Lysine Adsorption on Cation Exchange Resin. IV. Temperature Effects on Equilibrium and Kinetics in Batch and Column Systems

Abstract

Ion exchange equilibria and kinetics are determined for lysine adsorption on the strong acid cation exchanger DIAION SK‐1B at temperatures of 25, 40, and 60°C. The ion exchange equilibrium is found to be independent of temperature. Conversely, the kinetics of ion exchange increases dramatically as the temperature is increased. Average ion exchange selectivity coefficients of 6.0 g/cm³ and 0.52 are obtained for the ion exchange of divalent and monovalent cationic lysine with hydrogen ion, respectively. Resin phase diffusivities are determined by fitting batch binary ion‐exchange data with a mass transfer model based on the Nernst‐Planck equations. As the temperature is increased from 25 to 60°C, the resin phase diffusivity increases from 0.04×10^?6 to 0.14×10^?6 cm²/s for divalent lysine and from 0.16×10^?6 to 0.55×10^?6 cm²/s for monovalent lysine. The combination of temperature‐independent ion exchange equilibria and faster mass transfer at higher temperatures results in higher dynamic binding capacity and more efficient desorption of lysine when ion exchange is operated at an elevated temperature. This behavior is confirmed by means of column adsorption/desorption experiments whose results are found to be in agreement with a model incorporating the equilibrium and mass transfer data obtained in this work.     

Sorption of caesium by complex hexacyanoferrates iv. ion exchange kinetics and mechanism of sorption by potassium copper ferrocyanide

The kinetics of caesium sorption by potassium copper ferrocyanide have been studied. Liquid film diffusion is rate controlling in very dilute solutions of caesium (3.8 × 10^?6m). The average film diffusion coefficient was found to be 1.465 × 10^?9 m² s^?1 at 20°C and the activation energy for the corresponding process was found to be 15.14 kJ mol^?1. Chemical reaction rate controls the caesium-potassium ion exchange process at a higher caesium concentration of 3.8 × 10^?3m. The shell progressive reaction model was found applicable to the sorption process. The activation energy for the caesium-potassium ion exchange reaction was measured to be 74.85 kJ mol^?1. Finally, a comparison between the theoretical and the experimental sorption profile has been made to demonstrate the validity of the theory.     

Strengthening of Class Fibers: 11, Ion Exchange *

Soda-alumina-silica glass fibers were ion-exchanged in potassium nitrate at 400°C; their strength was measured before and after exchange. The potassium concentration distribution and the optical retardation were also measured. The results for unetched fibers are consistent with the premise that the kinetics of exchange are controlled by diffusion with D⋍×10⁻¹¹ cm²/s) and with the predictions of thermal stress analysis with a dilation coefficient of 2.8×10⁻⁴ (wt fraction potassium)⁻¹. The existence of a broad maximum in the plot of strengthening of unetched fibers vs time may be explained by the existence of Griffith flaws about 2 μm deep in the unexchanged glass. A deleterious effect from ion exchange was noted with etched fibers, in which even a short (½ h) exchange caused significant weakening.     

Kinetics of Exchange of Cs+, Co2+ and Sr2+ on Synthetic Hydrous Titanium Oxides

Abstract

In the present work, a study of the kinetics of adsorption of Cs⁺, Co²⁺, and Sr²⁺ on four hydrous titanium oxides, prepared in different media, and designated as Ti‐I, Ti‐II, Ti‐III, and Ti‐IV, was carried out. In the aqueous medium, the internal diffusion coefficients, D_i for Cs⁺ were found to be equal to 3.7×10^?9, 3.7×10^?9, 2.3×10^?9, and 1.5?10^?9 cm²/s, in Ti‐I, Ti‐II, Ti‐III, and Ti‐IV, respectively. For Co²⁺ and Sr²⁺, these values are equal to 0.96×10^?9 and 0.64×10^?9 cm²/s, respectively for Ti‐IV. In Ti‐IV, D_i for all ions generally increases on adding methanol or propanol. This is probably due to greater dehydration, leading to faster ion diffusion, and, hence, to a decrease of ion mobility due to stronger interaction with the surface. In all media in Ti‐IV, the order: D_i(Cs⁺)>D_i(Co²⁺)≥D_i(Sr²⁺) was found which is due to a stronger interaction of the bivalent ions with the exchange sites.     

