水及杂质积累对粗蒽溶剂结晶精制咔唑的影响

考察了粗蒽结晶分离过程在溶剂循环使用时二甲苯中杂质和乙醇中水的积累对精制咔唑的影响。结果表明,随着二甲苯循环次数的增加,原料中的主要杂质萘、菲和芴在回收二甲苯中逐渐积累,其中萘的浓度最高可达0.35 mg·ml^-1,滤饼中咔唑的含量降低2.77%（质量）左右,收率降低高达7.05%（质量）。同时,母液中杂质的积累使溶剂回收困难,二甲苯的损失率随着循环次数增加而增加,由单程实验的44.75%（体积）增加到循环3次时的79.17%（体积）。原料中的水分随着溶剂循环在回收溶剂中逐渐积累,循环使用3次后,乙醇的含水量高达6.65%（体积）。乙醇含水量在0～12%（体积）之间时,咔唑纯度在98%（质量）以上。含水量在0～6%（体积）时,咔唑的相对结晶度随含水量增加从45.67 %降到40.79 %;含水量为9%和12%时,相对结晶度分别为48.85% 和48.52%。     

从煤焦油分离提纯蒽和咔唑工艺改进探讨

溶剂结晶-精馏法是目前从煤焦油中分离提纯蒽和咔唑的比较先进成熟的已工业化工艺,其杂质的脱除主要在溶剂结晶部分,操作步骤多,但杂质分离效果还不是很理想,最终影响产品纯度。通过实验研究,发现结晶物中高杂质母液的滞留是该工艺杂质分离效果难以提高的关键因素。提出了溶剂结晶结合抽滤-精馏法新工艺,给结晶箱组合气液分离器,实现结晶同步抽滤功能,降低结晶物的母液滞留量,可提高分离效果,减少溶剂循环量,提高产品纯度和回收率,降低装置能耗,增加产能,有较好的经济性。     

粗蒽中蒽、菲、咔唑的分离与精制技术进展

综述了从粗蒽中分离和精制蒽、菲、咔唑的技术进展,介绍了物理分离法、化学分离法和复合法,并对各种方法进行了评述。结果表明,复合法因其流程简单、投资低和元环境污染等,具有推广价值。     

Determination of crystalline thermodynamics and behavior of anthracene in different solvents

To screen suitable solvents for anthracene crystallization, the solubilities of anthracene and metastable zone width were determined in four different solvents, N,N‐dimethyl formamide (DMF), xylene, tetrachloroethylene, and diethylene glycol dimethyl ether from 30 to 80 °C at atmospheric pressure using a self‐made crystallizer. The cooling modes, solvents, and the effects of carbazole on the solvent crystallization process of anthracene were also investigated. The composition of mother liquors and solid products were measured by gas chromatography; the solids were analyzed by scanning electron microscope, X‐ray diffractometer, differential scanning calorimetry, granulometer, and fluorescence spectrometer. The results showed that a uniform anthracene crystal was obtained when using DMF under the forced circulation cooling mode. Solid solution of anthracene and carbazole was initially detected in solvent crystallization. The existence of carbazole in solution has an obvious effect on the crystal morphology of anthracene, to some extent, is beneficial to the crystal growth of anthracene. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2160–2167, 2018     

Integrated solvent and process design for continuous crystallization and solvent recycling using PC‐SAFT

Solvent usage is a major source of environmental waste in pharmaceutical industry. The current paradigm shift toward continuous manufacturing in pharmaceutical industry has renewed the interest in continuous crystallization, which offers the prospect of easy solvent recycling. However, the selection of solvents for an integrated crystallization processes is nontrivial due to the likely trade‐off between optimal solvent properties for crystallization and solvent separation and recycling. A systematic approach for the simultaneous optimization of process conditions and solvent selection for continuous crystallization including solvent recycling is presented. A unified perturbed‐chain statistical associating fluid theory model framework is applied to predict thermodynamic properties related to solubility and vapor‐liquid equilibrium, which is integrated with a process model. A continuous mapping procedure is adopted to solve the optimization problem effectively. A case study based on continuous antisolvent crystallization of paracetamol with solvent separation via flash demonstrates the approach. © 2017 American Institute of Chemical Engineers AIChE J, 64: 1205–1216, 2018     

果糖结晶过程优化

通过实验筛选得到适合果糖结晶的混合溶剂,利用中通量结晶仪器Crystalline测定了果糖在水-乙醇（水的摩尔分数为0.39）混合溶剂中的溶解度和介稳区,采用Apelblat方程拟合了溶解度数据。基于热力学数据设计了晶种引晶的果糖冷却结晶工艺,过程优化得到的产品收率可达78.2%以上,纯度可达99%以上,晶体形貌规则,表面光滑,粒度分布窄。当晶体粒径大于100 μm时,利用粒度无关生长的粒数衡算方程建立了果糖连续结晶过程的动力学模型,模型表明晶体生长级数大于成核级数。     

