Experimental validation of hybrid distillation‐vapor permeation process for energy efficient ethanol–water separation

BACKGROUND: The energy demand of distillation‐based systems for ethanol recovery and dehydration can be significant, particularly for dilute solutions. An alternative separation process integrating vapor stripping with a vapor compression step and a vapor permeation membrane separation step, termed membrane assisted vapor stripping (MAVS), has been proposed. The hydrophilic membrane separates the ethanol–water vapor into water‐rich permeate and ethanol‐enriched retentate vapor streams from which latent and sensible heat can be recovered. The objective of this work was to demonstrate experimentally the performance of a MAVS system and to compare the observed performance with chemical process simulation results using a 5 wt% ethanol aqueous feed stream as the benchmark. RESULTS: Performance of the steam stripping column alone was consistent with chemical process simulations of a stripping tower with six stages of vapor liquid equilibria (VLE). The overhead vapor from the stripper contained about 40 wt% ethanol and required 6.0 MJ of fuel‐equivalent energy per kg of ethanol recovered in the concentrate. Introduction of the vapor compressor and membrane separation unit and recovery of heat from both membrane permeate and retentate streams resulted in a retentate ethanol concentrate containing ca 80 wt% ethanol, but requiring only 2.2 MJ fuel kg^?1 ethanol, significantly less than steam stripping alone. CONCLUSION: Performance of the experimental unit with a 5 wt% ethanol feed liquid corroborated chemical process simulation predictions for the energy requirement of the MAVS system, demonstrating a 63% reduction in the fuel‐equivalent energy requirement for MAVS compared with conventional steam stripping or distillation. Published 2009 by John Wiley & Sons, Ltd.     

Reducing the Energy Demand of Cellulosic Ethanol through Salt Extractive Distillation Enabled by Electrodialysis

One of the main challenges when a biochemical conversion technique is employed to produce cellulosic ethanol is the low concentration of ethanol in the fermentation broth, which increases the energy demand for recovering and purifying ethanol to fuel grade. In this study, two design cases implementing salt extractive distillation—with salt recovery enabled by a novel scheme of electrodialysis and spray drying—along with heat integrated distillation techniques of double-effect distillation and direct vapor recompression are investigated through process simulation with Aspen Plus® 2006.5 for reducing the thermal energy demand. Conventional distillation along with molecular sieve based dehydration is considered as the base case. Salt extractive distillation along with direct vapor recompression is found to be the most economical ethanol recovery approach for cellulosic ethanol with a thermal energy demand of 7.1 MJ/L (natural gas energy equivalents, higher heating value), which corresponds to a thermal energy savings of 23% and cost savings of 12% relative to the base case separation train thermal energy demand and total annual cost.     

Reducing the energy demand of corn‐based fuel ethanol through salt extractive distillation enabled by electrodialysis

The thermal energy demand for producing fuel ethanol from the fermentation broth of a contemporary corn‐to‐fuel ethanol plant in the U.S. is largely satisfied by combustion of fossil fuels, which impacts the possible economical and environmental advantages of bioethanol over fossil fuels. To reduce the thermal energy demand for producing fuel ethanol, a process integrating salt extractive distillation—enabled by a new scheme of electrodialysis and spray drying for salt recovery—in the water‐ethanol separation train of a contemporary corn‐to‐fuel ethanol plant is investigated. Process simulation using Aspen Plus® 2006.5, with the electrolyte nonrandom two liquid Redlich‐Kwong property method to model the vapor liquid equilibrium of the water‐ethanol‐salt system, was carried out. The integrated salt extractive distillation process may provide a thermal energy savings of about 30%, when compared with the contemporary process for separating fuel ethanol from the beer column distillate. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

