熔融结晶技术分离纯化有机化合物的研究进展

熔融结晶技术是利用被分离物质各组分间凝固点的差异,通过控制热量的输入和移出,使被分离组分从熔融液中结晶析出,经洗涤、发汗等操作,实现目标组分分离纯化的一种结晶技术。熔融结晶分离纯化技术由于具有不需要使用溶剂、能耗低、设备体积小、能得到高纯产品等优点,在有机化合物的分离纯化领域得到了广泛应用。本文简述了熔融结晶的方式,介绍了熔融结晶器的类型,综述了熔融结晶技术分离纯化有机同分异构体、有机化工原料、日用品、食品和药品的研究进展,分析了熔融结晶技术分离纯化有机化合物过程中存在的问题,展望了熔融结晶技术分离纯化有机化合物的发展方向。文中指出：随着熔融结晶技术的发展,以提高产品质量,减小能耗和降低成本为目的的耦合熔融结晶技术已成为熔融结晶技术发展的方向。以包含熔融结晶设备、工艺、晶体成核和生长动力学、发汗机理以及传热传质模型的系统工程将会成为熔融结晶分离纯化有机化合物的研究热点。     

对二甲苯结晶分离技术进展

总结了工业上现有的对二甲苯(PX)结晶分离技术,霞点介绍了针对高浓度PX原料而开发的对二甲苯熔融结晶分离技术,并对PX结晶分离工艺的开发提出了建议.进料PX浓度是结晶工艺路线选择的关键,而结晶过程的PX晶体粒度控制也十分重要;获得准确的PX结晶动力学数据是整个结晶分离工艺的关键;PX晶体洗涤塔是最有效的晶体提纯装置,将是未来PX结晶分离工艺开发的重点和难点.     

熔融温度对透辉石结晶生长的影响

透辉石陶瓷材料具有良好的机械性能和化学性能,已被广泛应用于建筑陶瓷、日用陶瓷、微晶玻璃等领域.系统研究透辉石结晶生长过程的影响因素,可为透辉石陶瓷材料的加工、工艺设计和应用提供结晶机制的理论依据.以天然岩石为原料,采用熔融法制备透辉石晶体,研究熔融温度对透辉石生长机制的影响.运用X射线衍射仪(XRD)、场发射电子探针(...     

湿法磷酸熔融结晶的静态与悬浮过程研究

熔融结晶法提纯物质具有能耗低、废液排放量少、操作流程简单等优点,近年来在提纯湿法磷酸中得到了广泛的关注。熔融结晶提纯磷酸又分为静态结晶和悬浮结晶两种方法。本文比较了静态和悬浮熔融结晶过程中结晶釜中温度分布、晶体形貌,考察了结晶时间对晶体收率、杂质去除率的影响。研究结果表明:相比于静态结晶,悬浮结晶所得晶体粒度小且分布均匀,晶体收率受结晶时间影响较小,对铁离子和氟离子的除杂效率更高。     

层熔融结晶法制备高纯度磷酸

动态层熔融结晶技术净化磷酸,具有分离效率高、能耗低、无污染等优点,绿色环保。采用程序冷冻法研究了动态层熔融结晶净化磷酸过程中的传质、传热、结晶动力学和杂质分布。研究表明,磷酸晶层生长速率随磷酸熔体起始浓度和冷端降温速率的增加而增加,达结晶平衡态时,晶层平均厚度随磷酸熔体起始浓度的增加和降温终点温度的降低而增加,研究建立了晶层的增长速率和平均厚度与过程操作参数的关联模型;晶层传热能力和杂质的分离效率随着磷酸熔体起始浓度和降温终点温度的降低而增加;采用优化的工艺条件,通过一次结晶纯化,可将质量分数为86.79%的磷酸溶液纯度提高至90.8%,杂质氟离子的质量分数由3×10~(-5)下降到4.5×10~(-6),杂质去除率达85%。     

熔融结晶技术及其应用

介绍了熔融结晶技术的发展现状、原理、特点、装置、优势以及应用。认为熔融结晶技术不需溶剂、耗能小、设备简单，对难精馏、高沸点有机化舍物分离提纯有独特功能。但结晶过程的耦合传质、传热理论研究还不够透彻；应加强结晶器和结晶分离技术的研究，提高分离效率，从而加快熔融结晶精制技术的发展应用。满足工业新材料应用的需要。     

硫酸镍间歇结晶过程的工艺优化

文章采用聚焦光束反射测量仪(FBRM)研究了硫酸镍间歇结晶过程晶体的成核和生长规律,考察了搅拌桨形式、降温方式、搅拌速率、晶种添加量和晶种粒度对结晶过程中结晶动力学的影响。结晶工艺条件优化后,得到了粒径大、晶型好、分布均匀的晶体产品,为硫酸镍间歇结晶过程的工艺优化和工业放大提供了依据。     

结晶分离技术新进展

概述了结晶分离理论和模拟优化的发展,综述了冷却剂直接接触冷却结晶、反应结晶、蒸馏-结晶耦合、氧化还原-结晶液膜、萃取结晶、磁处理结晶等结晶分离方法.合理设计结晶器及结晶工艺是实现结晶分离工业化的可靠保证,对降膜结晶装置、Bremband结晶工艺和板式结晶器进行评价.指出今后需深入进行新型结晶分离装置与工艺、工艺的工业化、结晶过程传热传质机理方面的研究.     

