Processing of ethanol fermentation broths by Candida krusei to separate bioethanol by pervaporation using silicone rubber‐coated silicalite membranes

BACKGROUND: Pervaporation employing ethanol‐permselective silicalite membranes as an alternative to distillation is a promising approach for refining low‐concentration bioethanol solutions. However, to make the separation process practicable, it is extremely important to avoid the problems caused by the adsorption of succinate on the membrane during the separation process. In this work, the pervaporation of an ethanol fermentation broth without succinate was investigated, as well as the influence of several fermentation broth nutrient components. RESULTS: Candida krusei IA‐1 produces an extremely low level of succinate. The decrease in permeate ethanol concentration through a silicone rubber‐coated silicalite membrane during the separation of low‐succinate C. krusei IA‐1 fermentation broth was significantly improved when compared with that obtained using Saccharomyces cerevisiae broth. By treating the fermentation broth with activated carbon, bioethanol was concentrated as efficiently as with binary mixtures of ethanol/water. The total flux was improved upto 56% of that obtained from the separation of binary mixtures, compared with 43% before the addition of activated carbon. Nutrients such as peptone, yeast extract and corn steep liquor had a negative effect on pervaporation, but this response was distinct from that caused by succinate. CONCLUSION: For consistent separation of bioethanol from C. krusei IA‐1 fermentation broth by pervaporation, it is useful to treat the low nutrient broth with activated carbon. To further improve pervaporation performance, it will be necessary to suppress the accumulation of glycerol. Copyright © 2009 Society of Chemical Industry     

生物乙醇原位分离技术的研究进展

生物乙醇是一种重要的可再生生物燃料,使用生物乙醇可大幅减少温室气体排放。为了建立更高效低能耗的生物乙醇回收工艺,原位分离（ISPR）技术应运而生。本文综述了近年来乙醇原位分离的研究进展,从原理及应用等进行多方面详细地介绍,包括气提、真空发酵、吸附、液-液萃取、渗透汽化、膜蒸馏等分离技术。针对分离性能、能耗成本等问题分析了不同分离技术耦合发酵过程的优势及不足,重点回顾了以渗透汽化为代表的膜分离技术,总结了渗透汽化膜材料的选择以及膜的制备方法,旨在提升乙醇分离膜性能优化乙醇分离工艺。为整合不同分离技术的特点及优势,聚焦多级耦合分离系统的开发对各级分离技术联用的性能及潜力进行剖析与评价,并在此基础上研判其发展前景。     

Stabilization of bioethanol recovery with silicone rubber‐coated ethanol‐permselective silicalite membranes by controlling the pH of acidic feed solution

In order to produce highly concentrated bioethanol by pervaporation using an ethanol‐permselective silicalite membrane, techniques to suppress adsorption of succinic acid, which is a chief by‐product of ethanol fermentation and causes the deterioration in pervaporation performance, onto the silicalite crystals was investigated. The amount adsorbed increased as the pH of the aqueous succinic acid solution decreased. The pervaporation performance also decreased with decreasing pH when the ternary mixtures of ethanol/water/succinic acid were separated. Using silicalite membranes individually coated with two types of silicone rubber, pervaporation performance was significantly improved in the pH range of 5 to 7, when compared with that of non‐coated silicalite membranes in ternary mixtures of ethanol/water/succinic acid. Moreover, when using a silicalite membrane double‐coated with the two types of silicone rubber, pervaporation performance was stabilized at lower pH values. In the separation of bioethanol by pervaporation using the double‐coated silicalite membrane, removal of accumulated substances having an ultraviolet absorption maximum at approximately 260 nm from the fermentation broth proved to be vital for efficient pervaporation. Copyright © 2005 Society of Chemical Industry     

Stabilized production of highly concentrated bioethanol from fermentation broths by Zymomonas mobilis by pervaporation using silicone rubber‐coated silicalite membranes

