液-液同向流中冰浆的形成

A new technique for ice slurry production was explored. Multiple small water-drops were formed in another immiscible chilled liquid by a single-nozzled atomizer and frozen in the fluidized bed by direct contact heat transfer. Experiments were conducted to investigate the dynamic behaviors of the ice crystal making system. The results demonstrate that the ice crystals could be produced continuously and stably in the vertical bed with the circulating coolant of initial temperature below -5℃. The size distribution of the ice crystals appears non-uniform, but is more similar and more uniform at lower oil flow rate. The mean ice crystal size rests seriously with the jet velocity and the oil flow rate. It decreases with decreasing the oil flow rate, and reaches the maximum at an intermediate jet velocity at about 16.5 m.s y. The ice crystal size is also closely related to the phenomenon of drop-coalescing, which can be alleviated considerably by reducing the flow rate or lowering the temperature of the carrier oil. However, optimization of liquid-liquid atomization is a more effective approach to produce fine ice crystals of desired size.     

一水盐酸环丙沙星初级成核机理的研究

A general expression for the ralationship between induction period and supersaturation was developed based on polynuclear approach.Different mechanism of primary nucleation in solution can be illustrated by the expression.The results of induction period determined by laser scatering method shows that the crystallization of ciprofloxacin hydrochloride monohydrate in water/ethanol or aqueous solution is by the mechanism of primary nucleation followed by one-dimensional diffusion growth,and then one-dimensional continuous or “birth and spread” growth on crystal face. The growth mechanism on the crystal face is affected by temperature and solvent.     

添加剂EDTA对氢氧化镁反应结晶过程的影响(英文)

The effects of additive ethylenediaminetetraacetic acid (EDTA) on crystallization process were investigated by the induc-tion time of MgSO4-NaOH system. Nucleation and growth rates, growth mechanism and particle size distribution of magne-sium hydroxide precipitation were involved with. The induction time in unseeded and seeded precipitation of magnesium hydroxide with and without additive EDTA was measured. The conductivity method was used to determine the induction period. Theoretical relations of the induction time and supersaturation ratio for different growth mechanisms and a combined analysis on the induction time were applied to determine nucleation and growth rates. The growth mechanism of magnesium hydroxide precipitation was dis-closed by analyzing the experimental data with and without additive. The analysis on induction time indicated that additive EDTA had a significant influence on both nucleation and growth of magnesium hydroxide precipitation. The mechanism underlying the effect of EDTA on crystal growth was 2-dimension nucleation-mediated growth model.     

导流筒浆态连续结晶器内鸟粪石的反应结晶动力学——器内流体力学的影响

A laboratory-scale reaction-crystallization process of struvite synthesis from diluted water solution of Mg2+, and ions was studied. The research covered the tests of two original constructions of continuous jet-pump Draft Tube Magma (DTM)-type crystallizers with internal circulation of suspension (upward/downward). Interactions between constructional, hydrodynamic and kinetic factors were established and discussed. Nucleation and linear growth rates of struvite crystals were calculated on the basis of population density distribution. Kinetic model of idealized Mixed Suspension Mixed Product Removal (MSMPR) crystallizer considering the size-dependent growth mechanism was applied (Rojkowski hyperbolic equation). For comparison purposes the kinetic data corre-sponded to a simpler, continuous draft tube-type crystallizer equipped with propeller agitator were analyzed. It was concluded that crystal product of larger size was withdrawn from the jet-pump DTM crystallizer of the descending flow of suspension in a mixing chamber.     

常压盐溶液脱硫石膏转化生成α-半水石膏

Direct phase transformation of flue gas desulfurization gypsum in hot salt solution at atmospheric pres-sure was investigated.The effects of temperature,salt species,salt concentration,solids content,pH and modifier were examined.The crystals obtained under different conditions and solubility of calcium sulfate in contact with solid gypsum were also determined.α-Calcium sulfate hemihydrate crystals of stubby columnar shape and regular pentahedral sides were obtained under the following conditions:salt concentration 20%-30%,operation tempera-ture 95-100 °C,solids mass content in the slurry 10%-30% and neutral pH.Thermodynamic analysis revealed that phase transformation of calcium sulfate dihydrate to α-calcium sulfate hemihydrate occurs because of the difference in solubilities between the two solid gypsum phases in this system.     

