反应与溶析结晶过程强化及数值模拟研究进展

反应与溶析结晶技术被广泛地用于无机与有机化学品的生产，如催化剂和药物活性组分。反应与溶析结晶过程通常是在高过饱和度条件下进行，具有快速的成核与生长速率，因此需要在结晶过程开始前实现不同反应物或溶析剂与溶液之间快速充分的混合，以避免不良混合造成过饱和度的空间不均匀分布，破坏晶体产品的性质。模型和数值模拟方法的分析和预测能力可以加深对过程现象的机理认识，促进结晶设备和操作条件的优化设计。本文综述了反应与溶析结晶的过程强化方法和数值模拟的研究进展。首先从结晶设备、外加能量场和膜技术辅助结晶三个方面对过程强化研究进行了阐述；然后介绍了数值模拟中常用的微观混合模型，包括涡流卷吸模型和基于联合组成概率密度函数的微观混合模型；最后对文献中的液液反应结晶、气液反应结晶和溶析结晶的数值模拟进行了总结与分析。针对已有研究的不足，提出了未来发展方向的一些展望。     

微尺度过程强化的结晶颗粒制备研究进展

结晶颗粒制备技术在化工、医药、电子、生物等领域具有不可替代的作用。近年来,随着化工过程强化和微化工技术的快速发展,基于微尺度的过程强化方法在晶体颗粒制备过程中得到广泛的应用,成为高端颗粒制备的前沿技术。本文系统综述了该领域的研究进展：围绕微流控组件,简述微结构混合器、微流体技术对提高微观混合效率的原理及其在纳米材料、药物结晶等领域的应用;围绕微尺度力场,综述超重力旋转填充床的结构设计、可视化研究,超声场为代表的声空化效应及外加力场对超细纳米颗粒制备和药物连续结晶过程的应用;进一步,针对新型膜微尺度传质强化过程,分析微孔膜材料强化传质过程以及膜表面的晶体颗粒“黏附-生长-脱落”运动行为,阐明影响微孔膜分散传质强化过程的关键结构和过程参数,系统论述致密膜液层强化传质的表面更新机制和控制结晶颗粒制备的多级膜操作系统。最后,展望微尺度过程传质强化的结晶颗粒制备技术发展趋势。     

腐殖酸聚集体对膜蒸馏过程膜污染的作用机理

膜污染是膜蒸馏过程应用于工业水处理中遇到的主要问题之一。选取水体中具有代表性的有机物（腐殖酸）、微溶无机盐（碳酸钙）作为典型污染物,研究有机腐殖酸聚集体对于膜蒸馏过程膜污染进程的影响规律,探讨天然有机物-无机微溶盐混合水体中腐殖酸聚集体对于无机盐结晶过程的控制机理。结果表明：膜蒸馏通量的衰减大致可分为由滤饼层的形成造成的不可恢复部分以及由浓差极化、膜孔“半润湿”而造成的可部分恢复的通量降低。Ca²⁺通过加速腐殖酸分子的聚集过程,使表面负电性降低的腐殖酸聚集体率先吸附在聚偏氟乙烯中空纤维膜内表面,形成有机基质污染层;碳酸钙在有机腐殖酸聚集体的诱导下在膜内表面异相成核,最终成长为稳定的晶体。腐殖酸聚集体为无机盐晶体在疏水性膜内表面的生长提供了异相成核的基础。可通过控制污染水体中有机物的含量控制微溶碳酸钙在膜内表面成核及生长,实现控制其在膜内表面附着进而诱发疏水膜发生亲水化的过程。     

膜辅助添加晶种的过硫酸铵冷却结晶在线监测与过程调控

冷却结晶是经典的溶液结晶过程,常用于分离溶解度随温度变化较大的物质,制备高品质晶体产品。直接进行降温会导致成核速率不可控,得到的晶体产品质量差。在工业中通常选择在溶液结晶介稳区内投放适量晶种来诱导成核,但晶种制备过程复杂,而且成功的添加晶种过程取决于晶种的粒度分布、数量、投放时机和操作人员的经验等因素,降低了产品质量的批次重复性。本文利用聚四氟乙烯（PTFE）中空纤维膜组件为结晶溶液和冷却液提供换热界面,结晶溶液温度降低,在膜界面处形成较均匀的过冷度梯度,进而在低过饱和度下发生异相成核,实现膜辅助添加晶种的过硫酸铵冷却结晶过程调控。膜组件中产生的晶种进入结晶釜中继续生长,将成核和生长过程进行解耦。在线结晶检测系统捕捉到的照片证实了通过控制膜组件使用温度和时长两个操作参数便可得到具有较好的形貌、较窄的粒度分布的晶种。相比直接冷却结晶,在相近的降温速率下,膜辅助添加晶种过程制备的晶体产品具有更大的平均粒径,且粒度分布更集中,表面更加光滑。因此,膜辅助冷却结晶呈现了良好的成核控制能力,有望实现晶种自动制备和添加功能,为高附加值晶体产品的冷却结晶过程开发提供了新方向。     

