Membrane‐assisted vapor stripping: energy efficient hybrid distillation–vapor permeation process for alcohol–water separation

BACKGROUND: Energy efficient alternatives to distillation for alcohol recovery from dilute solution are needed to improve biofuel sustainability. A process integrating steam stripping with a vapor compression step and a vapor permeation membrane separation step is proposed. The objective of this work is to estimate the energy and process costs required to make a fuel grade ethanol (0.5 wt% water) from 1 and 5 wt% ethanol aqueous streams using the proposed process. RESULTS: Using process simulation and spreadsheeting software, the proposed membrane‐assisted vapor stripping process was estimated to require as little as 8.9 MJ of fuel‐equivalent energy per kg of fuel grade ethanol recovered from a 1 wt% ethanol feed stream, 2.5 MJ kg^?1 for a 5 wt% ethanol solution. This represents an energy saving of at least 43% relative to standard distillation producing azeotropic ethanol (6 wt% water). Process costs were also found to be lower than for distillation at the 3.0 × 10⁶ kg‐ethanol year^?1 scale modeled. CONCLUSION: In this hybrid system, the stripping column provides high ethanol recoveries and low effluent concentrations while the vapor compression‐membrane component enables the efficient recovery of latent and sensible heat from both the retentate and permeate streams from the membrane system. Published in 2008 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.     

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。     

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。     

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     

Modelling of multicomponent gas separation with asymmetric hollow fibre membranes—methane enrichment from biogas

A mathematical model for the dynamic performance of gas separation with high flux, asymmetric hollow fibre membranes was developed considering the permeate pressure build‐up inside the fibre bore and cross flow pattern with respect to the membrane skin. The solution technique provides reliable examination of pressure and concentration profiles along the permeator length (both residue/permeate streams) with minimal effort. The proposed simulation model and scheme were validated with experimental data of gas separation from literature. The model and solution technique were applied to investigate dynamic performance of several membrane module configurations for methane recovery from biogas (landfill gas or digester gas), considering biogas as a mixture of CO₂, N₂ and CH₄. Recycle ratio plays a crucial role, and optimum recycle ratio vital for the retentate recycle to permeate and permeate recycle to feed operation was found. From the concept of two recycle operations, complexities involved in the design and operation of continuous membrane column were simplified. Membrane permselectivity required for a targeted separation to produce pipeline quality natural gas by methane‐selective or nitrogen‐selective membranes was calculated. © 2012 Canadian Society for Chemical Engineering     

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.     

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.     

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     

Pilot‐scale studies of process intensification by cyclic distillation

Process intensification in distillation systems receives much attention with the aim of increasing both energy and separation efficiency. Several technologies have been investigated and developed, as for example: dividing‐wall column, HiGee distillation, or internal heat‐integrated distillation. Cyclic distillation is a different method based on separate phase movement—achievable with specific internals and a periodic operation mode—that leads to key advantages: increased column throughput, reduced energy requirements, and better separation performance. This article is the first to report the performance of a pilot‐scale distillation column for ethanol‐water separation, operated in a cyclic mode. A comparative study is made between a pilot‐scale cyclic distillation column and an existing industrial beer column used to concentrate ethanol. Using specially designed trays that truly allow separate phase movement, the practical operation confirmed that 2.6 times fewer trays and energy savings of about 30% are possible as compared with classic distillation. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2581–2591, 2015     

Modeling and simulation for direct contact membrane distillation in hollow fiber modules

Direct contact membrane distillation (DCMD) offers an attractive operation for the separation of mixtures at atmospheric pressure with reasonable energy requirement. A new simultaneous heat and mass transfer model in DCMD in a hollow fiber configuration is presented. Flow regime in feed and permeate side, the variations of mean temperature and concentration along the membrane module, the length of the membrane, and various properties of membrane characteristics are taken into account in the present model. A system of nonlinear equations describing the DCMD process is solved numerically for each cell using the FSOLVE coding, which is a built‐in function in MATLAB^® to find the influence of the temperature and velocity of the feed and permeate streams, and the salt concentration of the feed along the module on the permeate flux. The predicted results by the new model show a good accord with a wide range of various experimental results available in the literature. © 2012 American Institute of Chemical Engineers AIChE J, 59: 589–603, 2013     