Rapid synthesis of CNTs@MIL-101(Cr) using multi-walled carbon nanotubes (MWCNTs) as crystal growth accelerator☆

In this work,hybrid material CNTs@MIL-101(Cr) was synthesized in 2 h using multi-walled carbon nanotubes(MWCNTs) as the crystal growth accelerator with hydrothermal method.The characteristic differences between the crystals of CNTs@MIL-101(Cr) and MIL-101 were investigated by N_2 adsorption–desorption isotherms,X-ray diffraction(XRD),scanning electron microscope(SEM) and thermogravimetric analyzer(TGA).The results showed that MWCNTs embedding in the hybrid material provide more mesoporous volumes than that of MIL-101.Moreover,the fast synthesized crystals of CNTs@MIL-101(Cr) still preserve the octahedral shape like MIL-101 and have a larger size ranging from 1.5 to 2.0 μm which were approximately three times larger than that of MIL-101.In the proposed mechanism,the roles of MWCNTs played in the crystallization were discussed where MWCNTs can be seen as coaxial cylindrical tubes composed of multi-layer graphenes and the place where nucleation and crystal growth processes occur at the tubes' out surface.Then,a crystal seeding layer bonding with the MWCNTs may be easily formed which accelerates the growth rate of MIL-101 crystals.Thus,larger crystals of CNTs@MIL-101(Cr) were formed due to the faster crystal growth rate of MIL-101.     

6.0mol•L－1KOH溶液中锌单晶（002）和（100）晶面的电化学行为

In this article, the electrochemical performance of the electrodes of zinc polycrystal, Zn（002） and Zn（100） single crystals were studied by the Tafel line extrapolation of the potentio-dynamic polarization curves, the cyclic voltammetry and the charge/discharge experiment. The results shows that in 6.0 mol·L^-1 KOH solution the corrosion rate of Zn polycrystal, Zn（100） and Zn（002） single crystals decreases in turn; and the reversibility and the charge/discharge performance of Zn single crystal was superior to Zn polycrystal. The dendrite growth of the surface of Zn polycrvstal was easier than Zn single crystal during the stages of charge/discharge.     

溶液自发结晶过程动力学参数研究

The batch cooling crystallization initiated from spontaneous nucleation for aqueous solution of potas- sium nitrate was studied.The concentration and transmittance data were acquired on line throughout the operation. Based on solute mass transfer in both liquid and solid phases,a kinetic model was deduced by assuming that the late period of primary nucleation resembles the initial period of the secondary nucleation.Nucleation and crystal growth stages were identified.Kinetic parameters were estimated piecewise from online experimental data and compared with those in literature.The estimated kinetic parameters for stages without apparent primary nucleation agreed well with those in literature.Further,a simulated concentration curve was also drawn from the estimated kinetic parameters and it matched well with that in experiment.     

Determination of the metastable zone and induction time of thiourea for cooling crystallization

The solubility,metastable zone width(MSZW),and induction time of thiourea for cooling crystallization were experimentally determined in the temperature range of 283-323 K. The solubility data could be well described by the Apelblat equation model as lnx=-99.55+1071.66/T+16.27 lnT. The determinations of the effects of various stirring and cooling rates indicated that the MSZW increased with increasing and decreasing cooling and stirring rates,respectively.Furthermore,the induction times at various temperatures and supersaturation ratios were also measured.The results indicated that homogeneous nucleation could occur at high supersaturation,whereas heterogeneous nucleation was more likely to occur at low supersaturation.Based on the classical nucleation theory and induction period data,the calculated solid-liquid interfacial tensions of thiourea in deionized water at 302.46 and 312.58 K were 2.86 and 2.94 mJ·m~(-2),respectively.     

