粗硼砂的氯化铵溶液浸提动力学

研究了反应温度、溶液浓度、固液比、固体粒径大小和搅拌速度对氯化铵溶液浸提粗硼砂(十水四硼酸钠,Na₂B₄O₇·10H₂O)动力学的影响。结果表明反应速率随反应温度、溶液浓度的增加和固体粒径、固液比的减小而增加,但搅拌速度对溶解速率无显著影响。根据均相和多相动反应力学模型研究了粗硼砂的溶解过程。结果表明溶解速率遵从假一级均相反应模型。粗硼砂在氯化铵溶液中溶解的活化能为82.73 kJ·mol^-1。     

A study of dissolution kinetics of a Nigerian galena ore in hydrochloric acid

The results of experimental investigation on the study of dissolution kinetics of a Nigerian galena ore in hydrochloric acid solution were discussed. The influence of acid concentration, temperature, particle size, stirring speed and solid/liquid ratio on the extent of dissolution was examined. The elemental analysis by XRF showed that the galena ore is composed mainly of PbS with metals such as Sn, Fe and Zn occurring as minor elements and Mn, Rb, Sr and Nb as traces. The XRD analysis indicated galena as the dominant mineral phase, with the presence of associated minerals, such as α-quartz (SiO₂), sphalerite (ZnS), cassiterite (SnO₂), pyrite (FeS₂) and manganese oxide (MnO₂).Results of leaching studies showed that galena dissolution in HCl solution increases with increasing acid concentration and temperature; while it decreases with particle diameter and solid/liquid ratio at a fixed stirring rate of 450 rpm. The study showed that 94.8% of galena was dissolved by 8.06 M HCl at 80 °C within 120 min with initial solid/liquid ratio of 10 g/L. The corresponding activation energy, E_a was calculated to be 38.74 kJ/mol. Other parameters such as reaction order, Arrhenius constants, reaction and dissociation constants were calculated to be 0.28, 73.69 s^?1, 1.73 ± 0.13 × 10³ and 1.37 ± 0.024 × 10⁴ mol L^?1 s^?1, respectively. The mechanism of dissolution of galena was established to follow the shrinking core model for the diffusion controlled mechanism with surface chemical reaction as the rate controlling step for the dissolution process. Finally, the XRD analysis of the post-leaching residue showed the presence of elemental sulphur, lead chloride and α-quartz.     

Beneficiation of zinc from electric arc furnace dust using hydrometallurgical approach

Zinc bearing wastes such as electric arc furnace dust (EAFD) obtained from steel making constitute an important resource for zinc extraction. Inclusion of heavy metals such as Pb, Cd, Cu, Cr, Ni, etc., in these wastes makes them hazardous to use and/or dispose. In the present research work, leaching kinetics of EAFD with sulfuric acid has been investigated and various experimental parameters such as concentration of lixiviant, stirring rate, sample particle size, liquid/solid proportion, and temperature of the reaction have been optimized. It has been found that the dissolution rate of EAFD increases with rise in temperature, acidic strength, rate of stirring, liquid to solid proportion and with reduction in EAFD particle size. From the analysis of leaching kinetic data by means of graphical and statistical methods, it has been evaluated that the leaching kinetics of EAFD is dictated by surface diffusion reaction. Apparent energy of activation for the leaching reaction of EAFD with sulfuric acid is found to be 13.1 kJ mol^–1 within the temperature range of 308 to 358 K.     

А kinеtiс аnаlysis fоr prоduсtiоn of саlсium bоrоgluсоnаtе frоm colemanite

In this paper, the kinetic model of colemanite dissolution in gluconic acid solutions was carried out in a batch reactor. The effects of the particle size, reaction temperature, stirring speed, gluconic acid concentration, and solid/liquid ratio on colemanite dissolution were experimentally studied. The empirical parameters were the gluconic acid concentration (0.05-0.2 M), the temperature (20-50°C), the solid/liquid ratio (0.05/500-1.5/500 g⋅L⁻¹), particle size (193.5-1000 μm), and stirring speed (400-700 rpm). The kinetic models for heterogeneous solid-liquid reactions were used with the dissolution data in evaluating the kinetic. The dissolution of colemanite in gluconic acid solutions was controlled by diffusion through the product layer. The activation energy was found to be 8.39 kJ⋅mol⁻¹. The rate expression associated with the dissolution rate of colemanite depending on the parameters chosen may be summarized as follows:      

