Parameters determining the agglomeration behavior of anhydrous L-ornithine-L-aspartate (LOLA) crystals prepared by drowning out crystallization

Crystallization of L-ornithine-L-aspartate (LOLA) by drowning out was performed for the production of the anhydrous form of LOLA. The needle-like LOLA crystals were formed and spherically agglomerated during precipitation in a semibatch crystallizer. The primary crystal size in the agglomerate remains unchanged after completion of the crystallization. Therefore, the agglomeration process of primary crystals played an important role for controlling LOLA crystal size. The agglomeration of LOLA crystals was governed by not only the physico-chemical parameters such as the temperature and feed concentration, but also the hydrodynamic parameters such as agitation speed and feeding rate. The crystal size and the shape have been shown to be important factors in product impurity and flowability. Thus, the optimum condition of LOLA crystallization process by drowning-out could be obtained.     

基于递归分析的喷雾气固流化床团聚状态识别

液体会影响喷雾气固流化中的颗粒循环模式,形成不同程度的颗粒团聚物,从而直接降低反应器的传热、传质效果。实验中向流化床喷入不同黏度的乙二醇溶液,来人工制造团聚现象。研究结果表明,喷入不同黏度的液体后,流化床内会形成不同的团聚结构,按照团聚物大小可分为四类：微团聚、成核团聚、黏结团聚以及糊状团聚。通过对不同工况中的压差波动信号进行递归分析,发现不同团聚状态下的递归图纹理结构有着明显的差异。与此同时,对50种流动条件下的递归特征量分布情况进行分析,以此来识别不同的团聚结构,整体识别率高达96.39%。结果表明：通过对压差信号的递归分析可以快速识别流化床中的团聚状态。     

Influences of seed crystals on agglomeration phenomena and product purity of m-chloronitrobenzene crystals in batch crystallization

Changes in the fraction of agglomerates, agglomeration kinetics and product purity of m-chloronitrobenzene (CNB) crystals with the number and size of seed crystals were examined in batch crystallization experimentally, and influences of seed types (ground and well-defined) on agglomerate purities were discussed. From the fraction of agglomerates and agglomeration kinetics, it was found that agglomeration occurred more frequently when the number of seed crystals was larger and its size was smaller. The amount of purity decrease by agglomeration was smaller for the smaller number of seeds and for the larger ones. As the number of the elementary crystals constituting agglomerates was smaller, the purity of agglomerates was higher. With ground crystals, more frequent agglomeration occurred and the purity of agglomerates was lower than those for the well-defined crystals.     

Flow induced phase inversion agglomeration: Fundamentals and batch processing

A novel agglomeration technique, based on flow induced phase inversion (FIPI) is described and applied to the batch preparation of polyethylene-bound abrasive calcite agglomerates. Water soluble polymers are used to agglomerate the needle-like crystals of tetraacetylethylene diamine and also sodium chloride crystals. In a typical isothermal FIPI agglomeration process primary particles are dispersed in the molten binder, which is subsequently inverted by the addition of sufficient amount of primary particles, which also defines the critical filler concentration at phase inversion, C_c. Agglomerate particle size is primarily a function of C_p – C_c where C_p is the mean concentration of filler. C_c decreases with increasing binder molecular weight and primary particle surface area. Agglomerate size distribution is affected by processing, mainly by the mixing time after phase inversion. For the non-isothermal FIPI agglomeration process, phase inversion is induced locally, by the addition of fine particles in the molten binder. Phase inversion is then propagated by cooling the dispersion during mixing. Agglomerate characteristics such as particle size, particle size distribution, binder concentration distribution in each agglomerate size range, agglomerate topology, binder morphology in the agglomerates, agglomerate strength, and agglomerate dissolution rate in water were evaluated. These agglomerate characteristics are related to the binder and filler properties as well as to the processing conditions.     

