溶析结晶在高浓盐水分盐中的研究

本文针对高盐废水的处理,提出了溶析结晶技术。以甲醇为溶析剂对含有高浓氯化钠、硫酸钠的溶液进行分离提纯,并分析了各种不同因素:温度、时间、溶剂比(甲醇体积∶溶液体积)、溶液质量浓度、溶液中溶质浓度比(b氯化钠∶b硫酸钠)下,溶质氯化钠、硫酸钠的析出率与纯度。实验表明,在常温下,溶剂比=1的条件下,对某煤化工高浓盐水中硫酸钠的一次收率为92.3%,纯度99%。     

溶析结晶法脱除钛白废酸中硫酸亚铁盐的研究

针对钛白粉工业的废酸,选用乙醇(Et OH)为溶析剂,研究了溶析结晶法脱除钛白废酸中硫酸亚铁盐的可行性。在5~30℃,采用激光检测法系统地测定了七水硫酸亚铁在水、硫酸溶液和醇酸混合水溶液中的溶解度,考察了溶析剂浓度、温度、硫酸浓度等因素对硫酸亚铁盐溶解度的影响。在此基础上,以钛白废酸(含硫酸20%(wt)、七水硫酸亚铁8%(wt)为对象,在搅拌结晶器中考察了溶析剂加入量、加入方式、搅拌速度、晶种和熟化时间等工艺操作条件对硫酸亚铁脱除率的影响。结果表明,以乙醇为溶析剂,可在常温下显著降低硫酸亚铁在硫酸溶液中的溶解度。在醇酸混合水溶液中,硫酸亚铁盐的溶解度主要受溶析剂浓度影响,与硫酸浓度无关。控制适宜的搅拌速度、溶析剂加入速度和熟化时间有助于提高硫酸亚铁的脱除率。适宜的溶析结晶条件为:温度为5~10℃,溶析剂与废酸的质量比1:1,溶析剂加料速度6 m L·min-1、熟化时间60 min。在此条件下,七水硫酸亚铁的脱除率可达到87%~91%。     

硝酸钙-磷酸-水-异丙醇体系中溶析结晶工艺研究

酸解液中氮磷的高效分离是发展硝酸法湿法磷酸的关键技术之一。提出采用溶析结晶使酸解液中磷以磷酸钙盐形式析出从而达到氮磷分离的研究思路。以异丙醇为溶析剂,通过单因素实验考察了溶析剂加入比（异丙醇与模拟酸解液质量比）、温度、五氧化二磷质量分数、溶析时间对析出晶体物相结构以及磷析出率的影响。结果表明,溶析时间不会影响析出晶体物相结构,增大溶析剂加入比、升高温度、降低五氧化二磷质量分数都会使得析出的晶体由磷酸二氢钙转变成磷酸氢钙。通过对比磷析出率得出适宜的工艺条件：溶析剂加入比为3∶1、温度为5.0 ℃、五氧化二磷质量分数为30%、溶析时间为1.0 h,在此条件下磷析出率可达73.58%。     

用偏钒酸铵制备偏钒酸钠工艺研究

对以偏钒酸铵为原料制取偏钒酸钠的工艺进行了研究。提出了以乙醇作为溶析剂,对偏钒酸钠溶液进行溶析结晶,并获得了良好效果。考察了制备过程中的主要影响因素,并确定了最佳工艺条件：碱溶pH=9~10、脱氨温度为90 ℃、浓缩终点溶液pH=7.5~8.0、浓缩终点总钒质量浓度为160 g/L、溶析剂与溶液体积比为1∶1、结晶时间为60 min。在最佳工艺条件下,通过碱溶除杂、脱氨浓缩、溶析结晶等工艺过程,制备出高纯度的偏钒酸钠,产品纯度达到99.5%以上。该方法工艺简单,对于生产高纯度的偏钒酸钠产品具有重要的指导作用。     

高纯偏钒酸钾制备工艺研究

以偏钒酸铵为原料,采用碱溶除杂、浓缩脱氨、溶析结晶的方法,制备的偏钒酸钾产品纯度大于99.5%。分析了制备过程的工艺原理,考察了pH、脱氨浓缩温度和钒浓度对偏钒酸钾成分的影响,探讨了溶析结晶的工艺条件。结果表明,影响偏钒酸钾质量的主要因素是碱溶除杂的pH和浓缩终点pH。制备过程的最佳工艺条件为：碱溶除杂pH为9~10、脱氨温度为95 ℃、浓缩终点pH为7.5~8.5、浓缩终点总钒质量浓度为180 g/L、溶析剂与溶液体积比为1∶1、结晶时间为30 min。滤液中残留的钒质量浓度低于3.0 g/L,钒收率达到98%以上。     