核黄素超声结晶工艺优化

核黄素作为药品、色素、营养及动物饲料添加剂被广泛应用,目前生产及销售的核黄素基本上都是针状晶习,其堆密度小、分散性和流动性差,影响压片等加工性能。本文对酸溶法、碱溶法等5种核黄素结晶纯化方法进行了筛选,发现酸溶法收率和纯度的综合效益最佳;在此基础上采用超声辅助结晶,对功率、时间及温度进行优化,通过透射电镜（TEM）及X射线衍射分析法（XRD）等表征方法对结果进行分析。最终确定超声结晶的最佳实验条件为：超声功率为400W,超声时间为40min,超声温度为50℃,核黄素的收率可达到95%,纯度超过96%。核黄素晶习和结晶度有所改善,便于加工应用。     

咔唑国内市场现状与未来预测

介绍了中国的咔唑生产、新建拟建项目、进出口、消费及供求平衡情况,并对未来中国咔唑的生产、进出口、消费和供求平衡情况进行了预测。     

相转化法聚合物/溶剂/非溶剂铸膜体系的热力学计算

计算了相转化法铸膜体系中常见的典型三元相图,分析了聚合物与溶剂之间、聚合物与非溶剂之间、溶剂与非溶剂之间的相互作用参数对聚合物/溶剂/非溶剂铸膜液体系相图的影响,以及体系温度和聚合物摩尔体积对聚合物/溶剂/非溶剂铸膜液体系相图的影响。根据溶剂-非溶剂汽液平衡数据和溶解度参数得到了溶剂-非溶剂、溶剂与聚合物以及非溶剂与聚合物之间的Flory-Huggins相互作用参数,从而获得了几种常见铸膜液体系的相图。同时,利用聚合物/溶剂/非溶剂铸膜液体系的相图数据对热力学模型的参数进行了优化,取得了与实验结果较一致的计算结果。     

Understanding and guiding the phase inversion process for synthesis of solvent resistant nanofiltration membranes

Since its introduction in membrane technology in the 1960's, phase inversion by means of immersion precipitation has been widely studied for the preparation of membranes to be applied in the fields of microfiltration (MF) and ultrafiltration (UF). However, much less knowledge is available about this process in terms of integrally skinned asymmetric nanofiltration membranes, especially for more hydrophobic polymers applied in solvent resistant nanofiltration (SRNF). This review focuses on the preparation aspects of integrally skinned asymmetric membranes to be applied in the field of SRNF via phase inversion. It starts with the explanation of the basic principles of the phase inversion process, covering both thermodynamic and kinetic aspects. Further, it summarizes the parameters that significantly influence final membrane performance and morphology, including polymer type and concentration, casting solvent, additives, evaporation time, and temperature, humidity, membrane thickness, composition, and temperature of coagulation bath and post‐treatment. Literature contained within this review constitutes the core references in the field of SRNF, but also several references on preparation of MF, UF, aqueous NF, and reverse osmosis (RO) membranes have been included to better clarify or illustrate certain aspects of the process. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42130.     

从蒽油中提取精蒽和精咔唑的新工艺

介绍了从蒽油中提取精蒽和精咔唑的新工艺，分析了设备安装及生产中需要注意的问题。     

制药结晶中的先进过程控制

结晶作为固-液分离的重要手段,是实现医药产品高端高值化的关键技术。药物结晶过程的精准控制决定了晶体产品的多晶型、晶习、粒度及粒度分布等诸多特性,对生产效率和产品质量的提升具有重要的意义。基于国内外对药物结晶过程控制的研究现状,结合相关案例,系统总结了制药结晶中先进过程控制的理论模型、监测手段和控制策略,重点分析讨论了过程控制在产品工程中的应用并对其发展趋势进行了展望。     

由铬酸钾制备铬酸钠结晶分离过程研究

以铬酸钾中间体为原料,系统地研究了采用结晶分离等常规手段制备铬酸钠产品的清洁制备方法。应用等温法分别测定了KNO3在Na2CrO4水溶液中和Na2CrO4在KNO3水溶液中的相平衡数据,绘制了溶解度曲线,确定采用先冷却结晶后蒸发结晶的方法制备铬酸钠晶体产品。考察了冷却结晶终点温度和物料配比,分析了分步蒸发结晶产品,确定了结晶最佳操作条件:K2CrO4与NaNO3的质量比在1∶(0.9～1.2),冷却结晶的终点温度控制在4℃。提出铬酸钾通过结晶方式转化为铬酸钠的整体工艺流程,并进行了全流程循环实验。采用重结晶法对铬酸钠产品进行精制,获得高纯度的铬酸钠晶体,质量分数由81.4%提高到92.2%,且粒径较大,粒度均匀。     

