熔融结晶的过程强化

熔融结晶作为一种绿色高效的分离技术具有选择性高、能量消耗低、无须溶剂参与等优势,但在结晶理论研究、连续化生产、专用结晶器设计和工业放大等方面仍面临挑战。熔融结晶分离效率受物系性质、原料纯度和晶体生长速率限制。因此,熔融结晶过程的合理设计和过程优化对提高熔融结晶技术的能量和过程效率具有重要意义。基于熔融结晶技术在化工分离过程中的实际需求和应用前景,从熔融结晶过程工艺优化、晶体层生长表面设计、过程工艺耦合三方面论述熔融结晶过程中晶体成核、生长的强化方式,为达到高效率、低能耗的熔融结晶分离过程提供可行性指导。最后,概述了目前熔融结晶技术的主要研究焦点并对发展方向进行了展望。     

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.     

加工条件对聚L-乳酸热性能的影响

为了更好地掌握聚L-乳酸(PLLA)的加工工艺,系统考察了PLLA熔融温度和时间对其热性能的影响。结果表明:增加熔融时间会使PLLA非等温结晶峰变得尖锐,熔融40 min后PLLA的非等温结晶峰最为显著,而熔融时间的增加会使等温结晶后的熔融过程呈现出熔融双峰现象;熔融温度的增加则会使PLLA非等温结晶峰变得更加尖锐。     

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。     

超柔软易染新型聚酯的热性能研究

超柔软易染聚酯是一种新型功能性聚酯产品。通过差示扫描量热测试,就其构成成分对玻璃化转变温度、冷结晶温度、熔点、熔融结晶温度的影响进行了研究,为后道加工工艺的选择提供参考依据。     

高纯度苯甲酸精制工艺述评

介绍了结晶法精制苯甲酸的三种工艺—升华结晶 ,溶液结晶 ,熔融结晶。重点评述了熔融结晶法的装置与应用现状 ,同时展望了苯甲酸精制的未来发展动向     

熔融结晶分离对硝基氯苯温度控制方案的设计与应用

介绍了对硝基氯苯熔融结晶分离的过程,并在结晶器温度控制方案中通过采用HONEYWELL公司的TPS系统的CL程序和RAMP/SOAK算法来满足熔融结晶的工艺控制要求,提高了结晶工序的控制性能.     

高品质异喹啉生产技术研究

文章简要介绍了目前异喹啉分离精制的工艺研究现状,在此基础上,提出了三步静态熔融结晶加一次精馏的生产方法,即把工业异喹啉经过三步熔融结晶提纯后,再通过精馏的手段对异喹啉产品进行提质,其中:静态熔融结晶工艺过程可将异喹啉提纯到≥98%,结晶工艺收率≥85%;而精馏提质所得异喹啉产品表现为无色透明状或白色结晶,水分含量≤0.05%,金属离子含量(包括钠、钾、铁、钙、镁等)均小于3 ppm,精馏工艺收率≥93%。     

熔融结晶法从异丙苯装置污苯中回收苯的研究

研究了熔融结晶法从异丙苯装置脱苯塔的塔顶产物(污苯)中回收苯的工艺条件。考察了不同操作条件对污苯结晶效果和苯回收率的影响,确定了熔融结晶操作的最佳条件。降温结晶的最佳操作条件:结晶恒温时间为90 min,结晶终温为-28℃。发汗操作的最佳操作条件:恒温时间为90 min,升温速率为0.10℃/min,发汗结晶终温为-15.0℃。在最佳工艺条件下,单级熔融结晶实验所得产品纯度在86.0%~96.0%之间,苯的回收率大于35.0%,将污苯经两级熔融结晶最终可得到苯质量分数大于99.50%的产品,可以作为合成异丙苯的原料被回收利用。     

固相聚合PET及饮料瓶的热性能研究

应用 DSC、 TGA和 TMA研究了固相聚合 PET树脂的双重熔融行为、热稳定性及瓶坯、包装瓶的结晶性能和膨胀性。结果表明 ,固相聚合 PET树脂在不同升温速度下的双重熔融行为反映出树脂结晶结构的完整性 ,可为确定固相聚合生产的工艺条件提供参考。对具有不同结晶性能和热稳定性的固相聚合 PET树脂 ,其制坯及吹瓶工艺条件应作必要调整。     

Isothermal crystallization and melting behaviors of nylon 11/nylon 66 alloys by in situ polymerization

Nylon 11/nylon 66 alloys were prepared by in situ polymerization. Analysis of the isothermal crystallization behaviors of nylon 11/nylon 66 alloys was carried out using differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The crystallization kinetics of the primary stage under isothermal conditions could be described by the Avrami equation. The crystal morphology observed by means of polarized optical microscope (POM). In the DSC scan after isothermal crystallization process, the multiple melting behaviors were found and each melting endotherm has a different origin. The real-time XRD measurements confirmed that no crystalline transition existed during the isothermal crystallization process. The multiple endotherms were experimentally evidenced due to melting of the recrystallizated materials or the lamellae produced under different crystallization processes. The equilibrium melting point of samples for isothermal crystallization was also evaluated.     