硝酸胺溶液浸提硬硼酸钙的动力学研究

对硬硼酸钙在硝酸铵水溶液的溶解在间歇式反应器中就搅拌速度、粒径大小、反应温度、固液比和溶液的浓度等参数的影响进行了研究。结果表明溶解速度随温度、硝酸铵水溶液的浓度以及粒径和固液比的增加而增加,但搅拌速度对溶解速度无重要影响。硬硼酸钙在硝酸铵水溶液中可以高达100%。硬硼酸钙的溶解动力学根据多相和均相反应模型进行了检验。实验数据表明有高的活化能,说明基于多相反应动力学模型的溶解速度可表达为：1-(1-X)^1/3=3.28 ×10⁴·D^{-0.653 7}·C^{1.295 8}·(S/L)^{-0.490 9}·e^-41.40/(RT)·t。反应过程的活化能为41.40 kJ·mol^-1。     

Reactions at the solid-liquid interface: surface-controlled dissolution of solid particles. The dissolution of potassium bicarbonate in dimethylformamide

We present a mathematical model for the surface-controlled dissolution of solid particles. This is applied to the dissolution of a solid having different particle size distribution functions: those of a monodispersed solid containing particles of all one size, a two-size-particle distribution, and a Gaussian distribution of the particle sizes. The dissolution of potassium bicarbonate in dimethylformamide is experimentally studied indirectly at elevated temperatures. We monitor the dissolution via the homogeneous deprotonation of 2-cyanophenol by dissolved KHCO3. The loss of 2-cyanophenol was detected electrochemically at a platinum microdisk electrode, and separately, the formation of the 2-cyanophenolate anion was monitored via UV-visible spectroscopic analysis. The results presented show that the kinetics of the loss of 2-cyanophenol behaves on one hand as a homogeneous chemical process and on the other hand as a dissolution-rate-controlled process. Initially, predissolved KHCO3 in solution deprotonates the 2-cyanophenol and homogeneous reaction dominates the observed kinetics, and at longer times, the observed kinetics is controlled by the rate of KHCO3 dissolution. Modeling of the experimental results for the surface-controlled dissolution of KHCO3 in dimethylformamide (DMF) yielded a mean value for the dissolution rate constant, k, at elevated temperatures; k was found to have a value of (1.1 +/- 0.3) x 10(-8) mol cm(-2) s(-1) at 100 degrees C, and the activation energy for the dissolution was 34.4 +/- 0.4 kJ mol(-1) over the temperature range 60-100 degrees C.     

Leaching of El-Missikat low-grade fluoritized uranium ore by sulfuric acid: mechanism and kinetic

A well-characterized low-grade fluoritized uranium samples from new occurrence in Gabal El-Missikat prospect, Eastern Desert, Egypt was subjected to sulfuric acid leaching. The effects of leaching parameters on uranium dissolution mechanism were investigated. The shrinking core model was used to model leaching reactions. The kinetics equations indicates that the reactions appear to be controlled by layer diffusion process. The activation energy for uranium dissolution was evaluated. Low activation energy value (2.54 kJ mol⁻¹) confirm the diffusion layer mechanism. The presence of fluoride ions in the solution increases the dissolution of uranium. The optimum process operating parameters were: sulfuric acid concentration: 1.5 M, solid–liquid ratio: 1:3, contact time 8 h; agitation speed rate 200 rpm; and ore particle size − 75 µm at temperature 60 °C, in the absence of an external oxidant. Under these experimental conditions, the extraction efficiency of uranium was about 91%.

     

Reaction kinetics of malachite in ammonium carbamate solution

The dissolution of malachite particles in ammonium carbamate (AC) solutions was investigated in a batch reactor, using the parameters of temperature, AC concentration, particle size, and stirring speed. The shrinking core model was evaluated for the dissolution rate increased by decreasing particle size and increasing the temperature and AC concentration. No important effect was observed for variations in stirring speed. Dissolution curves were evaluated in order to test shrinking core models for fluid-solid systems. The dissolution rate was determined as being controlled by surface chemical reaction. The activation energy of the leaching process was determined as 46.04 kJ mol^?1.     

