氟硅酸钾(钠)在湿法磷酸中的结晶动力学研究

在MSMPR结晶器中系统地研究了氟硅酸钾（钠）在湿法磷酸中的结晶动力学及主要杂质F^-、Mg^2 、Fe^3 、Al^3 的影响。结果表明,在纯硫磷混酸中,Na2SiF6为八面体晶体、K2SiF6为由立方体晶体聚在一起的聚晶;SO4^2-、Mg^2 结氟硅酸钾（钠）晶体生长有促进作用,F^-的影响不明显,Fe^3 、AI^3 能抑制其生长;四种杂质共存的模拟湿法磷酸及磷矿萃取磷本台氟硅酸钾（钠）晶体生长速率、平均粒径均明显减小,形态发生很大变化。     

碳酸锂结晶动力学研究

为了更好地指导生产,采用无蒸发恒容间歇反应器对Li2CO3自LiHCO3溶液中的结晶动力学进行了研究。实验结果表明,温度的升高及质量浓度的增大能显著提高结晶速率,低的系统压力及搅拌有利于结晶反应的进行。根据实验数据拟合得到了该结晶过程的宏观动力学方程。晶体的生长机制表明,扩散控制机制是Li2CO3自LiHCO3溶液中生长的主导机制。     

泰乐菌素结晶工艺研究

结晶过程是影响晶体质量的关键步骤。本实验采用溶析结晶工艺对泰乐菌素结晶过程进行研究,以收率、粒度和粒度分布为目标,考察了水和丙酮质量比、晶种加入量(质量分数)、结晶温度、初始浓度、搅拌转速、陈化时间和流加速率等操作因素对结晶过程的影响。结果表明:所有参数在考察的条件范围内都明显地影响产品的收率;除了温度和搅拌转速外,其他参数都对产品粒度有较明显的影响;对产品粒度分布影响较大的是晶种加入量,温度和搅拌强度。通过分析各种因素影响得到泰乐菌素较佳结晶工艺条件:水和丙酮质量比4∶1,晶种加入量0.5%,结晶温度40℃,初始质量分数1.08 g/g,搅拌转速250 r/min,陈化时间12 h,流加速率先0.3 m L/min,后0.89 m L/min。     

头孢地嗪钠溶剂化物结晶过程自催化动力学

采用在线拉曼光谱在不同结晶温度和溶液初始浓度的条件下,研究了头孢地嗪钠溶剂化物结晶过程的动力学行为,从热力学和成核机理的角度分析了温度和初始浓度对动力学的影响。根据动力学曲线的特征,将头孢地嗪钠溶剂化物的结晶过程假定为"自催化"过程。针对头孢地嗪钠溶剂化物结晶过程的特殊性,修正了Prout-Tompkins模型;并通过不同温度下的动力学数据,采用多元线性回归拟合了头孢地嗪钠溶剂化物结晶过程的自催化动力学模型参数E和k。     

Na_2CrO_4-NaOH-H_2O体系中Na_2CrO_4真空蒸发结晶动力学研究

在液相氧化法铬盐清洁生产工艺中,中间产品铬酸钠的结晶相分离为重要的组成部分,采用真空蒸发结晶的方法可从Na2CrO4-NaOH-H2O体系中分离得到铬酸钠晶体。文中研究了Na2CrO4在NaOH溶液中晶体成核与生长动力学规律。采用间歇动态法中的矩量变换法建立了结晶过程的动力学模型,用最小二乘法对动力学实验数据进行多元线性回归,得到了动力学参数,并验证了动力学模型的可靠性。结果表明:在粒度大于50μm的范围内,铬酸钠晶体的生长符合粒度无关生长模型;晶浆的悬浮密度、搅拌强度和过饱和度对成核速率均有显著影响;溶液过饱和度对成核速率的影响大于对生长速率的影响。结晶动力学的研究为液相氧化法铬盐清洁生产工艺中铬酸钠和氢氧化钠的分离工艺优化提供了理论基础。     

乙醇-水混合溶剂中5′-尿苷酸二钠的结晶介稳区

采用双光路激光法,在293.2～318.2 K温度范围内,研究了5′-尿苷酸二钠在不同比例乙醇-水混合溶剂中的溶解与超溶解特性,得到了5′-尿苷酸二钠的结晶介稳区。采用λh方程关联了4个体系的溶解度数据,进而分别求得各体系下的混合焓和结晶焓。同时,探讨了搅拌转速、pH值和钠离子浓度对结晶介稳区的影响。实验结果表明,与温度相比较,乙醇质量分数是影响溶解度和超溶解度的主要因素;随乙醇质量分数的增大,5′-尿苷酸二钠的溶解度和超溶解度显著减小;在相同条件下,溶液pH值和钠离子浓度的升高,以及搅拌转速的降低均会增大5′-尿苷酸二钠结晶介稳区的宽度。     

