The mechanisms governing the influence of the solvent composition on the agglomeration in a crystallization process have been investigated. Narrowly sieved paracetamol crystals were suspended in supersaturated acetone-water solutions, and were allowed to grow at isothermal conditions, after which the agglomeration was recorded. In all experiments the same sieve size fraction was used as well as the same magma density. In each experiment the supersaturation was kept constant. Experiments were performed in different solvent compositions at different supersaturation, crystal growth rate, solution viscosity, and agitation rate. For a statistically sufficient number of particles from each experiment, the number of crystals in each product particle was determined by image analysis and multivariate data evaluation. From the resulting number distributions of crystals per product particle, parameters defining the degree of agglomeration were extracted. The experimental results clearly establish that there is an influence of the solvent composition on the degree of agglomeration, which cannot be explained by differences in crystal growth rate, or differences in solution viscosity. The degree of agglomeration is found to decrease with increasing solvent polarity. It is, suggested that the mechanism by which the solvent influence relates to the crystal-solvent interaction and the physicochemical. adhesion forces between crystals in the solution.

The agglomeration of paracetamol during crystallization in different pure solvents has been investigated. Narrowly sieved crystals were suspended as seeds and allowed to grow and agglomerate at constant supersaturation and temperature. Particles from each experiment were examined by image analysis and multivariate data evaluation, for the number of crystals per particle. From the resulting number distribution, parameters defining the degree of agglomeration were extracted. The degree of agglomeration among the product particles is fairly low in water, methanol, and ethanol, while it is substantial in acetone particularly, but also in acetonitrile and methyl ethyl ketone. Surfaces of large, well-grown paracetamol crystals have been characterized by contact angle measurements. The surface free energy components of different crystal faces have been estimated using Lifshitz-van der Waals acid-base theory. The data are used for estimation of the solid-liquid interfacial free energy of each face in the solvents of the agglomeration experiments and the corresponding crystal-crystal adhesion free energy of pairs of faces. The degree of agglomeration in different solvents does correlate to the free energies of adhesion. This supports the hypothesis that the influence of the solvent on the crystal agglomeration relates to physico-chemical adhesion forces between crystal faces in the solution.

Reaction crystallization of salicylic acid has been investigated by experiments and modeling. In the experimental work, dilute hydrochloric acid has been added to an agitated aqueous solution of sodium salicylate in 1 L scale, and product crystals have been characterized by image analysis. The results show that the product crystal number mean size at first increases with increasing agitation rate but then gradually decreases again at further increase in stirring rate. At lower stirring rate, larger crystals are obtained when the feeding point is located close to the agitator instead of being located out in the bulk solution. The mean crystal size increases with decreasing feeding rate and with decreasing reactant concentrations. There is a decrease in mean size with increasing feed pipe diameter. These trends in the experimental results show great similarity with previous results on benzoic acid. The experimental results have been examined by a population balance model accounting for meso and micro mixing, and crystal nucleation and growth rate dispersion. It is found that the crystallization kinetic parameter estimation is quite complex, and the objective function hyper surface contains many different minima. Hence, parameter estimation has to rely on a combination of mathematical optimization strategies and a scientific understanding of the physical meaning of the parameters and their relation to current theories. As opposed to our previous work on benzoic acid, it has not been possible to find a set of kinetic parameters that provides for a good description of all experimental data.