蒸汽渗透技术在燃料乙醇生产中的应用研究进展

蒸汽渗透作为一种新型膜分离技术,可有效解决生物燃料乙醇生产中发酵产物浓度低、能源消耗量大、污染环境等诸多瓶颈问题。与渗透蒸发相比,蒸汽渗透技术具有分离性能好、进料清洁、能量损耗低、操作弹性大等优点,在燃料乙醇生产领域具备更广阔的应用前景。本文在比较渗透蒸发和气体分离技术的基础上,简述了蒸汽渗透过程的机理和特点。介绍了优先透水膜和优先透醇膜两类应用于燃料乙醇生产不同阶段的蒸汽渗透膜和这两类膜材料当前的研究进展,重点阐述了有机/无机杂化膜在成膜方法、杂化材料选择等方面的最新成果。回顾了蒸汽渗透在乙醇脱水方面的工业应用成果,指出该技术在发酵原位分离乙醇和替代精馏工艺方面所具有的优势,探讨了与固态发酵技术相结合进行一次相变生产燃料乙醇工艺实现的可能性,并提出未来亟待研究和解决的问题,为蒸汽渗透技术在燃料乙醇生产领域大规模发展提供参考。     

Modelling and simulation of a hybrid process (pervaporation–distillation) for the separation of azeotropic mixtures of alcohol–ether

This work reports the modelling and simulation of a hybrid process, based on the combination of distillation and pervaporation, for the separation of azeotropic mixtures of alcohol–ether. After having selected the separation of methanol‐2‐metoxi‐2,2‐dimethyl ethane (ETHER) as a motivating example the mathematical modelling of the distillation column was achieved and used together with a mass transfer model previously reported for the pervaporation operation in order to simulate the behaviour of the hybrid process for different compositions of the feed stream (case 1: 3.2 wt% methanol, 55.4 wt% C₄, 41.4 wt% ETHER, and case 2: 5.2 wt% methanol, 42 wt% C₄, 52.8 wt% ETHER). Simulation tasks were carried out with the process modelling system gPROMS and the results of alternative process configurations that result from the relative location of the separation technologies have been compared on the basis of the required membrane area. Finally, the design of the pervaporation unit including the overall processing costs is reported. Copyright © 2001 Society of Chemical Industry     

A new technique for recovering energy in thermally coupled distillation using vapor recompression cycles

Even though it has been proved that a fully thermally coupled distillation (TCD) system minimizes the energy used by a sequence of columns, it is well‐known that vapor/liquid transfers between different sections produce an unavoidable excess of vapor (liquid) in some of them, increasing both the investment and operating costs. It is proposed here to take advantage of this situation by extracting the extra vapor/liquid and subjecting it to a direct/reverse vapor compression cycle. This new arrangement restores the optimal operating conditions of some of the affected sections with energy savings of around 20–30% compared with conventional TCD columns. Various examples, including the direct and reverse vapor recompression cycles, are presented. Furthermore, in each example, all possible modes of distillation (direct, indirect and Petlyuk distillation) with and without vapor recompression cycles (VRC) are compared to ensure that this approach delivers the best results. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3767–3781, 2013     

The Chatham demonstration: From design to operation of a 20 m/d membrane-based ethanol dewatering system

Distillation/dehydration represents the largest fraction of the energy used in the production of ethanol. The Siftek™ technology introduced in this paper carries the potential of reducing energy consumption of distillation/dehydration by up to 50% through the single pass removal of water from the water/ethanol stream at the beer column outlet, using a novel membrane process.Siftek™ is a polymeric membrane that can be used to dry ethanol in the vapor phase. The membrane preferentially permeates water over ethanol in a continuous process. Energy reductions are obtained because this membrane is well suited to remove large quantities of water without phase change.The Siftek™ technology has been piloted since August 2006 in a Greenfield Ethanol plant in Tiverton, Ontario, Canada. The Tiverton unit has a capacity of 1 m³/d and has been producing fuel ethanol from a feed containing between 75 and 90 wt.% ethanol in a single stage system.Based on the successful operation of the pilot, it was decided to scale-up the technology. A two-stage membrane system with a capacity of 20 m³/d was built for the Greenfield Ethanol plant in Chatham, Ontario, Canada. The unit is equipped with full-scale commercial membrane modules and is capable of treating a beer-column feed containing 60-70 wt.% ethanol, producing > 99 wt.% fuel-grade ethanol.     

