Effect of struvite seed crystal on MAP crystallization

BACKGROUND: There has been considerable controversy over the effect of seed crystal additions on crystallization of magnesium ammonium phosphate hexahydrates (MAP). In this study, batch experiments were carried out to verify this effect using synthetic solutions. RESULTS: Addition of seed crystals could increase the rate of MAP crystallization and significantly shorten the reaction crystallization time, especially for solutions with a lower supersaturation ratio (Ω). Crystallization time of MAP with and without seed addition can be expressed by two different formulas, in which the crystallization with feed addition followed an exponential function, and the secondary formula fitted a two‐order power function. When 0.422 g L^?1 of seed crystals was added the equilibration time for crystallization calculated by the formula was reduced by 75 min for low supersaturation ratio solution and 26 min for medium supersaturation ratio solution. CONCLUSION: To increase the MAP reaction rate and to shorten induction and equilibration times, seed crystal addition should be practiced Copyright © 2011 Society of Chemical Industry     

Growth rates of ibuprofen crystals grown from ethanol and aqueous ethanol

To quantify the crystallization of racemic ibuprofen [2-(4-isobutyl-phenyl)-propionic acid] from aqueous ethanol it is necessary to know the growth rate kinetics. Growth rates were measured by adding SPG (size proportional growth) seed crystals to an isothermal non-nucleating batch crystallization and sampling during the batch. The supersaturation was measured by refractive index and the crystal size by laser light scattering (Malvern). To ensure the batch was non-nucleating the supersaturation was kept within the narrow secondary MZ (metastable zone). Measurements were made at three temperatures, 10, 25 and 40 °C. The growth rate was proportional (first order kinetics) to the solution supersaturation, expressed in mass ratio of ibuprofen to ethanol units. Despite the narrow MZ, the initial growth rates were substantial (up to 1 μm/min). Temperature has a large effect on growth rate with an activation energy of 13.7 kJ/mol. The water content affects the growth rate coefficient differently depending on the temperature.     

The growth and nucleation of ice in a batch Couette flow crystallizer

An experimental investigation into the crystallization characteristics of ice crystals from brine solution was carried out using a batch Couette flow crystallizer. Particle size distributions were determined by a photographic technique. The nucleation rate was correlated by the power law model: B⁰ = 26.2(P/V)^0.52 (δC^*)^1.8 μ^0.2₂ Qualitative growth characteristics were also inferred and found to be consistent with a diffusion controlling mechanism. The results obtained here suggest that early time data be emphasized in future batch crystallization experiments to more accurately determine the nucleation rate model.     

The role of meso-mixing in anti-solvent crystallization processes

This paper establishes links between the available turbulent mixing capability in a fed-batch reactor and important crystallization characteristics such as the metastable zone width (mszw) and product nucleation during the anti-solvent crystallization of benzoic acid. As demonstrated an increase in the locally dominant meso-mixing time scale, τ_D, facilitates the premature and subsequent sporadic nucleation of the solute. An alternative well mixed addition location, defined via computational fluid dynamics (CFD) simulations and turbulent mixing theory, allows this dispersion limiting time scale to be reduced by over 50% across all anti-solvent addition rate assessed. Additionally, a more direct pathway from the feed point to the well mixed region of the impeller is also presented. These more favorable hydrodynamic conditions improve supersaturation dispersion and blending which in turn eliminate the premature and additional nucleation of the solute throughout the batch. Correlations between the FBRM fines populations and τ_D are also presented. These relationship demonstrate the sensitivity to the systems crystal size when hydrodynamic properties are improved.     

Quantitative design of seed load for solution cooling crystallization based on kinetic analysis

Seed load of crystallization has a direct effect on the product qualities. To further reveal the effects of seed load on crystallization kinetics and improve the product size distribution, the aqueous solution of potassium nitrate (KNO₃–H₂O) is employed as a model system and the relevant kinetic experiments are conducted in a batch cooling crystallizer. The crystal nucleation and growth rate parameters are firstly estimated with the concentration and transmittance data using a mathematical model reported in our lab, and then the backward calculations with the help of the model parameters are successfully performed. It is found that the nucleation capacity decreases and growth capacity increases with increasing seed load, and the size distribution of crystal products tends to be more uniform. However, with the increasing of seed load, the linear growth rate of single crystal and the mean size of products both reduce accordingly. Based on the calculational and experimental results, a quantitative design scheme concerning seed load is proposed by further kinetic analyses, and the corresponding verification experiments are carried out. The results show that under the guidance of the proposed scheme, the size distribution of crystal products is more concentrated and the mean size of final particles can also escape from reducing obviously.     