In the present study, the recovery of rare earth elements (REEs) from an apatite concentrate in the nitrophosphate process of fertilizer production has been studied. The apatite concentrate has been recovered from iron ore tailings in Sweden by flotation. In the first step, the apatite is digested in concentrated nitric acid, after which Ca(NO3)2.4H2O is separated by cooling crystallization. The solution is then neutralized using ammonia whereby the REEs precipitate mainly as phosphates (REEPO4.nH2O) and together with calcium as REEn Cam (PO4)(3n + 2m) / 3. In this work, the degree of rare earth coprecipitation during seeded cooling crystallization of Ca(NO3)2.4H2O has been studied. The solubility of calcium nitrate tetrahydrate (Ca(NO3)2.4H2O) in acidic nitrophosphoric acid solutions in the temperature range of − 2 °C to 20 °C has been determined. For the neutralization step, it is shown that the calcium concentration and the final pH play an important role in determining the concentration of REEs in the precipitate. It is found that reaching maximum recovery of REE with minimum simultaneous precipitation of calcium requires careful control of the final pH to about 1.8. It is further observed that the precipitation yield of REEs and iron is favored by a longer residence time and higher temperature. Finally, the effect of seeding with synthesized REE phosphate crystals as well as a mixture of REE and Ca phosphates on the precipitation rate and the composition of the precipitate was studied.

Equilibrium isotherms and the adsorption kinetics of heavy metals onto chitosan were studied experimentally. Chitosan, a biopolymer produced from crustacean shells, has applications in various areas, particularly in drinking water and wastewater treatment due to its ability to remove metallic ions from solutions. The adsorption capacity of chitosan depends on a number of parameters: deacetylation degree, molecular weight, particle size and crystallinity. The purpose of this work was to study the adsorption of copper, zinc, mercury, and arsenic on chitosan produced from shrimp shells at a laboratory level.

The experimental work involved the determination of the adsorption isotherms for each metallic ion in a batch system. The resulting isotherms were fitted using the Langmuir model and the parameters of the equation were determined. Kinetic studies of adsorption for different metallic ions at different concentrations and with different particle sizes were performed in batch and column systems. Simplified models such as pseudo-first-order, pseudo-second-order, and intra-particle diffusion equations were used to determine the rate-controlling step. Some preliminary studies were carried out to address the application of chitosan as an adsorbent in the removal of heavy metals or other metallic ions from natural water and wastewater. The regeneration of chitosan was also studied.

The results showed that the adsorption capacity depends strongly on pH and on the species of metallic ions in the solution. The optimum pH value for the metallic cation adsorption was between 4 and 6, whereas for arsenic adsorption it was about 3. When the pH is not controlled, the adsorption capacity is independent of the initial pH with the solution reaching a final pH of about 7. It was also found that the Langmuir equation described very well the experimental adsorption data for each metallic ion. The adsorption capacity for the metals on chitosan follows the sequence Hg>Cu>Zn>As.

The study of the adsorption kinetics of these metallic ions shows that the particle size has a significant influence on the metal uptake rate for copper; but that it has only a slight influence on the adsorption rate of zinc and mercury in the range studied. Arsenic adsorption exhibited an interesting behaviour which depends strongly on the pH of the solution; the uptake increased at short adsorption times and then decreased at long times. The analysis of kinetic models showed that the pseudo-second-order adsorption mechanism is predominant, and the overall rate of the metallic ion adsorption process is therefore controlled by adsorption reactions and not by mass transfer for the range of particle sizes examined in this study.

With regard to the regeneration of chitosan, it was found that sodium hydroxide is a good agent for zinc and arsenic desorption, whereas ammonium sulphate and sodium chloride were the most suitable for copper and mercury desorption, respectively. The ability of chitosan to remove arsenic from natural water, and copper and zinc from mining waste water was verified. The use of these results for designing purposes is a subject for future work.

The arsenic speciation and arsenic removal in chitosan packed column were studied. Arsenic removal experiments were carried out with an arsenic standard solution (1.0 mg/l) and drilled well water samples from Limon Mine Community at different pH, water flowrate, and volume of adsorbent material. The simulation of arsenic speciation was carried out at a pH range from 0 to 12, a temperature of 25ºC, a pE equal to 4, and a total arsenic concentration of 1.34 x 10-5 mol kg-1. According to speciation calculations arsenic is found mainly in oxidized form in the conditions of Limon Mine’s drilled well waters, dihydrogen arsenate ion (H2AsO4-), and hydrogen arsenate ion (HAsO42-) being the major species. The experiments showed that arsenic adsorption depends mainly on the pH as well as the activity of functional groups that compose the chitosan structure. At pH 3 and volume of adsorbent material of 337.8 cm3 an adsorption of 94% was obtained from arsenic standard solution, and the arsenic present in the Limon Community’s water was almost totally removed at pH 3 and 7. The use of the results for designing purposes demands the breakthrough curves for chitosan to be determined.