膜蒸馏法淡化苦咸水中的膜污染初步研究

利用气隙式膜蒸馏考察了操作温度、料液中难溶盐种类及其饱和度以及料液中不溶颗粒等因素对膜渗透性能的影响。结果表明，硫酸钙、碳酸钙和氢氧化镁是苦咸水中的主要结垢物，它们在膜表面沉积、结垢，使膜通量下降，甚至会破坏膜的疏水性，对料液进行预处理可有效防止沉积物的出现。     

反应和沉淀中的质量传递

Shun Wachi 和 Alan G.Jones 模拟研究了气-液相反应结晶过程中的传质问题,他们的分析方法是把气-液反应传质膜理论与结晶过程的质量衡算及粒数衡算结合起来考虑,以文献报导的关于 Ca(OH)_2溶液吸收 CO_2过程为例进行了模拟,结果表明用可测的晶体粒粒度分布可表征由于传质阻力而引起的空间上过饱和度分布及成核粒子的非均匀性;在低传质     

浓盐溶液的膜蒸馏机理研究

考察了高浓度氯化钠溶液在直接接触式膜蒸馏操作中的热侧温度，冷侧温度，流速和料液浓度对膜渗透通量的影响。发现膜渗透通量随氯化钠溶液浓度的高而降低。当氯化钠溶液浓度约为25％时，膜渗透通量急剧下降。氯化钠溶液达到饱和时，膜渗透通量逐渐趋于稳定。研究认为此现象是由于膜面上有NaCl结晶形成而导致的。     

炭膜基亲水性无机微滤动态膜的制备研究

以水包油型油水乳化液分离为背景,以多孔管状炭膜为载体,以高岭土、ZrO2和Al2O3三种微米级无机颗粒为涂膜材料,对亲水性无机动态膜的制备进行初步的实验研究。实验采用错流操作方式在膜管内表面涂覆动态膜,考察涂膜过程中渗透通量随时间的变化,研究涂膜颗粒种类、载体平均孔径、制备操作压力、错流速度、涂膜液温度及涂膜液中阳离子浓度对动态膜结构及制备过程渗透通量的影响。实验结果表明,高岭土和ZrO2微米级颗粒是较适宜的炭膜基动态膜涂膜材料,且两种动态膜的渗透通量均随载体平均孔径的增大而增大、随操作压力和涂膜液温度的提高而提高;对高岭土动态膜的研究发现,其渗透通量随错流速度的增大而提高;对ZrO2动态膜的研究发现,其渗透通量随涂膜液中阳离子浓度的增大先减小后增大。     

膜结晶处理高浓度Na+、Mg2+//Cl——H2O溶液的结晶调控

利用真空膜蒸馏-结晶耦合技术处理多元高盐废水(Na⁺、Mg²⁺//Cl^--H₂O),回收纯水和高品质NaCl晶体产品,考察不同操作温度和不同无机盐离子浓度对膜蒸馏性能和NaCl晶体产品性质调控作用。结果表明随着温度升高导致饱和蒸气压增大,增大了跨膜压差,膜的渗透通量逐渐升高;随着溶液中Mg²⁺浓度的逐渐升高,膜的渗透通量呈下降的趋势,主要是由于水的质量分数下降和溶液黏度增加;膜蒸馏过程中,通过对比实验,分析了疏水微孔膜表面在膜蒸馏操作条件下表面晶体颗粒沉积的程度,证实了使用的中空纤维膜性能稳定,重复使用20次后仍能保持稳定通量;操作温度为65℃时,不同离子浓度的饱和原料液(MgCl₂质量占NaCl和MgCl₂总质量的0%、5.0%和10.0%)得到NaCl晶体产品平均粒径分别为91.04、91.38和122.56 μm,粒度分布的变异系数C.V.值分别为28.78、30.63和36.77,粒径分布集中,表面相貌平整,呈完美的立方体形态,没有团聚现象;同时,膜蒸馏得到的水纯度较高,电导率均小于5 μS?m^-1,采用选择性溶剂乙醇洗涤后的NaCl晶体产品纯度均大于98.15%。综上,通过膜蒸馏过程中渗透通量和膜界面的有效调控,在适宜的操作温度和较低的Mg²⁺含量下,膜蒸馏结晶过程从多元高盐废水(Na⁺、Mg²⁺//Cl^--H₂O)控制分离获得纯度较高、表面形貌完好、粒度均一的NaCl晶体产品。这一研究将为综合治理多元无机高盐废水,实现废水的近零排放和无机盐资源回用开拓新的思路。     