Novel semibatch supersaturation control approach for the cooling crystallization of heat-sensitive materials

This article introduces the application of a novel supersaturation control (SSC) approach for the crystallization of heat-sensitive materials. Traditional SSC implements parabolic temperature profile with slow initial cooling that maximizes growth over nucleation, however, which may also promote heat degradation. The proposed semibatch SSC fixes the crystallization temperature to a sufficiently low value to minimize thermal degradation, and manipulates the flow rate of a higher temperature feed stream to control the supersaturation. The high temperature feed is produced in a continuous dissolver before feeding, thus the solution spends considerably shorter time at high temperature than in the traditional batch cooling crystallization. This work demonstrates the effectiveness of the semibatch operation for the cooling crystallization of heat-sensitive substances by thorough simulation study as well as experimental investigations. The experimental validation confirmed the simulation results, and both analyses revealed the superiority of semibatch SSC for the crystallization of heat-sensitive materials.     

Mixing and Crystallization Kinetics in Gas‐liquid Reactive Crystallization

A study of gas‐liquid reactive crystallization for CO₂‐BaCl₂‐H₂O system was performed in a continuous flow crystallizer. The influences of mixing on the crystallization kinetics of barium carbonate crystals were investigated. The mixing parameters are stirrer speed, feed concentration, gas‐flow rate, pH of solution, addition rate of NaOH solution, and mean residence time. Under pH‐stat operation, the crystallization mechanism can be assessed by the addition rate of NaOH solution, which acts as an indicator for the absorption rate of carbon dioxide. Assuming a size‐independent agglomeration mechanism, the nucleation rate, growth rate and agglomeration kernel can be obtained, simultaneously, at steady state, by the method of moments. Evidence shows that feed concentration, feed rate, gas‐flow rate, and stirrer speed have a significant influence on the nucleation rates and mean particle sizes. This shows the effect of micromixing. The crystallization mechanism tends to be reaction limited when the feed concentration of barium chloride solution is higher than 5 mM, while at lower stirrer speeds and feed concentrations, the mechanism tends to be both mixing and reaction controlled. The growth rate depends on the mean supersaturation value and the pH of the solution and the mass‐transfer resistance cannot be completely eliminated in this work. For a monodispersal collision model, in the viscous sub‐range of turbulence, the agglomeration kernel can be expressed as β ∝ d^{3 –1/4}, showing a low efficiency of collision. The result is also demonstrated by the agglomeration kernel expression. Comparison with a liquid‐liquid‐mixing reactive crystallization system is also discussed.     

Crystallization of calcium sulphate hemihydrate in concentrated phosphoric acid solutions

We aim to show the existence of agglomeration by measuring and modelling secondary nucleation and crystal growth rates of calcium sulphate hemihydrate, CaSO₄-0.5 H₂O, in concentrated phosphoric acid solutions. Using a batch crystallizer we measured the evolution of the population density as a function of supersaturation, H₂SO₄ excess and stirring rates. All experiments were carried out at 90 °C in solutions at 40 wt.% of P₂O₅, simulating the usual conditions for crystallizing hemihydrate in the industrial processes of phosphoric acid production. Nucleation and growth rates were calculated from the population number densities, using the moments analysis method. A model is presented for describing the crystallization process of hemihydrate. It is shown that secondary nucleation and growth rates are quadratic functions of supersaturation. H₂SO₄ concentrations affect supersaturation but at the same supersaturation the growth rates are not significantly different. Nucleation is independent of the stirring rate, whereas growth rates are slightly affected for stirring rates up to 500 rpm. Taking agglomeration into account, the moments method fits very well the experimental data.     