Characterization of thermal behavior and kinetics of crystallization of a thermotropic rigid-chain copolymer

Thermal analysis was employed to estimate the heat of transition, equilibrium melting temperature and surface free energy of a thermotropic liquid crystal copolyester resin (70 mol% p-hydroxybenzoic acid and 30 mol% 2,6-hydroxynaphthoic acid). Specific heats and melting and crystallization behavior were evaluated using differential scanning calorimetry (DSC). Experiments over a wide range of cooling rates indicate two different crystallization processes: a rapid crystallization process and a slow crystallization process. The kinetics of the rapid crystallization process were evaluated using a non-isothermal method. The analysis indicates that the rapid crystallization process can be suitably described by the non-isothermal Avrami equation. The Avrami exponent is found to be equal to 2, which is in agreement with the nucleation and growth mechanism of the rigid rodlike molecules. The kinetics of the slow crystallization process, which were studied using an isothermal method, indicate that the degree of crystallinity varies linearly with log(time). The equilibrium melting temperature for this process is found to be 372°C. The Arrhenius plot yields a linear relationship in the lower temperature range.     

采用正交试验法优化山梨醇结晶的工艺

本文采用正交试验法优化山梨醇结晶的工艺条件,找出了原来产品熔点低的原因,对原装置上的结晶温度控制系统进行了改造,并对操作人员进行了培训,按优化的条件生产后,结晶山梨醇的熔点稳定达到101℃,其优化的条件为:结晶温度:70℃,结晶时间:40 min,晶种用量:15%。     

Influences of the chemical defects on the crystal thickness and their melting of isothermally crystallized isotactic polypropylene

Ziegler-Natta and Metallocene Catalysis isotactic polypropylene with different chemical defects were isothermally crystallized at various crystallization temperatures. The crystal thickness and their corresponding melting behavior were studied using small angle X-ray scattering, atomic force microscopy, optical microscopy, and differential scanning calorimetry. The equilibrium melt temperature of the samples was calculated from the Hofmann-Weeks extrapolation for the supercooling. Two lamellar populations were distinctly observed in all cases during the crystallization process. Relatively thicker and stable lamellar crystals which melt at higher temperatures were observed with lowering the supercooling and found catalysis dependence in these crystals. During melting, no significant recrystallization of the samples has been detected for higher crystallization temperature where recrystallization processes enhance the lamellae thickness. The melting of the crystals has found strong dependence with the crystallization temperatures, the catalysis process and the nature of the defects present in the isotactic polypropylene. The increase of the crystal lamellae thickness and their melting temperature might be presumably related with the chain folding mechanism as well as the stability of the crystals formed during the isothermal crystallization process. A combined plot of SAXS and DSC results is demonstrated for the equilibrium melting temperature followed by critical analysis of the results.     

On the triple melting behaviour of poly(ethylene succinate)

The morphology of melt-crystallized poly(ethylene succinate) (PES) was investigated by optical microscopy and scanning electron microscopy, and the melting behaviour of PES was studied by differential scanning calorimetry (DSC). At low crystallization temperature imperfect crystals were formed which could melt and recrystallize during the DSC scan. Triple melting peaks were observed, and the melting behaviour was strongly dependent on crystallization time and scan rate. It was observed that crystallization at high temperature perfected the crystals (dominant and subsidiary lamellae in the spherulitic structure). Increasing the scan rate reduced the chance for reorganization. However, at high crystallization temperature two melting peaks were observed. The material formed was much more perfect, so that the melting process was not dominated by recrystallization. Accordingly, the cause of dual melting is the existence of two kinds of crystal perfection.     

