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Chapter 15. Governing Resource Flows in a Circular Economy: Rerouting Materials in an Established Policy Landscape 第15章。管理循环经济中的资源流动:在既定的政策环境中重新安排材料
Pub Date : 2019-10-15 DOI: 10.1039/9781788016353-00375
P. Deutz, H. Baxter, D. Gibbs
The development of a Circular Economy, whereby resources are kept in circulation for the extraction of maximum value, has captured extensive policy and academic attention. The circularisation of material flows is likely to prove a task for a generation: the challenges are only beginning to be explored and the wider implications are seldom considered. However, circular economy-relevant policies are not new; EU policy makers have already made adjustments to remove inadvertent barriers to resource recovery. This chapter considers how resource recovery in the UK steel industry has been influenced by environmental policies, particularly the 2008 Waste Framework Directive's approach to enabling residues to lose, or avoid altogether, identification as wastes. In this context, we also consider the response to a proposed novel technology to recover vanadium, a high value component, from steel slag. Extensive analysis of policy-related documents at EU and UK level was carried out along with semi-structured stakeholder interviews (including producers of steel slag, industry bodies and regulators). Findings suggest that implementing reforms to earlier regulations necessitates changes to practices engendered by previous institutional arrangements. We face a risk of adding to layers of complexity rather than removing them. Circular economy theory and policy need to be aware of policy legacy.
发展循环经济,使资源保持流通以获取最大价值,已引起政策和学术界的广泛关注。物质流动的循环化很可能被证明是一代人的任务:挑战才刚刚开始被探索,更广泛的影响很少被考虑。然而,与循环经济相关的政策并不新鲜;欧盟的政策制定者已经做出了调整,以消除对资源回收的无意障碍。本章考虑英国钢铁行业的资源回收如何受到环境政策的影响,特别是2008年废物框架指令的方法,使残留物失去或完全避免被识别为废物。在此背景下,我们还考虑了从钢渣中回收高价值成分钒的新技术的响应。对欧盟和英国层面的政策相关文件进行了广泛的分析,并进行了半结构化的利益相关者访谈(包括钢渣生产商、行业机构和监管机构)。调查结果表明,要对以前的条例进行改革,就必须改变以前的体制安排所产生的做法。我们面临着增加而不是消除复杂性的风险。循环经济理论和政策需要意识到政策遗留问题。
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引用次数: 3
Chapter 5. Electrochemistry under Flow Conditions 第五章。流动条件下的电化学
Pub Date : 2019-09-18 DOI: 10.1039/9781788016094-00153
A. Folgueiras‐Amador, T. Wirth
Organic electrosynthesis is recognised as a green enabling methodology to perform reactions in an efficient and straightforward way. Electrons are used as the reagent to form anion and cation radical species from neutral organic molecules achieving oxidations and reductions by replacing toxic and dangerous reagents. Within this field, the use of microreactors in continuous flow is also concurrent with electrochemistry because of its convenient advantages over batch, such as: (i) low loading or no supporting electrolyte at all, due to the small distance between electrodes, providing significant advantages in downstream processing; (ii) high electrode surface-to-reactor volume ratio; (iii) short residence time; (iv) improved mixing effect. In this chapter the most relevant electrochemical flow reactors and electrochemical transformations performed in continuous flow are presented and discussed.