Optimization study of a batch chromatographic process based on Amberchrom-CG161C adsorbent for separation of valine from a ternary amino acid mixture

The optimal design of the batch chromatographic process for separation of valine (product) from isoleucine and leucine (side-products) was carried out by using the relevant optimization tool that was prepared on the basis of an up-to-date genetic algorithm. In such an optimal design, the flow rate, feed size (?feed), eluent gap size (?gap), and product collection time were optimized to maximize the valine productivity of the batch chromatographic process under consideration. The results showed that the valine productivity was governed by the flow rate in the region of low flow rates, whereas it was governed by the Δ _gap /Δ _feed factor in the region of high flow rates. Finally, the effect of valine yield on the productivity was investigated, followed by providing the proper operating conditions that could be advantageous to both valine productivity and valine yield.     

Determination of crystal growth rate for porcine insulin crystallization with CO2 as a volatile acidifying agent

Crystallization is controlled by two steps that determine the quality and the final size of the product, nucleation and growth, which are functions of supersaturation. Recently, Hirata et al. [1] crystallized insulin using CO₂ as a volatile acid to impose supersaturation on the system. The objective of the present work was to determine the growth kinetics of insulin crystallization in 50 mM NaHCO₃ solution with 0.4 mM ZnCl₂ in a CO₂ atmosphere at 15 °C, adjusting the parameters of the equation G = k_g × S^g to the experimental data. The solubility of insulin in the NaHCO₃/CO₂/ZnCl₂ system at 15 °C was determined as a function of pH in the range of 6.30–7.34. The crystal growth data allowed determination of the growth order “g” (g = 2.9). Although protein crystallization has some features that differ from the crystallization of less complex molecules, the apparent growth kinetics of insulin were successfully analyzed here with the same empirical methods used for small molecules, which can easily be scaled up for industrial applications to achieve specific size and purity, the goals of industrial crystallization. The method used in this work is a useful tool for describing and simplifying optimization of industrial protein crystallization processes.     

Automated self seeding of batch crystallizations via plug flow seed generation

In this study, seed slurry from a single addition anti-solvent plug flow crystallization of benzoic acid was used to seed the equivalent batch cooling crystallization. The experimental conditions were carried out to simulate automated self-seeding. This involves withdrawal of solution from a batch crystallizer, which is then mixed with anti-solvent within a plug flow crystallizer, in order to generate a seed slurry which is fed directly back to the batch crystallizer. This seeding strategy allowed the final CSD of the batch crystallization to be controlled by variation of the crystal size from the plug flow seeding device at a constant seed loading. The ability to use unequal feed/anti-solvent inlet flowrates (in the Roughton vortex mixer) proved effective in controlling the batch CSD at 2% seed loading and constant feed composition.     

Ammonia Removal from Aqueous Solutions by Iranian Natural Zeolite

Abstract

The capability of Iranian natural clinoptilolite for ammonia removal from aqueous solutions has been thoroughly studied. Both batch and continuous (column) experiments were carried out. The viability of this natural zeolite in reducing the leakage of ammonia to the environment through waste water streams was a main focus of this research. Through the batch experiments, the effect of process variables such as the size of zeolite particles, pH, and ammonia concentration of the feed solution on the kinetics of ammonia uptake were investigated. Ammonia removal occurred rapidly and within the first 15 minutes of contact time, a major part of ammonia was removed from the solution. An adsorption capacity about 17.8 mg NH₄ ⁺/g zeolite at feed ammonia concentration of 50 mg/L was obtained and the optimum range for pH was achieved about 5.5–7.6. The adsorption capacity of clinoptilolite in the continuous mode was about 15.16 and 15.36 mg NH₄ ⁺/g zeolite for the original and regenerated types of clinoptilolite, respectively, where feed ammonium concentration was 50 mg/L. Increasing the feed ammonium concentration to 100 mg/L did not reduce the capability of the column for its ammonium removal and up to a bed volume (BV) of 85, there was only less than 1 mg/L ammonium in the column outlet. Presence of cations such as Ca²⁺, Mg²⁺ and Na⁺ in the feed solution reduced the clinoptilolite adsorption capacity to about 11.68 mg NH₄ ⁺/g zeolite. Regeneration experiments were carried out using concentrated sodium chloride solutions, as well as tap water. Where tap water was used as the regenerant, gradual release of ammonium from exhausted clinoptilolite was observed.     

