微通道反应器在精细化工产品合成中的应用研究进展

综述了近2年微通道反应器在精细化工产品合成中的研究进展,包括硝化反应、酯化反应、氯磺化反应、氧化反应、加成反应、分解反应和氧化还原反应等.在微通道反应器中,以烧碱和液氯为原料生产次氯酸钠的氧化还原反应已实现工业化应用.     

微通道反应器合成聚乙二醇400连续流工艺研究

对微通道反应器合成聚乙二醇400连续流工艺进行研究，采用乙二醇、环氧乙烷为原料，加入固体碱催化剂，按照固定反应物料比和催化剂用量，通过对反应停留时间、反应温度等条件的考察获得最佳工艺条件。结果表明：当n(乙二醇)∶n(环氧乙烷)=1∶4.0、反应温度120℃、反应停留时间200s时，得到的产品分子量分布系数最小，反应效果最佳。此工艺充分利用连续流微通道反应器优良的传质传热特点，缩短了反应时间，提高了反应效率，降低分子量分布。     

微通道反应器连续法合成硝酸异辛酯

以硝硫混酸作为硝化剂,与异辛醇在微通道反应器中经硝化反应得到硝酸异辛酯。考察了反应温度、混酸配比、硝酸浓度、停留时间、反应物配比对产品收率的影响,优化出微通道反应器中合成硝酸异辛酯的适宜工艺条件,硝酸异辛酯的收率97.8%,纯度达99.5%。微通道反应器连续法合成硝酸异辛酯具有操作简单、反应时间短、收率高、安全可靠等优点,具有工业化应用前景。     

连续化微通道反应器在染料颜料合成中的应用

近年来连续化微通道反应器作为一项新兴技术,在染料、颜料合成中开始得到应用。本文综述了微反应器技术在染料和颜料科研和生产方面的进展。与传统的间歇式反应不同,连续化微通道反应器的特点是,连续进料,瞬间混和,精确控制反应时间。该技术在重氮化、偶合反应中的应用,取得了高于常规反应器的收率和纯度。应用于颜料合成,取得了粒径窄分布的产品,并大幅度提高了颜料的应用性能。应用于合成中间体的硝化反应,提高了选择性和工艺的安全性。     

重氮乙酸乙酯的连续合成工艺研究

以甘氨酸乙酯盐酸盐和亚硝酸钠为原料,研究了在微通道反应器中重氮乙酸乙酯的连续流合成工艺。考察了亚硝酸钠用量、反应温度、酸用量、停留时间等工艺条件对反应结果的影响。由于该反应为强放热反应,且产物在高温下稳定性差,因此,若采用传统釜式间歇操作容易造成局部过热,存在较大的安全隐患和产物分解的缺陷;普通的管道反应器又难以克服非均相的传质障碍导致收率偏低。微通道反应器在保持良好的传热效率同时,能打破相界面障碍,保证反应液充分混合,非常适合该工艺的开发。利用微通道反应器的上述优点,进行工艺条件的筛选,提高了反应效率并得到较高的收率。     

陶瓷基微反应器制备的研究进展

微反应器中亚毫米级的流体通道具有高效的传质传热效应,使其能够强化反应过程。随着微细加工技术的发展,制备出了耐高温耐腐蚀的陶瓷基微反应器,适用于更严苛的反应条件,然而陶瓷基微反应器的制备存在微结构成型工艺复杂、密封难度较大等问题。本文主要介绍不同陶瓷材料微反应器的制备工艺,重点论述陶瓷基微反应器制备过程中常规微加工技术的优化和新型微加工技术的引入,对比这些技术对微结构成型的改善效果。列举常用的陶瓷微通道密封连接方法,概述其特点和适用范围。并提出在陶瓷基微反应器制备的后续研究过程中,应注重陶瓷基微反应器制备的成功率和新技术的开发,完善陶瓷基微反应器的性能,将陶瓷基微反应器引入到更广泛的应用体系中。     

微反应器中2-氨基-5-硝基吡啶合成的连续流工艺研究

以哈氏合金材质的微反应器板块(容积8.2 mL)为核心组件，构建2-氨基-5硝基吡啶合成的微通道反应体系。以2-氨基吡啶和发烟硝酸-硫酸混酸体系为原料，利用微反应器强传质传热的特性来提升2-氨基-5-硝基吡啶的收率，并研究工艺温度、反应原料物质的量比、停留时间等因素对该硝化反应的影响。结果表明：微反应器中2-氨基-5-硝基吡啶合成的最佳工艺优化方案为反应温度为35℃,发烟硝酸/2-氨基吡啶物质的量比为1.15∶1,反应停留时间为60 s。     