有机电合成被认为是一种绿色的使能方法,以有效和直接的方式进行反应。电子作为试剂,由中性有机分子形成阴离子和阳离子自由基,通过取代有毒和危险的试剂实现氧化和还原。在该领域,连续流微反应器的使用也与电化学同时进行,因为它比批量更方便,例如:(i)低负荷或根本没有支撑电解质,由于电极之间的距离小,在下游处理中提供了显着的优势;(ii)高电极表面与反应器体积比;(三)停留时间短;(四)提高了混合效果。在本章中,介绍和讨论了最相关的电化学流动反应器和在连续流动中进行的电化学转化。
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引用次数: 5
Chapter 2. Green Biotransformations under Flow Conditions 第二章。流动条件下的绿色生物转化
Pub Date : 2019-09-18 DOI: 10.1039/9781788016094-00050
E. García‐Verdugo, Raúl Porcar, S. Luis, P. Lozano
The development of continuous green biocatalytic processes is a highly useful toolbox for the synthesis of fine chemicals and pharmaceuticals that has grown tremendously over the past decade. This chapter highlights some of the most relevant advances in the field of biocatalytic transformations under flow conditions in both conventional and in neoteric solvents (e.g. ionic liquids, ILs; supercritical fluids, SCFs), as alternative non-aqueous reaction media. Several examples are provided (e.g. KR and DKR of sec-alcohols and amines, C–C bond formation, reduction, transamination, trans-esterification, etc.) where the use of continuous flow techniques enables the development of more efficient processes and multiple reaction steps to be combined into a single continuous operation.
连续绿色生物催化工艺的发展是一个非常有用的工具箱,用于合成精细化学品和药物,在过去的十年中有了巨大的增长。本章重点介绍了在传统和新兴溶剂(如离子液体、ILs;超临界流体(SCFs)作为替代的非水反应介质。提供了几个例子(例如,仲醇和胺的KR和DKR, C-C键的形成,还原,转氨化,反式酯化等),其中使用连续流动技术可以开发更有效的过程和多个反应步骤组合成一个单一的连续操作。
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引用次数: 0
Chapter 14. Integrated Microreaction Systems of Microdevices with Conventional Equipment 第14章。微设备与常规设备的集成微反应系统
Pub Date : 2019-09-18 DOI: 10.1039/9781788016094-00440
G. Luo, J. Deng, K. Wang
The microreaction technology for a continuous flow process has been evolving from a pure research tool in chemical engineering to a ubiquitously applicable technique in the field of chemical synthesis. For chemists, it is difficult to set up a laboratory-scale microreaction system because their focus is on chemistry rather than chemical engineering. The configuration of a laboratory-scale microreaction system as an initial mode connects chemistry and industrial design, therefore, it is vital to decide the final feasibility, complexity and cost of industrial microreaction system engineering. This chapter will describe four categories of microreaction systems according to physicochemical properties of chemical processes, elaborate in detail how to analyze the characteristics of chemical processes, and build integrated microreaction systems based on microreactors and conventional chemical equipment through four typical examples. Finally, a brief summary and perspectives on microreaction systems is also presented in this chapter. The content may provide some general references for the applications of microreaction technologies.
连续流过程微反应技术已从单纯的化工研究工具发展成为化学合成领域中普遍应用的技术。对于化学家来说,建立一个实验室规模的微反应系统是很困难的,因为他们的重点是化学而不是化学工程。实验室规模微反应系统的配置作为初始模式连接着化学和工业设计,因此,决定工业微反应系统工程最终的可行性、复杂性和成本至关重要。本章将根据化学过程的理化性质对四类微反应系统进行描述,并通过四个典型实例详细阐述如何分析化学过程的特点,构建基于微反应器和常规化工设备的集成微反应系统。最后,本章还对微反应系统进行了简要的总结和展望。其内容可为微反应技术的应用提供一定的参考。
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引用次数: 0
Chapter 9. Continuous Flow Synthesis of Nanomaterials 第9章。纳米材料的连续流动合成
Pub Date : 2019-09-18 DOI: 10.1039/9781788016094-00316
A. Kulkarni, Rajashri B. Jundale
Continuous flow synthesis of nanoparticles is now a well-accepted and reliable synthesis approach that gives consistent product properties. This chapter aims to do a critical analysis of the recent work in some of the relevant areas and gives specific recommendations where flow synthesis of nanomaterials can be realized as a reliable manufacturing process. The chapter also highlights the typical engineering issues that one needs to consider while transforming a batch synthesis protocol into continuous mode and its scale-up.