MODELLING AND ANALYSIS OF PARTICLE FORMATION DURING AGGLOMERATIVE CRYSTAL PRECIPITATION PROCESSES

While nucleation and crystal growth are normally considered to be the primary particle formation processes during industrial crystallization, secondary processes including crystal agglomeration and breakage can have a determining effect on product form, especially of precipitates. In addition to the usual overall size distribution, primary and secondary particle size, particle structure and morphology then become important characteristics affecting both product quality and downstream processing performanc

In this paper, the kinetics of processes which determine the formation of both primary particles and crystal agglomerates are briefly reviewed together with established and recent population balance and simulation techniques for analysing and predicting primary and secondary particle size distributions and total specific surface area. These approaches are then illustrated by some experimental and modelling studies of agglomerative precipitation reported recently in the literature.     

Agglomeration of magnesium particles in magnesium-sodium nitrate combustion

Agglomeration phenomenon of magnesium particles during combustion of Mg NaNO₃ propellant has been studied. High speed photographs of combustion zones and the burning surface temperature data indicate that the metal particles form agglomerates on the burning surface in varying degree depending on the mass fraction of NaNO₃. It is found that the increase of oxidizer content increases the metal agglomeration and the agglomerate size depends on the initial particle size of the ingredients. An attempt has been made to predict the size of the agglomerates based on the consideration that the agglomerate size depends on the thickness of the molten oxidizer layer enveloping the metal particles in the condensed phase and surface heat flux providing local temperature environment to agglomerate the metal particles and to eject from the burning surface for the vapour phase combustion. The results were compared with the experimental data. The prediction describes fairly well the observed effects of the concentration and particle size.     

Aluminum Agglomeration on Burning Surface of NEPE Propellants at 3–5 MPa

Aluminum agglomeration and agglomerate sizes of NEPE propellants were studied by cinephotomicrography at pressures of 3 and 5 MPa. Accumulation, aggregation, and agglomeration of aluminum particles similar to that at pressures below 1 MPa were observed. Coalescence of two agglomerates on the burning surface is obtained for the first time. A decrease in the burning rate from 8 to 5 mm s⁻¹ leads to about 20 % increase in the agglomerate diameter. The pressure is found to have no direct influence on the agglomerate diameter when the burning rate is kept constant. The evolution of the agglomerate diameter according to the increase of the virgin aluminum size from 16 to 36 μm is convex in shape and reached its maximum at a particle diameter of 29 μm. Increasing the amount of RDX crystals added in the propellants causes a larger agglomerate diameter. The experimental mass average agglomerate diameters were compared with various agglomeration models. It is found that Hermsen and Salita empirical models have a higher accuracy for NEPE propellants rather than Becksted, Liu, or pocket models.     

Statistical simulation of aluminum agglomeration during combustion of heterogeneous condensed mixtures

A statistical model of aluminum agglomeration during combustion of solid composite rocket propellants is considered; the model describes the process dynamics, beginning from propellant heating in the combustion wave and ending by separation of agglomerates from the burning surface. An algorithm of computing the agglomeration process by the Monte Carlo method is proposed. A series of computations of aluminum agglomeration is performed; the density distribution functions for agglomerate sizes are derived; the dependence of the mean-mass size of agglomerates on the mean-mass size of ammonium-perchlorate particles is determined. The model proposed predicts power dependences of the mean-mass size of agglomerates on pressure and burning rate, which agrees with available experimental data.__________Translated from Fizika Goreniya i Vzryva, Vol. 41, No. 2, pp. 62–74, March–April, 2005.     

Effect of agglomerate properties on agglomerate stability in fluidized beds

Fluidized bed agglomeration is used to stabilize particulate mixtures and reduce dust emissions. This technology is applied to a variety of production processes for the pharmaceutical, chemical, fertilizer and food industries. In most of these applications, agglomerate stability is an essential criterion. Agglomerates and granules that do not conform to size and shape specifications may create problems in downstream processes, such as tableting, thus compromising process efficiency and product quality. When an agglomerate is formed in a fluidized bed, it can grow by incorporating other bed particles, split into smaller fragments, or be eroded by fluidized bed solids. The objective of the present study is to determine the critical agglomerate liquid content at which the rates of agglomerate growth and shrinkage are balanced when artificial agglomerates made from glass beads and water are introduced into a fluidized bed. This study examined the effects of agglomerate size, agglomerate density, liquid viscosity, binder concentration, and fluidizing gas velocity on the critical initial liquid content. This study found that small agglomerates and low density agglomerates displayed higher critical initial moisture contents. When the viscosity was increased by using sugar solutions, agglomerates were very stable and had very low critical initial moisture contents. The study also found that as the superficial gas velocity increased, the agglomerates started to fragment, rather than erode.     

