冰晶尺寸及其对微波辅助冷冻干燥的影响

Freeze drying of an aqueous solution would result in the non-uniform distribution of solute concentration.Because ice is almost transparent to microwave, therefore such a non-uniform distribution may affect the microwave assisted freeze drying. The direct observation of the ice crystals formed under microscope reveals that the ice crystal sizes formed from de-ionized water depend on the cooling rate with fast cooling rate giving smaller ice crystals as expected. Once there is a sufficient amount of solute mixed with the de-ionized water, for example the reactive red,the size and its distribution are not very much dependent on either cooling rate or the final temperature provided there is sufficient time of cooling and the final temperature is not too low. The size of ice crystals formed within the solution of reactive red is usually below 100μm with a freezing rate of 1℃·min^-1 for a droplet of the size of less than 1 mm. A simplified simulation indicates that such a small ice crystal would not cause a significant non-uniform distribution of temperature for microwave assisted freeze drying. When the ice crystal size is larger than 5 mm, heat conduction from the solute concentrated region to the ice region mav need to be considered.     

Ice Crystal Sizes and Their Impact on Microwave Assisted Freeze Drying

Freeze drying of an aqueous solution would result in the non-uniform distribution of solute concentration. Because ice is almost transparent to microwave, therefore such a non-uniform distribution may affect the microwave assisted freeze drying. The direct observation of the ice crystals formed under microscope reveals that the ice crystal sizes formed from de-ionized water depend on the cooling rate with fast cooling rate giving smaller ice crystals as expected. Once there is a sufficient amount of solute mixed with the de-ionized water, for example the reactive red, the size and its distribution are not very much dependent on either cooling rate or the final temperature provided there is sufficient time of cooling and the final temperature is not too low. The size of ice crystals formed within the solution of reactive red is usually below 100 μm with a freezing rate of 1℃·min-1 for a droplet of the size of less than 1 mm. A simplified simulation indicates that such a small ice crystal would not caus     

25℃下l-盐酸耐氨酸和l-盐酸精氨酸在其溶液中的扩散系数

The diffusion coefficients** of l-lysine hydrochloride and l-arginine hydrochloride in their aqueous solutions at 25℃ were determined by the metallic diaphragm cell method which is characterized by accuracy, promptness and convenience. Meanwhile, the densities and viscosities of the solutions were also determined. Based on all these data a semi-empirical model for correlating the diffusion coefficients of solid organic salts in their aqueous solutions at 25℃ was proposed. The fitting result of this model is comparatively satisfactory. Compared to a former model,Gordon Model, this model can avoid a number of difficulties and arduous work.     

Removal of Phosphate from Aqueous Solution with Modified Bentonite

Bentonite combined with sawdust and other metallic compounds was used to remove phosphate from aqueous solutions in this study. The adsorption characteristics of phosphate on the modified bentonite were investigated, including the effects of temperature, adsorbent dosage, initial concentration of phosphate and pH on removal of phosphate by conducting a series of batch adsorption experiments. The results showed that 98% removal rate of phosphate was obtained since sawdust and bentonite used in this investigation were abundantly and locally available. It is concluded that modified bentonite is a relatively efficient, low cost and easily available adsorbent for the removal of phosphate from aqueous solutions.     

统计速率理论研究乙醇-水溶液中硫酸钾晶体的溶解动力学

Dissolution kinetics of K2SO4 crystal in aqueous ethanol solutions was studied on-line with ion selective electrode. The concentration of K2SO4 was calculated from the determined electromotive force in which the activity coefficient of components in the liquid phase was calculated with the Pitzer equation. Dissolution kinetic parameters in the modified statistical rate theory were regressed. The correlation results show that dissolution rate of K2SO4 is slower in aqueous ethanol solutions than that in aqueous solutions. The two most important reasons are as follows: (1) The solubility of K2SO4 in aqueous ethanol solutions is lower than that in aqueous solutions, which causes a decrease of the driving force of mass transfer. (2) The process of surface reaction of K2SO4 became slower due to the addition of ethanol, so that the whole process is mainly dominated by the surface reaction instead of mass transfer.     

