THE MORPHOLOGY OF SPRAY-DRIED PARTICLES A QUALITATIVE VIEW

ABSTRACT

Industrial and pilot plant spray-dried materials were obtained from various manufacturers and qualitatively examined in order to identify structural and morphological features. Three distinct categories of particle morphology were identified. Namely, crystalline, skin forming and agglomerate. A number of unusual morphological phenomena were also noted Selected properties such as powder flowability. particle size and particle friability, were found to be directly related to morphological structure. Single particles were also produced in a convective drying process analogous to spray drying, in which, different solids or mixtures of solids were dried from solutions, slurries or pastes as single suspended droplets. The localised chemical and physical structures were analysed, and the results related to experimental conditions viz. drying air temperature and initial solids concentration. There was a strong similarity between the industrial spray-dried material and those dried experimentally. The morphologies of multicomponent mixtures were found to be complex, with the respective migration rates of the solids being dependent on drying temperature. The results are of relevance to dryer optimisation and to the optimisation of product characteristics, They also go some way to validating the single droplet drying technique as a useful analytical tool in spray drying research, and possibly other particulate processing industries.     

Modeling Particle Formation at Spray Drying Using Population Balances

There have been several efforts to simulate the physical processes in a single droplet during spray drying in the last several years, but most of the models do not describe the solid formation in detail. In this work, the development of the microscopic solid structure in a droplet during spray drying is simulated. A radial-symmetric model of the droplet is used to simulate the mass and heat transport. The solid formation at every radial discretization point is obtained by the solution of population balances. This way, the distribution of the particle number density in the droplet depending on the macroscopic process parameters can be predicted. The model equations are solved in a normalized coordinate system to be able to describe the shrinkage of the droplet. The suitability of these population balances will also be discussed. For the validation, monodisperse single droplets consisting of a solution or suspension are dried with constant boundary conditions.     

Single Droplet Drying Technique to Study Drying Kinetics Measurement and Particle Functionality: A Review

Advances in the study of the rate processes in spray drying have helped improve product quality. Single droplet drying (SDD) is an established method for monitoring the drying kinetics and morphological changes of an isolated droplet under a controlled drying environment, mimicking the droplet convective drying process in spray drying. To enhance particle quality requires understanding of both the particle formation process and knowledge of how different particle properties are affected by the drying conditions used. The latest development in the SDD technique enables evaluation of these aspects by incorporating a dissolution test in the drying experiment. The experiment is realized by attaching a solvent droplet to a dried/semi-dried single particle in situ and then video-recording the resultant morphological changes. Some of the particle (e.g., crystallinity) properties obtained under different drying conditions can be modelled using the measured droplet drying kinetics. This paper reviews the applications of SDD experiments in measuring the drying kinetics and monitoring the droplet morphological changes during drying. Some examples of extending the glass filament SDD technique to examine particle functionalities are discussed. SDD experiments are shown to be a powerful tool for particle engineering due to its ability to study both the external convective transport process of a single droplet and to understand the different particle functionalities of the resultant single dried particle.     

Unraveling the droplet drying characteristics of crystallization‐prone mannitol – experiments and modeling

Spray‐dried mannitol is a potential lactose replacement in pharmaceutical formulations, yet the drying behavior of individual mannitol droplets within the spray chamber has not been fully understood. This work explored the drying characteristics of mannitol by employing the reaction engineering approach (REA) in data analysis. A glass filament single droplet drying technique was used to monitor the changes in droplet temperature, mass, and diameter. The drying kinetics data obtained clearly demonstrated the droplet “wet‐bulb” period, the crust formation, and the crystallization phenomena. The master activation‐energy curves developed from REA modeling responded sensitively to varying drying temperatures, which could have led to different crystallization events. The deviation of these plots from the expected norms that do not encounter a phase change was used effectively to discern the physics involved. A REA kinetic model was proposed to assist in process optimization of large‐scale spray‐drying operations. © 2017 American Institute of Chemical Engineers AIChE J, 63: 1839–1852, 2017     

COMPARISON OF SUPERHEATED STEAM AND AIR OPERATED SPRAY DRYERS USING COMPUTATIONAL FLUID DYNAMICS.