Investigation of the dispersion of carbon black agglomerates of various sizes in simple-shear flows

The dispersion of spherical carbon black agglomerates suspended in polydimethyl siloxane liquid and subjected to simple shear flows has been studied in a cone-and-plate shearing device. Sets of dispersion experiments were carried out for agglomerates of various size and packing density. For agglomerates of equal density and under conditions of equivalent cone rotation rates, the dispersion rates of small agglomerates were smaller than those observed for larger agglomerates. Since the agglomerates occupy a significant fraction of the flow domain, the magnitude and distribution of shear stress acting on the agglomerate at a fixed cone rotation rate depends on the ratio of agglomerate size relative to the size of the gap between the cone and plate. To investigate whether this effect could cause the observed variation in dispersion behavior, we performed three-dimensional simulations of the flow fields within the cone-and-plate device and calculated the resulting stress fields acting on spherical agglomerates. These results helped guide additional experiments in which the peak stress acting on agglomerates of various sizes was matched. However, even under matched stress conditions, the dispersion kinetics was found to vary according to the agglomerate size. In addition, the dispersion kinetics for identical sized agglomerates was found to depend on their processing history. Both of these results lead to the conclusion that some other effect, likely the infiltration of the processing fluid within the agglomerate structure, also influences the dispersion behavior.     

Investigation of kinetics of agglomerate growth in oil agglomeration process

In this study, the kinetics of agglomerate growth in a batch oil agglomeration process has been studied using bituminous coal. The effect of operating variables such as kerosene concentration, pulp density and speed of agitation on the agglomeration process was investigated. It has been found that the second-order kinetic equation describes the growth of agglomerates adequately. The growth of the agglomerates in the oil agglomeration process shows a self-preserving growth. Using this, a characteristic curve has been developed. For the prediction of the size distribution of the agglomerates, the d₅₀ values of the agglomerates must be known. Therefore, a model has been developed by using the kinetic equation for estimation of d₅₀ values of agglomerates for this coal. It was shown that the size distribution of the agglomerates for any levels of the process variables studied can be predicted using the equation of characteristic curve and d₅₀ values. Knowledge obtained from this study will be helpful for technological advancement of this kind of study.     

A Chemical Model for the Dispersion of Fillers in a Polymeric Matrix

Particle size distribution affects strongly physical and mechanical properties of filled polymers. The proposed model uses agglomerate size population balance in its new mathematical formulation expressing agglomeration, break‐up and erosion as an evolution of one particle subjected to mean‐filed type interaction with others. The erosion parameters have been calculated with experiments in an internal mixer. Controlled breakup of agglomerates was carried out through capillary dies to evaluate breakup parameters. Calcium carbonate filled polypropylene system was used to validate the formulation.     

流化床液固共存区域团聚结构表观黏结特性

通过TEB雾化喷嘴制造流化床团聚结构,利用层叠筛分方法对原始颗粒、成核聚团、黏结聚团、糊状聚团4种结构加以尺度区分,成功地实现了不同团聚阶段的分区域辨识.实验选取团聚结构最为稳定的异质共存区域为研究对象,对其黏结过程的表观结构特性和组织特性进行了分析.研究结果表明:成核聚团是诱导黏结聚团产生及增长的基本元素,团聚结构的黏结增长导致结构孔隙度随之增加,随着注入液体对孔隙结构的不断填充,结构逐渐趋于饱和,共存区域内任何尺度的团聚结构黏结增长速率均相同;尽管在异质共存区域内的团聚结构处于同一流化条件下,成核聚团及黏结聚团两者的水分含量及固体体积分数却表现出了明显的差异.     