In vitro dissolution study of uranium dioxide and uranium ore with different particle sizes in simulated lung fluid

Inhalation is one of the most important routes for aerosol particles of uranium compounds to enter the body. The main step for uranium to be available for blood circulation and for interaction with bio-molecules is the dissolution of the particles. Particle size effects on dissolution of uranium dioxide and uranium ore were studied in simulated lung fluid using the “batch/filter” method. Samples were fractionated to ten size ranges from <0.43 μm to >10 μm by cascade impaction prior to dissolution experiments. Dependence of dissolution kinetics on particle size and on the amount of uranium trioxide contained in the particles was observed.     

Leaching of Celestite in Sodium Hydroxide Solutions and Kinetic Modelling

In this study, the dissolution kinetics of celestite in solutions of sodium hydroxide was investigated by batch process. The results showed that the parameters which had the greatest effect on the dissolution of celestite in sodium hydroxide solutions were reaction temperature, the concentration of sodium hydroxide and stirring speed. It was determined that the dissolution rate increased with increased stirring speed, sodium hydroxide concentration, reaction time and temperature and decreased with increasing particle size and solid-liquid ratio. The leaching process fitted the shrinking core model with diffusion through the product layer model as the rate-determining step. The activation energy of the dissolution of celestite was calculated as 62.24?kJ/mol. A semi-empirical kinetic model was obtained for dissolution of celestite in sodium hydroxide solution.     

Study on the selective leaching of low-grade phosphate ore for beneficiation of phosphorus and rare earths using citric acid as leaching agent

In the study the organic/inorganic chemical leaching and enrichment technology were used for selective extraction of the dolomite which co-existed in the Zhijin low-grade phosphate ore for beneficiation phosphorous and rare earths (RE) by using citric acid as leaching agent. The effects of acid concentration, reaction time, reaction temperature, liquid/solid ratio, and particle size on P₂O₅ and rare earths grade and the recovery ratio of them were investigated. The results show that under the optimized experimental conditions (acid concentration 9%, reaction time 240 min, reaction temperature 40°C, liquid/solid ratio 50: 1, and ore particle size 0.18–0.125 mm) the P₂O₅ grade can be increased from 15.47 to 34.82%, and P₂O₅ recovery rate comes up to 88.02%. The rare earths are mainly enriched in the leaching residues. Meanwhile, the recovery rate of rare earths is 72.08%. ΣREO grade can be increased from 978.06 × 10^–4 to 1998 × 10^–4%. In addition, the reaction kinetics of the chemical reaction between citric acid and dolomite are also discussed, the results show that the leaching process is controlled by chemical reaction. The activation energy for leaching was found to be 36.6337 KJ mol^–1 and k₀ was 3.67×104 s^–1, and the rate of the leaching based on the chemical reaction-controlled process could be expressed as 1–(1–a)^1/3 = 3.67 × 10⁴e^–36.63/RTt. Compare to the conventional process, the method provided in this study not only has advantages including higher phosphate concentration and rare earth grade, and higher recovery rate, but also using less amount of chemicals. Meanwhile, the citric acid can be recycled, avoiding discharge wastewater.     

Dissolution kinetics of cerussite in an alternative leaching reagent for lead

The dissolution kinetics of cerussite was investigated using methanesulphonic acid (MSA) as an alternative leaching reagent. The effects of particle size, stirring speed, acid concentration, and reaction temperature on the lead dissolution rate were determined. The dissolution process followed the kinetic law of the shrinking-core model, and a corresponding mixed control model was found suitable for representing the rate-controlling step. The mixed kinetic model comprised two stages: surface chemical reaction (283 K to 303 K) and diffusion through the product layer (303 K to 323 K). The activation energies of these sequential stages were 43.20 kJ mol^?1 and 17.20 kJ mol^?1, respectively. The corresponding dissolution kinetic equations are also presented to describe the dissolution reaction. The results indicated that methanesulphonic acid could be used as an effective leaching reagent for extracting lead from cerussite minerals.     