Since pervaporation performance of ethanol‐permselective silicalite membrane, which is an aluminum‐free hydrophobic zeolite, in the separation of fermentation broths by yeast are negatively affected by succinic acid, the potential of pervaporation using silicone rubber‐coated silicalite membranes of ethanol fermentation broths, not containing succinic acid, by Zymomonas mobilis was investigated for the reliable production of concentrated bioethanol. In the separation of fermentation broths, the pervaporation performance was influenced by nutrients used for the preparation of fermentation broths. In the separation of a broth prepared with yeast extract, pervaporation performance was greatly compromised by accumulation of a substance(s) having an ultraviolet absorption maximum at approximately 260 nm not only in total flux, but also in permeate ethanol concentration compared to the separation of binary ethanol/water mixtures. When supplying a prepared broth with corn steep liquor without the accumulation of a substance(s) having an ultraviolet absorption maximum at approximately 260 nm, the permeate ethanol concentration did not decrease. Treating the prepared broth with activated carbon was effective in restraining the decrease in total flux. Pervaporation performance is also deteriorated by the adsorption of lactic acid contained in corn steep liquor onto the silicalite crystals. In the separation of ternary mixtures of ethanol/water/lactic acid, accomplished by adjusting the ternary mixtures to pH > 5, more than 90% of the permeation flux in the separation of binary ethanol/water mixtures was obtained, and the permeate ethanol concentration was comparable to that obtained in the separation of binary mixtures. For stably performing pervaporation, it is important to prepare ethanol fermentation broths by Zymomonas mobilis in which lactic acid concentration is as low as possible. Copyright © 2007 Society of Chemical Industry     

渗透汽化在生物燃料乙醇制备中的研究进展

渗透汽化作为一种新型的膜分离技术应用于发酵法制备生物燃料乙醇,不但能减少产物对微生物的抑制作用,而且可以脱水制备高纯度燃料乙醇,因而具有显著的优势。本文对渗透汽化在发酵法制备燃料乙醇中所涉及的膜材料、耦合工艺、应用现状和经济评价进行了详细的综述,并对发展趋势作了展望。     

POMS Membrane for Selective Separation of Ethanol from Dilute Alcohol-Aqueous Solutions by Pervaporation

Lignocellulosic biomass has potential as an alternative to corn as starting material for the production of ethanol for the development of non-fossil fuel energy sources. In this case, low concentration bioethanol is gained by yeast fermentation and it has to be efficiently recovered and concentrated. For this purpose pervaporation separation of dilute alcohol-aqueous solutions was carried out using a poly(octhylmethyl siloxane) [POMS] membrane. The effect of different process parameters (feed composition, feed temperature, feed flow rate, permeate pressure) on pervaporation performance were investigated and discussed in terms of the separation factor and the total flux. The membrane studied was ethanol to water selective at ethanol feed concentrations lower than 2.5% w/w, while the highest permeability was achieved at feed temperature of 95°C.     

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     

Process operation performance of PDMS membrane pervaporation coupled with fermentation for efficient bioethanol production

There would be strong product inhibition on ethanol fermentation process if ethanol is not removed in situ from broth. PDMS membrane pervaporation coupled with fermentation is a promising process for efficient bioethanol production since ethanol inhibition is relieved or eliminated. From the perspective of process operation, membrane separation performance, ethanol fermentation performance and the subsequent processing on membrane downstream are the three key issues. This review aims at contributing a comprehensive overview on the operation performance of the integrated process. The state-of-the-art of the three key issues related to the operation performance is focused. Finally, the tentative perspective on the possible future prospects of the integrated process is briefly presented.     