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     

流动溶液中维生素C单晶生长动力学

引　言随着精细化工、生化、医药和染料工业的发展 ,结晶过程越来越受到重视[1] .人们充分认识到晶体生长速率在结晶器设计或评价中的作用 ,必须获取温度、过饱和度和流速等因素影响的准确信息 .结晶动力学是决定晶体产品粒度分布的重要因素 ,是进行结晶器分析、设计、操作和模     

氯化钾间歇冷却结晶生长规律及粒度控制实验研究

采用聚焦光束反射测量技术（FBRM）考察了氯化钾（KCl）间歇冷却结晶过程中晶体成核和生长规律,重点研究了降温速率对KCl水溶液冷却时产生过饱和度的影响,以及添加晶种的相关条件（如晶种粒径和添加量等因素）与KCl晶体产品粒度的关系。同时,采用直接冷却刺激起晶产生“晶种”,并控制其生长达到控制晶体产品粒度的目的。结果表明,在添加晶种条件下,程序降温过程产生的低过饱和度不易引起爆发成核,且晶种的添加量决定着晶体产品的平均粒度与理想生长模型的偏差。另外,降温速率是冷却刺激起晶产生“晶种”粒径的关键因素。     

CRYSTAL DISSOLUTION AND GROWTH IN A LEAN FLUIDIZED-BED CRYSTALLIZER

Dissolution and growth rates of potassium alum crystal were measured in a lean fluidized-bed crystallizer in which the flow rate of solution was set near the settling velocity of seed crystals. The dissolution rates were shown to be linear with respect to undersaturation. The mass transfer coefficient of crystal growth and the surface integration coefficient were determined using the two-step model with a surface integration kinetics of second-order. Mass transfer coefficients for dissolution and growth were found to be independent of the crystal size and the solution velocity, and were jointly correlated in a form derived from the Froessling equation. The surface integration rate turned out to be a function of crystal size, which was responsible for the size-dependent growth of potassium alum crystal.     

CRYSTAL DISSOLUTION AND GROWTH IN A LEAN FLUIDIZED-BED CRYSTALLIZER

Dissolution and growth rates of potassium alum crystal were measured in a lean fluidized-bed crystallizer in which the flow rate of solution was set near the settling velocity of seed crystals. The dissolution rates were shown to be linear with respect to undersaturation. The mass transfer coefficient of crystal growth and the surface integration coefficient were determined using the two-step model with a surface integration kinetics of second-order. Mass transfer coefficients for dissolution and growth were found to be independent of the crystal size and the solution velocity, and were jointly correlated in a form derived from the Froessling equation. The surface integration rate turned out to be a function of crystal size, which was responsible for the size-dependent growth of potassium alum crystal.     

青霉素亚砜结晶生长与成核动力学

利用Mydlarz 和 Jones 模型（MJ2）,对乙酸丁酯中青霉素亚砜的成核与生长动力学进行研究。通过矩量法对MJ2模型进行处理后,利用晶体产品的粒度分布计算得到青霉素亚砜的生长速率与成核速率,然后利用最小二乘法拟合回归求解出成核与生长动力学方程参数。通过实验设计考察了过饱和度、温度与搅拌速度对青霉素亚砜晶体成核和生长过程的影响。研究表明青霉素亚砜晶体生长速率随过饱和度比的增加呈现指数型增长,确定青霉素亚砜晶体生长属于晶体表面生长控制过程。由于高速搅拌会增加青霉素亚砜晶体的破碎,促进了二次成核过程,随着搅拌速度的增加,晶体生长速率出现小幅下滑,而成核速率则明显升高。青霉素亚砜成核与生长动力学研究将有助于工业生产过程优化。     

二硼化镁超导晶体的制备与形貌表征

利用镁助熔剂法制备出六方片状的二硼化镁（MgB2）单晶,并通过扫描电子显微镜和金相显微镜对MgB2晶体形貌进行了研究。结果发现,（111）、（101）和（011）晶面的生长速率远远大于（1-10）、（100）和（010）晶面生长速率,即晶体沿口或6轴的生长速率明显很大,而沿c轴的生长速率很小,甚至随着晶体生长并未发生变化。在MgB2单晶中首次观察到{0001}晶面层的解理与石墨相似,对MgB2单晶的生长机制进行了讨论。     

氟硅酸钾(钠)结晶生长的动力学研究

采用静态法实验研究了溶液初始浓度、温度、搅拌强度及挂片材质对氟硅酸钾 (钠 )在湿法磷酸溶液中结晶生长的影响 ;结果表明 ,初始浓度增加能明显提高结晶速度、缩短诱导期 ,搅拌的影响不明显 ,氟硅酸钾 (钠 )晶体生长过程由晶体的表面反应控制 ,并根据实验结果得到其结晶生长的动力学方程。采用低表面能的聚氯乙烯和聚四氟乙烯塑料可以显著降低结垢形成速率     