阿奇霉素二水合物溶析结晶工艺优化

针对阿奇霉素二水合物的溶析结晶工艺,考察了结晶的初始浓度、溶析剂流加速率以及搅拌强度对结晶产品的粒度分布的影响规律,确定了优化的工艺参数为结晶温度40 ℃,初始浓度0.32 g/g,搅拌速率为200 r/min,溶析剂滴加速率为200 μL/min。在此条件下可获得粒度分布约为300 μm到800 μm且主粒度约为580 μm的产品,克服目前结晶产品存在的聚结、粒度分布不均一等问题。     

高纯硼酸制备过程中的结晶动力学

采用HCl气体液相酸化硼砂的中和反应,并结合重结晶法与离子树脂交换法,制备了高纯H3BO3产品. 实验考察了H3BO3-NaCl-H2O体系中溶液过饱和度、结晶温度、结晶时间、搅拌速度及溶液中所含杂质等因素对H3BO3结晶过程的影响. 结果表明,溶液浓度为18.26%、结晶温度为10℃、结晶时间为480 min、搅拌速度为300 r/min,并选取适当的降温方式有利于H3BO3析晶,结晶率大于83%,晶体呈细小颗粒状. 体系中所含的NaCl杂质促进了H3BO3析晶. 由实验数据得到该体系中H3BO3的结晶动力学曲线,并建立了结晶动力学方程,结晶反应级数为2.     

溶析结晶在医药领域的研究进展

结晶作为一种传统的分离和提纯工艺，广泛运用于医药、化工、材料等领域。随着对结晶工艺的深入研究和对晶体产品质量越来越高的要求，结晶不再仅仅用于物质的分离和提纯，更重要的是根据产品功能的需要，制备特定结构的晶体。作为结晶的重要组成部分，溶析结晶因其操作简单、能耗相对较低、适用于热敏性物质等优势受到了广泛的关注。本文从溶析结晶相较于其他溶液结晶的不同点出发，重点介绍了溶析结晶热力学、溶析结晶动力学和工艺过程的研究，以及与溶析结晶相关的超临界流体技术和球形结晶技术。溶析结晶热力学关注了溶解度的测定方法和如何通过相图来确定合适的操作条件；溶析结晶动力学，详细描述了间歇、连续溶析结晶动力学模型的建立；工艺过程的研究，包括溶析剂与含有待结晶物质混合、结晶过程的控制和优化。同时本文对溶析结晶目前存在的问题进行了总结，并对未来的发展作了展望。     

乙酸钠强化溶析结晶处理废水中高浓度硝酸盐的研究

针对工业生产过程产生的高浓度硝酸盐废水，或者反渗透、离子交换后的高浓度硝酸盐废水，提出了利用无水乙酸钠强化无水乙醇溶析结晶法去除高浓度硝酸盐的技术。考察了无水乙醇、无水乙酸钠、氧化钙、温度、pH以及搅拌速率对硝酸盐结晶的影响，并对比了加入无水乙酸钠前后去除溶液中NO₃^--N的效果。结果表明：NO₃^-质量浓度为183.5 g/L(即NO₃^--N质量浓度为49.4 g/L)时，去除NO₃^--N的最佳去除条件为，80 mL无水乙醇，1.8 g无水乙酸钠，0.014 g氧化钙(Ca²⁺质量浓度为1.00 g/L)，温度为40℃，pH为13；与无水乙醇溶析结晶处理高浓度硝酸盐废水相比，无水乙酸钠会进一步提高硝酸盐结晶率约10个百分点，说明后加入无水乙酸钠对无水乙醇溶析结晶去除高浓度硝酸盐具有明显的强化作用。     