An Investigation of Error Sources in Computational Fluid Dynamics Modelling of a Co-current Spray Dryer

The paper is focused on identifying error sources in computational fluid dynamics(CFD) predictions of a spray drying process. Seven groups of drying and atomisation parameters were selected for analysis and 13 simulation trials were performed. The theoretical results were compared with experimental data and sensitivity of the simulation results to the analysed factors was determined. The following parameters affecting the accuracy of CFD spray modelling were found: gas turbulence model, particle dispersion, atomising air, initial parameters of atomisation and heat losses to the environment. A major difference in the errors committed during modelling of spray drying process for fine and coarse sprays was observed.     

计算流体力学在顺流喷雾干燥器模拟中的误差源研究

The paper is focused on identifying error sources in computational fluid dynamics(CFD) predictions of a spray drying process. Seven groups of drying and atomisation parameters were selected for analysis and 13 simulation trials were performed. The theoretical results were compared with experimental data and sensitivity of the simulation results to the analysed factors was determined. The following parameters affecting the accuracy of CFD spray modelling were found: gas turbulence model, particle dispersion, atomising air, initial parameters of atomisation and heat losses to the environment. A major difference in the errors committed during modelling of spray drying process for fine and coarse sprays was observed.     

喷雾干燥法制备载药微球时的形貌与粒度控制

Drug-loaded microspheres are usually used as a biophysically targeted delivery system. The morphology and size distribution of the microspheres are key effects on the efficiency in therapy. The microspheres could be prepared by the spray drying method, and the characterization could be controlled by varying the drying conditions. The whole preparation process is highly efficient, and suitable for commercialization. In this work, a case for preparation of the microspheres of tanshinone (TAN) solid dispersions was studied, and the mechanisms of morphology and size control of microspheres during the spray drying process were investigated. The effects of inlet temperature, concentration and components of precursors, and feed rate on the morphology and size distribution of products were studied. The results showed that the morphology of the dry products depended on the inlet temperature, the components of precursor and feed rate. Among them, temperature was the most important factor. The size of microspheres was mainly controlled by the concentration of the precursor. This work might be a reference for morphology and size control of targeted drug delivery microspheres by the spray drying method.     

AB-8树脂吸附反式1,2环己二醇热力学和动力学(英文)

AB-8 resin was used as an adsorbent for the removal of trans-1,2-cyclohexandiol(CHD) from aqueous solutions.Batch experiments were carried out to investigate the effect of contact time and temperature on sorption efficiency.The adsorptive thermodynamic properties and kinetics of CHD from water onto AB-8 resin were studied.The Langmuir and Freundlich isotherm models were employed to discuss the adsorption behavior.Thermodynamic parameters such as G,H and S were calculated.The results indicate that the equilibrium data are perfectly represented by Langmuir isotherm model.Thermodynamic study reveals that it is an exothermic process in nature and mainly physical adsorption enhanced by chemisorption with a decrease of entropy process.The kinetics of CHD adsorption is well described by the pseudo second-order model.The adsorbed CHD can be eluted from AB-8 resin by 5% ethanol aqueous solution with 100% elution percentage.     

Solubilities of vinyl chloride in emulsifier solutions

1 INTRODUCTIONVinyl chloride(VC)is a slightly water-soluble monomer.But its solubility in water(～10g·L~(-1))is much higher than that of olefins(0.1～1g·L~(-1)).The solubilityof VC is an important parameter in suspension,emulsion and miniemulsionpolymerizations.The presence of emulsifier in aqueous medium will enhance the solubil-ity of VC.The solubility of VC depends not only on the types and concentration of theemulsifier,but also on the temperature and pressure.Unfortunately,the solubilities ofVC in emulsifier solutions are rarely reported in literatures.     

