Pilot-scale experimental studies on ethanol purification by cyclic stripping

Cyclic distillation is a proven process intensification method for enhanced separation of various mixtures. It uses an alternative operating mode based on separate phase movement which leads to important practical advantages (vs conventional mode) such as increased column throughput, lower equipment cost (using much less trays at the same reflux ratio) and reduced energy requirements by 20–35% (smaller reflux ratio at the same number of stages), and better separation performance (up to three times). However, if the impurities to be separated are in very low amounts in the feed then distillation is not favorable from an energy use viewpoint. This article is the first to report the practical performance of a continuous process for ethanol purification by air stripping using a cyclic mode of operation, a novel process that avoids the costs of distillation. The purification of ethanol food grade (96.4 vol%) from volatile impurities (0.5 vol%) such as esters, aldehydes, and alcohols, is carried out in a hydro-selective column with five stages. The lightweight impurities are removed from a stream that is the head fraction of a distillation column. This is usually a waste stream amounting to 3–6% of the plant production rate. By concentrating the stream with impurities, more ethanol is produced such that the losses are reduced to only 1–1.5% of the plant capacity. Based on the experimental results presented in this work, a process consisting of two air stripping columns using cyclic operation is proposed for industrial implementation.     

蒸馏过程强化技术研究进展

蒸馏过程强化技术作为我国现代化学工业发展的重要研究领域,是过程强化概念在化学工业成功应用的典范之一。随着近些年的发展,蒸馏过程强化技术的研究已形成了一套较完整的体系,但也出现了一系列新的难题与挑战。为此,本文针对混合物相对挥发度与气液传质两个蒸馏过程强化的基础理论本质问题,以基础理论创新、关键技术突破和关键装备研究进展为主线,从强化原理、研究进展、工业应用及发展3方面系统介绍共沸蒸馏、萃取蒸馏、反应蒸馏这3类典型的引入质量分离剂强化的蒸馏过程及其耦合技术;微波、超重力场等典型外场作用下的引入能量分离剂强化的蒸馏过程,并系统介绍以新型塔内件及新型塔结构为切入点的基于先进设备强化的蒸馏过程,为迎接这一领域新的难题和挑战提供新思路。     

Dynamic process intensification: Fundamentals and implementation to ternary distillation

Distillation remains a key technology for separating liquid mixtures. Its versatility comes with the disadvantage of high energy consumption. We previously used empirical arguments to introduce dynamic process intensification (DPI) as a strategy for improving the energy efficiency of binary distillation. In this article, we focus on ternary distillation; we begin by providing a rigorous basis for DPI, then formulate the problem of identifying the operating states for DPI as a nonlinear optimization problem. Via an extensive case study considering a hydrocarbon mixture, we demonstrate that reboiler energy use can be reduced by more than 2.3% relative to an equivalent column operating at steady state. We prove that this result is due to the fact that DPI aims to satisfy product flow and quality constraints on average in time, affording broader opportunities for optimizing column economics than steady-state operation, where constraints are met strictly at all times.     

Dynamic process intensification of binary distillation based on output multiplicity

Process intensification focuses largely on process and equipment design. Much less emphasis has been placed on operational changes to achieve cost savings and increased efficiency. This article introduces the concept of dynamic intensification, defined as changes to the dynamics, operating strategy and/or control of a process that lead to a substantially more efficient processing path. This idea is illustrated in the context of binary distillation. Output multiplicity properties are exploited to establish a new periodic operating mode based on switching between two auxiliary products, which, on a time-average basis, is more energy efficient than steady-state operation. An extensive case study is presented concerning the distillation of a propanol–acetic acid mixture, confirming the theoretical developments. In contrast to previous research (e.g., on cyclic distillation), the present concept has significant advantages as it relies on existing hardware and exploiting system nonlinearity, rather than using specialized equipment operated in a discontinuous fashion. © 2018 American Institute of Chemical Engineers AIChE J, 65: 1162–1172, 2019     