带有侧线采出回流的部分透热精馏的节能优化

以正丙醇-异丙醇体系为例，研究了带有侧线采出回流的部分透热精馏操作。在该操作中，精馏段侧线采出气相，经塔外冷凝后回流至塔内采出板上方；提馏段某塔板被同轴的夹套式中间再沸器环绕，侧线采出该板处的气相回流至塔内采出板上方。通过单因素分析和响应面法对精馏段和提馏段操作的相关工艺参数分别进行了模拟优化，并对相应操作的热力学性能和分离性能的变化进行了分析。最终优化结果表明：达到规定的分离效果，带有侧线采出回流的部分透热精馏相较于绝热精馏有效能损失降低了26.5%。带有侧线采出回流的部分透热精馏操作通过合理分配能量、降低对热剂和冷剂的品位要求和提高能量利用率，最终达到节能目的。     

Recovery of 2,4‐dichlorophenol from acidic aqueous streams by Membrane Aromatic Recovery System (MARS)

This study describes the successful recovery of 2,4‐dichlorophenol (DCP) from wastewater using the Membrane Aromatic Recovery System (MARS). In the MARS process a non‐porous membrane separates a wastewater stream and a stripping solution. DCP is extracted from the wastewater and concentrated in its ionic form in the stripping solution, with pH ? pK_a DCP. The MARS extraction stage was operated in batch mode with the stripping solution placed inside, and the wastewater stream outside, the membrane tubes. Advantages of this configuration are avoidance of membrane blockage, reduction of stripping solution volume and operational flexibility. The stability and mass‐transfer characteristics of two different membrane materials, poly(dimethylsiloxane) (PDMS) and ethylene–propylene diene terpolymer (EPDM), were tested in DCP solutions with different acidities in order to simulate real industrial waste streams. EPDM exhibits one order of magnitude lower mass‐transfer rates than PDMS (1.4 × 10^?7 m s^?1 vs 20 × 10^?7 m s^?1 at 30 °C and 2.4 × 10^?7 m s^?1 vs 39 × 10^?7 m s^?1 at 60 °C), however its higher resistance to acid attack provides higher membrane lifetimes. This can be crucial for MARS processes treating real acidic industrial wastewater. A 97% recovery of DCP with a water content of 15 wt% was obtained upon neutralisation of the stripping solution. Copyright © 2004 Society of Chemical Industry     

Distillation technology – still young and full of breakthrough opportunities

Throughout history, distillation has been the most widespread separation method. However, despite its simplicity and flexibility, distillation still remains very energy inefficient. Novel distillation concepts based on process intensification, can deliver major benefits, not just in terms of significantly lower energy use, but also in reducing capital investment and improving eco‐efficiency. While very likely to remain the separation technology of choice for the next decades, there is no doubt that distillation technology needs to make radical changes in order to meet the demands of the energy‐conscious modern society. This article aims to show that in spite of its long age, distillation technology is still young and full of breakthrough opportunities. Moreover, it provides a broad overview of the recent developments in distillation based on process intensification principles, for example heat pump assisted distillation (e.g. vapor compression or compression–resorption), heat‐integrated distillation column, membrane distillation, HiGee distillation, cyclic distillation, thermally coupled distillation systems (Petlyuk), dividing‐wall column, and reactive distillation. These developments as well as the future perspectives of distillation are discussed in the context of changes towards a more energy efficient and sustainable chemical process industry. Several key examples are also included to illustrate the astonishing potential of these new distillation concepts to significantly reduce the capital and operating cost at industrial scale. © 2013 Society of Chemical Industry     

Pervaporation properties of polyvinyl alcohol/ceramic composite membrane for separation of ethyl acetate/ethanol/water ternary mixtures