液体物料冷冻干燥的热点问题

液体物料冷冻干燥广泛应用于制药工业。其过程工艺的重要性正赢得世界范围的研究关注。文献已证实科学方法能够用最少的试差来提高产品质量。过程工艺的建立和规划需要系统地理解冷冻、冷冻干燥、材料科学和质热传递等物理化学过程。本文就液体物料冷冻干燥过程做了简要评述,并对其过程的热点问题做了分析。     

Controlled freezing and freeze drying: a versatile route for porous and micro‐/nano‐structured materials

Freeze drying is a process whereby solutions are frozen in a cold bath and then the frozen solvents are removed via sublimation under vacuum, leading to formation of porous structures. Pore size, pore volume and pore morphology are dependent on variables such as freeze temperature, solution concentration, nature of solvent and solute, and the control of the freeze direction. Aqueous solutions, organic solutions, colloidal suspensions, and supercritical CO₂ solutions have been investigated to produce a wide range of porous and particulate structures. Emulsions have recently been employed in the freeze drying process, which can exert a systematic control on pore morphology and pore volume and can also lead to the preparation of organic micro‐ and nano‐particles. Spray freezing and directional freezing have been developed to form porous particles and aligned porous materials. This review describes the principles, latest progress and applications of materials prepared by controlled freezing and freeze drying. First of all the basics of freeze drying and the theory of freezing are discussed. Then the materials fabricated by controlled freezing and freeze drying are reviewed based on their morphologies: porous structures, microwires and nanowires, and microparticles and nanoparticles. The review concludes with new developments in this area and a brief look into the future. Copyright © 2010 Society of Chemical Industry     

冷冻干燥法制备层状多孔羟基磷灰石支架过程中的溶剂升华行为

采用水基羟基磷灰石(hydroxyapatite,HA)浆料,经冷冻干燥和烧结工艺(1 250℃烧结3 h)制备了层状多孔HA支架.研究了冷冻温度、干燥压力和干燥温度对水基HA浆料中溶剂升华行为的影响.结果表明:随着冷冻温度的降低,多孔HA支架的层间距逐渐减小,支架的升华时间增加;由于样品的干燥过程同时受到传热和传质的...     

Use of ozone for the preparation of functional silk fibroin-based biomaterial loaded with bioactive compounds for biomedical applications

Silk fibroin (SF) can be used for the preparation of porous functional biomaterials due to its biocompatibility, biodegradability, and minimal in?ammatory reactions. High porosity and homogenous interconnected pore structure is a challenge for the preparation of porous biomaterials. Porous SF foam materials can be formed by bubbling inert gases through aqueous solutions and subsequent freeze drying process. In this study, SF foam structures were prepared by first purging ozone gas and then freeze drying of this ozone-treated aqueous SF solution. Resulting porous materials were efficiently loaded with plant extract for the preparation of functional biomaterials having antimicrobial properties. The interactions of SF with ozone led to chemical modifications that improved both foaming and hydrophobic properties. Intensive ozone treatment caused the crystallinity degree of untreated SF to decrease from 48% to 42%. Ozone treatment also resulted in a significant reduction in surface tyrosine content from 55% to 43%. The use of ozone gas for the preparation of SF foam material enhanced the adsorption capacity of phenolic compounds. The enhancement in the adsorption of phenolic compounds on SF foam structure can be attributed to the oxidation-dependent increase in hydrophobicity.     

A STUDY OF THE FREEZE DRYING OF SOME LIQUID FOODS IN VACUO AND AT ATMOSPHERIC PRESSURE

A technique of freeze drying at atmospheric pressure was developed and used to test dry milk, some fruit juices, and solutions of coffee extract. Samples of the same food products were also freeze dried in vacuum. The influence of certain product characteristics, notably dimensions and concentration, on the mechanisms of the freeze drying operations are discussed, comparing the atmospheric technique to the vacuum process.     

Effect of Dielectric Material on Microwave Freeze Drying of Skim Milk

Abstract:

A simultaneous heat and mass transfer model of the dielectric material–assisted microwave freeze drying was derived in this study considering the vapor sublimation-desublimation in the frozen region. The mathematical model was solved numerically by using the finite-difference technique with two moving boundaries. Silicon carbide (SiC) was selected as the dielectric material, and the skim milk was used as the representative solid material in the aqueous solution to be freeze-dried. The results show that the dielectric material can significantly enhance the microwave freeze drying process. The drying time is greatly reduced compared to cases without the aid of the dielectric material. Profiles of the temperature, ice saturation, vapor concentration, and pressure during freeze drying were presented. Mechanisms of the heat and mass transfer inside the material sphere were analyzed. For an initially unsaturated frozen sample of 16 mm in diameter with a 4-mm-diameter dielectric material core, the drying time is 288.2 min, much shorter than 380.1 min of ordinary microwave freeze drying and 455.0 min of conventional vacuum freeze drying, respectively, under typical operating conditions.     