纳米颗粒的连续流动合成现在是一种被广泛接受和可靠的合成方法,可以提供一致的产品性能。本章旨在对一些相关领域的最新工作进行批判性分析,并给出具体建议,使纳米材料的流动合成成为一种可靠的制造工艺。本章还强调了在将批量合成协议转换为连续模式及其扩展时需要考虑的典型工程问题。
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引用次数: 1
Chapter 16. Upscaling the Aza-Diels–Alder Reaction for Pharmaceutical Industrial Needs in Flow Chemistry 第十六章。流动化学中制药工业需要的Aza-Diels-Alder反应的升级
Pub Date : 2019-09-18 DOI: 10.1039/9781788016094-00485
G. Pascual-Coca, F. Tato, J. F. Soriano, R. Ferritto-Crespo
In this work, the aza-Diels–Alder (aDA) reaction involving cyclopentadiene (CPD) as a dienophile was optimized and scaled up to obtain 1 kg h−1. The Diels–Alder Reaction (DA) involving CPD is scarce in industrial production because of the difficulty of generating CPD in safe and proper conditions. Here, we describe a methodology to continuously generate CPD up to 60 mL min−1 and incorporate an aDA reaction at a low temperature for industrial scale processing. The optimization of the aDA reaction from batch mode in the lab to a continuous flow, multi-kilogram scale is described in detail. Beyond the role of solvent, temperature and acid catalysis in the reaction, different configurations of flow reactors and different reactor sizes were key to the development and construction of the scale-up process to reach the targeted production. The introduction of static mixers into the flow process had a significative impact on the overall productivity of the system. Particular attention was paid to maintaining green chemical principles, reducing solvent use and minimizing impurities in the process. The final setup reached a continuous simple and safe production, taking full advantage of flow chemistry technological benefits in its operation.
在这项工作中,以环戊二烯(CPD)为亲二试剂,对aza-Diels-Alder (aDA)反应进行了优化和放大,得到1 kg h−1。涉及CPD的Diels-Alder反应(DA)在工业生产中很少,因为很难在安全和适当的条件下生成CPD。在这里,我们描述了一种连续生成CPD高达60 mL min - 1的方法,并在工业规模处理的低温下加入aDA反应。详细描述了aDA反应从实验室的批处理模式到连续流、多公斤级的优化过程。除了溶剂、温度和酸催化在反应中的作用外,不同的流动反应器配置和不同的反应器尺寸是开发和建设放大工艺以达到目标生产的关键。在流动过程中引入静态混合器对系统的整体生产率产生了重大影响。特别注意保持绿色化学原则,减少溶剂的使用和尽量减少过程中的杂质。最终装置实现了连续、简单、安全的生产,充分发挥了流动化学技术在运行中的优势。
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引用次数: 0
Chapter 4. Perspectives on the Use of Flow Systems to Carry Out Organic Photochemical Reactions 第四章。利用流动系统进行有机光化学反应的展望
Pub Date : 2019-09-18 DOI: 10.1039/9781788016094-00129
K. Mizuno, K. Kakiuchi
Organic photochemical reactions have been conducted using classic batch conditions for over a half century. Beginning in the 21st century, several efforts were conducted to develop reactions of this type, performed in a convenient, controllable and safe manner using flow micro reactors. This chapter describes the general methods used for flow micro photochemical reactions and some typical organic transformations that have been performed using this approach, including inter- and intra-molecular photocycloadditions, photocyclizations, photoadditions, photoisomerizations, photosubstitutions, photooxygenations, photorearrangements, heterogeneous photocatalytic reactions and photoinduced organometallic reactions.