In further purification of ethyl acetate (EAC) process, azeotropic distillation or extractive distillation is usually applied. High energy consumption limits the economic profit of the process. In this study, pervaporation separation of EAC/ethanol (EA)/water ternary mixtures using the ceramic-supported polyvinyl alcohol (PVA) composite membrane was investigated to substitute the azeotropic distillation or extractive distillation. Swelling experiments were performed to evaluate the sorption characteristic of the membrane. Flory-Huggins theory was applied to study the interaction between the membrane and the penetrant. The UNIFAC model was adopted to investigate the variation of the penetrant activity in the membrane. The effects of operation temperature, feed water content and feed flow rate on the PV performance of the membrane were systematically investigated. The composite membrane exhibited high PV performance with the total flux of 2.1 kg·m⁻²·h⁻¹ and 94.9 wt% permeate concentration of water (operation condition: feed composition 82.6 wt% EAC, 8.4 wt% EA, 9 wt% water, feed temperature 60 °C, feed flow rate 252 mL· min⁻¹). The PV performance of the membrane varied slightly over a continuous PV experiment period of 110 h. Our results demonstrated that the PVA/ceramic membrane was a potential candidate for the purification of EAC/EA/water ternary mixtures.     

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.     

Energy Saving in Crude Oil Atmospheric Distillation Columns by Modifying the Vapor Feed Inlet Tray

Optimization of a typical crude oil atmospheric distillation unit and reduction of energy conservation were carried out through modifying the implementation and change in the flash zone of the tower. A conventional procedure in such units involves the combination of liquid and vapor product of the prefractionation train surge drum upon introduction to the tower. However, it is theoretically illustrated and represented by simulation means that introducing the vapor feed into the upper stages of the distillation column separately can lead to an energy saving of 12.6 % in the condenser duty, an increased liquid‐to‐gas flow (L/G) at certain points of the column, and hence to a reduction in diameter and investment costs of new tower designs of approximately US$ 0.7 million a^–1. The proposal can be put into practice without the need of additional equipments or additional cost of difficult rerouting the streams. An industrial case study of a steady‐state crude oil distillation unit is given by simulation provision of AspenHysys™.     

Suppression of Osmotic Distillation in Gas Membrane Processes

Abstract

Suppression of osmotic distillation of water is important for the commercial scale application of gas membranes. We have equalized the water vapor pressure on either side of the membrane by increasing the temperature of the stream with the lower water vapor pressure. The experimentally determined temperature gradient is many times larger than predicted from water vapor pressure–temperature data. The larger temperature gradient may be explained by considering the heat flux across the membrane. The economic viability of adjusting the temperature of the feed and strip streams to suppresses water vapor transport depends on the additional energy costs involved.     

A new process for fuel ethanol dehydration based on modeling the phase equilibria of the anhydrous MgCl2 + ethanol + water system

The use of ethanol as a fuel for motor engines has attracted significant attention because of its possible environmental and economic advantages over fossil fuel. However, the energy demand for the ethanol dehydration process significantly impacts its production cost. A new and energy efficient process is developed on the basis of salt extractive distillation, which uses recycled MgCl₂ granules as a separating agent. Vapor‐liquor‐equilibria (VLE) data for the ternary MgCl₂ + ethanol + water system, and the three constituent binary systems were measured at 30, 60, 90, and 101.3 kPa. A large enhancement of relative volatility of the ethanol + water system in the presence of MgCl₂ is observed throughout the entire ethanol concentration range, which completely broke the azeotrope. The salt effect of MgCl₂ is thought to be the result of energetic interactions and the hydration equilibrium reaction of the Mg²⁺ ion with water molecules. The calculation results by the mixed‐solvent electrolyte model embedded in the OLI platform equipped with new model interaction parameters and equilibrium constant (obtained via the regression of experimental VLE data), provided for a satisfactory means of simulating the MgCl₂ salt extractive distillation process. Finally, the process was proven feasible at the laboratory‐scale resulting in large granules of recovered MgCl₂ and a product of 99.5 wt % ethanol. © 2014 American Institute of Chemical Engineers AIChE J, 61: 664–676, 2015     