超重力精馏传质过程强化理论分析

超重力精馏技术是一种新型的过程强化精馏技术,文中通过实验与理论分析,探讨其传质过程强化的作用机理。以乙醇/水为物系,多级旋转填料床为主要设备,在常压操作条件下,进行超重力精馏实验研究。在超重力因子为31—196,原料流量为15—30 L/h,原料摩尔分数为0.089 1—0.283 1,回流比为1.0—2.5的操作条件下,超重力装置的理论塔板高度为12.7—152 mm,比传统精馏塔低1个数量级。通过分析流体在超重力装置内的流动状态,提出超重力精馏过程的传质原理及传质单元——液膜。通过理论分析,认为超重力精馏传质过程克服了双膜理论、渗透理论与表面更新理论中的瓶颈,是超重力精馏传质过程强化的根本原因。     

Understanding process intensification in cyclic distillation systems

The most effective separation possible in distillation columns takes place in the hydrodynamic regime where there is perfect displacement of the liquid and vapor streams. This can be achieved in distillation equipment with separate phase movement (SPM). Such an innovative route for process intensification in distillation is called cyclic distillation. The required process conditions are the lack of liquid outflow from the tray during vapor admission and the lack of liquid mixing in adjacent trays upon outflow of liquid. Remarkably, the throughput of such a column that operates in a controlled cycle mode is two or more times higher than the throughput reachable with conventional operation, at equivalent separation performance.In this study, a theoretical stage model with perfect displacement is proposed and the theory of the process working lines is developed. An adequate mass transfer model is also described along with the mode of calculation of tray columns operating in the cyclic operation mode. Sensitivity analysis was used to determine the effect of the key model parameters. The theoretical developments were implemented at industrial scale and subsequent testing showed an increase in the separation efficiency of 2-3 times as compared to the standard process.     

膜蒸馏过程强化及优化技术研究进展

膜蒸馏作为一种新型的膜分离技术,具有脱盐率高、可处理高浓度原料液等技术优势,近年来引起学术界及工业界的广泛关注.膜蒸馏技术可被应用于海水淡化,工业废水/苦盐水脱盐及糖、盐、果汁、有机/无机酸、碱液等的浓缩过程.但由于当前膜蒸馏能耗及成本较高,一定程度上限制了该技术的工业化.本文重点介绍了可用于强化膜蒸馏过程和优化该过程能量利用的方法及研究进展,主要包括膜材料和膜制备方法/工艺的进展、膜蒸馏过程操作条件的优化、改进膜组件和辅助装置的应用、太阳能和低品位热源的使用、蒸发冷凝潜热的回收以及耦合其他分离过程的复合膜蒸馏系统,同时分析了膜蒸馏技术处理高盐工业废水的应用前景,最后探讨和总结了膜蒸馏过程强化及优化的研究方向,为该技术的进一步发展提供了科学性指导.     

A mass and energy balance stage model for cyclic distillation

Cyclic distillation is an emerging process intensification technology, which can improve separation efficiency compared to conventional distillation. As most current models only account for the mass transfer, there is a lack of a stage model for cyclic distillation processes, which includes considerations of both mass and energy transfer. Such a model is presented in this article, and using this model, selected case studies, describing binary and multiple component systems with both ideal and nonideal liquid phases, are investigated. The presented stage model allows for the modeling of both mass and energy transfer for a cyclic distillation process and allows for multiple feed locations, as well as side draws. With the energy balances included, the dynamic vapor flow rate can be described. This was shown to have a significant effect on the separation, especially for cases where the change in the vapor flow over the column height was high.     

