO₃ mixtures by hydrogen gas was studied by thermogravimetric analyses (TGA). The reduction experiments were carried out both isothermally and nonisothermally on shallow powder beds in the temperature interval 673 to 1073 K. During the experiments, the reductant gas flow rate was kept just above the starvation rate for the reaction to ensure that chemical reaction was the rate-controlling step. The composition and microstructures of the reaction products were analyzed after each experiment by X-ray diffraction (XRD) as well as by microprobe analyses. In the temperature interval 673 to 923 K, copper oxide was found to be preferentially reduced in the early stages of the experiment followed by the reduction of tungsten oxide. The reaction mechanism was found to be affected by a reaction/transformation in the starting copper-tungsten oxide mixtures in the temperature interval 923 to 973 K. At temperatures higher than 973 K, the reduction of the complex oxide formed was found to have a strong impact on the reaction kinetics. The activation energy was evaluated, from the isothermal as well as nonisothermal reduction experiments, for the two stages of reduction identified. The XRD and scanning electron microscopy (SEM) studies indicated the formation of a metastable solution of copper in tungsten at about 923 K. The advantage of the hydrogen reduction route toward the bulk production of alloy powders in the nanosize is demonstrated.     

Direct Copper Precipitation from a Loaded Chelating Extractant by Pressure Hydrogen Stripping

The kinetics of direct copper precipitation from a loaded chelating extractant (Kelex 100) using hydrogen in an autoclave (pressure hydrogen stripping) was studied. Copper, in powder form, was found to precipitate rapidly from loaded Kelex 100/decanol/kerosene solvents by reaction with hydrogen at pressures between 520 and 4000 kPa and temperatures from 443 to 488 K. The overall process has heterogeneous nucleation characteristics. Nuclei are provided through slow thermal dissociation of the copper chelate. The freshly produced metallic copper, acting autocatalytically, accelerates the precipitation kinetics. In addition to temperature and pressure, the effects of seeding, agitation, copper concentration, ligand concentration, and copper chelate age were investigated. Some physical and chemical properties of the powder product were also determined.     

Kinetic studies of reduction of CoO and CoWO4 by hydrogen

The present work deals with the studies of the kinetics of reduction of CoO and CoWO₄ in flowing hydrogen gas by thermogravimetric method. The reduction studies for CoO were carried out in the temperature range of 637 to 837 K, while for CoWO₄ reduction, the temperature range was 837 to 1173 K. In the case of the reduction of CoWO₄, the reaction products after reduction were analyzed by X-ray diffraction as well as scanning electron microscopy. The activation energy for the reduction of CoO was found to be of 54.3 kJ/mol. Cobalt tungstate was reduced to a mixture of Co₇W₆ and W, and the activation energy for the reaction is 90.0 kJ/mol. The results are discussed in the light of the reduction kinetics of other transition metal oxides and tungstates under similar conditions.     

Reduction-Carburization of NiO-WO<Subscript>3</Subscript> Under Isothermal Conditions Using H<Subscript>2</Subscript>-CH<Subscript>4</Subscript> Gas Mixture

Ni-W-C ternary carbides were synthesized by simultaneous reduction–carburization of NiO-WO₃ oxide precursors using H₂-CH₄ gas mixtures in the temperature range of 973 to 1273 K. The kinetics of the gas–solid reaction were followed closely by monitoring the mass changes using the thermogravimetric method (TGA). As a thin bed of the precursors were used, each particle was in direct contact with the gas mixture. The results showed that the hydrogen reduction of the oxide mixture was complete before the carburization took place. The nascent particles of the metals formed by reduction could react with the gas mixture with well-defined carbon potential to form a uniform product of Ni-W-C. Consequently, the reaction rate could be conceived as being controlled by the chemical reaction. From the reaction rate, Arrhenius activation energies for reduction and carburization were evaluated. Characterization of the carbides produced was carried out using X-ray diffraction and a scanning electron microscope (SEM) combined with electron dispersion spectroscopy (SEM-EDS) analyses. The grain sizes also were determined. The process parameters, such as the temperature of the reduction–carburization reaction and the composition of the gas mixture, had a strong impact on the carbide composition as well as on the grain size. The results are discussed in light of the reduction kinetics of the oxides and the thermodynamic constraints.     