助剂对氟硅酸钠(钾)诱导时间和界面能的影响

通过测定不同过饱和浓度下的氟硅酸钠和氟硅酸钾在磷酸介质中的结晶诱导时间,并将诱导时间与经典的初级均相成核理论相结合,研究了自制的聚合物型助剂对氟硅酸钠(钾)在磷酸溶液中的界面能的影响。结果表明:助剂可以延长氟硅酸钠和氟硅酸钾的结晶诱导时间,增大其界面能,从而增大成核难度,有效的缓解氟硅酸钠与氟硅酸钾结垢。并通过循环冷却系统来模拟湿法磷酸生产中的真空过滤过程,验证了助剂的阻垢效果,对比发现:100 mg/kg添加量下的结垢速率由未添加时的0.1564 g/h减小至0.06554 g/h。     

湿法磷酸过滤管道系统氟硅酸钾(钠)结垢沉积模型

采用冷却模拟系统研究了湿法磷酸过滤管道系统中氟硅酸钾(钠)垢的形成过程.据此采用沉积-脱除的结垢机制,并借助粒数衡算方程及成垢离子的质量平衡方程建立了氟硅酸钾(钠)过饱和溶液在管内流动中结垢析出模型,通过对模型的数值求解得到了管壁表面氟硅酸钾(钠)结垢量、结垢速率及粒度分布,与实验结果基本相符.     

硼精矿加压碱解制备水合偏硼酸钠

采用NaOH-H2O体系加压溶出硼精矿制备水合偏硼酸钠．正交实验结果表明,影响硼溶出的因素顺序为,碱浓度>时间>液固比>温度. 考察了初始NaOH溶液浓度、液固比、反应时间、反应温度、矿石粒度和搅拌速度对硼溶出的影响,最优条件[初始NaOH浓度25%(w)、液固比4:1(w)、反应时间2 h、反应温度140℃、搅拌速度500 r/min、高压釜表压0.2 MPa]下,硼转化率达95.91%. 湿硼泥经三级逆流浆化洗涤(各级洗涤温度90℃、洗水与湿硼泥质量比3:1、时间1 h)可实现Na2O和B2O3的高效回收,烘干的终硼泥Na2O和B2O3含量分别为0.35%和0.45%(w),含42.91%(w) MgO的终硼泥可作为提镁的优质原料. 溶出液添加CaO苛化并高温放置陈化脱色除杂,再降温至25~30℃,恒温结晶6 h后抽滤,结晶率大于70%,晶体用无水乙醇、饱和偏硼酸钠溶液洗涤,40℃烘干12 h,物相为NaB(OH)4,纯度约为90%.     

降膜结晶分离技术实验研究

采用萘－硫茚物系对新型高效降膜结晶技术的分离提纯机制进行了实验研究．考察了管外降膜结晶过程中结晶时间、料液流量、冷却水初始进口温度、冷却水降温速率及原料浓度对分离提纯效果的影响．实验发现降膜结晶过程中晶层生长并不完全是光滑界面的生长,而在某些条件下表现为粗糙界面的生长,即生长过程在某些条件下表现为两相区界面的生长．进一步对辅助提纯－发汗过程的工艺参数—发汗时间、发汗初始浓度的影响进行了实验研究．实验结果可用于降膜结晶传热传质机理的数值模拟．     

CRYSTALLIZATION KINETICS OF 2-CHLORO-4,6-DINITRORESORCINOL BY BATCH COOLING CRYSTALLIZATION METHOD

Crystallization kinetics of 2-chloro-4,6-dinitroresorcinol in ethanol was studied by the method of intermittent dynamic analysis. The nucleation rate and crystal growth rate of 2-chloro-4,6-dinitroresorcinol under different crystallization temperatures and stirring rates were estimated. The results show that with an increase of crystallization temperature, both the nucleation rate and crystal growth rate increase. It is further found that when the stirring rate increases, the nucleation rate increases and the crystal growth rate decreases. The technological conditions of cooling crystallization of 2-chloro-4,6-dinitroresorcinol were studied. It is found that when the stirring rate is 180 rpm and the solution is cooled slowly to ? 8°C, the particle size of the products is even and the highest yield of 2-chloro-4,6-dinitroresorcinol is 40.6%.     