有机光化学反应已经在经典的批处理条件下进行了半个多世纪。从21世纪开始,人们进行了几次努力来开发这种类型的反应,使用流动微反应器以方便、可控和安全的方式进行。本章描述了流动微光化学反应的一般方法,以及使用这种方法进行的一些典型的有机转化,包括分子间和分子内的光环加成、光环化、光加成、光异构化、光取代、光氧化、光重排、非均相光催化反应和光诱导的有机金属反应。
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引用次数: 0
Chapter 12. New Microreactor Designs for Practical Applications Realized by Additive Manufacturing 第十二章。基于增材制造的新型微反应器设计
Pub Date : 2019-09-18 DOI: 10.1039/9781788016094-00388
P. Löb
Continuous processing is playing an increasing role in the development and manufacturing of pharmaceuticals and fine chemicals. Linked to this development is the interest in flow chemistry that means milli- or even microstructured reactors and their use for continuous processing. These reactors enable a precise control over the chemical process due to their small internal structuring and with that the access to unusual process conditions (Novel Process Windows). Additionally, other more operational advantages of interest for chemical production purposes are linked to the flow chemistry approach – like addressing the need for flexible and modular production concepts, the straightforward scale-up approach and the amenability to automated operation and integration of process analytical technologies. Classic unit operations like mixing and heat exchange are thereby already addressed by a range of commercially available devices. With the advent or broader uptake of additive manufacturing techniques in general, these technologies are also increasingly applied for miniaturized chemical reactors. While current examples mainly stem from lab-scale investigations, there is a clear trend and ambition towards addressing industrial application and the related harsh process conditions and higher throughput ranges. This chapter briefly recaps central aspects of flow chemistry and the related reactor technology before introducing the main additive manufacturing techniques used for the realisation of microsystems and micro- and milli-structured reactors as well as describing corresponding examples. A special focus is given thereby on selective laser melting to realize finely structured 3D chemical reactors in metal since this technique is seen as most promising for realising structured reactors against the background of industrial chemical production.
连续加工在药品和精细化学品的开发和生产中发挥着越来越重要的作用。与这一发展相关的是对流动化学的兴趣,这意味着微米甚至微结构反应器及其用于连续处理。这些反应器由于其内部结构小,并且可以进入不寻常的过程条件(新过程窗口),因此可以精确控制化学过程。此外,化工生产的其他更多操作优势与流动化学方法有关,例如解决灵活和模块化生产概念的需求,直接的放大方法以及自动化操作和过程分析技术集成的适应性。因此,混合和热交换等传统单元操作已经由一系列商用设备解决。随着增材制造技术的出现或广泛采用,这些技术也越来越多地应用于小型化化学反应器。虽然目前的例子主要来自实验室规模的调查,但有一个明显的趋势和雄心,即解决工业应用和相关的苛刻工艺条件和更高的吞吐量范围。本章简要概述了流动化学的核心方面和相关的反应器技术,然后介绍了用于实现微系统和微结构和微结构反应器的主要增材制造技术,并描述了相应的例子。因此,特别关注选择性激光熔化以实现金属中精细结构的3D化学反应器,因为该技术被认为是在工业化学生产背景下实现结构化反应器的最有希望的技术。
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引用次数: 3
Chapter 10. NMR Microcoils for On-line Reaction Monitoring 第十章。用于在线反应监测的核磁共振微线圈
Pub Date : 2019-09-18 DOI: 10.1039/9781788016094-00340
M. V. Gomez, A. Velders
Nuclear Magnetic Resonance (NMR) spectroscopy is one of the most important and powerful analytical tools available to the scientific community, and to synthetic chemists in particular. Standard, commercially available, high-field NMR spectrometers (running from 4.7 to 23.5 T, corresponding to 200, respectively 1000 MHz 1H Larmor frequency) have their radiofrequency antennas incorporated in probe heads that allow measuring samples in 5 mm tubes. Commercial probe heads that allow on-flow monitoring of reactions are based on, typically 5 mm, saddle coil designs, but these require relatively large amounts of material and/or have poor filling factors and correspondingly poor mass sensitivity. In 1994 Sweedler and co-workers launched the field of microcoil NMR spectroscopy, and the past two decades have seen several groups starting to fabricate their own small-volume probe-heads. Here we provide an overview of the different types of NMR microcoils that haven been developed to measure volumes in the lower microliter and (sub-)nanoliter scale, and then focus on the main geometries of microcoils exploited for use in reaction monitoring as solenoids, planar spiral, and stripline coils. Several examples are presented of on-flow and stationary reaction monitoring with such microcoils. The rapid progress in the field promises that many more groups will enter the field of NMR microcoil reaction monitoring in the coming years.