Micronization of tolbutamide using rapid expansion of supercritical solution with solid co-solvent (RESS-SC) process

Micronization of a sulfonylurea antidiabetic agent, tolbutamide, using rapid expansion of supercritical solution with solid co-solvent (RESS-SC) process was investigated in this study. Menthol was selected as the solid co-solvent in the RESS-SC process owing to its high vapor pressure and ease of removal by sublimation. The tolbutamide particles were micronized successfully from its original mean size of 89.4 ??m to the smallest mean size of 2.1 ??m through the RESS-SC process. The use of solid co-solvent in this process enhanced the saturated solubility of tolbutamide in supercritical carbon dioxide and inhibited the particle growth during pressure expansion after the nozzle. In addition, polymorph conversion from form I to form II after the RESS-SC process was confirmed by XRD and DSC analyses. Measurements of the dissolution rate profiles before and after the RESS-SC process were also investigated. It is shown that the micronized tolbutamide by the RESS-SC process had novelty in dissolution behavior compared to that of the original compound. Its dissolution rate was enhanced by 8.8 times after the RESS-SC process.     

Frequency Response Method for Measuring Mass Transfer Rates in Adsorbents via Pressure Perturbation

A new apparatus for the measurement of equilibria and dynamics for gas-phase adsorption systems is utilized to examine the adsorption of carbon dioxide on BPL activated carbon. The apparatus has a flow-through configuration. For dynamics, with constant inlet flow, pressure within the adsorbent-containing section is varied sinusoidally, and the time-dependent outlet flow rate is measured to determine an amplitude ratio and phase lag. Studies are made of temperature effects and particle size effects. Results are compared with several mathematical models. Frequency response data show that the BPL system follows surface (or micropore) diffusion kinetics. The rate of adsorption for the activated carbon is found to be only weakly dependent on the bulk particle size.     

Kinetics of the γ-radiation-induced polymerization of ethylene in liquid carbon dioxide

The γ-radiation-induced polymerization of ethylene with the use of liquid carbon dioxide as a solvent, was studied from the viewpoint of kinetics. The polymerization was carried out at conversions less than 10% under the pressure ranging from 100 to 400 kg./cm.², dose rates 1.3 × 10⁴?1.6 × 10⁵ rad/hr., and temperatures of 20–90°C. The concentration of carbon dioxide varied up to 84.1 mole-%. The polymerization rate and the polymer molecular weight were observed to increase with reaction time. This observation, however, becomes less pronounced with increasing concentration of carbon dioxide and with rising temperature. The exponents of the pressure and the dose rate were determined to be 2.3 and 0.85 for the rate, and 2.0 and ?0.20 for the molecular weight, respectively. From the kinetic considerations for these results, the effect of carbon dioxide on the initiation and termination reaction in the polymerization was evaluated.     

Kinetics of corrosion and dissolution of uranium dioxide as a function of pH

A continuous flow-through reactor with a thin layer of solid particles (size ranging from 100 to 300 μm) was used to obtain a deeper knowledge on the mechanism of dissolution of UO₂ under oxidizing conditions. Using this methodology the dissolution rate of uranium dioxide was determined at three different oxygen partial pressures (5, 21, and 100% in nitrogen) and as a function of pH (between 3 and 12) in a noncomplexing medium. From the results of these experiments the following rate equation was derived: In addition, XPS characterizations were performed to determine the U(IV)/U(VI) ratio on the solid surface at different experimental times and conditions. These results showed that at acidic conditions (pH below 6.7) the final solid surface presents a stoichiometry close to UO₂, while at alkaline conditions the final solid surface average composition is close to UO_2.25. This information was integrated with the results of the leaching experiments to present a model for the mechanism of dissolution of uranium dioxide under the experimental conditions. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 261–267, 1997.     