Methyl Ethyl Ketone Production through an Intensified Process

Methyl ethyl ketone (MEK) is widely used in the industry and is mainly produced from petroleum. Some works have projected MEK as a possible fuel since its performance in spark engines has overcome the performance of gasoline in certain indexes. Two intensified alternatives to produce MEK are introduced here, consisting of a reactive distillation column, an extractive distillation column, and three conventional distillation columns. The direct alternative resulted as the most promising when it was evaluated based on energy consumption, greenhouse gas emissions, and an environmental index. The obtained energy consumption for MEK production was 11.62 MJ kg_MEK⁻¹ for the entire process. Moreover, those intensified alternatives showed better performance indexes in comparison with a conventional process.     

A new hybrid membrane separation process for enhanced ethanol recovery: Process description and numerical studies

Ethanol is a biofuel, produced through the fermentation of sugars derived from biomass. Its usefulness as a fuel is limited by the energy intensive nature of the ethanol separation process. The ethanol recovery process is inefficient due to the dilute nature of the fermentation product and the presence of the ethanol?water azeotrope. This investigation presents a new hybrid separation process for energy efficient ethanol recovery. The new process is a hybrid of distillation and pervaporation. However, as opposed to most other hybrid processes, the distillation and pervaporation processes are combined into single unit. An overview of the proposed system was provided and differences to the conventional separation process were highlighted. A mathematical model was derived to explain the transport phenomena occurring in the hybrid process. The model was then used to compare the process to distillation. It was shown that the hybrid process is capable of breaking the ethanol-water azeotrope. It was also demonstrated that the pervaporation process, which is associated with both material and energy transfer, induces partial condensation of the vapor and thereby affects the efficiency of vapor?liquid contacting. Simulations were presented to show the impact of reflux ratio and pervaporation flux on the performance of the process.     

Process analysis and optimisation of hybrid processes for the dehydration of ethanol

Promising hybrid processes for ethanol dewatering consist of different combinations of distillation with adsorption and/or vapour permeation. This paper presents an analysis and optimisation of these hybrid processes using non-equilibrium models and an evolutionary algorithm. Four different membrane assisted configurations are compared with a benchmark process consisting of distillation and pressure swing adsorption. In total 12 cases were investigated while assuming different feed and product compositions at different production capacities: three ethanol mass fractions in feed 45, 80, 92 wt.%, two product purities 99.6, 99.95 wt.% and two production capacities 25,000, 250,000 m³/year. The influence of decisive operating and structural variables on important target variables such as total membrane area is demonstrated. Finally, the processes are evaluated regarding operating costs and energy consumption depending on product purity and production capacity. The operating costs of the membrane assisted configurations differ only in a small range of −3% to 6% from those of the benchmark. The energy consumption of the membrane assisted configurations without distillation is up to 30% lower compared to the benchmark. Especially the combination of vapour permeation and adsorption is a promising alternative allowing for producing ethanol with high purities at lower operating pressures compared to the vapour permeation as stand alone process.     

Cyclic distillation technology – a mini‐review

Process intensification in distillation systems has received much attention during past decades, with the aim of increasing both energy and separation efficiency. Various techniques, such as internal heat‐integrated distillation, membrane distillation, rotating packed bed, dividing‐wall columns and reactive distillation were studied and reported in the literature. All these techniques employ the conventional continuous counter‐current contact of vapor and liquid phases. Cyclic distillation technology is based on an alternative operating mode using separate phase movement which leads to key practical advantages in both chemical and biochemical processes. This article provides a mini‐review of cyclic distillation technology. The topics covered include the working principle, design and control methods, main benefits and limitations as well as current industrial applications. Cyclic distillation can be rather easily implemented in existing columns by simply changing the internals and the operating mode, thus bringing new life to old distillation towers by significantly increasing the column throughput, reducing the energy requirements and offering better separation performance. © 2016 Society of Chemical Industry