CRYSTALLIZATION KINETICS OF 2-CHLORO-4,6-DINITRORESORCINOL BY BATCH COOLING CRYSTALLIZATION METHOD

Crystallization kinetics of 2-chloro-4,6-dinitroresorcinol in ethanol was studied by the method of intermittent dynamic analysis. The nucleation rate and crystal growth rate of 2-chloro-4,6-dinitroresorcinol under different crystallization temperatures and stirring rates were estimated. The results show that with an increase of crystallization temperature, both the nucleation rate and crystal growth rate increase. It is further found that when the stirring rate increases, the nucleation rate increases and the crystal growth rate decreases. The technological conditions of cooling crystallization of 2-chloro-4,6-dinitroresorcinol were studied. It is found that when the stirring rate is 180 rpm and the solution is cooled slowly to - 8°C, the particle size of the products is even and the highest yield of 2-chloro-4,6-dinitroresorcinol is 40.6%.     

高氯酸铵的球形化结晶工艺和性能表征

为获得球形化高氯酸铵(AP),利用重力法测试了AP在水中的溶解度,采用Vant′t Hoff方程和Apelblat方程对溶解度数据进行拟合,建立溶解度模型;采用冷却结晶法制备了球形化AP晶体,分析了结晶液初始质量分数、搅拌速率、降温速率及养晶时间对产品形貌及粒度分布的影响;分别对非球形AP原料和球形化AP样品进行了吸湿性能、松散堆积密度、流散性、热稳定性的表征。结果表明,AP在水中的溶解度随着温度的升高而增加,Apelblat方程和Vant′t Hoff方程的R²接近于1,且MAPD均小于3%;最佳冷却结晶工艺为:搅拌速率为230r/min,结晶液初始质量分数为35%,降温速率为0.5℃/min,养晶时间为3h;球形化AP样品的吸湿性能、松散堆积密度、流散性、热稳定性相比于非球形AP原料有明显改善。     

聚合物辅料对阿司匹林结晶动力学影响机制的非平衡热力学建模及预测

探究聚合物辅料对难溶性药物结晶的影响机制,是指导无定形固体分散体制剂设计和制备中辅料筛选的关键。研究了不同因素（温度、搅拌速率、聚合物浓度、聚合物分子量和聚合物种类等）对阿司匹林晶体生长动力学的影响。首先,采用基于三种不同晶体生长机制的化学势梯度模型结合UNIQUAC活度系数模型,描述和预测了阿司匹林在不同条件下的结晶动力学。进一步分析了不同因素对晶体生长速率常数k_t和结晶热力学推动力?\mu的影响以及对阿司匹林结晶动力学的影响机制。结果表明,阿司匹林晶体生长速率随着结晶温度、聚合物浓度的增加而降低,随搅拌速率的增加而升高;聚乙烯吡咯烷酮（PVP K25）和羟丙基甲基纤维素（HPMC E3）显著抑制了阿司匹林的晶体生长,在PVP K25和HPMC E3水溶液体系下阿司匹林的晶体生长属于二维成核机制,在纯水和PEGs水溶液体系下晶体生长属于粗糙生长机制。所采用的化学势梯度模型能很好预测不同温度和搅拌速率下阿司匹林的结晶动力学,可有效减少实验所需的人力、物力和财力。研究可为固体分散体制剂制备中聚合物的筛选提供理论研究基础。     

水解偏钛酸粒度分布影响因素分析

以攀枝花某钛白粉厂的工业硫酸氧钛浓钛液为原料,采用外加晶种水解工艺制备水解偏钛酸,通过检测钛液水解过程中浆料透过率的变化间接检测水解过程反应速率的变化,通过分析水解过程不同时间段的偏钛酸粒度分布,确定了影响偏钛酸粒度分布的主要因素。在此基础上考察了钛液浓度、F值、铁钛比、水解晶种加量、熟化搅拌时间对偏钛酸粒度分布的影响。结果表明钛液沸腾后快速水解,再随钛液浓度降低水解速率逐渐降低,浆料粒度逐渐长大,二次沸腾20 min后,浆料的粒度分布逐渐稳定,后期保温过程对粒度分布影响不大;钛液浓度、铁钛比、F值、晶种加量和熟化期间搅拌时间均对偏钛酸粒度分布有影响,D50随着钛液浓度的增加而减小,随F值和铁钛比的增大而增加,随着晶种加量的增加而减小,随熟化期搅拌时间的延长而降低。     