En este trabajo se simuló la especiación del cianuro y componentes relacionados en soluciones de lavado de colas cianuradas de minerales de oro de la Mina El Limón, utilizando el programa geoquímico PHREEQC. Se consideró un modelo de especiación iónica formado por un conjunto de reacciones químicas y de especies principales en fase acuosa (hierro, cobre, cinc, calcio y aluminio, cloruro y cianuro), en distintas condiciones de pH, Eh y concentraciones de cianuro. Las simulaciones muestran que las concentraciones de las especies iónicas y complejas dependen principalmente del pH de la solución y de la concentración de cianuro disponible en el sistema, reproduciéndose en forma satisfactoria los valores de pH y solubilidad de metales medidos en el sistema. El cianuro forma complejos de alta estabilidad química con los metales disueltos, observándose que las especies de Fe-CN son altamente estables incluso a pH ácido donde prácticamente no existe el ión cianuro libre (CN-) producto de la formación del componente gaseoso HCN.

This study is concerned with the use of chitosan produced from shrimp shell waste for the removal of Cu(II), Hg(II), Pb(II) and Zn(II) from gold ore tailing solutions containing cyanide. This work involved the study of equilibrium and kinetic adsorption, the physicochemical characterization of mining effluents and desorption using different regenerating solutions. The experimental results showed that the adsorption capacity of chitosan is a function of the solution pH and that the optimum pH for these metallic ions is 6, except for Hg (pH 4). The equilibrium data were described using the Langmuir, Freundlich, Redlich-Peterson and SIPS isotherm models. The Langmuir equation was used to find the maximum adsorption capacity for Cu (79.94 mg/g), Hg (109.55 mg/g), Pb (58.71 mg)g) and Zn (47.15 mg/g). To determine the rate-controlling mechanism for metallic ion adsorption, pseudo-first-order, pseudo-second-order and the Elovich equation kinetic models were tested with experimental adsorption kinetic data. Tests conducted with gold ore tailing solutions indicated that chitosan is effective to remove these metallic ions above 70%. Desorption studies revealed that the regeneration of chitosan saturated with these metallic ions depends on the type and concentration of the regenerating solution ((NH(4))(2)SO(4), H(2)SO(4), HCl, NaOH and NaCl).

    La minería y la extracción de oro en operaciones a pequeña escala han contribuido a la contaminación de los recursos acuáticos de Nicaragua durante décadas. En este trabajo se investigó un proceso de biosorción a bajo costo para la remoción de iones mercurio (II) de soluciones estándar y de aguas naturales usando quitosano como adsorbente. La regeneración del adsorbente también fue estudiada. Los resultados mostraron que la adsorción de iones mercurio fue independiente del pH en el rango de pH 4-10 y que la capacidad se reduce considerablemente a pH 2. Los estudios de la cinética mostraron una fase inicial rápida de adsorción seguida por una fase más lenta. Por otro lado, se comprobó que los datos experimentales se ajustan al modelo de Langmuir, y se determinó, mediante el uso de este modelo, una capacidad de adsorción de 106 mg Hg/g quitosano. Una solución acuosa de NaCl demostró ser una opción barata y eficiente para la regeneración del adsorbente; además, el adsorbente mostró una capacidad de adsorción alta después de la regeneración. Se encontró que la concentración de mercurio en 4 de las 8 muestras recolectadas cerca de la ciudad de la Libertad, excedían ligeramente los niveles permisibles (1.09-2.25 μg Hg L-1) para agua de consumo humano según las normas CAPRE. Además, se determinó que la capacidad de adsorción de mercurio es menor en aguas naturales que en las soluciones estándares.