Hydrogen Reduction Kinetics of Magnetite Concentrate Particles Relevant to a Novel Flash Ironmaking Process

A novel ironmaking technology is under development at the University of Utah. The purpose of this research was to determine comprehensive kinetics of the flash reduction reaction of magnetite concentrate particles by hydrogen. Experiments were carried out in the temperature range of 1423 K to 1673 K (1150 °C to 1400 °C) with the other experimental variables being hydrogen partial pressure and particle size. The nucleation and growth kinetics expression was found to describe the reduction rate of fine concentrate particles and the reduction kinetics had a 1/2-order dependence on hydrogen partial pressure and an activation energy of 463 kJ/mol. Unexpectedly, large concentrate particles reacted faster at 1423 K and 1473 K (1150 °C and 1200 °C), but the effect of particle size was negligible when the reduction temperature was above 1573 K (1300 °C). A complete reaction rate expression incorporating all these factors was formulated.     

A novel cyclic process using CaSO4/CaS pellets for converting sulfur dioxide to elemental sulfur without generating secondary pollutants: Part II. Hydrogen reduction of calcium-sulfate pellets to calcium sulfide

The reduction of calcium sulfate to produce calcium sulfide is a part of the cyclic process for converting sulfur dioxide to elemental sulfur that is described in Part I. The kinetics of the hydrogen reduction of nickel-catalyzed calcium-sulfate pellets were investigated using a thermogravimetric analysis (TGA) technique at reaction temperatures between 1023 and 1088 K and hydrogen partial pressures between 12.9 and 86.1 kPa. The reactivity of nickel-catalyzed calcium-sulfate pellets was demonstrated by the conversion of 70 pct fresh nickel-catalyzed calcium sulfate to calcium sulfide in 20 minutes at 1073 K under a hydrogen partial pressure of 86.1 kPa. Furthermore, the reactivity remained relatively intact after ten cycles of reactions and regenerations. This observed characteristic of the pellets is important because the solids must be reusable for repeated cycles to avoid generating secondary pollutants. The nucleation and growth rate expression was found to be useful in describing the kinetics of the reaction, which had an activation energy of about 167 kJ/mol (∼40 kcal/mol) in all reaction cycles except for the first regenerated samples that were lower at 146 kJ/mol (35 kcal/mol). The reaction order with respect to hydrogen partial pressure was 0.22 in all cycles with the exception of the first regenerated sample for which it was 0.37.     

Concentration dependence of hydrogen diffusivity in amorphous Fe40Ni38Mo4B18 alloy

Hydrogen permeation in amorphous Fe₄₀Ni₃₈Mo₄B₁₈ alloy was studied using an electrochemical technique in the temperature range 303–348 K. Hydrogen diffusivities were calculated by several methods. They increased as the charging current density increased. The surface, concentration, and trapping effects on hydrogen diffusion were carefully examined. It was suggested that the surface impedance was not existent and diffusivity was affected by the “intrinsic” concentration and trapping effects. When diffusivities were correlated with hydrogen concentration, the effective activation energy decreased from 36.8 to 34.8 kJ/mol as the surface hydrogen concentration increased from 1000 to 6000 mol H/m³. Under the same charging current density, hydrogen concentration in the alloy decreased as temperature increased. Therefore, lower effective activation energies would be obtained if diffusivities were correlated with the charging current density. The concentration dependence of hydrogen diffusivity was rationalized on the basis of the structural features of amorphous alloys.     

Hydriding/dehydriding behaviors of La2Mg17-10 wt.%Ni composite prepared by mechanical milling

The structure and hydriding/dehydriding behaviors of La2Mg17-10 wt.%Ni composite prepared by mechanical milling were investigated. Compared with the un-milled sample, the as-milled alloys were ready to be activated and the kinetics of hydrogen absorption was relatively fast even at environmental temperature. The composite milled for 10 h absorbed 3.16 wt.% hydrogen within 100 s at 290 K. The kinetic mechanisms of hydriding/dehydriding reactions were analyzed by using a new model. The results showed that hydrogenation processes for all composites were controlled by hydrogen diffusion and the minimum activation energy was 15.3 kJ/mol H2 for the composite milled for 10 h. Mechanical milling changed the dehydriding reaction rate-controlling step from surface penetration to diffusion and reduced the activation energy from 204.6 to 87.4 kJ/mol H2. The optimum milled duration was 5 h for desorption in our trials.     