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。     

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。     

Ultrareinigung organischer Substanzen durch Schmelzkristallisation

Ultrapurification of organic chemicals by melt crystallization. The need for ultrapure organic compounds is increasing fast. Purities up to 99.999 wt% are required for compounds like caprolactam and phenol. Ultrapurification by melt crystallization is promising from a cost-efficiency point of view, provided that the desired separation can be achieved in a single crystallization operation. When growing the crystals in a suspension a large solid-liquid interface can be made available, permitting a small rate of crystal growth and reducing the rate of solute incorporation. As a consequence, however, complete separation between crystals and melt has to be established. An efficient crystal-liquid separation can be attained using so-called crystal separation columns. Two types can be distinguished: non-packed and packed columns. In a packed column crystal transport is accomplished using a force like pressure. The separation efficiency of a single crystallization operation could be improved further by recrystallization. When procedures become available which are based not only on experimental experience but mainly on physical and technology knowledge, a broad application of suspension crystallization may be expected.     

丙交酯的提纯技术

对丙交酯提纯技术,包括萃取,精馏,熔融,结晶技术作了介绍,分析了不同工艺的优缺点,并从工程设计的角度进行总结,指出熔融结晶技术能耗低,操作灵活,绿色环保,是一个相对比较适合的分离提纯技术。     

Surface Properties – A Key for Nucleation in Melt Crystallization Processes

Numerous organic products which are commercially refined by crystallization exhibit wide metastable zones, for example, xylene, bisphenol‐A, isocyanates, or pyridine derivatives. The practical meaning for layer crystallization processes is that a high degree of subcooling on crystallization surfaces is necessary to start nucleation at the beginning of a crystallization stage. The subsequent crystallization runs then uncontrolled, at much higher rates than designed until the subcooling has been dissipated. As a consequence dendritic crystal growth sets in, which is disadvantageous in terms of the separation efficiency of the crystallization process. A practicable countermeasure is seeding which, however, requires more complex equipment and generates additional process steps, resulting in additional costs. In this work an alternative way of reducing the negative impact of subcooling on crystallization, which is based on the reduction of the metastable zone itself rather than on the bypassing it, has been investigated. The width of the metastable zone depends on the activation energy for nucleation which in turn depends on the interfacial surface tension between the melt and the surface of the crystallization element. It has been shown in this work that the activation energy for nucleation and so the supercooling in a xylene isomer mixture can be considerably reduced when replacing stainless steel by PTFE as a material for the crystallization surface. In follow‐up trials it was found that the crystallization surfaces do not need to be wholly covered by PTFE but that just small PTFE nucleation zones on steel surfaces have the same positive effect on the separation by crystallization. Applied in industrial equipment such nucleation zones might contribute to the cost optimization of commercial layer crystallization processes.     

Thermal analysis of solids production processes

The present work investigates the energy consumption of a solids production process. Such a process consists of three different operation units: crystallization/precipitation, solid-liquid separation by centrifuges or filters and drying of wet crystals. Each unit is analyzed with the objective of minimizing the energy consumption. Operating conditions, process design and other characteristic parameters (crystal size, porosity and physical proporties) are discussed with the aim to evaluate their influence on the process.     

熔融结晶洗涤分离过程的传递行为

通过对熔融结晶洗涤分离的操作模式和提纯机理进行分析,按照滤饼洗涤原理建立了流体流动模型,得到晶层内的压力分布。同时对晶层进行质量和热量衡算,建立了传质和传热模型,求得了晶层内杂质浓度分布和温度分布表达式。分布表达式表明了压力、浓度、温度与之相关的参数的关系,这个结果对熔融结晶洗涤分离过程的参数确定和操作过程的进一步实验研究具有重要的应用价值。     

Hybrid Distillation/Melt Crystallization Process Using Thermally Coupled Arrangements: Optimization with evolutive algorithms

Innovative hybrid processes offer significant cost savings, particularly for azeotropic or close-boiling mixtures. Hybrid separation processes are characterized by the combination of two or more different unit operations, which contribute to the separation task by different physical separation principles. Despite of the inherent advantages of hybrid separation processes, they are not systematically exploited in industrial applications due to the complexity of the design and optimization of these highly integrated processes. In this work we study a hybrid distillation/melt crystallization process, using conventional and thermally coupled distillation sequences. The design and optimization were carried out using, as a design tool, a multi-objective genetic algorithm with restrictions coupled with the process simulator Aspen Plus™, for the evaluation of the objective function. The results show that this hybrid configuration with thermally coupled arrangements is a feasible option in terms of energy savings, capital investment and control properties.     

尼龙6/聚酯(PET)共混体系结晶相分离的研究

用差示扫描量热（ＤＳＣ）考察尼龙６／聚酯（ＰＥＴ）共混体系的结晶行为，表明是结晶相分离的。不同条件下，结晶相分离的过程和形成的结晶态不同，反映在热行为上，如熔融过程和相应特征参数值，便随着处理的条件、组成比等而改变。研究结果还表明，当尼龙６组分的质量分数Ｗ ＰＡ－６＜ ０．１ 时，它被ＰＥＴ 阻隔而不再结晶，因两者形成部分氢键，酯基对尼龙６ 结晶影响的结果，尼龙６／聚酯（ＰＥＴ）共混体系中尼龙６ 的熔融峰温，随组成比的变化呈现波浪形曲线。