ZIF-L/PDMS混合基质膜蒸气渗透耦合发酵强化乙醇生产效率的研究

蒸气渗透（VP）膜分离不存在膜污染风险,在生物乙醇生产中具有广阔的应用前景。将聚二甲基硅氧烷（PDMS）膜和以二维沸石咪唑骨架（ZIF-L）为填充基质制备的PDMS（ZIF-L/PDMS）混合基质膜,分别用于VP膜分离与菊粉水解液发酵制乙醇过程的耦合,分析了二者在耦合过程中的分离性能和发酵性能。探究了不同膜分离方式、不同类型膜及操作条件对膜分离性能的影响。实验结果表明,当料液浓度为5%（质量）、蒸气循环流量为1.5 L·min^-1时,ZIF-L/PDMS混合基质膜的VP性能高于渗透汽化（PV）,归一化总通量达到1148.78 g·m^-2·h^-1,分离因子高达19.14,显著提升了乙醇分离性能。ZIF-L/PDMS混合基质膜用于VP耦合发酵,实现了耦合过程的高渗透性和乙醇选择性,与文献报道相比,乙醇移除效果最优,乙醇产率和时空产率分别达到0.421 g·g^-1、3.07 g·L^-1·h^-1,两个指标明显高于单独发酵,极大地提高了乙醇生产效率。因此,ZIF-L/PDMS混合基质膜在原位分离发酵乙醇方面具有很大的应用潜力。     

Dehydration of alcohol fuels by pervaporation

Presented are experimental results of the dehydration of a liquid mixture with same composition as fusel oil, a by-product from fermentation of sugar cane to ethanol for use as fuel. Investigations on the pervaporative separation of water from the initial solution were performed with two different pervaporation membranes. Flux through the membranes depends strongly on the water concentration and on feed temperature.     

REMOVAL OF VOCs FROM THE AQUEOUS SOLUTIONS BY PERVAPORATION USING A FILLING-TYPE MEMBRANE

The membranes were prepared by the incorporation of highly hydrophobic silicalite and carbon molecular sieves (CMS) from different precursors into the PDMS casting solutions. The pervaporative removal of VOCs, such as benzene, from aqueous solutions was carried out using the separation factor and permeation flux as the evaluating parameters. The effects of the CMS types and structures, feed concentrations on the pervaporation performance were preliminarily investigated.     

Effects of synthesis conditions on the pervaporation properties of poly[1‐(trimethylsilyl)‐1‐propyne] useful for membrane bioreactors

An integrated fermentation and membrane‐based recovery (pervaporation) process has certain economical advantages in continuous conversion of biomass into alcohols. This article presents new pervaporation data obtained for poly[1‐(trimethylsilyl)‐1‐propyne] (PTMSP) samples synthesized in various conditions. Three different catalytic systems, TaCl₅/n‐BuLi, TaCl₅/Al(i‐Bu)₃, and NbCl₅ were used for synthesis of the polymers. It was found that the catalytic system has a significant influence over the properties of membranes made from PTMSP. Although a combination of a high permeation rate and a high ethanol–water separation factor (not less than 15) was provided by all PTMSP samples, the PTMSP samples synthesized with TaCl₅/n‐BuLi showed significant deterioration of membrane properties when acetic acid was present in the feed. In contrast, the PTMSP samples synthesized with TaCl₅/Al(i‐Bu)₃ or NbCl₅ showed stable performance in the presence of acetic acid. When using a multicomponent mixture of organics and water, the copermeation of different organic components results in lower separation factor for both ethanol and butanol. These data are consistent with nanoporous morphology of PTMSP. It was demonstrated that pervaporative removal of ethanol improved the overall performance of the fermentation process. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2271–2277, 2004     

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.     

Pervaporative dehydration of diethylene glycol through a hollow fiber membrane

In this study, the pervaporative dehydration of diethylene glycol (DEG) through a commercial hollow fiber membrane was investigated at various feed temperatures in the range of 333–363 K with feeds containing 0.5–2.0 wt % water. Unlike the usual pervaporative dehydration process in which water is less volatile than the organic solvent, the feed mixture used in this study contained the organic component DEG, which is less volatile than water, resulting in unique permeation behaviors. The permeation behaviors of the individual components were investigated as functions of the feed temperature and feed composition. In particular, the effect of the low vapor pressure characteristics of DEG was investigated. Semi‐empirical equations for predicting the individual component fluxes and separation factor were quantified directly from actual dehydration pervaporation of DEG. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Separation of phenanthrene/N‐tetradecane mixtures (model diesel) via pervaporation using an aromatic polyimide membrane