Solid supported evaporation (SSE) is a simple, nonselective method for isolating nonvolatile compounds from a solution. The solution is put in contact with porous polymer beads onto which the compound deposits upon evaporation of the solvent. This brings some advantages over direct evaporation to dryness in terms of safety, thermal decomposition, and solid handling, as the loaded beads form a free flowing granular material that is easily recovered. In this paper, SSE in a semicontinuous operating mode is investigated where the solution is continuously fed to (respectively sprayed over) an agitated bed of dry beads put under vacuum. It is found that under conditions where the solvent evaporation fate is high with respect to the feed rate, high bead loadings can be achieved before extensive sticking of beads and compound to the vessel walls occurs. The type of compound and solvent had little influence on the process performance, and, in cases where this was explored, the bead loading was found to be homogeneous. Based on a balance equation for the solvent fed to the system, a model is developed that results in a simple scale up criterion. The latter was successfully applied for transferring SSE from lab to the kilo lab scale.

The breakup of small solid aggregates in homogeneous and isotropic turbulence is studied theoretically and by using direct numerical simulations at high Reynolds number, Re-lambda similar or equal to 400. We show that turbulent fluctuations of the hydrodynamic stress along the aggregate trajectory play a key role in determining the aggregate mass distribution function. The differences between turbulent and laminar flows are discussed. A definition of the fragmentation rate is proposed in terms of the typical frequency at which the hydrodynamic stress becomes sufficiently high to cause breakup along each Lagrangian path. We also define an Eulerian proxy of the real fragmentation rate, based on the joint statistics of the stress and its time derivative, which should be easier to measure in any experimental setup. Both our Eulerian and Lagrangian formulations define a clear procedure for the computation of the mass distribution function due to fragmentation. Contrary, previous estimates based only on single point statistics of the hydrodynamic stress exhibit some deficiencies. These are discussed by investigating the evolution of an ensemble of aggregates undergoing breakup and aggregation.

A two-dimensional (2-D) model for a heap or dump bioleaching of a copper ore containing mainly chalcocite and pyrite has been developed. The rate of the mineral sulfide dissolution was related to the rate of oxidation by bacteria attached onto the ore surface. The latter was calculated using the model of Michaelis-Menten, where both temperature and dissolved oxygen in the leach solution were taken into account by the kinetic equation. Oxygen transport through the ore bed was associated with natural air convection originating from the decrease in gas density inside the ore bed, which was attributable not only to heating, but also to humidification and decrease in the oxygen concentration. The model was used to estimate air-velocity fields and profiles of temperature and oxygen concentrations as well as mineral conversions during the bioleaching operation for ore beds with different pyrite contents, bacterial populations, widths, heights, and permeabilities. The model provides a useful tool for the design, improvement, and optimization of industrial operating conditions.

Polymorphism, crystal shape and solubility of 1,4-dihydroxyanthraquinone (quinizarin) have been investigated in acetic acid, acetone, acetonitrile, n-butanol and toluene. The solubility of FI and FII from 20 degrees C to 45 degrees C has been determined by a gravimetric method. By slow evaporation, pure FI was obtained from n-butanol and toluene, pure FII was obtained from acetone, while either a mixture of the two forms or pure FI was obtained from acetic acid and acetonitrile. Slurry conversion experiments have established an enantiotropic relationship between the two polymorphs and that the commercially available FI is actually a metastable polymorph of quinizarin under ambient conditions. However, in the absence of FII, FI is kinetically stable for many days over the temperature range and in the solvents investigated. FI and FII have been characterized by infrared spectroscopy (IR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), transmission and ordinary powder X-ray diffraction (PXRD) at different temperatures. The crystal structure of FII has been determined by single-crystal XRD. DSC and high-temperature PXRD have shown that both FI and FII will transform into a not previously reported hightemperature form (FIII) around 185 degrees C before this form melts at 200-202 degrees C. By indexing FIII PXRD data, a triclinic P (1) over bar cell was assigned to FIII. The solubility of quinizarin FI and FII in the pure organic solvents used in the present work is below 2.5% by weight and decreases in the order: toluene, acetone, acetic acid, acetonitrile and n-butanol. The crystal shapes obtained in different solvents range from thin rods to flat plates or very flat leaves, with no clear principal difference observed between FI and FII.