氢氧根对半水硫酸钙晶体形貌的影响机理

以二水硫酸钙为原料在氢氧化钠-水体系中水热合成不同形貌的半水硫酸钙晶体,并通过XRD、XPS和电导率等手段对水热产物进行表征,研究了OH^-对水热产物晶体形貌的影响机理。结果表明,在碱性条件下可获得不同形貌的半水硫酸钙晶体,随着OH^-浓度的增大,纤维状形貌水热产物的含量减小而短柱状形貌的含量增多,且当OH^-浓度为1.0×10^-2 mol/L时水热产物以短柱状形貌为主。OH^-影响半水硫酸钙晶体形貌的原因：OH^-会消耗溶液中的Ca²⁺,从而促进二水硫酸钙的溶解,而Ca²⁺浓度的减少不利于半水硫酸钙晶体的成核生长;同时,OH^-对二水硫酸钙的促溶作用会增加溶液中SO₄^2-的浓度,从而促进半水硫酸钙晶体沿（110）和（200）晶面的生长;此外,OH^-在（002）晶面选择性吸附并与该晶面的Ca²⁺反应生成Ca（OH）⁺和Ca（OH）₂,从而阻碍半水硫酸钙晶体沿该晶面的生长。在以上3种作用下半水硫酸钙晶体形貌由纤维状向短柱状转变。本研究可为碱性条件下生产不同形貌半水硫酸钙晶体提供一定的理论依据。     

A mechanistic growth model for inorganic crystals: Growth mechanism

Inorganic crystals grown from solution find wide application. A mechanistic growth model based on the spiral growth mechanism that operates at low supersaturation on inorganic crystal surfaces is presented. The long‐range electrostatic interactions on inorganic crystal surfaces are captured by methods developed in our previous article (Dandekar and Doherty, AIChE J., in press). The interactions of kink site growth units with the solvent molecules partially determine the growth kinetics. Relevant experimental parameters are systematically accounted for in the expression for the kink incorporation rate along step edges on the crystal surfaces. The growth model accurately predicts the asymmetric growth spirals on the surface of calcite crystals. The effect of supersaturation and ionic activity ratio on the step velocities of the acute and obtuse spiral edges is also correctly captured. This model can be used to predict the shapes of solution grown inorganic crystals and to engineer the growth process to design inorganic solids with functionally desirable shapes. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3720–3731, 2014     

水溶液晶体的空间生长及其地基模拟实验

空间水溶液晶体生长是通过搭载人造卫星、宇宙飞船和空间站等飞行器,在微重力条件下从水溶液中进行晶体生长实验.许多透明单晶体,诸如:KDP(磷酸二氢钾,potassium dihydrogen phosphate)、ADP(磷酸二氢铵,ammonium dihydrogen phosphate)、TGS(硫酸三甘氨酸,triglycine sulfae)、沸石和α-碘酸锂(α-LiIO3)等无机非线性光学晶体,尿素等有机非线性光学晶体以及蛋白质等生物晶体,均可采用水溶液法生长.美国、前苏联、西欧和日本等国在从事空间材料科学研究的高科技发展计划中,均把水溶液晶体生长作为一项重要项目.由于水溶液晶体生长方法的研究在地面上已有丰富的基础,而且具有温度低,能耗小,可实现原位实时观察等优点,所以,它是探索空间晶体生长原理和方法、研究晶体生长微重力效应的重要材料制备技术.由于空间晶体生长受搭载条件限制,空间实验的次数与地面相比是十分稀少的,为了获得空间实验的高成功率,在地面上必须建立相应的实验基地,开展深入的地基研究工作.本文将分别从空间实验和地基研究两个方面作系列介绍,包括蛋白质晶体,沸石晶体,α-LiIO3晶体的空间生长以及TGS,NaClO3(sodium chlorate,氯酸钠),Sr(NO3)2(strontium nitrate,硝酸鍶)和Ba(NO3)2(barium nitrate,硝酸钡)等晶体生长过程的原位实时观察,并展望了空间晶体生长的发展前景.