Industrial batch crystallization of a plate-like organic product. In situ monitoring and 2D-CSD modelling. Part 2: Kinetic modelling and identification

The batch seeded cooling solution crystallization of a fine organic material, exhibiting a platelet-like habit, was investigated and a model of the time variations of the crystal size distribution (CSD) was designed using two-dimensional population balance equations. Activated surface secondary nucleation and attrition secondary nucleation mechanisms were considered, coupled with growth mechanisms of two main dimensions of the crystal, resulting in a set of eight kinetic parameters. The model relates the effects of the main batch operating conditions: seeding temperature, cooling rate and total area of the seed particles, on both the supersaturation profile and bi-dimensional CSD. Surface secondary nucleation occurs first since it is promoted by the introduction of seeds and remains active as long as the relative supersaturation exceeds a threshold value of about 16%. It vanishes below which could be expected as we deal with an activated mechanism. Contact secondary nucleation occurs later when the concentration of solid is sufficient. It is spread over time until supersaturation disappears at the end of the batch process. This contact secondary mechanism is assumed to be the dominant nucleation mechanism as it generates about two-thirds of the final crystal number. Sharp desupersaturation profile following the introduction of seeds, which was observed experimentally, is shown to be quantitatively described through the growth of seed particles. The termination of the batch process is more difficult to represent. Due to crystal attrition, distinct growth rates between initial and secondary crystals or growth rate dispersion might explain such difficulty.     

草甘膦连续结晶技术的开发与应用

测定了实际料液中草甘膦的溶解度和过饱和度特性,并根据此特性设计建立了由2个Krystal结晶器串联组成的年产10000t草甘膦连续结晶系统.运行结果表明:系统设计合理,达到了设计目标;连续结晶工艺相对间歇结晶工艺具有占地面积小、自动化程度高、操作简单、操作人员少、产品粒度均匀、节能降耗达50%以上等优点;系统可连续稳定运行60 d以上.     

Continuous reactive crystallization of pharmaceuticals using impinging jet mixers

For reactive crystallization of pharmaceuticals that show a rapid reaction rate, low solubility of active pharmaceutical ingredient and hence a large supersaturation, it was found in a recent study that a process design which integrates an impinging jet mixer and batch stirred tank produces high quality crystals. The current investigation examines if the short processing time of reactive crystallization permits the impinging jet mixer—stirred tank design to be modified to operate in a continuous mode. The new design combines an impinging jet mixer for feed introduction and reaction with a continuous stirred tank reactor (CSTR) and tubular reactor for crystal growth. A study of reactive crystallization of sodium cefuroxime (an antibiotic), using first a 1L CSTR then scaling to a 50L CSTR, found that the new design produces crystals of higher crystallinity, narrower particle size, and improved product stability, than batch crystallizers. © 2016 American Institute of Chemical Engineers AIChE J, 63: 967–974, 2017     

On the prediction of crystal shape distributions in a steady-state continuous crystallizer

Zhang and Doherty [2004. Simultaneous prediction of crystal shape and size for solution crystallization. A.I.Ch.E. Journal 50, 2101-2112] have provided a one-dimensional analysis of crystallization based on the assumption that the relative face-specific growth rates of a (2-D) crystal are independent of supersaturation and hence invariant with time. Subsequent work by these authors [Zhang, Y., Sizemore, J.P., Doherty, M.F., 2006. Shape evolution of 3-dimensional faceted crystals. A.I.Ch.E. Journal 52, 1906-1915) consider shape evolution of single three-dimensional crystals with morphological changes. In this work, we present a multidimensional population balance approach accounting for dependence of the relative face-specific growth rates on supersaturation, a situation more commonly encountered. For example, Joshi and Paul [1974. Effect of supersaturation and fluid shear on habit and homogeneity of potassium dihydrogen phosphate crystals. Journal of Crystal Growth 22, 321-327] and Mullin and Whiting [1980. Succinic acid crystal-growth rates in aqueous solution. Industrial & Engineering Chemistry Fundamentals 19, 117-121] report face-specific growth rates with different dependence on the supersaturation. Thus it has been observed that there exists significantly different crystal shapes in a crystallizer [Yang, G., Kubota, N., Sha, Z., Louhi-Kultanen, M. Wang, J., 2006. Crystal shape control by manipulating supersaturation in batch cooling crystallization. Crystal Growth and Design 6, 2799-2803]. Consequently, the population of crystals at any instant will have widely varying crystal shapes and sizes depending upon the initial crystal shape and size distribution. Computations are presented for the shape distributions of the crystal population emerging from a steady-state continuous crystallizer for two cases: (1) feed without crystals including nucleation for the formation of new crystals, and (2) feed with seed crystals of known shape, with suppressed nucleation. In the range of mean residence times investigated, the calculated crystal volume distributions for the first case show geometrically dissimilar shapes without morphological variations. However, in the second case, because the feed crystals of the chosen shape were susceptible to morphological changes, the volume distributions display this feature with shape and size distributions for each of a number of different morphologies. By varying operating conditions such as the flow rate, the inlet supersaturation, and the shapes of feed crystals, the proposed model can clearly be used to manipulate the crystal shape and size distributions and their morphologies.     