Influence of lanthanon hydride catalysts on hydrogen storage properties of sodium alanates

NaAlH4 complex hydrides doped with lanthanon hydrides were prepared by hydrogenation of the ball-milled NaH/Al+ xmol.% RE-H composites (RE=La,Ce;x=2,4,6) using NaH and Al powder as raw materials. The influence of lanthanon hydride catalysts on the hydriding and dehydriding behaviors of the as-synthesized composites were investigated. It was found that the composite doped with 2 mol.% LaH3.01 displayed the highest hydrogen absorption capacity of 4.78 wt.% and desorption capacity of 4.66 wt.%, respectively. Moreover, the composite doped with 6 mol% CeH 2.51 showed the best hydriding/dehydriding reaction kinetics. The proposed catalytic mechanism for reversible hydrogen storage properties of the composite was attributed to the presence of active LaH3.01 and CeH2.51 particles, which were scattering on the surface of NaH and Al particles, acting as the catalytic active sites for hydrogen diffusion and playing an important catalytic role in the improved hydriding/dehydriding reaction.     

Kinetic studies of the oxidation of γ-aluminum oxynitride

The present article deals with the investigations of the oxidation kinetics of γ-aluminum oxynitride (AlON) in the temperature range of 1173 to 1773K by thermogravimetry. Oxidation experiments with AlON powder and plates have been carried out in air, both in isothermal as well as nonisothermal modes. Oxidation of AlON resulted in the formation of Al₂O₃. The results showed that the rate of oxidation was negligible below 1273 K and, at higher temperatures, showed an increase with increasing temperature. Both isothermal studies as well as experiments with ramped temperature clearly indicated that the mechanism of the reaction changes around 1600 K. In the nonisothermal mode, the oxidation curve showed a plateau region in this temperature range. The difference between the two reaction steps was explained on the basis of the formation of a metastable alumina phase in the lower temperature region and stable corundum phase at higher temperatures. The buildup of the product layer would lead to a diffusion-controlled reaction kinetics. In the nonisothermal experiments, the phase transformations in alumina product layer at higher temperatures would lead to crack formation, thereby leading to even direct chemical reaction. From the experiments for the isothermal oxidation of AlON powder, the overall activation energy for the reaction rate with chemical control was determined to be 218 kJ/mole in the temperature range of 1273 to 1573 K and 78 kJ/mole in the range of 1573 to 1773 K. The overall activation energy for the diffusion step was found from the isothermal oxidation of AlON plates to be 227 kJ/mole.     

High temperature chlorination kinetics of a niobium pyrochlore

The chlorination kinetics of a niobium (Cb) pyrochlore has been studied between 1873 and 2223 K, the chlorine concentration in helium varying between 0 and 20 pct. The pyrochlore was subjected to a preliminary thermal treatment at 1473 K in order to remove fluorine which escaped under the form of niobium oxyfluorides. This left NaNbO₃, CaNb₂O₆ and residual refractory oxides. The large chlorination reaction rate difference between NaNbO₃ and CaNb₂O₆ made possible the definition of distinct chlorination reaction rates for these constituents. It was found that the decomposition of CaNb₂O₆ is the controlling step in the chlorination of this constituent, while Nb₂O₅ (NbO₂ + NbO₂ at the prevailing temperatures) chlorination is very fast. The reaction is second order with respect to CaNb₂O₆ concentration and first order with respect to chlorine partial pressure between 1873 and 2023 K, a distinct reaction rate equation being obtained at 2223 K. Reaction rate constants have been calculated and vary between 3 and 10 moleJ.kg ·min for the temperature range considered. The NaNbO₃ reaction rate is first order with respect to total Nb₂O₅ concentration and 2.5 order with respect to chlorine partial pressure for the temperature range covered (1973 to 2223 K). Reaction rate constants are much higher than in the former case, being respectively 148 (1873 K), 214 (2023 K) and 518 (2223 K) mole/kg-min. Reaction orders may be affected by an error varying between 16 and 40 pct. The reaction rate constants are found accurate within 40 pct for CaNb₂O₆ and 25 pct for NaNbO₃.     