有机膜精确调控传质的新型溶析结晶及过程强化

溶析结晶是一种环保、高效的结晶方法,在温敏性、低溶解度物系的晶体生产领域具有不可替代的重要作用。但是,传统溶析结晶过程中溶液过饱和度的时空均一性差,传质调控为微米级尺度,容易爆发成核,是亟待解决的关键问题。本文提出利用聚醚砜（PES）中空纤维膜,为溶析剂与结晶溶液之间的传质提供均匀稳定的界面,实现结晶溶液与溶析剂的精确混合和结晶过程强化,开发了一种新型的溶析结晶传质调控技术。溶析剂在压力差驱动下均匀渗透通过有机膜,在结晶溶液一侧的膜外表面形成溶析剂液膜层,通过表面液膜的不断更新,将传统溶析结晶的毫米级宏观混合转变为亚微米级尺度的微观混合,实现过饱和度的均匀分布。同时,这层液膜的存在,避免了结晶溶液直接接触膜表面,有效地解决了异相成核附着导致膜污染的问题。实验中,对壳程流速做出周期性改变后,渗透通量可即时发生一致的线性响应变化,证实有机膜调控传质过程的精确性和灵敏性。PES膜重复使用多次后,渗透通量仍可以保持稳定。相比传统的滴加式溶析结晶,在相同的溶析剂传质速率下,有机膜调控过程制备的晶体产品,形貌更加规整、粒径分布更集中。因此,在溶析剂精确传质和抗污染方面,有机膜调控的溶析结晶过程均表现出良好的性能,为药物、大分子结晶的高效工业化制备开拓了新的思路。     

两种天然甜味剂甜菊苷和瑞鲍迪苷A在不同溶剂中的溶解度测定

用高效液相色谱（HPLC）法测定了两种天然甜味剂甜菊苷和瑞鲍迪苷A在不同纯溶剂中的固液平衡数据,温度范围为288.15~328.15 K。从实验数据知,所有研究的体系的溶解度均随温度的升高而增大。实验数据用三参数方程和NRTL模型拟合,拟合结果显示,两种模型均有好的拟合结果。由得到的溶解度数据,可指导甜菊苷与瑞鲍迪苷A的分离及结晶纯化溶剂的选择。     

溶析结晶法分离铬酸钾

首次测定了不同温度下铬酸钾在甲醇-水和乙醇-水混合溶剂中的饱和溶解度,结果表明,在同一温度下,铬酸钾的饱和溶解度随甲醇/水和乙醇/水质量比的增加而显著降低;在相同的甲醇/水或乙醇/水质量比条件下,铬酸钾的饱和溶解度随温度的增加而增加. 提出了以乙醇作为溶析剂、采用溶析结晶法分离铬酸钾的新工艺,并对溶析结晶过程中各相关参数对结晶相分离效率的影响进行了理论分析和实验研究,表明采用溶析结晶方法从水溶液中分离铬酸钾是可行的,为钾系亚熔盐法铬盐清洁工艺中铬酸钾的高效分离提供了新思路.     

Preparation of hybrid PU/PCL fibers from steviol glycosides via electrospinning as a potential wound dressing materials

In this study, the synthesis and application of biocompatible steviol glycosides based polyurethane/poly (ε-caprolactone) (PU/PCL) fibers was performed by electrospinning as a potential wound dressing materials that can be used for the closure of nonhealing wounds. During electrospinning, steviol glycoside-based polyurethane structures were used in blend formation with poly (ε-caprolactone) for easy producibility. Steviol glycosides are a natural abundant and easily accessible source as the main component of the wound dressing material due to their free hydroxyl groups, high biocompatibility, and hydrophilicity. The structure of steviol glycosides is composed of saccharide units and the free OH groups. Thus, steviol glycosides act as a crosslinker within the polyurethane structure and provides mechanical strength. For the production of steviol glycosides based PU/PCL fibers first, the steviol glycosides as a monomer were isolated from the stevia rebudiana. Then, polyurethane structures containing stevia glycoside were synthesized with hexamethylene diisocyanate, lactose and PEG-200 by solution polymerization technique. PCL was added to the prepared polyurethanes in a ratio of 1:2 and formation of nanofiber structure. The prepared wound dressing material was characterized by Fourier transform infrared, atomic force microscopy, and scanning electron microscope techniques. Swelling degree, water content and oxygen permeability assay of the steviol glycosides based PU/PCL wound dressing material was determined. In biocompatibility test, cell viability value of PU/PCL fibrous materials in indirect cytotoxicity test was determined as 86.9% and cell adhesion on hybrid PU/PCL fibers was showed as morphological. In accordance with this target, the steviol glycosides based PU/PCL wound dressing material can be produced easily and low cost. As a result, the wound dressing materials obtained with their high biocompatibility and low costs will be an effective and fast method for the healing of open wounds of diabetics.     