Experimental and theoretical study on the agglomeration arising from fluidization of cohesive particles—effects of mechanical vibration

A novel technique that can prevent the disruption of agglomerates when sampling the agglomerates from a fluidized bed has been developed and has been applied to the investigation of the agglomeration behaviour of cohesive particles during fluidization with and without mechanical vibration. A new model for the prediction of agglomerate size has also been established on the basis of the energy balance between the agglomerate collision energy, the energy due to cohesive forces and the energy generated by vibration. The accuracy of the model is tested by comparing the theoretical results with the experimental data obtained both in the present work and in the literature. Effects of gas velocity and mechanical vibration on agglomeration for two cohesive (Geldart group C) powders in fluidization are examined experimentally and theoretically. The experimental results prove that mechanical vibration can significantly reduce both the average size and the degree of the size-segregation of the agglomerates throughout the whole bed. However, the experiments also reveal that the mean agglomerate size decreases initially with the vibration intensity, but increases gradually as the vibration intensity exceeds a critical value. This suggests that the vibration cannot only facilitate breaking the agglomerates due to the increased agglomerate collision energy but can also favour the growth of the agglomerates due to the enhanced contacting probability between particles and/or agglomerates. Both the experimental and theoretical results show that a higher gas velocity leads to a smaller agglomerate size.     

Agglomeration during the Drying of Fine Silica Powders, Part II: The Role of Particle Solubility

The effect of particle solubility and the dissolution rate on agglomeration was studied by drying silica and titania particles from aqueous slurries with pH values in the range of 2–12. The agglomerate strength and strength distribution were measured by a calibrated ultrasonic force, and the strength increased as the solubility and dissolution rate increased. Two silica powders of different particle size (60 nm and 500 nm) were studied, and smaller-sized particles formed stronger agglomerates. The drying rate of the powders was varied by using spray drying and tray drying, and slower drying was shown to lead to higher agglomerate strength. The agglomerate strength of titania powder (insoluble in water) was independent of pH, whereas the agglomerate strength of silica was dependent on pH. It was concluded that the solubility and dissolution rate are important parameters that govern the strength of agglomerates.     

Rheology of methane hydrate slurries during their crystallization in a water in dodecane emulsion under flowing

An original experimental set-up was developed and used for studying crystallization and rheology of methane hydrate/water/dodecane system. Methane is injected in a water in dodecane emulsion at low temperature and high pressure in order to form methane hydrate crystals and to move the suspension by gas lift. It behaves as a Newtonian fluid. Dynamic viscosity and conversion of water and gas into gas hydrate crystals were measured during the process for various water contents. Experimental results were explained by means of a model including nucleation, growth and agglomeration. Due to the high value of crystal and drop concentrations, agglomeration takes place through three-body collisions between one water drop and two already formed agglomerates. Resulting agglomerates were considered as fractal-like ones. During crystallization and agglomeration, the effective volume fraction of drops and porous agglomerates is increased, and then suspension viscosity increases. When all water drops are crystallized, agglomeration stops and viscosity does not change.     

Size Distribution Change of Titania Nano-Particle Agglomerates Generated by Gas Phase Reaction,Agglomeration, and Sintering

In the manufacturing of nanometer-sized material particlulates by aerosol gas-to-particle conversion processes, it is important to analyze how the gas-phase chemical reaction, nucleation, agglomeration, and sintering rates control the size distribution and morphology of particles. In this study, titania particles were produced experimentally by the thermal decomposition of titanium tetraisopropoxide (TTIP) and oxidation of titanium tetrachloride (TiCl 4 ) using a laminar flow aerosol reactor. The effect of reaction temperature on the size and morphology of the generated particles was investigated under various conditions. The size distributions of agglomerates were measured using a DMA/CNC system. The size distributions of primary particles were measured using TEM pictures of the agglomerates sampled by a thermophoretic aerosol sampler. In order to model the growth of both agglomerates and primary particles simultaneously, a two-dimensional discrete-sectional representation of the size distribution was employed, solving the aerosol general dynamic equation for chemical reaction, agglomeration, and sintering. Qualitative agreement between the experimentally observed results and the simulation are satisfactory for the large variations in reactor temperature explored.     