Hydrogen Storage Properties of Graphite-Modified Mg-Ni-Ce Composites Prepared by Mechanical Milling Followed by Microwave Sintering

The Mg₁₇Ni_1.5Ce_0.5 hydrogen storage composites with different contents of graphite were prepared by a new method of mechanical milling and subsequent microwave sintering. The small particle size (~25 ??m) and the low echo ratio of power indicate that graphite plays an important role not only as a lubricant during mechanical milling but also as a supplementary heating material during microwave sintering. As a catalyst in the hydriding/dehydriding (H/D) reaction, graphite also improved the hydrogen storage properties of the composites. The hydrogen absorption and desorption capacities of Mg₁₇Ni_1.5Ce_0.5 with 5 wt pct graphite were 5.34 and 5.30 wt pct H₂ at 573 K (300 °C), its onset temperature of dehydriding reaction was 511 K (238 °C), and its activation energies of H/D reaction were 40.9 and 54.5 kJ/mol H₂, respectively. The kinetic mechanisms of the H/D reaction are also discussed.     

Preparation of Cu-Ni alloys through a new chemical route

A copper-nickel alloy has been prepared from an aqueous solution of the nitrates of copper and nickel, through co-formation of their ultrafine mixed oxides, by heating around 650 K followed by reduction with hydrogen at a very low temperature (below 623 K). The effect of temperature (473 to 623 K) on the kinetics of the hydrogen reduction of the co-formed oxides of Ni and Cu has been studied. The activation energy of the reduction reaction has been calculated and found to be 35.8 kJ/mole. A mechanism for the kinetics of the process has been suggested. It has been possible to get high-purity Cu-Ni alloy powder (50 at. pct each) free of any detectable oxygen, from their co-formed oxides, by hydrogen reduction at 623 K in less than 20 minutes. Although the X-ray analysis of the co-formed oxides has shown separate peaks for CuO and NiO, the alloy powder has exhibited a single peak with a d spacing lying in between those of Cu and Ni. It is suggested that the alloying of the two metals has taken place during the H₂ reduction of nanosized oxide particles of copper and nickel, prepared by the aforementioned chemical route. The alloy powder has been sintered at 1273 K. The density and hardness of the consolidated alloy have been measured and found to be close to the theoretical values. The alloy has also been subjected to cold reduction and annealing, in addition to metallograph examination and characterization by a scanning electron microscope (SEM), to confirm the homogeneity of the alloy.     

A Kinetic study of leaching of coal pyrite with nitric acid

The leaching of coal pyrite with nitric acid has been investigated. The temperature ranged from 313 to 363 K, and the concentration of nitric acid was varied from 0.154 to 1.54 mol/l. A coal sample of 50 grams was leached in a reactor containing 500 ml of solution in an open system. It was observed that the leaching reaction could remove 47 pct of the pyrite sulfur in seven minutes and 88 pct in 30 minutes at 343 K with 1.54 mol/l of nitric acid. The reaction order with respect to hydrogen and nitrate ion activity was found to be first order. The activation energy for the initial stage of the reaction was determined to be 14.7 K cal/mol (61.5 kJ/mol). A mathematical model was developed on the basis of mixed kinetics (reaction zone model) to explain the leaching rates. Good agreement between experimental rate data and predicted rate curves by the developed model was obtained. Ultimate analysis was used to determine the extent of nitration of the leached coal. This nitration was found to be insensitive to the reaction temperature and acidity of the solution.     

Phase evolution,hydrogen storage thermodynamics and kinetics of ternary Mg_(90)Ce_5Sm_5 alloy

Greatly stable thermodynamics and sluggish kinetics impede the practical application of Mg-based hydrogen storage alloys.The modifications of composition and structure are important strategies in turning these hydrogen storage properties.In this study,Mg-based Mg_(90)Ce_5 Sm_5 ternary alloy fabricated by vacuum induction melting was investigated to explore the performance and the reaction mechanism as hydrogen storage material by X-ray diffraction(XRD),scanning electron microscope(SEM),transmission electron microscopy(TEM) and pressure-composition isotherms(PCI) measurements.The results indicate that the Mg-based Mg_(90)Ce_5 Sm_5 ternary alloy consists of two solid solution phases,including the major phases(Ce,Sm)5 Mg_(41) and the minor phases(Ce,Sm)Mg_(12).After hydrogen absorption,these phases transform into the MgH2 and(Ce,Sm)H_(2.73) phase,while after hydrogen desorption,the MgH2 transforms into the Mg phase,but the(Ce,Sm)H2.73 phases are not changed.The alloy has a reversible hydrogen capacity of about 5.5 wt% H_2 and exhibits well isothermal hydrogen absorption kinetics.Activation energy of 106 kJ/mol was obtained from the hydrogen desorption data between 573 and 633 K,which also exhibits the enhanced kinetics compared with the pure MgH2 sample,as a result of bimetallic synergy catalysis function of(Ce,Sm)H_(2.73) phases.The rate of hydrogen desorption is controlled by the release and recombination of H_2 from the Mg surface.Furthermore,the changes of enthalpy and entropy of hydrogen absorption/desorption were calculated to be-80.0 kJ/mol H_2,-137.5 J/K/mol H_2 and 81.2 kJ/mol H_2,139.2 J/K/mol H_2,respectively.     