反应精馏过程耦合强化技术基础与应用研究述评

反应精馏技术是过程强化概念在化学工业成功应用的典范。由于反应与精馏耦合的高度复杂性和非线性,反应-精馏相互影响机制、耦合方式及其过程能效调控与优化成为制约该技术广泛应用的关键科学问题。综述了近二十年来国内外反应精馏技术从基础研究到工业应用的概况,包括反应精馏过程的可行性分析与概念设计方法、稳态模拟过程优化与动态模拟控制策略设计、兼具催化反应与气液传质的高效内构件开发以及反应精馏在各领域的应用。探讨了目前制约反应精馏广泛应用关键问题的解决方法与途径,阐明了普适性的反应精馏过程开发方法,总结了基于反应精馏过程耦合的新型过程强化技术,指出了反应精馏技术的发展趋势。     

Shortcut assessment of alternative distillation sequence schemes for process intensification

Finding good process schemes is a difficult task due to its search among multiple alternatives. In literature, several methods are successfully implemented as computer tools, but their use is limited to their developers. There are several useful rules of thumb and heuristics providing useful guidelines, but sometimes these are contradictory. Some authors tried to rank the various alternatives, defining heuristic equations to provide a quantitative parameter to choose among possible solutions. In this paper, mathematical model of distillation columns is simplified, assuming infinite number of stages. The resulting proposed equation has a great similarity to one of the previous heuristic ones. A simple equation not relying on heuristics and easy to use in calculation is provided to evaluate the distillation sequence energy efficiency (DSE) for each alternative. This allows to quantify the advantages derived from process intensification for a given feed composition. The proposed equation is dimensionless, as the Carnot efficiency is used instead of the temperature difference between distillate and bottoms. On the other hand, intermediate results provide also useful information. For instance, the Carnot efficiency of each column indicates when a heat pump or enhanced distillation would be useful. The recovery efficiency for each particular compound allows an easy comparison between alternatives, considering variations on the feed composition. The new equation is verified comparing its results with cases already solved in literature using different methods. The results show that all the methods in literature are able to provide the best sequence, except the heuristics-based ones that are not providing an overall sequence evaluation. The novelty of the proposed DSE method resides in its ease of application, compared to nowadays available methods, and requires only the feed composition and products boiling points.     

Enhancing mass and energy integration by external recycle in reactive distillation columns

The synthesis and design of reactive distillation columns separating reacting mixtures with the most unfavorable relative volatilities (i.e., the reactants are the heaviest and lightest components with the products being the intermediate ones) are described. The unfavorable thermodynamics poses great difficulties in combining the reaction operation and the separation operation involved and limits severely the potential of reactive distillation columns in the reduction of capital investment (CI) and operating cost. To remove the limitation, we propose two strategies for facilitating the synthesis and design of this kind of reactive distillation columns in this article. One is to arrange prudentially the reactive section so as to strengthen internal energy integration between the reaction operation and the separation operation involved; that is, while the reactive section should be placed at the bottom of the reactive distillation columns separating exothermic reactions, it should be at the top of the reactive distillation columns separating endothermic reactions. The other is to introduce an external recycle flow between the two ends of the reactive distillation columns to reinforce internal mass integration and internal energy integration between the reaction operation and the separation operation involved; that is, whereas the external recycle flow should be directed from the top to bottom of the reactive distillation columns separating exothermic reactions, it should be from the bottom to top of the reactive distillation columns separating endothermic reactions. Separation of four hypothetical ideal (i.e., two quaternary and two ternary systems, respectively) and two real nonideal (i.e., two quaternary systems) reacting mixtures is chosen to evaluate the proposed strategies. The results show that they can considerably lower energy requirement besides a further reduction in CI. © 2012 American Institute of Chemical Engineers AIChE J, 59: 2015–2032, 2013     

A fundamental principle and systematic procedures for process intensification in reactive distillation columns

A fundamental principle is developed for process intensification through internal mass and energy integration in reactive distillation columns and three systematic procedures are devised for process synthesis and design. For reactive distillation columns involving reactions with highly thermal effect, process intensification can be achieved with an exclusive consideration of internal energy integration between the reaction operation and separation operation involved. However, in the case of a highly endothermic reaction with an extremely low reaction rate and/or small chemical equilibrium constant, internal mass integration has also to be considered between the reactive section and stripping section. For reactive distillation columns involving reactions with negligibly or no thermal effect, process intensification can be performed with an exclusive consideration of internal mass integration. For reactive distillation columns involving reactions with moderately thermal effect, process intensification must be conducted with a careful trade-off between internal mass and energy integration. Five hypothetical and two real reactive distillation systems are employed to evaluate the principle and procedures proposed. It is demonstrated that intensifying internal mass and energy integration is really effective for process intensification. Not only can the thermodynamic efficiency be improved substantially, but also the capital investment can be further reduced.     