Kinetics of Ion Exchange of Zr/Sn(IV) Phosphonate–Phosphate Hybrid Materials for Separation of Lanthanides from Oxidized Actinides

ABSTRACT

The kinetics of ion exchange of Zr/Sn(IV) phosphonate–phosphate hybrid ion exchange materials have been studied with several types of ions of specific interest to nuclear fuel recycling including Nd³⁺ at 4.5 and 43 mM and NpO₂⁺ at 2.9 mM spanning multiple HNO₃ concentrations. In most cases, the equilibrium was reached in less than 12 h. The ion exchange behavior followed that of pseudo first-order adsorption with rates ranging from 0.430–4.10 h^?1 to 0.290–0.435 h^?1 for Nd³⁺ and NpO₂⁺, respectively. A separation with both Nd³⁺ and NpO₂⁺ present was performed, resulting in separation factors of 1.9–12, 1.7–6.6, and 2.0–5.7 at 1 × 10^?1, 1 × 10^?2, and 1 × 10^?3 M HNO₃, respectively.     

Anion exchange of uranium from aqueous sulphuric acid solutions: Diffusion kinetics

The ion exchange kinetics of uranium sorption from acidic sulphate solutions onto weak and strong base resins has been studied. In order to facilitate experimentation and analysis, isotopic redistribution experiments of uranyl sulphate ions (with U-235 as a tracer) under conditions of particle diffusion control have been performed. Also, self-diffusion experiments for sulphate ions (with S-35 as a tracer) and counter diffusion measurements involving uranyl sulphate-sulphate exchange have been performed. The ion exchange of uranium is a slow reaction and appears to be particle diffusion controlled at all solution conditions of practical interest. For a weak base resin (Relite MG-1), the self-diffusion coefficient of uranyl sulphate ions changes with particle size, increasing from 1.49 to 4.88 × 10^?9 cm²/s as the particle diameter is reduced from 0.146 to 0.054 cm. With a strong base resin (Dowex-1×8), the self-diffusion coefficient of uranyl sulphate ions remains reasonably constant with varying particle diameter at a value of 1.76 × 10^?9 cm²/s. Sulphate ion self-diffusion coefficients were also constant with particle size (2.50 × 10^?7 cm²/s) and the counter exchange diffusivity lies between the values for the individual species; a typical value is 1.53 × 10^?8 cm²/s. It is argued that resin matrix structure has a significant effect on uranium kinetics and that a knowledge of the relevant diffusion coefficients will provide a rational basis for the design of ion exchange processes and plant equipment.     

Study of the Kinetics of Copper Extraction with (anti)-2-Hydroxy-5-nonylbenzophenone Oxime Using a Rotating Diffusion Cell

Abstract

A rotating diffusion cell was used to study the chemical reaction in which copper is transferred from an aqueous sulfate phase to an organic phase containing a copper-complexing agent (purified anti-2-hydroxy-5-nonylbenzo-phenone oxime) dissolved in n-decane. A mathematical model was developed to describe the contributions of the kinetic and diffusive resistances to the overall resistance to mass transfer. Application of this model to the experimental data enabled an overall rate equation for the reversible copper extraction reaction to be written. The active oxime species in the extraction reaction was found to be the monomer with first-order kinetics. The extraction reaction rate was also found to be dependent on aqueous phase hydrogen ion concentration with negative first-order kinetics. The extraction rate constant was determined as 1.3 × 10^?5 cm/s. Assumption that the reverse rate is dependent on hydrogen ion concentration with first-order kinetics enabled the reverse rate constant to be calculated as 6.8 × 10^?3 cm⁴/mol·s.     

CONVECTIVE-AIR DRYING KINETICS OF OSMOTICALLY PRE-TREATED BLUEBERRIES

Abstract

The second stage convective drying behavior of osmo-dehydrated blueberries was evaluated in a forced-air cabinet dryer (temperature: 50°C, relative humidity: 14%, air velocity: 0.6 m/s) with a cross-flow tray arrangement. Fick's second law of unsteady state diffusion was used to model the air drying kinetics. The results showed that the convective-air drying of the blueberries occurred in two falling rate periods. The effective diffusion coefficients, D_eff, during the first falling rate period ranged from 1.19 × 10^?10 m²/s to 2.14 × 10^?10 m²s and ranged from 4.04 × 10^?11 m²/s to 1.32 × 10^?10 m²/s during the second falling rate period. Among the pre-treatment conditions, the temperature and sucrose concentration during osmotic dehydration significantly (p < 0.05) influenced the air drying time, while the effect of contact time was not significant (p > 0.05).     