This work investigates the ternary phase behavior of the two enantiomers of ibuprofen and water. The two enantiomers crystallize as a racemic compound and exhibit a thermodynamically stable liquid-liquid phase separation (LLPS), which extends over the entire enantiomeric composition range. First, the generic phase behavior of racemic compound forming systems exhibiting a stable LLPS is derived by exploiting the consolidated knowledge of conglomerate forming systems obtained in the first part of this series. Below the onset temperature of the LLPS, the system behaves like a typical racemic compound forming system. As for conglomerate forming systems, the onset of the LLPS is found to occur through a ternary monotectic equilibrium, where a new, solute-rich liquid phase emerges inside each solid-solid-liquid phase region. Then, the ternary phase diagram of the ibuprofen/water system in the temperature range from 40 to 82 °C is presented together with the outcome of a thorough experimental investigation. Our theoretical considerations are in excellent agreement with experimental results.

A methodology for the design of cooling crystallization processes for chiral resolution from nonracemic initial solutions is presented. Such processes are encountered when chiral resolution is attained by hybrid processes, where the crystallization step is preceded by a pre-enrichment step accomplished by either asymmetric synthesis or another separation technique. The work focuses on substances that crystallize as conglomerates and accounts for the occurrence of oiling out, i.e., an undesired liquid liquid phase separation during crystallization. The generic ternary phase diagrams for conglomerate-forming systems with and without oiling out are derived. This knowledge is then applied to identify suitable operating conditions for chiral resolution. As crystallization is started from saturated solutions, the crystallization process is characterized by three parameters: the initial enantiomeric excess and the initial temperature, which together implicitly define the position of the operating point in the phase diagram, and the final operating temperature, which defines the composition and the amount of the phases present at the end of crystallization. For any initial enantiomeric excess, the methodology yields distinct areas in the initial versus final temperature plane containing pairs of operating temperatures that are suitable for chiral resolution. Such operating map bears great potential in improving the design and optimization of chiral resolution processes by crystallization.

The objective of this study was to investigate the effect of the distribution in size of free-flowing particles for the evolution in tablet structure and tablet strength. For sucrose and sodium chloride, three powders of different size distributions were prepared by mixing predetermined quantities of particle size fractions. For paracetamol, three batches with varying particle size distributions were prepared by crystallisation. The powders were formed into tablets. Tablet porosity and tensile strength were determined directly after compaction and after short-term storage at two different relative humidities. Tablets were also formed after admixture of a lubricant (magnesium stearate) and the tablet tensile strength was determined. For the test materials used in this study, the spread in particle size had no influence on the evolution in tablet porosity and tensile strength during compression. However, the spread in particle size had a significant and complex influence on the short-term post-compaction increase in tablet tensile strength. The effect of the spread was related to the instability mechanism and the presence of lubricant. It is concluded that the distribution in size of free-flowing particles is not critical for the tablet porosity but may give significant effects on tablet tensile strength due to a post-compaction reaction.