Research advances in thermally coupled intensification technology for special distillation

In the production and separation process of petroleum, medicine, chemical industry and other industries, it is often accompanied by the production of azeotropic or similar boiling point mixtures. Its high-efficiency and energy-saving separation is a prerequisite for industrial clean production and sustainable development. Special distillation as an effective separation method attracts substantial attention from researchers. However, special distillation is a process with high-energy consumption. Therefore, the development of intensification technology for special distillation with low costs and reliable performance is of great significance for the economy and energy sustainable development. According to the heat and mass transfer laws of special distillation, this work introduces the research advances of thermally coupled distillation, dividing wall column, side-stream distillation, organic Rankine cycle, heat pump and different pressure thermally coupled technologies in energy saving special distillation process from the intensification principles and retrofitting technologies. In addition, this work outlines the challenge and opportunity of intensification technology to provide references of the theoretical research and application to special distillation.     

直接接触式膜蒸馏过程的膜曝气强化

针对直接接触式膜蒸馏（direct contact membrane distillation,DCMD）过程存在的膜通量小及膜污染问题,设计了一种新型结构的膜蒸馏组件。以蔗糖溶液为处理液,考察了膜组件装填密度Φ、膜曝气量q、蔗糖浓度c与温度T₀对DCMD过程的影响。结果表明：随着Φ、q的增加,DCMD过程的膜通量先增大,后逐渐降低,Φ、q均存在最优值;随着c的增加,膜通量逐渐降低;随着T₀的增加,膜通量增大;对c为30%（mass）的蔗糖溶液进行DCMD法处理330 min时,膜曝气可使DCMD的初始膜通量J_initial提升24.7%、膜通量衰减率ΔJ降低55.0%,维持高膜通量的连续运行时间t₀延长4倍。主要原因是膜曝气强化了DCMD过程的传热传质,进而强化过程的分离性能;有效控制了DCMD过程的浓差极化,进而延缓过程的膜污染进程。研究结果有利于推进DCMD的工程化应用。     

特殊精馏热耦合强化技术研究进展

在石油、医药、化工等行业生产和分离过程中,常伴随着共沸或沸点相近混合物的产生,其高效节能分离是工业清洁生产和可持续发展的前提。作为一种分离共沸或近沸等难分离混合物的重要手段,特殊精馏引起了广泛关注。然而,特殊精馏对能源的消耗量非常大,开发低成本、性能可靠的特殊精馏强化技术对实现经济和能源的可持续发展具有重要意义。基于对特殊精馏塔内外传质传热规律的研究,本文从强化原理和工艺改进技术两方面,重点介绍了热耦精馏、隔壁塔、侧线精馏、有机朗肯循环、热泵精馏、差压热耦合等内外热耦合强化技术在特殊精馏节能增效等方面的研究进展,并展望了其未来发展的挑战和机遇,以期为特殊精馏在热耦合强化方面的理论研究与应用提供参考。     

Process intensification of distillation using a microwick technology to demonstrate separation of propane and propylene

Process intensification (PI) of distillation using a microchannel distillation (MCD) device successfully reduced the height of a theoretical plate (HETP) in separating propane and propylene to 1.2 cm, representing 10 theoretical stages. Mass transfer is enhanced using thin wicking structures that are 0.17 mm thick in counterflow with vapor. Liquid is segregated in the wicks by applying a siphon relative to the vapor phase, which also enables the device to operate horizontally. A scalable device containing 11 wicks was operated cryogenically in total reflux. The HETP varied between 1.2 and 4.5 cm, representing a dramatic reduction over commercial structured packings and comparable to other PI approaches. Significant improvements are expected with further development. Potential application for intensified distillation processes include distributed manufacturing and difficult separations involving close boiling compounds and meeting high purity specifications. The ultimate application is isotopic enrichment, where the number of stages required is typically multiple thousands. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3690–3699, 2018     