Strategies to optimize phosphate removal from industrial anaerobic effluents by magnesium ammonium phosphate (MAP) production

BACKGROUND: Owing to more stringent phosphate discharge requirements and the increasing prices of fertilizers, beneficial recovery and reuse of phosphate from industrial anaerobic effluents is becoming an important issue. Phosphate recovery by struvite or magnesium ammonium phosphate (MAP) permits its recycling in the fertilizer industry because struvite is a valuable slow release fertilizer. Two different approaches to MAP crystallization depending on initial levels of phosphate in the wastewaters were tested and compared. RESULTS: For low‐phosphate‐containing anaerobic effluents (<30 mg PO₄^3?‐P L^?1), a novel approach using ureolytic induced MAP formation with MgO addition appeared to be suitable. The residual phosphate concentrations in the effluent ranged from 5 to 7 mg PO₄^3?‐P L^?1 and the separated matter contained residual amounts of Mg(OH)₂. High‐phosphate‐containing anaerobic effluents (100 to 120 mg PO₄^3?‐P L^?1) were treated efficiently using air stripping combined with MgCl₂ and NaOH reagents, yielding residual phosphate levels of 8 to 15 mg PO₄^3?‐P L^?1 and spherical pure MAP crystals of 0.5 to 2 mm. CONCLUSION: Results show that depending on the initial phosphate concentrations in the wastewaters and the ammonium and magnesium levels, the strategy selected for struvite crystallization is a determinative factor in achieving a cost effective technology. Copyright © 2008 Society of Chemical Industry     

Kinetic Characteristics of Amino Acid Salt Crystallization in Methanol‐Water System

Nucleation and growth mechanisms and kinetics of crystals of an amino acid salt were investigated in a methanol‐water system by measuring and evaluating the induction time as a function of the supersaturation ratio and temperature in batch salting out crystallization experiments. Discrimination between the possible crystallization mechanisms, and estimation of the kinetic parameters were carried out using nonlinear parameter identification. The results concerning the growth mechanism obtained were checked additionally by measuring the induction time as a function of number density of seed crystals.     

Application of Full Factorial Design for Removal of Polycyclic Aromatic Dye from Aqueous Solution Using 4A Zeolite: Adsorption Isotherms,Thermodynamic and Kinetic Studies

In this study, removal of the cationic dye acridine orange (AO) from aqueous solution using 4A zeolite was studied. The adsorption experiments were performed using batch system, and full factorial design was employed for investigating the condition of removal efficiency of dye. The four most important operating variables were the initial pH of the solution, the concentration of dye, the contact time, and the temperature. The 18 experiments were required to investigate the effect of variables on removal of the dye. The results were statistically analyzed to define important experimental variables and their levels using the analysis of variance (ANOVA). A regression model that considers the significant main and interaction effects was suggested and fitted the experimental data very well. Model predictions were found to be in good agreement (R² = 99.99%, adjusted R² = 99.86%) with experimental data. The optimized conditions for dye removal were at initial pH 3.0, 20.0 mg L^?1 dye, temperature 298.0 K and 80.0 min adsorption time. The experimental data were analyzed by the Langmuir, Freundlich, Temkin and Sips adsorption models. The maximum predicted adsorption capacities for AO was obtained as 29.851 mg g^?1. The adsorption thermodynamic parameters, namely ΔH°_ads, ΔG°_ads and ΔS°_ads, were determined. Furthermore, the kinetic of AO adsorption on the 4A zeolite was analyzed using pseudo-first- and second-order kinetic models and the results showed that the removal was mainly a pseudo-second-order process.