Solubility enhancement of steviol glycosides and characterization of their inclusion complexes with gamma-cyclodextrin

Steviol glycosidesrebaudioside (reb) A, C and D have low aqueous solubilities. To improve their aqueous solubilities, inclusion complex of steviol glycosides, reb A, C and D and gamma cyclodextrin were prepared by freeze drying method and further characterized by means of differential scanning calorimetry, Fourier transform infrared spectroscopy and Raman spectroscopy. The effect of gamma cyclodextrin on chemical shifts of the steviol glycosides was also studied in proton NMR experiments as well as in solid state (13)C CP/MAS NMR experiments. These results indicated that the steviol glycosides were clearly in inclusion complex formation with the gamma cyclodextrin which also results in solubility enhancement of these steviol glycosides. Phase solubility studies showed that amounts of soluble reb A, C and D increased with increasing amounts of gamma cyclodextrin indicating formation of 1:1 stoichiometric and higher order inclusion complexes.     

结晶法从含氟废水中合成粗颗粒冰晶石

以颗粒粒径和含水率为考察指标,研究了结晶法从含氟废水中合成粗颗粒冰晶石的可行性。实验结果表明,在废水氟质量浓度低于4.5 g/L、废水流量为1.3 L/h、结晶反应pH为4.1~6.6、反应温度为45 ℃条件下,延长晶种停留时间可以有效增大冰晶石的粒径,降低冰晶石含水率,氟回收率稳定在80%左右。采用沉淀与固液分离一体化反应器对氟质量浓度为4.0 g/L的废水进行了连续处理,在废水流量为20 L/h、结晶反应pH为4.0~7.0、反应温度为45 ℃条件下,合理控制晶种停留时间,依靠停留在反应器底部晶种的作用,可以合成得到含水质量分数低于30%、粒径满足要求的冰晶石产品。     

Catalytic Hydrogenation of the Sweet Principles of Stevia rebaudiana,Rebaudioside B,Rebaudioside C,and Rebaudioside D and Sensory Evaluation of Their Reduced Derivatives

Catalytic hydrogenation of rebaudioside B, rebaudioside C, and rebaudioside D; the three ent-kaurane diterpene glycosides isolated from Stevia rebaudiana was carried out using Pd(OH)₂. Reduction of steviol glycosides was performed using straightforward synthetic chemistry with the catalyst Pd(OH)₂ and structures of the corresponding dihydro derivatives were characterized on the basis of 1D and 2D nuclear magnetic resonance (NMR) spectral data indicating that all are novel compounds being reported for the first time. Also, the taste properties of all reduced compounds were evaluated against their corresponding original steviol glycosides and sucrose.     

Preparation and characterization of poly(ethylene‐co‐vinyl alcohol) membranes via thermally induced liquid–liquid phase separation

Porous membranes were prepared through the thermally induced phase separation of poly(ethylene‐co‐vinyl alcohol) (EVOH)/glycerol mixtures. The binodal temperature and dynamic crystallization temperature were determined by optical microscopy and differential scanning calorimetry measurements, respectively. It was determined experimentally that the liquid–liquid phase boundaries were shifted to higher temperatures when the ethylene content in EVOH increased. For EVOHs with ethylene contents of 32–44 mol %, liquid–liquid phase separation occurred before crystallization. Cellular pores were formed in these membranes. However, only polymer crystallization (solid–liquid phase separation) occurred for EVOH with a 27 mol % ethylene content, and the membrane morphology was the particulate structure. Scanning electron microscopy showed that the sizes of the cellular pores and crystalline particles in the membranes depended on the ethylene content in EVOH, the polymer concentration, and the cooling rate. Furthermore, the tendency of the pore and particle sizes was examined in terms of the solution thermodynamics of the binary mixture and the crystallization kinetics. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 853–860, 2003     

静态熔融结晶法提纯均四甲苯（英文）

The purification and separation of durene from the mixture containing durene isomers were studied. Since the boiling points of tetramethyl benzene isomers are very close but their melting points are of great differences, stat-ic melt crystallization was applied to separate and purify durene from its isomers. Crystallization experiments were carried out under various operating conditions. The effects of cooling rate, crystallization temperature, sweating temperature and sweating time on the yield and purity of crystal were investigated. Orthogonal exper-imental design method was adopted to analyze the factors that may affect the yield of durene. Under the optimal crystal ization conditions, the purity of durene could reach as high as 99.06%with the yield of 75.3%through one crystal ization process. By fitting purification data based on sweating time in isothermal operations, the purifica-tion rate coefficient was obtained.