MASS TRANSFER AND DIFFUSION COEFFICIENT DETERMINATION IN THE WET AND DRY SALTING OF MEAT

ABSTRACT

Dehydrated salted meat is widely used in Brazil as a very important source of animal protein. The main objective of this kind of processing is water removal. initially by osmotic pressure changes and then by drying, resulting in a product with intermediate moisture levels.

In this work, mass transfer and salt diffusion in pieces of meat submitted to wet and dry salting were studied. Slabs of beef m. trapezius with an infinite plate geometry were salted in a NaCl saturated solution or in a dry salt bed, at two temperatures (10 and 20°C) and different time exposures (120 min and 96 hours). Equilibration studies were extended up to six days.

It was observed that water loss increased with salt uptake, for increasing periods of times. At 20°C the moisture loss was higher than it was at 10°C in both salting processes. On the other hand, the kinetics of salt uptake and moisture loss were of greater importance in the process of dry salting than in that of wet salting.

The salt diffusion coefficient for wet salting was 0.26 × 10^?10m²/s at20°C and 0.25 × 10^?10 m²/s at 10°C and for the dry salting the values were 19.37 × 10^?10 m²/s at 20°C and 17.21 × 10^?10 m²/s at 10°C.     

Ion‐exchange adsorption of calcium ions from water and geothermal water with modified zeolite A

The modified zeolite A was prepared by a two‐step crystallization method to remove scale‐forming cations from water and geothermal water. The adsorption kinetics, mechanism and thermodynamics were studied. The calcium ion adsorption capacity of the modified zeolite A was 129.3 mg/g (1 mg/g = 10^?3 kg/kg) at 298 K. The adsorption rate was fitted well with pseudo‐second‐order rate model. The adsorption process was controlled by film diffusion at the calcium ion concentration less than 250 mg/L (1 mg/L = 10^?3 kg/m³), and it was controlled by intraparticle diffusion at the concentration larger than 250 mg/L. The calculated mass‐transfer coefficient ranged from 2.23 × 10^?5 to 2.80 × 10^?4cm/s (1 cm/s = 10^?2m/s). Dubinin–Astakhov isotherm model could appropriately describe the adsorption thermodynamic properties when combined with Langmuir model. The adsorption process included not only ion exchange but also complexation between calcium and hydroxyl ions. The adsorption was spontaneous and endothermal. The high adsorption capacity indicates that the modified zeolite A is a suitable adsorption material for scale removal from aqueous solution. © 2014 American Institute of Chemical Engineers AIChE J, 61: 640–654, 2015     

Ascorbic Acid Thermal Degradation during Hot Air Drying of Camu-Camu (Myrciaria dubia [H.B.K.] McVaugh) Slices at Different Air Temperatures

Abstract

Air drying of camu-camu slices was performed in order to estimate the effect of air temperature on the kinetics of ascorbic acid thermal degradation. Moisture variation during the air drying process was monitored gravimetrically by weighing the trays at predetermined time intervals. The experimental points were adjusted by Fick's diffusion model and by the Page empirical model. The effective diffusion coefficient (D_eff) ranged from 8.48 × 10^?10 to 1.34 × 10^?9 m²/s.The ascorbic acid content was evaluated in samples taken during the drying process using Iodine titration, and the results modeled by the Weibull equation. Concerning ascorbic acid retention the best drying condition required air at 50°C. The ascorbic acid retention was 78%, when the moisture content of the product reached 10% (wet basis).     