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     

Selective separation of copper (II) and cobalt (II) from wastewater by using continuous cross‐flow micellar‐enhanced ultrafiltration and surfactant recovery from metal micellar solutions

Performance of continuous cross‐flow micellar‐enhanced ultrafiltration (MEUF) method was investigated for the selective separation of copper (Cu²⁺) and cobalt (Co²⁺) from the aqueous phase using sodium dodecyl sulfate (SDS) as an anionic surfactant and iminodiacetic acid (IDA) as a chelating agent. Operating parameters such as operating time (10–120 min), cross‐flow rate (100–250 mL/min), pH of the solution (2.8–5.6), molar concentration ratio of the chelating agent to metals (the C/M ratio, 0.5–2.5), molar concentration ratio of the surfactant to metals (the S/M ratio, 5–8) and mode of operation were studied to investigate the effectiveness of the process on selective separation. At optimal parameters, above 90% selective separation (Cu²⁺ in permeate and Co²⁺ in retentate) was achieved. Two methods were studied for the separation of Co²⁺ and SDS from retentate stream; acidification followed by UF and addition of chelating agent followed by UF with surfactant recovery of 75% and 83%, respectively, and Co going into the permeate.     

Reliable production of highly concentrated bioethanol by a conjunction of pervaporation using a silicone rubber sheet‐covered silicalite membrane with adsorption process

For the production of highly concentrated bioethanol by pervaporation using an ethanol‐permselective silicalite membrane, pervaporation performance was investigated using a silicalite membrane entirely covered with a silicone rubber sheet to prevent direct contact with acidic compounds. By using a resistance model for membrane permeation, the separation factor of the covered silicalite membrane towards ethanol can be estimated from the individual pervaporation performances of the silicalite membrane and the silicone rubber sheet. No decrease in the ethanol concentration through the silicone rubber sheet‐covered membrane was caused when ethanol solutions containing succinic acid were supplied. By directly passing the permeate‐enriched ethanol vapor mixed with water vapor through a dehydration column packed with a molecular sieve of pore size 0.3 nm, highly concentrated bioethanol up to 97% (w/w), greater than the azeotropic point in the ethanol/water binary systems, can be obtained from 9% (w/w) fermentation broth. Copyright © 2004 Society of Chemical Industry     

Removal of Dissolved VOCs from Water with an Air Stripper/Membrane Vapor Separation System

Abstract

Treatment of water contaminated with volatile organic compounds (VOCs) is a major problem for the United States chemical industry. Currently, VOCs are removed from moderately contaminated wastewater streams by processes such as steam stripping and from dilute wastewaters by air stripping combined with a carbon adsorption off-gas treatment system. This paper describes the development and performance of a hybrid process that combines air stripping with membrane organic-vapor separation to recover VOCs from the stripper off-gas. A number of prototype systems have been constructed and evaluated. The optimum system appears to be a tray stripper fitted with a high-pressure compression-condensation membrane separation unit. Such a system can remove 95 to 99% of the VOCs present in contaminated water; the removed VOCs are recovered as a liquid condensate. The economics of the technology are competitive with alternative processes, particularly for streams containing more than 500 ppm VOC and having flow rates less than 10 to 30 gal/min.     

L‐Lysine Monohydrochloride Syrup Concentration using a Membrane Hybrid Process of Ultrafiltration and Vacuum Membrane Distillation

The development of energy saving membrane separation processes is finding a unique position in process industries. One of the important areas where they are employed is the biotechnology industry. This industry has its own specifications and requirements, e.g., levels of diluteness, thermal, chemical and shear fragility. Membrane separation processes have the characteristics necessary to match these specifications and needs. In this research, the determination of the experimental concentration of L‐Lysine monohydrochloride (L‐lysine‐HCl) syrup was investigated using ultrafiltration (UF) and vacuum membrane distillation (VMD) hybrid membrane processes. Four parameters that are known to have significant influence on the UF process were examined, i.e., pressure difference across the membrane, feed concentration of L‐lysine‐HCl, feed velocity on the membrane surface, and pH. For the VMD unit, pressure difference and pH were replaced with feed temperature and vacuum pressure on the permeate side of membrane. Each process was carried out separately and the results were used to design a bench‐scale process. In order to save time and money, the Taguchi method of experimental design was employed. The effects of feed concentration, pressure difference across the membrane, feed velocity on the membrane surface, and pH on the target variable, i.e., the membrane flux, in the UF process were 39.93, 38.65, 9.36, and 9.59 %, respectively. For the VMD process, these values were 64.79, 22.16, 6.21, and 2.14 % for feed temperature, feed concentration, vacuum pressure on the permeate side, and feed velocity on the membrane surface, respectively.     