基于液桥效应圆筒制粒机的铁矿粉制粒机理研究

针对圆筒制粒机中存在有不同量级粒径颗粒的制粒问题，本工作对现有的液桥力计算式进行了修正，建立了相对应的离散元模型，通过实验测试与仿真相结合，探讨了修正系数对颗粒运动的影响，得到了修正系数以0.6适宜；以铁矿粉混合料的堆积角为参考，通过仿真和实验测试得到了混合料的物性参数，以此为基础，探讨了铁矿粉混合料颗粒的运动规律与团聚机理及其团聚体的分布，结果表明，团聚体颗粒的自旋速度越大、所受剪切力越小，则越有利于制粒；团聚体粒径沿圆筒的径向呈现先增大后减少的变化，且在靠近混合料表层下存在一个“高效制粒区”，在该区域团聚体的粒径最大、剪切力最小、自旋速度较大，同时建议可采用颗粒碰撞频率或能量损失作为判据来终止颗粒的团聚，以达到节能降耗的目的，所得结论可为铁矿粉圆筒制粒机的研发提供设计依据。     

A numerical study on agglomerate formation in a fluidized bed of fine cohesive particles

Two-dimensional (2D) DEM simulation was conducted to investigate the mechanism of agglomeration in a fluidized bed of cohesive fine particles. For the present simulation, granules were numerically generated from Geldart group C particles starting from initial agglomerates of an intermediate size. Particle pressure and agglomerate sizes were measured numerically. The behavior of agglomerates around a bubble were tracked in detail. Breakage of agglomerates above a bubble as assumed in the development of the Iwadate and Horio (Powder Technol. 100 (1998a) 223) model (I–H model) was numerically confirmed. Spots of high in-bed compression force, where agglomerate growth is supposed to take place, was clearly observed in the wake region below each bubble. Numerical results for agglomerate sizes compared fairly well with those predicted by the I–H model redeveloped for 2D cases to validate its mechanistic picture for agglomerate size determination.     

Agglomeration Characteristics of Aluminum Particles in AP/AN Composite Propellants

Most solid rockets are powered by ammonium perchlorate (AP) composite propellant including aluminum particles. As aluminized composite propellant burns, aluminum particles agglomerate as large as above 100 μm diameter on the burning surface, which in turn affects propellant combustion characteristics. The development of composite propellants has a long history. Many studies of aluminum particle combustion have been conducted. Optical observations indicate that aluminum particles form agglomerates on the burning surface of aluminized composite propellant. They ignite on leaving the burning surface. Because the temperature gradient in the reaction zone near a burning surface influences the burning rate of a composite propellant, details of aluminum particle agglomeration, agglomerate ignition, and their effects on the temperature gradient must be investigated. In our previous studies, we measured the aluminum particle agglomerate diameter by optical observation and collecting particles. We observed particles on the burning surface, the reaction zone, and the luminous flame zone of an ammonium perchlorate (AP)/ammonium nitrate (AN) composite propellant. We confirmed that agglomeration occurred in the reaction zone and that the agglomerate diameter decreased with increasing the burning rate. In this study, observing aluminum particles in the reaction zone near the burning surface, we investigated the relation between the agglomerates and the burning rate. A decreased burning rate and increased added amount of aluminum particles caused a larger agglomerate diameter. Defining the extent of the distributed aluminum particles before they agglomerate as an agglomerate range, we found that the agglomerate range was constant irrespective of the added amount of aluminum particles. Furthermore, the agglomerate diameter was ascertained from the density of the added amount of aluminum particles in the agglomerate range. We concluded from the heat balance around the burning surface that the product of the agglomerate range and the burning rate was nearly constant irrespective of the added amount of aluminum particles. Moreover, the reduced burning rate increased the agglomerate range.