ABSTRACT

In this paper a numerical simulation of a spray dryer using the computational fluid dynamics (CFD) code Fluent is described. This simulation is based on a discrete droplet model and solve the partial differential equations of momentum, heat and mass conservation for both gas and dispersed phase.

The model is used to simulate the behaviour of a pilot scale spray dryer operated with two drying media : superheated steam and air Considering that there is no risk of powder ignition in superheated steam, we choosed a rather high inlet temperature (973 K). For the simulation, drop size spectrum is represented by 6 discrete droplets diameters, fitting to an experimental droplets size distribution and all droplets are injected at the same velocity, equal to the calculated velocity of the liquid sheet at the nozzle orifice.

It is showed that the model can evaluate the most important features of a spray dryer : temperature distribution inside the chamber, velocity of gas, droplets trajectories as well as deposits on the walls. The model predicts a fast down flowing core jet surrounded by a large recirculation zone. Using superheated steam or air as a drying medium shows only slight differences in flow patterns. Except for the recirculation which is tighter in steam.

The general behaviour of droplets in air or steam are quite the same : smallest droplets are entrained by the central core and largest ones are taken into the recirculation zone. In superheated steam, the droplets penetrate to a greater extent in the recirculation zone. Also, they evaporate faster. The contours of gas temperature reflect these differences as these two aspects are strongly coupled. In both air and steam there is a “cool” zone which is narrower in steam than in air. Finally, the panicle deposit problem seems to be more pronounced in air than in steam.

Adding to the inherent interest in using superheated steam as a drying medium, the model predicts attractive behaviour for spray drying with superheated steam. In particular. under the conditions tested with the model, a higher volumetric drying rate is obtained in superheated steam.     

甘露醇喷雾干燥过程中液滴粒度分布变化的群体粒数衡算模拟和实验研究

利用群体粒数衡算（population balance，PB）计算机模拟和实验研究了甘露醇水溶液的喷雾干燥过程中液滴的粒度分布的变化规律。液滴干燥过程中的颗粒粒度的萎缩速率，在群体粒数衡算模型中描述为液滴的逆（或负）生长项，通过单个液滴反应动力学方法（reaction engineering approach，REA）获得。基于单个液滴干燥的反应工程方法模型REA和群体粒数衡算模型PB集成建立了PBREA模型。PBREA 模型的求解是通过高分辨率数值方法。本文模拟研究了不同工况下，不同粒径液滴的干燥时间、液滴平均含湿量以及液滴粒度分布随时间的变化。结果显示，液滴粒径越大，干燥时间越长，模型预测的颗粒平均粒径为实验值的1.0~1.5倍，粒度分布跨度是实验值的0.61~0.89倍。模拟误差主要来源于液滴及颗粒粒径分布统计精度、单个静止液滴与群体运动液滴干燥的差异、热导率及扩散系数是经验值3个方面。在使用Buchi 290 小型喷雾干燥仪进行的实验中，使用了图像采集和分析方法得到了液滴及颗粒的数密度分布，并和模拟结果做了对比。结果表明该模型可以有效地预测喷雾干燥过程中干燥颗粒的平均粒度及分布跨度。     

Modeling Particle Formation at Spray Drying Using Population Balances

There have been several efforts to simulate the physical processes in a single droplet during spray drying in the last several years, but most of the models do not describe the solid formation in detail. In this work, the development of the microscopic solid structure in a droplet during spray drying is simulated. A radial-symmetric model of the droplet is used to simulate the mass and heat transport. The solid formation at every radial discretization point is obtained by the solution of population balances. This way, the distribution of the particle number density in the droplet depending on the macroscopic process parameters can be predicted. The model equations are solved in a normalized coordinate system to be able to describe the shrinkage of the droplet. The suitability of these population balances will also be discussed. For the validation, monodisperse single droplets consisting of a solution or suspension are dried with constant boundary conditions.     