The objective of this study was to investigate the effect of fracture strength of paracetamol particles on their compactability. For this purpose two series of paracetamol particles were prepared by crystal agglomeration and by granulation using different solvents. A free flowing particle size fraction of all types of particles was characterized with respect to their shape, degree of agglomeration and single fracture strength. The powders were compressed to tablets and the compression mechanism of the particles and the evolution in tablet micro-structure were assessed by compression parameters derived from the Heckel and Kawakita equations and by a tablet permeabililty coefficient. Tablet tensile strength and porosity were determined. The degree of deformation and fragmentation during compression varied between agglomerates and granules and was dependent on their failure strength. The granules varied in compactability with particle failure strength while the agglomerates showed limited variation. It is proposed that, the dominant mechanism of compression for the granules was permanent deformation while for the agglomerates it was fragmentation. It was thus found that the compression mechanism of the particles was dependent on both the degree of agglomeration and the particle failure strength.

In this work crystal growth and nucleation of b-FeF₃×3H₂O and crystallization of chromium (III), iron (III) and nickel (II) fluoride hydrates from mixed acid (1-3 mol/kg HNO₃ and 1-6 mol/kg free HF) have been investigated.

The solubility of b-FeF₃×3H₂O has been determined in solutions of different hydrofluoric acid (1-7mol/ kg) and nitric acid (0-7mol/ kg) concentrations at 30, 40 and 50°C. The total iron concentration at equilibrium ranges from about 1 to 35 g/kg solution. In the range of investigated conditions the solubility in terms of total iron content increases with increasing temperature and decreases with increasing concentration of hydrofluoric acid and nitric acid. The results are analysed by examining the chemical speciation in the solutions.

The crystal growth kinetics of b-FeF₃×3H₂O crystals have been studied by performing seeded isothermal desupersaturation experiments in solutions of 1.5-3.0 mol/ kg nitric acid and 1.4- 5.6 mol/ kg free hydrofluoric acid at 30, 40 and 50°C. The results show that the crystal growth is surface integration controlled. When the driving force is based on a proper speciation no clear correlation of the growth rate with hydrofluoric acid or nitric acid concentration is found. The rate is about the same in industrial pickle liquor as in pure acid solutions. The growth rate at a supersaturation ratio (c(FeF₃)_free/c_s(FeF₃)_free) of 2 was found to be 5.2×10^-12m/s at 30°C, 7.9×10^-12m/s at 40°C and 20×10^-12m/s at 50°C. Thus, the crystal growth rate at 50°C is about four times higher than at 30°C. The temperature dependence of the rate constant corresponds to an activation energy of 55kJ/ mol.

Crystallization from solutions supersaturated with both Cr(III) and Fe(III) has been investigated and it has been observed that Fe(III) and Cr(III) crystallizes in the form of Cr(Fe)F₃×3H₂O which is isostructural with CrF₃×3H₂O. Iron(III) and nickel(II) crystallizes into an unidentified fluoride hydrate crystal.

The crystal growth rate of CrF₃×3H₂O at 50°C is about the same as the growth rate of b-FeF₃×3H₂O crystals.

The influence of hydrofluoric acid and nitric acid concentration on the growth rate of beta-FeF3 center dot 3H(2)O crystals has been studied in different hydrofluoric acid (4.7-10.7 mol/(kg H2O)) and nitric acid (2.1-4.6 mol/(kg H2O)) mixtures at 50 degrees C. Seeded desupersaturation experiments were performed and the results were evaluated by considering the chemical speciation using two different speciation programs. The growth rate at 50 degrees C at a supersaturation ratio of 2, expressed in terms of free FeF3, was found to be in the range of (0.4-3.8) x 10(-11) m/s. The growth rate order was found to be two or higher in all experiments. The low growth rate and high growth rate order indicate that the growth rate is governed by the surface integration step. The growth rate was found to be independent of variations in acid concentrations: this is in accordance with the assumption of a surface integration controlled growth rate.