介电材料辅助的微波冷冻干燥的实验研究

设计、加工和装配了一套实验室规模的微波冷冻干燥装置,旨在实验验证介电材料对微波冷冻干燥液体物料的强化作用。介电材料用烧结的碳化硅(SiC),石英玻璃作为介电材料的参照物;甘露醇,一种典型的药物赋形剂被选为待干溶液中的溶质。实验结果表明使用介电材料可以有效地强化微波冷冻干燥过程。与传统冷冻干燥相比干燥速率大大加快,在试验条件下干燥时间可以节省20%。微波加热逐渐生效并且主要体现在干燥过程的后半部分。当溶液中的固含量很低或者固体物质具有很小的介电损耗因子时,如果不用介电材料,微波加热的效果不明显。     

Optimal Control of the Secondary Drying Stage of Freeze Drying of Solutions in Vials Using Variational Calculus

Abstract:

The problem of operating freeze drying of pharmaceutical products in vials loaded on trays of freeze dryer to obtain a desired final bound water content in minimum time is formulated as an optimal control problem. Two different types of freeze dryer designs were considered. In the type I freeze dryer design, upper and lower plate temperatures were controlled together, while in the type II freeze dryer design, upper and lower plate temperatures were controlled independently. The heat input to the material being dried and the drying chamber pressure were considered as control variables. Only the scorch temperature was considered as a constraint on the system state variables during the secondary drying stage, because all the free water content (frozen water) is removed from the solid matrix during the primary drying stage of freeze drying. Necessary conditions of optimality for the secondary drying stage of freeze drying process in vials were derived and presented by using rigorous multidimensional unsteady-state mathematical models. The theoretical approach presented in this work was applied in the freeze drying of skim milk. Significant reductions in drying times of the secondary drying stage of the freeze drying process in vials were observed and more uniform bound water and temperature distributions in the material being dried were obtained compared to the conventional operational policies.     

Optimal Control of the Primary Drying Stage of Freeze Drying of Solutions in Vials Using Variational Calculus

The problem of operating freeze drying of pharmaceutical products in vials placed in trays of a freeze dryer to remove free water (in frozen state) at a minimum time was formulated as an optimal control problem. Two different types of freeze dryer designs were considered. In type I freeze dryer design, upper and lower plate temperatures were controlled together, while in type II freeze dryer design, upper and lower plate temperatures were controlled independently. The heat input to the material being dried and the drying chamber pressure were considered as control variables. Constraints were placed on the system state variables by the melting and scorch temperatures during primary drying stage. Necessary conditions of optimality for the primary drying stage of freeze drying process in vials are derived and presented. Furthermore, an approach for constructing the optimal control policies that would minimize the drying time for the primary drying stage was given. In order to analyze optimal control policy for the primary drying stage of the freeze-drying process in vials, a rigorous multi-dimensional unsteady state mathematical model was used. The theoretical approach presented in this work was applied in the freeze drying of skim milk. Significant reductions in the drying times of primary drying stage of freeze drying process in vials were obtained, as compared to the drying times obtained from conventional operational policies.     

瓶装物料的冻干规律研究

以脱脂牛奶为物料,进行了瓶装物料的冷冻干燥试验,探索了加热温度,辐射温度与冻干室压强对冻干过程的影响规律,分析了所得冻干曲线的特征,并对冻干机理和物料温度的监测井行阐述,得到在加热温度与辐射温度相同时恒温恒压操作的最佳参数,并提出了一些强经冻干过程的措施。本研究对实验冻干生产有一定的指导作用,也为瓶装物料的二维理论模型研究提供了基础。