核磁共振(NMR)波谱是科学界,特别是合成化学家最重要和最强大的分析工具之一。标准,商用,高场核磁共振光谱仪(运行从4.7到23.5 T,分别对应200,1000 MHz 1H拉莫尔频率)有其射频天线纳入探头,允许测量样品在5毫米管。允许对反应进行流动监测的商业探头通常基于5毫米的鞍形线圈设计,但这些探头需要相对大量的材料和/或填充系数较差,相应的质量灵敏度也较差。1994年,斯韦德勒和同事们开创了微线圈核磁共振波谱学领域,过去20年里,几个研究小组开始制造自己的小体积探头。在这里,我们概述了不同类型的核磁共振微线圈,这些微线圈已被开发用于测量较低微升和(亚)纳升尺度的体积,然后重点介绍了用于反应监测的微线圈的主要几何形状,如螺线管、平面螺旋线圈和带状线线圈。给出了用这种微线圈进行流动和静止反应监测的几个实例。随着该领域的快速发展,未来几年将有更多的研究团队进入核磁共振微线圈反应监测领域。
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引用次数: 0
Chapter 11. Flow Chemistry Systems Based on Membranes 第十一章。基于膜的流动化学系统
Pub Date : 2019-09-18 DOI: 10.1039/9781788016094-00366
J. Sánchez-Marcano
In flow chemistry systems based on membranes, a dense or porous membrane is activated with a catalyst or a biocatalyst in order to couple reaction and separation in the same unit, resulting in an intensified process called catalytic membrane reactor (CMR). In this chapter the basic principles and concepts of CMRs are defined and the different configurations: CMRs for selective product removal, CMRs for the selective additions of reactants, flow-through membrane reactors (FTMRs) and enzymatic membrane reactors (EMRs) are described. Furthermore, a short account of some representative works of the peer reviewed literature and monographs works is given. CMRs have been successfully applied at laboratory scale to enhance the conversion of reactions which are limited by the thermodynamic equilibrium through selective product removal, in oxidation and hydrogenation reactions and improving the contact between the catalyst and substrates while decreasing mass transfer limitations. CMRs have already proven economic and strategic value in bio-transformations for the high-added value chemicals production. Such processes which take place at low temperature allow the use of polymer membranes which are commercially available materials. Further advances are expected on the development inorganic membranes for high temperature applications to be applied in high temperature reactions.
在基于膜的流动化学系统中,用催化剂或生物催化剂激活致密或多孔膜,以便在同一单元中将反应和分离耦合起来,从而产生一种称为催化膜反应器(CMR)的强化过程。在本章中,定义了cmr的基本原理和概念,并描述了不同的配置:选择性产物去除的cmr,选择性添加反应物的cmr,流式膜反应器(FTMRs)和酶促膜反应器(EMRs)。此外,还简要介绍了一些同行评议文献和专著的代表性作品。cmr已经成功地应用于实验室规模,通过选择性去除氧化和氢化反应中的产物来提高受热力学平衡限制的反应的转化,并改善催化剂和底物之间的接触,同时降低传质限制。cmr已经被证明在高附加值化学品生产的生物转化中具有经济和战略价值。这种在低温下进行的过程允许使用商业上可用的聚合物膜。高温无机膜在高温反应中的应用前景广阔。
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引用次数: 1
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