Crystallization from hydrofluoric acid/nitric acid solutions supersaturated with Fe(III) and Cr(III) has been investigated. Iron and chromium crystallizes into a solid solution in the form of Cr(Fe)F-3 center dot 3H(2)O, which is isostructural with CrF3 center dot 3H(2)O and alpha-FeF3 center dot 3H(2)O. By seeded isothermal desupersaturation experiments, the growth rate of beta-FeF3 center dot 3H(2)O crystals at 50 degrees C has been studied in hydrofluoric acid and nitric acid solutions containing Cr(III). It is found that the growth rate of beta-FeF3 center dot 3H(2)O is essentially uninfluenced by the presence of 5 g/kg Cr(III). At 50 degrees C and a supersaturation ratio of 2 (c(FeF3)(free)/c(s)(FeF3)(free)), the growth rate is (0.8-2.2) x 10(-11) m/s in 3 mol/(kg solution) HFfree and 3 mol/(kg solution) HNO3.

Crystallization of nickel fluoride hydrate from mixed pickle acid and the influence of Ni(II) on growth rate of beta-FeF3 center dot 3H(2)O have been studied. Iron and nickel crystallize into an unidentified Fe/Ni fluoride hydrate crystal having the overall mol ratio of Ni, Fe, and F equal to 1:2:8, which is in accordance with the number of fluoride ions needed to balance the positive charges of Ni and Fe. The most probable empirical formula of this material is (FeF3)(2)NiF2(H2O)(6-10). By seeded isothermal desupersaturation experiments, growth rate of beta-FeF3 center dot 3H(2)O crystals at 50 degrees C has been studied in a hydrofluoric acid and nitric acid solution containing Ni(II). It is found that the growth rate of beta-FeF3 center dot 3H(2)O is essentially uninfluenced by the presence of 4 g/kg Ni(II).

Crystal growth of beta-FeF3 • 3H(2)O has been investigated in mixtures of 3 mol kg(-1) hydrofluoric acid and 3 mol kg(-1) nitric acid at 30, 40 and 50 degrees C. Seeded isothermal desupersaturation experiments have been performed in the range: 1.3 < S < 3.6. Solution samples were analysed for total iron concentration with inductively coupled plasma atomic emission spectroscopy. The true supersaturation driving force was estimated by a proper speciation using the software SSPEC using appropriate stability constants. Growth rate parameters of the BCF surface diffusion growth rate equation and the empirical power-law equation have been estimated by fitting the supersaturation balance equation using a nonlinear optimization procedure. The results show that the growth rate is surface integration controlled. The growth rate at a supersaturation ratio of 2 was found to be 3.5 x 10(-12) m s(-1) at 30 degrees C, 7.4 x 10(-12) m s(-1) at 40 degrees C and 16 x 10(-12) m s(-1) at 50 degrees C. The activation energy of the rate constant of crystal growth was found to be 61 kJ mol(-1). .

Stainless steel is pickled in mixed acid solutions (1-3 M HNO3 and 0.5-4 M HF). The spent solution is usually neutralized with lime, and in Sweden about 18,000 tons/yr of metal hydroxide sludge is disposed as landfill waste. We are developing a cost-saving and environmentally friendly process, involving crystallization of beta-FeF3 . 3H(2)O, where the metal content is recovered and the acid is recycled. Iron has been successfully separated from spent pickle bath solutions by precipitation of beta-FeF3 . 3H(2)O in a continuous crystallizer (10 L scale) where the solution is concentrated by nanofiltration. The crystal growth rate of beta-FeF3 . 3H(2)O has been determined in industrial pickle bath solutions at 50 degrees C and the results have been compared to previous measurements in pure HF/HNO3 solutions prepared in the laboratory. The growth rate of beta-beta eF(3) . 3H(2)O crystals at 50 degrees C is in the order of 10(-11) m/s in both industrial and pure acid mixtures.