Analysis of intraparticle diffusion on adsorption of crystal violet on bentonite

Abstract

In the present work, kinetics of crystal violet (CV) adsorption on bentonite was studied by pore volume and surface diffusion model (PVSDM), surface diffusion model (SDM), and pore volume diffusion model (PVDM). The adsorption decay curves were obtained in batch system using different adsorbent dosages. The PVDM model did not interpreted the kinetic adsorption since the calculated value of D_p equal to 5.64?×?10^?7 cm² s^?1 predicted a slower adsorption than that obtained by the experimental data. The PVSDM results indicates that the intraparticle diffusion is predominantly due to surface diffusion (93%) and the pore volume diffusion can be negligible. Once the surface diffusion was the limiting step, the estimation with one (D_s) and two (D_sq and α) parameters were tested in the SDM model. The statistical analysis revealed that the one-parameter SDM model was most appropriate to predict the CV adsorption on bentonite. The optimal values of Ds ranged from 6.19?×?10^?10 to 6.49?×?10^?10 cm² s^?1, and decrease with the adsorbent dosage.     

Bending-beam study of water sorption by thin poly(methyl methacrylate) films

A bending-beam technique has been employed to study the effects of film thickness (7–55 μm) and rate of cooling during film preparation (～ 6°C/h to a dry ice quench) on sorption characteristics of water by poly(methyl methacrylate) films coated on thin fused quartz beams (? 84 μm thick). In each experiment, the curvature of a polymer coated beam exposed to liquid water was monitored as a function of time by a low power laser pointer. With the use of a transport model which considers the sorption process as the linear superposition of contributions from Fickian diffusion and a first-order polymer molecular relaxation process, the beam curvature data were analyzed to determine the governing transport kinetics and associated transport parameters such as water diffusion coefficient and relaxation rate constant. From curvature analysis for thin films (7–13 μm in thickness), it was found that water diffusion proceeds at early times in a Fickian-like manner with a diffusion constant of 2–4 × 10^?9 cm²/s. At later times, significant relaxation contributions lead to non-Fickian diffusion behavior, an effect that is more pronounced as the film thickness or sample cooling rate decreases. In addition, sorption of water was found to reduce the film stress (initially tensile at ? 10⁸ dyn/cm²) at a rate that increases with sample cooling rate. The high initial film stress not present in free-standing films may account for the relatively higher diffusion coefficient (～ 2 × 10^?8 cm²/s) found here for very thick (55 μm) PMMA coatings. Because the bending-beam technique uses coated samples, it is especially well suited for studying penetrant transport into polymer coatings.     

Absence of Donnan Exclusion at High‐Concentration Ion Exchange for Macroporous Anionic Resin

Abstract

High‐concentration ion exchange has been studied for an anionic macroporous resin. The mechanism of interaction of Lewatit MP‐500 (strong base resin) with several high‐concentration inorganic salts was analyzed in order to determine the effect of the Donnan potential in the process.

The systems under study were Cl^?, SO₄ ^2? as counter‐ions and K⁺, Na⁺ as co‐ions in different combinations as single electrolytes. These salts were chosen because of their interest as raw materials in the fertilizer industry. The study focuses mainly on the behavior of high‐concentration (over 1 M) counter‐ and co‐ions in the anionic resin. The results showed that Donnan exclusion does not take place completely and that electrolyte penetration inside the resin is observed. Furthermore, a certain amount of ion exchange was observed for the co‐ions (K⁺ and Na⁺) when the resin was presaturated with sulphate and chlorides that were present in the solution. Equilibrium and kinetics data were obtained under these special experimental conditions. Equilibrium constants were obtained for counter‐ions and adsorption constants for co‐ions using a constant separation factor isotherm, while diffusion coefficients were obtained using a pore diffusion model.     

MASS TRANSFER IN BANANA CHIPS DURING OSMOTIC DEHYDRATION

ABSTRACT

The effects of temperature ( 50, 60 and 70 °C ), sucrose concentration ( 50, 60 and 70° Brix ) and pH ( 6,7 and 8 ) on the mass transfer during osmotic dehydration of banana chips were studied. Fitting a diffusion model gave apparent diffusivity values varied from 2.77 to 2.66 × 10^?9 m² s^?1 and depending on temperature and sucrose concentration but not on pH changes. The effct of syrup/product volume ratio on the mass transfer kinetics was also investigated.     