Sorption kinetics for the removal of aldehydes from aqueous streams with extractant impregnated resins

The sorption kinetics for the removal aldehydes from aqueous solutions with Amberlite XAD-16 and MPP particles impregnated with Primene JM-T was investigated. A model, accounting for the simultaneous mass transfer and chemical reaction, is developed to describe the process. It is based on the analogy to the diffusion and reaction in a stagnant liquid sphere, but corrected for the porosity and particle properties influencing the diffusion. The developed model describes the kinetic behavior of the process in the low concentration region rather well. However, in the high concentration region, larger discrepancies are observed. Initially, the influence of the flow rate was investigated to eliminate the effect of the external mass transfer. The influence of the particle morphology was investigated for both physical and reactive sorption. Physical sorption experiments were used to determine the factor τ that takes the particle properties influencing the diffusion into account. It was shown that the diffusion is faster in XAD-16 than in MPP impregnated systems. Reaction rate constant k _x was determined by fitting the model to the experimental data. Sorption of benzaldehyde appears to be significantly slower (k _x ∼10⁻⁴ l/mol s) than the sorption of pentanal (k _x ∼10⁻³ l/mol s) due to the slower chemical reaction. The influence of the particle size was investigated for the sorption of pentanal with XAD-16. It was observed that the particle size does influence the diffusion term, but does not have an effect on the reaction rate. On the other hand, the extractant loading influences the reaction rate slightly in the low concentration region, whereas the initial concentration of the solute has more pronounced effect.     

Kinetics of dissolution of metal powders and metal oxides

Current approaches to study of the kinetics of the dissolution of metallic powders and metal oxides are discussed. The applicability of the various kinetic equations to the rate of a topochemical reaction is discussed. It is determined by features of the appearance and growth of the nuclei of the solid product, by the change in the size of the interface of the solid phases, and by the effect of the reaction product. For the case of the kinetics of reaction of copper, nickel, cobalt, zinc, cadmium, and lead powders and their oxides with aqueous and nonaqueous solutions of ammonium salts it was shown that the conditions of formation, the properties, and the behavior of the product layer formed on the surface of the reacting particle can have a determining effect on the kinetics and mechanism of the reaction. The results from the kinetic experiment are examined in terms of a model described by the generalized topochemical equation =1 – exp(–ktⁿ) and also a model based on an analysis of the reaction rate constants at various sections of the kinetic curve. Correlations were established between the coefficient n in the generalized topochemical equation and also the rate constant and density or solubility of the reaction product formed on the surface of the reacting particle.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 31, No. 5, pp. 284–297, September–October, 1995.     

Simulation of the effect of hydroxyethylidenediphosphonic acid on the kinetics of copper(II) oxide dissolution in sulfuric acid

The effect of hydroxyethylidenediphosphonic acid (HEDP) on the kinetics of copper(II) oxide dissolution in aqueous sulfuric acid was studied. The addition of HEDP in acidic media decreases the CuO dissolution rate. The simulation of these processes showed that the inhibiting effect is due to the decrease in the concentration of the intermediate compound (CuOH⁺), which restricts the dissolution of Cu²⁺ ions, due to adsorption of the HEDP ions (H₄Y^?) on the oxide surface.     

Kinetics and Mechanism of Oxidation of l‐Histidine by Permanganate Ions in Sulfuric Acid Medium

The reaction kinetics for the oxidation of l ‐histidine by permanganate ions have been investigated spectrophotometrically in sulfuric acid medium at constant ionic strength and temperature. The order with respect to permanganate ions was found to be unity and second in acid concentration, whereas a fractional order is observed with respect to histidine. The reaction was observed to proceed through formation of a 1:1 intermediate complex between oxidant and substrate. The effect of the acid concentration suggests that the reaction is acid catalyzed. Increasing the ionic strength has no significant effect on the rate. The influence of temperature on the rate of reaction was studied. The presence of metal ion catalysts was found to accelerate the oxidation rate, and the order of effectiveness of the ions was Cu²⁺ > Ni²⁺ > Zn²⁺. The final oxidation products were identified as aldehyde (2‐imidazole acetaldehyde), ammonium ion, manganese(II), and carbon dioxide. Based on the kinetic results, a plausible reaction mechanism is proposed. The activation parameters were determined and discussed with respect to a slow reaction step.