Experimental determination and mathematical modeling of the drying kinetics of a single droplet of colloidal silica

ABSTRACT

Colloidal silica has been used frequently as a model material of drying in the past two decades. Several models of single droplet drying have been validated against the sole experimental evidence by Ne?i? and Vodnik (Kinetics of droplet evaporation. Chemical Engineering Science 1991, 46(2), 527–537), in which relatively scattered experimental data on drying of single droplet of colloidal silica were provided. Due to the importance of this sort of data, the drying of single droplet of colloidal silica was determined more accurately under more extensive conditions in this work. The effect of air temperature on the drying of single droplet of colloidal silica was probed as well as the evolution of particle morphology. The droplet of colloidal silica was found to shrink irregularly during drying due to uneven exposure of droplet surface to air stream. The moisture within the droplet appears to transfer freely to the surface, keeping the surface highly moist. For a large part of drying process, drying of single droplet of colloidal silica is similar to the evaporation of water droplet, which can be predicted well using a simple mathematical model.     

MECHANISMS OF DRYING OF SKIN-FORMING MATERIALS.III. DROPLETS OF NATURAL PRODUCTS.

ABSTRACT

Drying studies were carried out on single droplets suspended from a rotating nozzle in a horizontal wind tunnel. Droplets were of solution of a third type of skin-forming material, namely the natural products skim milk or fructose. Droplet weight and temperature were measured during the drying process. Dried crusts were recovered and examined by Scanning Electron Microscopy.

With this type of material a skin first forms at any drying condition on the surface of the droplet at a cerlain stage of drying. A crust subsequently forms beneath the skin. The final dried panicle retains the structure and properties of the original powder, unless the material is dried at very high temperatures. e.g. >300 °C. which result in burning.

An increase in air temperature resulted in the formation of a smoother skin offering a higher resistance to vapour diffusion. At temperatures over 100 °C droplets exhibited puffing or ballooning phenomena; i.e. they inflated and deflated many times before forming the final dried particles.     

益生菌在喷雾干燥过程中的活性变化与保护策略

肠道菌群对于人体健康具有重要影响。口服足量的活性益生菌,有助于缓解急慢性肠炎、治疗腹泄、改善消化,已在临床治疗中得到一定应用。在食品市场上,益生菌干粉制剂亟需一种生产成本低、制粉简便的生产方法。喷雾干燥的生产能力强、制粉快速,但干燥过程中,雾化液滴经历一个快速升温与脱水过程,对其中的益生菌带来热胁迫、脱水胁迫、氧化胁迫等多种不利因素,造成菌体活性的大量损失。而喷雾干燥塔的结构,使塔内的液滴干燥过程难以追踪,不利于研究益生菌的失活历程以及探索益生菌与载体材料间的相互作用。本文从雾化液滴在干燥塔内的干燥历程着眼,回顾了益生菌活性随液滴干燥动力学变化的趋势,讨论了益生菌在喷雾干燥中经受的亚细胞结构损伤与功能性损伤,并系统总结了目前文献中报道的提升干燥后益生菌活性的主要方法,包括提升菌体耐受性、优化喷雾干燥条件和采用合适的保护性载体,并着重阐述了载体材料与益生菌细胞间的相互作用关系以及干燥历程的重要影响。文章指出为最大程度上保存喷雾干燥粉末中益生菌的活性,应综合微生物、干燥过程与食品化学（材料学）等领域的保护策略,设计一体化统合生产方案。依据微生物-保护载体间的相互作用设计高效保护配方载体,研发统合从微生物细胞培养至粉末储藏的新型生产工艺,是实验室及工业中合理设计工业级喷雾干燥过程、大量生产高活性益生菌制剂的关键。     

FRUIT AND VEGETABLE POWDERS PRODUCTION TECHNOLOGY ON THE BASES OF SPRAY AND CONVECTIVE DRYING METHODS

ABSTRACT

The peculiarities of fruit and vegetable powders production technology based on spray & convective drying methods are shown.