The Synerqistic Solvent Extraction of Manganese by Macrocyclic Crown Ethers in Combination with Didodecylnaphthalene Sulfonic Acid: Effect of Macrocycle Substituents

Abstract

Crown ethers in combination with organophilic cation exchangers synergize the extraction of certain metai ions from aqueous solutions, and their selectivity has been thought largely dependent on the correspondence between the crown other's cavity diameter and the metal ion diameter. This work focuses on two crown ethers, tert. -butylbenzo -15-crown-5 (tBB15C5). and tert, -butylcyclohexano 15-crown-5 (tBC15C5) each of which has a cavity diameter of 1.7 to 2.2 × 10^?10 m. and their extraction of Mn²⁺ (ionic diameter 1.4 to 2.2 × 10^?10 m) from aqueous nitrate solutions. The organophilic cation exchanger used was didodecylnaphthalene sulfonic acid (HDDNS). The data show no observable complexes of the manganese salt of HDDNS     

OSMOTIC DEHYDRATION KINETICS OF BLUEBERRIES

Abstract

The kinetics of moisture loss and solids gain during osmotic dehydration of blueberries under different conditions of temperature (37°C - 60°C), concentration of the sucrose solution (47°Brix - 70°Brix) and contact time between fruit and sucrose solution (0.5 h - 5.5 h) were studied, and modeled based on Fick's law of unsteady state diffusion. The study showed that all factors influenced moisture loss and solids gain (p<0.001), both generally increasing with temperature (T) and sucrose concentration (C). Based on the diffusion model, the calculated effective moisture diffusivity (D_m) ranged from 1.98 × 10^?10 to 5.10 × 10^?10 m²/s and the effective solids diffusivity (D_s) ranged from 2.54 × 10^?11 to 2.22 × 10^?10 m²/s. Both D_m and D_s showed increasing trends with temperature and sucrose concentration, and could be modeled as quadratic functions of T and C.     

Divalent Amino Acid Adsorption on Cation Exchange Resin

Abstract

Mass transport of divalent amino acids, arginine and histidine, was investigated in an ion exchange system using DIAION SK104, SK1BL, and SK112. Ion exchange equilibrium constants of arginine were 5.0 g/cm³ for SK104 (4 wt% D.V.B.), 25.0 g/cm³ for SK1BL (8 wt% D.V.B.) and 25.0 g/cm³ for SK112 (12 wt% D.V.B.). The ion exchange equilibrium constant of histidine was 8.0 g/cm³ for SK1BL (8 wt% D.V.B.). Resin phase diffusivities of divalent amino acids are measured by batch uptake experiments. Resin phase diffusivities of divalent arginine were decreased from 9.0 × 10^?8 cm²/s to 1.6 × 10^?8 cm²/s while the D.V.B. content in resin increases from 4 wt% to 12 wt%. Resin phase diffusivity of histidine for 8 wt% D.V.B. resin was 7.0 × 10^?8 cm²/s. The steric hindrance model was able to describe measured resin phase diffusivities.     

Chloride/sulfate exchange on anion resins. Kinetic investigations. Chemical control in selective exchanges

Rate determinations for the Cl^-/SO⁼₄ exchange on anion resins in very diluted systems (1 ÷ 6 × 10^-3N), where resin selectivities for the divalent ion are drastically raised by the electroselectivity effect, show convincing evidence that the chemical reaction rate on fixed charges controls the overall process kinetics. Activation energies, in particular, (up to 16.83 kcal/eq) are definitely out of the range for usual diffusion-controlled kinetics.A spherically-symmetrical diffusion model with a billiard-ball-like mechanism of site-to-site jumping of ions inside the resin is suggested.     

TRANSFER RATE AND SEPARATION OF Sr2+ and Cs+ BY SUPPORTED LIQUID MEMBRANES UTILIZING SYNERGIZED CROWN ETHER CARRIERS

ABSTRACT

The rate of the isotopic exchange of Na? and Cs? between hydrous silicon-titanium(IV) oxide in the relevant ionic form and aqueous solution was determined radiochemically. The rate was controlled by the diffusion of the ions in the exchanger particles. The diffusion coefficients at 5 °C are (3.9±0. 1)×10^?11m² s^?1 and (2.4± 0. 1)×10^?11 m² s^?1respectively, for Na? and Cs? in the exchanger equilibrated with solutions at pH 6. The activation energies are 31±5 kJ mol^?1 and 20±5 kJ mol^?1 for Na? and Cs? diffusion, respectively. The diffusion coefficients of the ions decreases with increasing pH of the solutions equilibrated with the exchanger, whereas their activation energy is independent of pH. The results were interpreted in terms of the strength of the electrostatic interaction between the counter ions and the ion-exchange sites.