微通道反应器对CLT酸合成过程中的硝化反应的影响研究

在微通道反应器内对CLT酸合成过程中的硝化反应进行了研究,考察了原料流速、反应温度、反应器片数对硝化反应的影响。较优工艺参数组合:3-氯-4-甲基苯磺酸体积流速10. 2 m L/min,硝酸体积流速1. 5 m L/min,反应温度25℃,反应器片数2片。与常规反应器相比,转化率提高了4. 58%。     

微反应技术在氢化反应中的应用进展

氢化反应是有机合成中的一类重要反应,应用广泛.目前,氢化反应大多是在高压反应釜中间歇进行,有存在爆炸风险、转化率和选择性低等缺点,因此,开发新的、安全、高效的氢化工艺是必要的.微通道反应器能精确控制温度和反应时间,并且混合均匀,传质性能高,能极大提高反应选择性和生产产量,减少催化剂损耗.总结了微通道反应器中烯烃、炔烃、...     

微通道反应器中合成碘代芳烃

在自制聚四氟管微通道反应器内,考察了取代芳胺重氮盐和碘化钾反应连续合成碘代芳烃的工艺过程。以碘苯为模型底物,考察了管道内径、体积流速、停留时间、反应温度等对反应的影响,得到最佳的工艺条件为:管道内径0.8 mm,体积流速1 004.8μL/min,停留时间75 s,反应温度20℃。在该条件下,碘苯产率为79.0%,时空转化率为9.41×103mol/(m3·h),比常规反应高出两个数量级。在上述最佳工艺条件下,分别研究了其他碘代芳烃在微通道反应器内的合成。     

Multifunktionale Reaktoren

In multifunctional reactors chemical and physical unit operations are carried out simultaneously. Traditionally chemical reaction engineering considers mass and heat transfer processes in combination with chemical reactions. However, the term multifunctional reactor points to an extended and more detailed view of process integration. By application of these reactors it is possible to save investment and/or operating costs, to meet environmentally relevant limits or to improve process safety. Mechanical and thermal unit operations are especially good candidates for integration with a chemical reaction step. In this contribution selected multifunctional reactors are presented, which were either adopted from the literature or are the subject of the authors' own research activities.     

Organische Synthese mit mikrostrukturierten Reaktoren

Organic Synthesis with Microstructured Reactors This article describes the chances microstructured reactors offer for chemical plant engineering. This suitability for chemical production is commonly regarded to be the key to the market penetration. Seen in the long term, there is potential that new plants can be equipped with microstructured reactors. Only economic balances, however, which draw up profitability, will open the door to the usage of chemical micro process engineering for plant construction. Main arguments for using microstructured reactors are thus enhanced conversion and selectivity, increased space‐time yields, waste reduction and more safety via small reactor volumes. Credit‐card sized reaction systems allow one to perform the screening of multi‐phase reactions. More prominent, similar screening is carried out for single‐step reactions. Moreover, safe processing with microstructured reactors in the explosive regime enlarges the traditional range of processing. The reaction guidance by microstructured reactors can further influence subsequent processing steps such as product purification and, in this way, can lower the energy costs of processes.     

自热制氢反应器研究进展

介绍了同心圆式反应器、板式反应器、壁反应器、微通道反应器在自热重整反应制氢中的特点。同心圆式反应器的传热是控制步骤,为强化传热而开发了空间形状不同和流体经过反应器不同腔体的先后顺序不同的反应器;板式反应器易于组装、拆卸和放大,而且热效率也比较高,是目前十分活跃的研究领域,重点在于操作参数和设计的优化及其高效壁载制氢催化剂的研制;壁反应器的反应表面和换热表面不分离,具有较高的热量耦合效果;微通道反应器具有优越的传热性能,但对加工和流体的性质有比较苛刻的要求。另外,不同燃料制氢机理的研究及其过程参数的稳态、瞬态模拟,为反应器的设计提供了理论依据。而制氢过程并行单元的研究为系统的集成奠定了基础。最后,指出开发板式壁反应器以及开展其在CO变换、净化方面的研究有较好的发展前景。     

Flow Chemistry – A Key Enabling Technology for (Multistep) Organic Synthesis

Laboratory scaled flow‐through processes have seen an explosive development over the past decade and have become an enabling technology for improving synthetic efficiency through automation and process optimization. Practically, flow devices are a crucial link between bench chemists and process engineers. The present review focuses on two unique aspects of modern flow chemistry where substantial advantages over the corresponding batch processes have become evident. Flow chemistry being one out of several enabling technologies can ideally be combined with other enabling technologies such as energy input. This may be achieved in form of heat to create supercritical conditions. Here, indirect methods such as microwave irradiation and inductive heating have seen widespread applications. Also radiation can efficiently be used to carry out photochemical reactions in a highly practical and scalable manner. A second unique aspect of flow chemistry compared to batch chemistry is associated with the option to carry out multistep synthesis by designing a flow set‐up composed of several flow reactors. Besides their role as chemical reactors these can act as elements for purification or solvent switch.     