The experimental data related to the drying kinetics of apple juice droplets as well as the production flow diagrams and the performance of a spray dryer intended for the treatment of hygroscopic pasty products are presented.     

Multi-Scale Multiphase Modeling of Transport Phenomena in Spray-Drying Processes

Spray drying is an extensively used technology in process engineering for receiving small particles by rapid moisture evaporation from a spray of droplets. This contribution summarizes achievements and results of the comprehensive scientific research on multi-scale multiphase modeling of transport phenomena in spray-drying processes undertaken by our research group: (1) study of particle formation on the scale of an individual droplet; (2) modeling and simulation of droplet–droplet and particle–particle collisions in a spray; (3) study of gas-spray mixing; (4) 2D and 3D study of spray drying by an innovative multi-scale simulation tool coupled to a commercial CFD software. The proposed multi-scale multiphase model of transport phenomena in a spray-drying process has been developed based on a thorough analysis of previously published experimental and theoretical works. The content of this paper will be useful for both academia and industry; e.g., pharmaceutical, biotechnology, chemical, ceramics, materials, nutrition, and other applications of spray drying.     

MULTI-STAGE SPRAY DRYING METHOD IN MANUFACTURING HEAVY DUTY DETERGENTS

Collision of droplets; counter-current spray dryer; drying rate; heat transfer; nonphosphated detergent; spray drying

The spray drying method of non-phosphated granular detergents is studied to decrease the amount of agglomerate particles. The formation of agglomerates is mainly influenced by the concentration of droplets in spray cloud and the water content of droplets at the time of collision. The overlaps of different spray clouds should be de- creased.

The drying rate near the nozzle zone is considerably faster than that calculated by Ranz-Marshal’s equation. According to these phenomena, “Multi-stage spray drying” is developed, which is characterized by in stalling plural spraying stages in a spray dryer.

Consequently, non-phosphated detergents are manufactured with the same powder properties and productivity as phosphated detergents.     

Influence of Spray Drying Parameters on the Formation of β-Phase Poly(vinylidene fluoride)

A simple one-step spraying method to produce poly(vinylidene fluoride) (PVDF) in the desired conformation is presented. The content of the piezoelectric β-phase is measured at different spray drying conditions and during electrospray. The influence of a strong electrical field and charges on the droplet are investigated separately from the electrospray setup with a pneumatic atomizer. For this purpose, the electric field is integrated into a pneumatic atomization process by a plate capacitor and the charge of the droplets by corona discharge. To investigate the drying properties, the drying temperature and the flow rate of dry air are examined. The presented process offers the possibility to deposit PVDF films or to produce PVDF powders, in their piezoelectric β- and γ-phases or in the nonpolar α-phase.     

Formation process of core‐shell microparticles by solute migration during drying of homogenous composite droplets

Particle formation process during spray drying profoundly impacts particle morphology and microstructure. This study experimentally investigated the formation of core‐shell‐structured microparticles by one‐step drying of composite droplets made of Eudragit^® RS (a polycationic acrylic polymer in nanoparticle form) and silica sol. The formation of an incipient surface shell was monitored using single droplet drying technique, and the freshly formed shell was recovered for subsequent analyses. Adding silica to RS precursor increased the shell formation time and altered the properties of the incipient shell from water‐dispersible to nondispersible. The incipient shell formed from RS/silica droplets with mass ratios of 1.5%:1.5% and 0.5%:2.5% showed ingredient segregation with a preferential accumulation of RS, similar to the shell region of dried microparticles. After shell formation, excess silica sol in the liquid phase could flow inward, producing a dense core. This mobility‐governed solute migration would be useful for constructing core‐shell microparticles using other precursor systems. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3297–3310, 2017     