This study investigated the transport coefficients involved in mass and heat transfer during the drying of a porous solid partially saturated with multicomponent mixtures.  It included the coefficients governing liquid transport through the solid, the matrix of multicomponent diffusion coefficients in the liquid phase, and the effective thermal conductivity.  As it is not possible to determine these coefficients by theoretical considerations alone and considerable experimental work is required to determine them in a broad range of process conditions, the principle of this study has been the use of mathematical models complemented with some empirical parameters.  These empirical parameters were determined by comparison between measurements in specially designed experiments and the results of mathematical models that describe the process.  In addition, the application of the multicomponent diffusion coefficients is described in two cases where liquid diffusion is important: convective evaporation of a multicomponent stationary liquid film and a falling film.

To study liquid transport through the solid, isothermal drying experiments were performed to determine the transient composition profiles and total liquid content of sand samples wetted with ternary liquid mixtures with different initial compositions and temperatures.  A mathematical model including mass transfer by capillary movement of the liquid and interactive diffusion in both the gas and liquid phases was developed.  To simulate the capillary movement of liquid mixtures, parameters experimentally determined for single liquids were weighed according to liquid composition. A fairly good agreement between theoretical and experimental liquid composition profiles was obtained considering that axial dispersion was included in the model.

To study the matrix of multicomponent diffusion coefficients in the liquid phase, the redistribution of liquid composition in a partially filled tube exposed to a longitudinal temperature gradient was analysed.  Experimental work was carried out using two main ternary mixtures with different initial compositions and temperature gradients.  Experimental data were compared with the results of a theoretical model that describes the steady-state liquid composition distribution in a partially filled non-isothermal tube to find the empirical exponent that modifies the matrix of thermodynamic factors.  Correlations for the exponents as a function of temperature were determined for each particular multicomponent mixture.

The effective thermal conductivity of a porous solid containing multicomponent liquid mixtures was studied by measuring the liquid composition, liquid content and temperature distributions in a cylindrical sample dried by convection from the open upper side and heated by contact with a hot source at the bottom side.  Simulations performed at a quasi steady state were compared with experiments to estimate the adjusting geometric parameter of Krischer’s model for effective thermal conductivity, which includes the contribution of the evaporation-diffusion-condensation mechanism. The results revealed that a resistance corresponding to a parallel arrangement between the phases seems to dominate in this case.

In the study of the convective drying of a multicomponent stationary liquid film, the equations describing interactive mass transfer were decoupled by a similarity transformation and solved simultaneously with a conduction equation by the method of variable separation.  Variations of physical properties along the process trajectory were taken into account by a stepwise application of the solution in time intervals with averaged coefficients from previous time steps.  Despite simplifications, the analytical solution gives a good insight into the selectivity of the drying process and is computationally fast.  On the other hand, numerical simulations of the convective evaporation of the multicomponent falling liquid film into an inert gas with a co-current flow arrangement of the phases almost always revealed a transition from liquid-phase-controlled conditions to a process in which neither the gas nor the liquid completely controls the evaporation.

The results obtained in this work would be useful in implementing models to improve the design, process exploration and optimisation of dryers by incorporating the solid-side effects to describe the drying of liquid mixtures along the whole process.

Este trabajo consiste en un estudio de transferencia simultánea de calor y masa con la finalidad de determinar la matriz de coeficientes de difusión multicomponente en fase líquida. La literatura reporta una fórmula semi-empírica desarrollada por Bandrowski y Kubaczka para calcular la matriz de coeficientes de difusión multicomponente, método que separa las contribuciones cinética y termodinámica a la transferencia de masa e incluye un exponente empírico para realizar cálculos más precisos. El presente trabajo propone la estimación del exponente empírico en un amplio rango de temperaturas estudiando la redistribución de composición en un capilar no isotérmico y no saturado, tomando en consideración las no idealidades descritas por la matriz de coeficientes de factores termodinámicos. Para tal fin, se ha utilizado el sistema ternario agua-etanol-acetona a dos diferentes rangos de temperaturas y dos diferentes grados de saturación. Los resultados muestran que el método es efectivo ya que se obtuvieron valores consistentes del exponente empírico que modifica la matriz de factores termodinámicos. Además, se evidencia que el exponente es dependiente de la temperatura.