Application of membrane distillation technology in the treatment of table olive wastewaters for phenolic compounds concentration and high quality water production

Direct contact membrane distillation process (DCMD) is proposed for the treatment of table olive wastewaters (TOW) for high quality water production and concentration of their phenolic compounds. The main objective was to investigate the effectiveness of DCMD process to concentrate phenolic compounds from TOW that can be reused as a potential source for powerful natural antioxidants. The performance of three commercial membranes, made from polytetrafluoroethylene supported by polypropylene net (TF200, TF450 and TF1000), were tested. The permeate fluxes and polyphenols concentration in both the permeate and retentate have been monitored under different DCMD operating temperatures. It was found that the three membranes exhibit an excellent separation coefficient (greater than 99.5%) even after 4 h of DCMD operation with TOW. High concentration factors were obtained with the membrane TF450 at 70 °C, while the membrane TF200 having the lowest pore size was found to be more resistant to fouling phenomenon compared to the other membranes since the reduction of its water permeate flux after TOW treatment did not exceed 2.9%. High quality of the permeate was obtained with phenolic concentration lower than 16 mg of TYE/L. In addition, the values of electrical conductivity of the permeate were lower than 193 μS/cm for the membranes TF450 and TF200, and lower than 355 μs/cm for the membrane TF1000. Consequently, DCMD proved to be an effective process for the treatment of TOW for high quality water production and a phenolic-rich concentrate.     

Energy optimization of bioethanol production via gasification of switchgrass

In this article, we address the conceptual design of the bioethanol process from switchgrass via gasification. A superstructure is postulated for optimizing energy use that embeds direct or indirect gasification, followed by steam reforming or partial oxidation. Next, the gas composition is adjusted with membrane‐PSA or water gas shift. Membrane separation, absorption with ethanol‐amines and PSA are considered for the removal of sour gases. Finally, two synthetic paths are considered, high alcohols catalytic process with two possible distillation sequences, and syngas fermentation with distillation, corn grits, molecular sieves and pervaporation as alternative dehydration processes. The optimization of the superstructure is formulated as an mixed‐integer nonlinear programming problem using short‐cut models, and solved through a special decomposition scheme that is followed by heat integration. The optimal process consists of direct gasification followed by steam reforming, removal of the excess of hydrogen and catalytic synthesis, yielding a potential operating cost of $0.41/gal. © 2011 American Institute of Chemical Engineers AIChE J, 2011     

基于MVR热泵精馏的乙醇-异丙醇分离工艺

常规精馏分离乙醇-异丙醇小温差体系的能耗较高,为此本文将两种机械蒸汽再压缩（MVR）热泵精馏工艺,即塔顶蒸汽直接压缩供热和塔底液相闪蒸压缩供热精馏工艺应用于乙醇-异丙醇的分离研究。利用Aspen Plus化工流程模拟软件中的严格精馏模块RadFrac.和压缩机模块Compr.,选用Wilson-RK方程计算物性数据,以分离过程的能耗最低为目标函数,对以上提出的两种MVR热泵精馏工艺分别在不同操作压力工况条件下进行了模拟与优化,得到了各自相关的工艺参数和设备参数。研究结果表明：与常规精馏工艺相比,以上两种MVR热泵精馏工艺节能分别为93.2%和93.4%。利用模拟得到的相关数据,估算了以上两种MVR热泵精馏工艺的平均年总费用,并进行了综合经济效益评价。结果表明：以上两种MVR热泵精馏工艺的平均年总费用基本持平,因此以上两种MVR热泵精馏工艺均是分离该体系较为合适的方法。