Single-droplet drying processes at varying environmental conditions

Abstract

Modeling and numerical simulations of the single-droplet drying process are commonly executed based on the assumption of constant boundary conditions. In this study, the validity of this assumption and its influence on the model prediction of the final particle morphology is investigated. Accordingly, numerical simulations of the single-droplet drying process were conducted at different drying conditions. Five boundary conditions were examined: (a) constant inlet drying air condition based on the most commonly used assumption, (b) varying drying conditions, (c) constant average drying conditions, (d) partially varying drying conditions whereby all drying conditions were changed apart from the droplet’s relative velocity, and (e) velocity varying condition whereby all the drying conditions were averaged apart from the relative velocity of the droplet. The boundary conditions for the last four cases were calculated using three-dimensional simulations of the spray drying process of the particles that possessed pure solvent properties. The final product morphologies have been examined, i.e., the morphologies of hollow or full porous particles as predicted by the simulations of the single-droplet drying process. It has been found that the variation of the drying boundary conditions had considerable influence on the droplet’s shrinking rate as well as on the efficiency of the process, while the dried particle morphology depended on its shell strength. The influence was more pronounced when the initial droplet diameter and its shell strength increased.     

Study of the drying behavior of high load multiphase droplets in an acoustic levitator at high temperature conditions

Experimental data on the drying behavior of suspension droplets is limited, despite its importance in industrial applications for material processing, chemical or the food industry involving spray dryers. This fact is particularly significant for high load and temperature conditions, as found in such industrial applications. In this work, the drying behavior of acoustically levitated multiphase droplets has been experimentally investigated. The acoustic tube levitator has been modified in order to allow experiments to be performed at high temperature conditions. The flow rate, temperature and relative humidity of this air stream can be controlled by an air conditioning system. A CMOS camera and a back-light illumination system are used to measure the droplet cross-sectional area and vertical position of the droplet during the drying process. The experiments have been performed using water–glass particle suspensions. The glass particles have a mean particle size and relative density of 13 μm and 2.5, respectively. The effect of the air temperature (60 °C<T<120 °C), initial volume of the droplet (0.05 μl<V₀<0.7 μl), initial solid mass load (0.01<Y_S<0.5) and relative humidity of the air (0.05<HR<0.45) on the mean porosity of the grain, first drying period duration and liquid evaporation rate has been analyzed by means of a parametric screening matrix and also by means of a central composite design (CCD) experimental design. The most important parameters to be considered for the porosity and the drying behavior in the range of variables analyzed are the initial solid mass load and the initial droplet volume. The relative humidity of the air exerts a moderate influence on the drying behavior of the droplet and the temperature has only a very low impact on the mean porosity. In addition, particular attention should be given to the drying behavior of small droplets, which result in a very low mean porosity values for high solid mass loads. The CCD confirms that the initial droplet volume, the solid mass load and their interaction exert significant influence on the three responses.     

Reaction Engineering Approach (REA) to model the drying kinetics of droplets with different initial sizes—experiments and analyses

Droplets with different initial sizes, which are typical in conventional liquid atomization for spray drying applications, will result in varying drying and crust formation histories. It is essential for any droplet drying model to accurately capture such fundamental phenomena. This study used a newly constructed glass-filament single droplet rig to evaluate the applicability of the Reaction Engineering Approach (REA) in describing such effect. For the three initial sizes (1, 2 and 3 μL) tested, the glass filament gravimetric method clearly distinguished the different drying kinetics and the crust formation phenomenon, delineated by the drying behavior. Analysis from the drying kinetics revealed that the main premise of the REA, which utilizes a material-specific master activation energy curve, is applicable to droplets of different initial sizes at all the three air temperatures tested. This allowed the REA to accurately predict the different temperature and moisture histories given by droplets with different initial sizes. The result supports the REA as a good modeling approach for a wide range of initial droplet conditions. A new master curve approach was proposed to predict the diameter change of droplets with different initial concentrations. Validation with the current and past experimental data revealed that this approach has strong potential to account for the different feed concentrations typically found in spray drying applications.