Process intensification on the separation of benzene and thiophene by extractive distillation

The separation of benzene and trace thiophene by extractive distillation was intensified in two aspects, that is, selection of a suitable entrainer and improvement of the process. The mixture of dimethylformamide (DMF) and an ionic liquid (IL) was chosen as the entrainer. Vapor–liquid equilibrium (VLE) experiments using pure DMF and a mixed entrainer were conducted, and UNIFAC model for ILs was extended to the benzene‐thiophene‐DMF‐IL system. The results demonstrated that volatilization loss of DMF in the vapor phase was significantly reduced by adding IL. Moreover, an improved process with only four columns using a mixed entrainer was proposed. The results indicated that the improved process is more promising for decreasing energy consumption and equipment investment compared with the conventional six‐column process. The total heat duties of reboilers and condensers was decreased by 6.47% and 6.41%, respectively. The process intensification strategy may be directly extended to separate trace components of other systems. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4470–4480, 2015     

萃取塔数学模型及过程强化的若干研究进展

萃取塔因生产能力大、占地面积小、密闭性好等优点,在石油、化工、生物、医药和环境工程等多领域被广泛应用。本文从以下几个方面介绍了萃取塔近些年的研究进展：综述了传统萃取塔（脉冲萃取塔、转盘塔与Kühni塔等）的水力学、轴向扩散与传质模型的发展,分析比较了表面张力、传质方向、放大效应等因素对模型的影响;介绍了计算流体动力学（CFD）在萃取塔中单液滴、单相流模拟、液-液两相流模拟、外加能量模拟、与群体平衡模型（PBM）耦合模拟中的应用进展;介绍了国内外设计开发的新型萃取塔,包括改变传统塔的内构件和引入多种外场能量等方式来强化相间传质。研究表明,将先进实验研究方法、准确经验模型和可靠理论计算相结合,将会是萃取塔研究的重要手段和方向。     

一种通用的反应蒸馏塔综合与设计方法

反应精馏是反应过程和分离过程耦合为一体的单元操作,已成为当今研究的重要领域。然而,到目前为止并没有一套通用简便的方法去指导反应精馏过程的综合与设计,严重限制了它的广泛应用。本文在过程强化原理的基础上提出了一种反应蒸馏塔通用的综合与设计方法,并利用2种反应蒸馏系统来评价所提出的设计策略。结果表明,该综合设计方法可以简便高效地搜索出反应蒸馏塔的最优结构,适用于不同类型的反应蒸馏塔的综合与设计。     

A review on process intensification in internally heat-integrated distillation columns

Internally heat-integrated distillation column (HIDiC) is the most radical approach of a heat pump design, making efficient use of internal heat-integration: the rectifying section of a distillation column operating at a higher pressure becomes the heat source, while the stripping part of the column acts as a heat sink. Remarkably, a HIDIC can bring up to 70% energy savings compared to conventional distillation columns. This is highly appealing regarding the fact that distillation is one of the most energy intensive operations in the chemical process industry accounting for over 40% of the energy usage. This review paper describes the latest developments concerning this promising but difficult to implement process intensification technology, covering all the major aspects related to the working principle, thermodynamic analysis, potential energy savings, various design configurations and construction options (ranging from inter-coupled or concentric columns, shell and tube and plate–fin heat exchanger columns to SuperHIDiC), design optimization, process control and operation issues, as well as pilot-scale and potential industrial applications. Further advancement, i.e., development of HIDiC technology for multi-component mixture separations is an extremely challenging research topic, especially when HIDiC becomes associated with other technologies such as dividing-wall column (DWC) or reactive distillation (RD).