Chlorination kinetics of a niobium pyrochlore in the Gas-Solid phase

The chlorination kinetics of a niobium (columbium) pyrochlore has been studied in the gas-solid phase, for temperatures between 1373 and 1573 K, using a high temperature differential tungsten reactor. Chlorine-helium mixtures were used which contained between 0 and 60 pet helium. It is shown that the kinetic study reduces to one of CaNb₂O₆ chlorination. In order to obtain information on the true reaction mechanisms involved and avoid side effects like difficulty of access of the reactant gas throughout the sample mass subjected to reaction, the reaction rate has been determined from decreasing amounts of initial solid sample. The reaction rate obtained by extrapolation to nil sample values was considered to be the true reaction rate that would be observed if a single particle were subjected to chlorination with the prevailing conditions. Using a reactant gas flow rate which provided a purely chemical reaction process (no film diffusion effects), it has been found that the reaction is of the continuous-reaction type model, while the reaction rate is nearly first order with respect to the chlorine concentration at the solid-gas interface. The rate constants are 0.21 (at 1373 K), 0.46 (at 1473 K) and 0.92 (at 1573 K) min⁻¹.atm⁻¹. The energy of activation was found equal to 129 KJ/mol. The theoretical maximum error, calculated from a knowledge of the error made on temperature, time, sample weight and Nb₂O₅ analysis, does affect the reaction order by ± 20 pct, the reaction rate by ± 20 pct and the energy of activation by ± 25 pct.     

The effect of cyanide and lead ions on the cementation rate,stoichiometry and morphology of silver in cementation from cyanide solutions with zinc powder

The cementation of silver on zinc powder from solutions with a wide concentration range of cyanide has been investigated in the absence and presence of lead ions through stirred reactor batch tests and scanning electron microscopy studies on the cementation product. The concentration of cyanide ions affected the morphology of the product, the nature of cementation reaction and the cementation kinetics. Three cyanide-dependent concentration regimes have been identified: a low cyanide concentration regime in which silver cementation followed an ion-exchange type reaction taking place at the zinc/aqueous solution interface, and the silver deposited around the zinc particle in a uniform growth; a high cyanide concentration regime, as in plant practices, in which the cementation of silver followed an overall chemical reaction involving the evolution of hydrogen and a one-to-one molar silver-to-zinc stoichiometry (In this regime, both the anodic oxidation and the cathodic reduction reactions occurred at distinct interfaces and the silver deposited in a dense-branching morphology.), and an intermediate cyanide concentration regime which is a transition between the two previous regimes. In the low and intermediate regimes, lead and cyanide ions did not affect the morphology of the cemented silver, but increased the silver cementation kinetics owing to Zn(OH)₂ instability. Within the high cyanide concentration regime, lead ions did not appreciably change the cementation kinetics. They modified the pattern of the silver deposit from a dense-branching to a dendritic morphology.     

Re-oxidation Kinetics of Flash-Reduced Iron Particles in H2-H2O(g) Atmosphere Relevant to a Novel Flash Ironmaking Process

A novel flash ironmaking process based on hydrogen-containing reduction gases is under development at the University of Utah. The goal of this work was to study the possibility of the re-oxidation of iron particles in a H₂-H₂O gas mixture in the lower part of the flash reactor from the kinetic point of view. The last stage of hydrogen reduction of iron oxide, i.e., the reduction of wustite, is limited by equilibrium. As the reaction mixture cools down, the re-oxidation of iron could take place because of the decreasing equilibrium constant and the high reactivity of the freshly reduced fine iron particles. The effects of temperature and H₂O partial pressure on the re-oxidation rate were examined in the temperature range of 823 K to 973 K (550 °C to 700 °C) and H₂O contents of 40 to 100 pct. The nucleation and growth kinetics model was shown to best describe the re-oxidation kinetics. The partial pressure dependence with respect to water vapor was determined to be of first order, and the activation energy of re-oxidation reaction was 146 kJ/mol. A complete rate equation that adequately represents the experimental data was developed.