Crystallization kinetics and melting behaviour of microbial poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate)

Isothermal and non‐isothermal crystallization kinetics of microbial poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate) [P(3HB‐3HHx)] was investigated by differential scanning calorimetry (DSC) and ¹³C solid‐state nuclear magnetic resonance (NMR). Avrami analysis was performed to obtain the kinetic parameters of primary crystallization. The results showed that the Avrami equation was suitable for describing the isothermal and non‐isothermal crystallization processes of P(3HB‐3HHx). The equilibrium melting temperature of P(3HB‐3HHx) and its nucleation constant of crystal growth kinetics, which were obtained by using the Hoffman–Weeks equation and the Lauritzen–Hoffmann model, were, respectively, 121.8 °C and 2.87 × 10⁵ K² when using the empirical ‘universal’ values of U* = 1500 cal mol^?1. During the heating process, the melting behaviour of P(3HB‐3HHx) for both isothermal and non‐isothermal crystallization showed multiple melting peaks, which was the result of melting recrystallization. The lower melting peak resulted from the melting of crystals formed during the corresponding crystallization process, while the higher melting peak resulted from the recrystallization that took place during the heating process. Copyright © 2005 Society of Chemical Industry     

聚乙烯醇/马来酸酐接枝聚丙烯共混物的热行为研究

采用熔融共混法制备了一种聚乙烯醇(PVA)/马来酸酐接枝聚丙烯(PP-g-MAH)共混物膜,通过差示扫描量热仪研究了共混物膜的结晶和熔融行为。结果表明,随着共混物中PP-g-MAH含量（不超过50 %）的增加,PVA相的结晶和熔融温度升高,结晶度增加,结晶速率增加,而随着PVA含量（超过30 %）的增加,PP-g-MAH的结晶及熔融温度降低,结晶度降低,结晶速率增加。用Ozawa法对共混物中PVA相的非等温结晶动力学研究表明,共混物中PVA相在191~197 ℃开始主期结晶,在173~189 ℃进入次期结晶阶段。     

Crystallization and melting behavior of partially miscible six‐armed poly(l‐lactic acid)/poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) blends

The crystallization kinetics and spherulitic morphology of six‐armed poly(L‐lactic acid) (6a‐PLLA)/poly(3‐hydroxybutyrate‐co?3‐hydroxyvalerate) (PHBV) crystalline/crystalline partially miscible blends were investigated with differential scanning calorimetry and polarized optical microscopy in this study. Avrami analysis was used to describe the isothermal crystallization process of the neat polymers and their blends. The results suggest that blending had a complex influence on the crystallization rate of the two components during the isothermal crystallization process. Also, the crystallization mechanism of these blends was different from that of the neat polymers. The melting behavior of these blends was also studied after crystallization at various crystallization temperatures. The crystallization of PHBV at 125°C was difficult, so no melting peaks were found. However, it was interesting to find a weak melting peak, which arose from the PHBV component for the 20/80 6a‐PLLA/PHBV blend after crystallization at 125°C, and it is discussed in detail. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42548.     

Comparison of crystallization behaviors of poly(ε‐caprolactone) in confined environment with that in bulk

The spatial confinement of poly(ε‐caprolactone) (PCL) in the matrix of PMMA was synthesized by insitu polymerization and characterized by WAXD and SEM. The nonisothermal crystallization behavior and the kinetics of PCL in PMMA/PCL (85/15) blend and pure PCL were investigated by means of DSC. Jeziorny and Ozawa's theoretical prediction methods were used to analyze the crystallization kinetics. The melting behavior after cooling was also studied. There was an additional interesting phenomenon of double‐melting peak for pure PCL. Peaks at lower temperature shifted to lower temperature, and peaks at higher temperature did not shift with the increasing cooling rate. This behavior can be due to recrystallization. For the high‐crystallization activity energy and low‐crystallization rate, PCL in bulk would recrystallize during the melting process, and displayed a double‐melting behavior. Under spatial confinement of the rigid PMMA, PCL had much lower crystallization activity energy and had only one melting peak. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Determination of Metastable Zone Width and Nucleation Induction Period of Palm Oil and its Olein/Stearin in Melting Layer Crystallization

Measurement methods of metastable zone width (MZW) and nucleation induction time for melting layer crystallization of palm oil (PO) and its olein/stearin (POL/PST) were established, and the effects of cooling rate (corresponding to various supercoolings) on MZWs and induction time for melting layer crystallization of PO, POL, and PST were determined. The results indicated that the MZW coherently rose with increasing cooling rates with respect to PO and POL, while it declined with higher cooling rates for PST. The induction period results demonstrated that the nucleation induction periods of PO, PST, and POL decreased with increasing supercoolings, and the lag time for nucleation negatively correlated to the melting point of oils at the same supercooling. These data could offer significant instruction in designing and controlling the melting layer crystallization process for palm oil.