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。     

A novel hollow fiber membrane-assisted antisolvent crystallization for enhanced mass transfer process control

Herein, a novel hollow fiber membrane-assisted antisolvent crystallization (MAAC) was proposed to enhance the mass transfer control over the antisolvent crystallization. A polyethersulfone membrane module was introduced as the key device for antisolvent transfer and solution mixing. An antisolvent liquid film layer was formed on the membrane surface and mixed with the solution. The liquid film also prevented the membrane from directly contacting with crystallization solution. By controlling both the shell side flow velocity and the antisolvent transfer, the antisolvent permeation rate achieved sensitive, stable, and accurate control during long-term and repeated utilization. The interfacial mass transfer rate of MAAC was 0.66 mg cm⁻² s⁻¹, which was only 1/50 that of conventional droplet antisolvent crystallization. MAAC also provided crystal products with better morphologies and narrower size distributions than the conventional process. The stable performances of MAAC in terms of its accurate antisolvent mass transfer and antifouling capabilities were also highlighted. © 2018 American Institute of Chemical Engineers AIChE J, 65: 734–744, 2019     

Controlled liquid antisolvent precipitation using a rapid mixing device

Particle formation by the liquid antisolvent (LAS) process involves two steps: mixing of solution–antisolvent streams to generate supersaturation and precipitation (which includes nucleation and growth by coagulation and condensation) of particles. Uniform mixing conditions ensure rapid and uniform supersaturation, making it a precipitation controlled process where the particle size is not further affected by mixing conditions and results in precipitation of ultra-fine particles with narrow particle size distribution (PSD). In this work, we demonstrate that the use of an ultrasonically driven T-shaped mixing device significantly improves mixing of solution and antisolvent streams for precipitation of ultra-fine particles in a continuous operation mode. LAS precipitation of ultra-fine particles of multiple active pharmaceutical ingredients (APIs) such as itraconazole (ITZ), ascorbyl palmitate (ASC), fenofibrate (FNB), griseofulvin (GF), and sulfamethoxazole (SFMZ) in the size range 0.1–30 μm has been carried out from their organic solutions in acetone, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), and ethanol (EtOH). Classical theory of homogeneous nucleation has been used to analyze the result, which suggests that higher nucleation rate results in finer particle size. Interestingly, experimental determination of degree of supersaturation indicates that higher supersaturation does not necessarily result in higher nucleation rate and nucleation rates can be correlated to solvent polarity.     

Antisolvent crystallization in porous hollow fiber devices

This paper examines antisolvent crystallization under a new perspective and in the unique environment offered by porous hollow fiber membrane devices. The latter are compact, extremely efficient on a volumetric basis, easy to scale up and control. Their inherent characteristics promote the creation of homogeneous concentration conditions on a scale considerably smaller than existing industrial crystallizers without the necessity of a large energy input, properties that are desirable but rarely achieved in industrial crystallizers.Mixing studies were performed to examine the maximum achievable supersaturation in porous hollow fiber devices. It was shown that they are able to offer the supersaturation levels necessary to perform antisolvent crystallization. Moreover, supersaturation is created uniformly due to the large number of feed introduction points, the membrane pores. In addition, radial mixing is substantial in contrast with traditional tubular devices and the characteristic time involved in this process is comparable to the device residence time.Porous hollow fiber antisolvent crystallization of aqueous L-asparagine monohydrate systems proved successful. Mean crystal sizes up to two times smaller compared to batch stirred crystallizers were obtained in standalone membrane hollow fiber crystallizers (MHFC) and their combinations with completely stirred tanks. The CSD was confined below for the former and for the latter, levels that are sufficient for most pharmaceutical crystalline products, for which bioavailability and formulation concerns dictate the desired CSD. In addition, porous hollow fiber devices achieved comparable or slightly higher nucleation rates with respect to batch stirred crystallizers and similar values compared to tubular precipitators. Considerable improvements can be obtained by carefully designing membrane hollow fiber crystallizers.     