Review: Parametric Study on the Performance of Progressive Cryoconcentration System

Progressive cryoconcentration (PC) is gaining acceptance in solution concentration process as it could provide an easy separation and ice purification with relatively low energy. In fact, the advantages of PC process as compared to the other concentration methods have led the growth of related studies that aim to provide the best system or condition for the separation process involved. Apart from the provision of appropriate equipment, the PC process should also be conducted at its optimum conditions of operating parameters involved, which could give the highest separation efficiency. Hence, relationship between the parameters, which covers both manipulated and determinant parameters should be studied first. This review summarizes the previous conducted studies on the effect of various operating parameters on the PC performance, which includes effect of coolant temperature, solution flowrate, initial solution concentration, freezing time, ice crystal front growth rate, and stirring rate.     

Crystallization kinetics and technology of 2-chloro-4,6-dinitro-resorcinol

The crystallization kinetics of 2-chloro-4,6-dinitro-resorcinol were studied by the method of intermittent dynamic analysis. The nucleation rate and crystal growth rate of 2-chloro-4,6-dinitro-resorcinol under three groups of conditions (27°C, 180 rpm; 33°C, 180 rpm; 33°C, 240 rpm) were estimated. The results show that, by increasing the temperature of the solution, both the nucleation rate and crystal growth rate increase. It is further found that, when the stirring rate increases, the nucleation rate increases and the crystal growth rate decreases. On the basis of the study of the crystallization kinetics, the effect of the operational parameters on the crystallization was studied. It is proved that, when the stirring rate is 180 rpm and the solution is cooled slowly to −8°C, the particle size of the crystals is even, the quality of the crystals is good, and the yield of the crystals is 40.6%. Published in Russian in Teoreticheskie Osnovy Khimicheskoi Tekhnologii, 2007, Vol. 41, No. 3, pp. 338–342. The text was submitted by the authors in English.     

SAPO-34分子筛晶化机理及晶化动力学研究

对SAPO-34分子筛晶化过程中预相形成、诱导期内晶核生成、晶体生长和晶化过程的研究进行综述。SAPO-34分子筛晶化过程首先形成不稳定的层状预相结构,进而发展为具有有序排列晶格骨架的晶核。结晶热力学控制晶相结构,晶化动力学控制晶体成核和生长速率。影响晶化动力学的关键因素是温度和浓度,成核速率和晶体生长速率互相竞争控制晶粒大小。晶化过程的Si取代机理和Si分布影响分子筛酸性。晶化动力学研究结果表明,温度升高,结晶速率增加,成核时间缩短。     

黑钛液中七水硫酸亚铁结晶动力学性质

采用平衡法研究了七水硫酸亚铁在黑钛液中的溶解度,通过拟合得到了其溶解度方程,并利用FBRM在线监测溶液结晶情况,测量了其结晶介稳区.通过间歇动态法研究了七水硫酸亚铁的结晶动力学,采用矩量变化法求解了粒数衡算方程,并利用最小二乘法对动力学实验数据进行多元线性回归后得到七水硫酸亚铁成核速率和生长速率方程,结果表明:搅拌速率和降温速率对七水硫酸亚铁结晶过程影响显著,因此,针对搅拌速率和降温速率对结晶工艺的影响进行了分析,并对优化前后七水硫酸亚铁产品进行了对比,发现优化后晶体呈规则的棱形,产品粒度明显增大,小颗粒晶体显著减小.     

Oxygen transfer to cassava starch solutions in an aerated,well-mixed bioreactor: Experimental and mass transfer studies

Experimental and mass transfer studies of oxygen transfer to cassava starch solution in an aerated, well-mixed bioreactor of 2 L have been carried out. The volumetric mass transfer coefficient was estimated and parametric studies were performed to study the effect of process variables of stirring rate, aeration rate, concentration of starch and temperature on the volumetric mass transfer coefficient. From the experimental results, it is evident that the first two and the last variables are directly proportional to the volumetric mass transfer coefficient. However, the volumetric mass transfer coefficient is inversely proportional to the concentration of the starch. Also, the saturation dissolved oxygen concentration is greatly affected by temperature and starch solution concentration. Whereas, stirring and aeration rates have neutral impacts on saturation dissolved oxygen concentration. Simulated data generated from obtained volumetric mass transfer coefficient agrees well with the experimental data, which indicates the accuracy of the coefficient.