生物质双相溶剂体系制备5-羟甲基糠醛的过程强化研究进展

5-羟甲基糠醛（HMF）作为一种基于木质纤维素类生物质的重要平台化合物,是多类高价值化学品和液体燃料的前体,但因理化性质不稳定,其高效制备面临巨大挑战。单一溶剂体系中生物质降解所得HMF产率低且副产物多,在原反应相中加入有机溶剂实现反应过程中HMF的原位萃取可大幅提高其选择性,目前采用双相溶剂体系已成为研究主流。本文在介绍双相溶剂体系、有机溶剂、反应原料、催化剂等影响生物质液相降解制备HMF的基础上,揭示优化反应条件强化两相溶剂界面传质对提高产物产率和反应效率的重要作用,并围绕增强相界面扰动和优化溶剂体系两个主要方面,重点综述了基于传质强化的生物质两相溶剂体系降解制备HMF的研究现状,最后对未来发展趋势进行了展望。     

Chiral control of enantiomers through crystallization: Moving from ternary phase diagrams to design spaces

Although chiral purity is a critical quality attribute for many synthetic drugs, current industrial strategies for establishing chiral purity control are underdeveloped. Such strategies have relied on the construction of ternary phase diagrams, system classification, and case‐specific operating policies. These policies have been developed to provide enantiopure solids, regardless of product specification or target. In this article, new operating policies are developed for obtaining solids that meet, but do not exceed, chiral purity specifications for arbitrary systems. These policies can provide significant yield improvements over the current practice. Additionally, this work provides an approach for the creation of design spaces based on the collection of limited, small scale data. This approach has been extended to sequential re‐crystallizations and can be used to determine “global” optimal policies within a synthetic route. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3323–3331, 2018     

甲醇-水溶剂中L-苯丙氨酸结晶热力学

在293.15~322.15 K温度范围内，研究L-苯丙氨酸无水物在甲醇-水混合溶剂中溶解度和超溶解度特性，得到L-苯丙氨酸无水物结晶介稳区，计算了成核级数及成核速率，考察了不同初始温度和降温速率对介稳区宽度的影响，并通过研究L-苯丙氨酸297.15 K和302.15 K的转晶水活度，依据溶解度特性绘制L-苯丙氨酸-甲醇-水在该温度下的三元相图。溶解度数据用Apelblat方程、λh方程关联、van t Hoff方程拟合。结果表明，L-苯丙氨酸无水物溶解度随温度的升高而增大，随甲醇体积分数的增加而减小；L-苯丙氨酸无水物结晶介稳区宽度在相同条件下，随初始温度的升高，降温速率的降低变窄；L-苯丙氨酸转晶水活度随温度的升高而增大。     

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。     

盐湖卤水冬季析硝制备高纯元明粉工艺研究

以NaCl-Na2SO4-H2O三元水盐体系相图为理论指导,对东台吉乃尔盐湖冬季析硝进行了无水硫酸钠提纯工艺研究。对无水硫酸钠粗产品制备过程中的恒温搅拌时间、加水量等工艺条件进行了优化。设计了以冬季析硝为原料生产高纯元明粉产品的整个工艺路线,为综合开发利用盐湖资源提供基础数据。     

基于响应曲面法的反应-萃取-结晶工艺优化

氯化钙与二氧化碳通过反应-萃取-结晶工艺制备碳酸钙和氯化氢气体是制碱废液资源化利用的有效途径。用响应曲面中的Box-Behnken Design(BBD)设计实验,考察了氯化钙浓度、萃取剂体积分数、相比和温度4 个因素对反应-萃取-结晶耦合工艺中氯化钙转化率、有机相中氯化氢浓度以及产物碳酸钙的平均粒度的影响及交互作用,并分别建立了三响应值与影响因素间的回归方程。三响应预测最佳值分别为:氯化钙转化率95.08%、有机相氯化氢浓度1.126 mol·L^-1、碳酸钙平均粒度48.71 μm;相应的实验值分别为92.35%、1.123 mol·L^-1 和49.14μm。预测值与实验值接近,误差较小,说明建立的模型对于反应-萃取-结晶工艺的分析和预测准确可靠。     

苦卤合成碱式硫酸镁晶须及后序分离工艺

用苦卤与工业液碱NaOH水热反应合成碱式硫酸镁(MOS)晶须,考察了原料配比、反应温度、液碱浓度及反应时间对液相组成和产品形貌的影响,用XRD和SEM等手段对产品进行表征,并对反应后母液进行钾盐和钠盐分离。结果表明,适宜的MOS合成条件为Mg~(2+)与OH~-摩尔比1:1.5及NaOH浓度4 mol/L、反应温度200℃、反应时间7 h。合成晶须后的母液按Mg~(2+)与OH~-理论摩尔比1:2反应,使母液中Mg~(2+)完全转化为Mg(OH)_2晶体。除镁后母液根据0和25℃时Na~+, K~+//C~l-, SO_4~(2-)-H_2O四元体系相图、25和100℃时NaCl-KCl-H_2O三元体系相图,通过蒸发浓缩结晶和低温结晶分离出NaCl, Na_2SO_4?10H_2O和KCl。