New liquid membrane technology for simultaneous extraction and stripping of copper(II) from wastewater

In this paper, a new liquid membrane technique, hollow fiber renewal liquid membrane (HFRLM), is presented, which is based on the surface renewal theory, and integrates the advantages of fiber membrane extraction, liquid film permeation and other liquid membrane processes. The results from the system of CuSO₄+D2EHPA in kerosene+HCl show that the HFRLM process is very stable. The liquid membrane is renewed constantly during the process, the direct contact of organic droplets and aqueous phase provides large mass transfer area. These effects can significantly reduce the mass transfer resistance in the lumen side. Then the mixture of feed phase and organic phase flowing through the lumen side gives a higher mass transfer rate than that of stripping phase and organic phase, because the aqueous layer diffusion of feed phase is the rate-controlling step. The overall mass transfer coefficient increases with increasing flow rates and D2EHPA concentration in the organic phase, and with decreasing initial copper concentration in the feed phase. The overall mass transfer coefficient also increases with increasing pH in the feed phase, and reaches a maximum value at pH of 4.44, then decreases. Also, there is a favorable w/o volume ratio of 20:1 to 30:1 for this process. Compared with hollow fiber supported liquid membrane and hollow fiber membrane extraction processes, HFRLM process has a high mass transfer rate. Mathematical model for the HFRLM process based on the surface renewal theory is developed. The calculated results are in good agreement with experimental results under the conditions studied.     

Particle Shape and Purity in Membrane Based Crystallization

Well‐controlled crystallization is the best method for preparing materials that are uniform in shape, size, structure and purity. The driving forces for crystallization are local gradients of supersaturation as the source and desupersaturation as the drain. Very high local supersaturation causes a high growth rate and represents a limiting factor for unstable modifications and product impurities. Hybrid membrane technology provides an interesting tool for controlling and limiting the maximum level of supersaturation due to defined mass transfer across the membrane. In this paper, the level of crystal growth rate in the system NaCl/KCl/water is varied by using different crystallization techniques. Vacuum evaporation crystallization (high growth rate) is compared to membrane based evaporation crystallization (low growth rate) and the results are interpreted in terms of product purity, particle shape and size. Membrane based crystallization in combination with effective solid/liquid separation as well as high performance analytics is suggested as a significant ultrapurification methodology.     

液膜技术原理及中空纤维更新液膜

液膜技术可以实现萃取和反萃的耦合,具有独特的分离优势。因为具有非平衡传质的特性,液膜技术传质推动力大,萃取相用量很少。回顾了液膜技术的原理,指出液膜技术的关键在于形成一层厚度薄且相当稳定的液膜相。分析介绍了近年来发展起来的各种液膜技术的优缺点,提出了一种中空纤维更新液膜技术,其体积传质系数比传统萃取塔的大530倍。     

Nucleation and Supersaturation in Drowning‐Out Crystallization using a T‐Mixer

In order to assess the performance of drowning‐out crystallization using a T‐mixer, nucleation and supersaturation were studied. The particle size was changed considerably with the solvent fraction and the feed rate, which were the main parameters controlling the supersaturation. At S = 1.7, the boundary point between homogeneous and heterogeneous nucleations was found from a log‐log plot of supersaturation rate versus maximum supersaturation. Drowning‐out crystallization using a T‐mixer could easily generate high supersaturations of up to 50, which were adjusted by the feed rate and the ratio of solvent to antisolvent. Nano‐ and micron‐sized particles can be prepared by drowning‐out crystallization using a T‐mixer.     

MASS TRANSFER IN MEMBRANE ABSORPTIONDESORPTION OF AMMONIA FROM AMMONIA WATER

Hydrophobic membrane can provide fast mass transfer for absorption-desorption of gasesform liquid to absorbent.The removal of ammonia from ammonia water and absorption with dilutesulphuric acid was studied in a pilot plant with polypropylene hollow fiber column,The removalrate and influences of operation temperature,flow rate and concentration on mass transferperformances were discussed mathematically.Experimental results and computer calculation show thatthe ammonia removal rate is not affected by the feed concentration for a given system.Both partialand overall mass transfer coefficients vary along the axis of the fiber,and the mass transfer for themembrane process is controlled by membrane resistance.