Preface

Interest in the diverse aspects of the catalysis of organic reactions for fine chemicals applications has been growingworldwide in both academic and industrial research. Fine Chemicals Catalysis may be defined as the catalysis of complexorganic reactions for application in the production of pharmaceuticals, pharmaceutical intermediates, agrochemicals, andspecialty chemicals such as perfumes and flavorings. Traditionally, high product selectivity has been the paramountconcern rather than high production efficiency in the commercial organic synthesis of fine chemicals. However, bothmarket and environmental pressures are increasingly motivating a movement towards efficient catalytic alternatives tostoichiometric organic transformations. Industrial research and development in fine chemicals has long been the realm of synthetic organic chemists, withlittle contribution being made from scientists specifically trained in catalysis. The academic community in heterogeneouscatalysis, with its traditional focus on petrochemical and bulk chemical catalytic applications, is just beginning to playa significant role in fine chemicals research. By contrast, academic research in homogeneous catalysis, and especiallyasymmetric catalysis, has been prolific and boasts a number of important successful links to commercial processes.There has been, regrettably, scant communication between the research communities in heterogeneous and homogeneouscatalysis in either industry or academia. An issue of Topics in Catalysis devoted to the broad area of fine chemicals seems timely since it allows us to focus oncurrent pioneering work, both in heterogeneous and homogeneous catalysis, both in academic and industrial research, tohighlight the connections between seemingly diverse work, and to help to spark new ideas and draw in new researchersto the field. All of the contributions are invited papers. This revised version was published online in June 2006 with corrections to the Cover Date.     

小型特种精细化工过程自动化和信息化研究发展趋势探讨

针对采取小批量间歇性批次生产方式、工艺介质腐蚀性强、危险性大的小型特种精细化工生产工艺研究试验过程自动化、信息化程度不高,导致工艺研究试验中获取数据较少、过程机理研究不够透彻、人工操作多、安全风险高、研究试验消耗大及效率不高等问题,综述了期待通过智能控制、在线分析、模拟仿真和虚拟制造、工况监测及预测性维护以及信息管理和生产调度等关键技术的研究和应用,提高小型特种精细化工生产工艺过程的自动化和信息化程度,实现小型特种精细化工生产工艺过程的数字化、虚拟化和智能化,降低生产安全风险和试验消耗,提高小型特种精细化工生产工艺研究试验的成功率和效率,达到小型特种精细化工生产工艺过程的数字化设计和精准生产的目标。     

Microchannel reactor architecture enables greener processes

Green Chemistry is a design philosophy that aims to reduce or eliminate negative environmental impacts resulting from the production and use of chemicals. Microchannel process technology offers process intensification, in the form of enhanced heat and mass transfer, to a wide range of chemical reactions. This paper describes how the application of microchannel technology can help producers achieve the goals of Green Chemistry and minimize the environmental consequences of chemical and fuel production. The examples used to illustrate these advantages are Velocys’ Fischer-Tropsch synthesis for biomass-to-liquids, DSM and Karlsruhe collaboration for fine chemical production, and Stevens Institute's work in applying microchannels to the production of hydrogen peroxide, as well as a detailed study of how microchannel architecture can minimize pollutant emissions from steam methane reforming.     

精细化工的今天、明天

本文首先指出 :值此生物质经济时代来临之际 ,新的催化剂、新的合成方法以及绿色溶剂和绿色工艺的出现和应用必将给精细化工发展带来良机 ,特别是生物质资源开发和利用将使化学工业翻开新的一页。文中介绍了在精细化工领域出现的一些新催化剂、绿色溶剂、绿色工艺和技术 ,以及在定制化学品中的新试剂、新反应和新产品 ,讨论了这些新的绿色工艺和技术及新产品在高科技领域应用的可能性     

生物柴油连续化生产设备及工艺进展

“碳中和”目标提出后，各行各业都在寻求减少碳排放的方法，生物质能源的使用是实现碳中和目标的重要手段之一。生物柴油以其优良的燃烧性能及环保性能成为一种较为理想的生物质燃料，其生产工艺是近年研究热点。连续化生产工艺对生物柴油的规模化制备与推广有着重要意义。目前连续化制备生物柴油的反应装置主要有微反应器、固定床反应器、管式反应器、膜反应器。本文综述了近年来国内外采用连续化工艺制备生物柴油的研究进展。这些研究表明，通过优化反应器结构、使用助溶剂、提高催化剂活性等均可提高生物柴油的收率。最后本文还分析了各反应器存在的不足，并提出了相应的建议，对生物柴油连续化生产进行了展望，以期为低成本、低能耗的生物柴油生产提供参考。