The present investigation focuses on the separation of phenanthrene (a polyaromatic hydrocarbon) from n‐tetradecane (model diesel composition) via pervaporation using a fabricated aromatic polyimide membrane. The experiments demonstrate preferential permeation of the polyaromatic for all films within the studied experimental range. The influence of operating temperature, membrane pretreatment time, membrane composition, and membrane thickness on the pervaporative performance were investigated. Statistical software Design Expert 7.1.4 was used to derive the regression equation describing the effect of the above mentioned factors on the pervaporation separation index. These factors are optimized using response surface methodology. The highest value of pervaporation separation index obtained is 1.5277 kg m^?2 h^?1 and the corresponding optimized condition is: operating temperature 493 K, pretreatment time 16.55 h with a membrane composition of 2.76 wt% of phenanthrene in polyamic acid and thickness 53.22 µm. POLYM. ENG. SCI., 57:392–402, 2017. © 2016 Society of Plastics Engineers     

Novel PVA-silica nanocomposite membrane for pervaporative dehydration of ethylene glycol aqueous solution

To effectively suppress the swelling of poly(vinyl alcohol) (PVA) membrane, polymer-inorganic nanocomposite membranes composed of PVA and γ-mercaptopropyltrimethoxysilane (MPTMS) were prepared by in situ sol-gel technique for pervaporative separation of water-ethylene glycol (EG) mixtures. Effects of the types of catalyst for sol-gel process and MPTMS content on the physical and chemical structure of PVA-silica nanocomposite membranes (designated as PVA-MPTMS hereafter) were investigated by ²⁹Si NMR, FTIR, SEM, XRD and TGA-DTA. Due to the formation of more compact crosslinked structure, nanocomposite membranes exhibited enhanced thermal stability. It was found that when 50 wt% of MPTMS was incorporated into PVA, the nanocomposite membranes possessed optimum pervaporation performance for 80 wt% EG aqueous solution at 70 °C. Unexpectedly, there was no improvement in the pervaporation performance of PVA-MPTMS nanocomposite membranes after mercapto group was oxidized into sulfonic group.     

Development of a mathematical model for studying bioethanol–water separation using hydrophilic polyetherimide membrane

An essentially predictive mathematical model was developed to simulate pervaporation process. The group contribution method UNIFAC was used for calculating the upstream activity coefficients. The diffusion coefficient in the membrane was predicted using free‐volume theory. Free‐volume parameters were determined with viscosity and temperature data, and the binary interaction solvent–polymer parameter was calculated by a group‐contribution lattice‐fluid equation of state (GCLF‐EOS). A simulator named PERVAP was developed applying the mathematical model. Pervaporation process was simulated for separating bioethanol–water through polyetherimide membrane. The simulated results were validated using experimental data of bioethanol/water separation through polyetherimide membrane. The model presented a satisfactory performance compared to experimental data. Related to the simulation of the studied separation, a 99% molar enriched bioethanol stream was obtained with a recovery of 94%. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Biohydrogen and Bioethanol Production from Biodiesel-Based Glycerol by Enterobacter aerogenes in a Continuous Stir Tank Reactor

Crude glycerol from the biodiesel manufacturing process is being produced in increasing quantities due to the expanding number of biodiesel plants. It has been previously shown that, in batch mode, semi-anaerobic fermentation of crude glycerol by Enterobacter aerogenes can produce biohydrogen and bioethanol simultaneously. The present study demonstrated the possible scaling-up of this process from small batches performed in small bottles to a 3.6-L continuous stir tank reactor (CSTR). Fresh feed rate, liquid recycling, pH, mixing speed, glycerol concentration, and waste recycling were optimized for biohydrogen and bioethanol production. Results confirmed that E. aerogenes uses small amounts of oxygen under semi-anaerobic conditions for growth before using oxygen from decomposable salts, mainly NH₄NO₃, under anaerobic condition to produce hydrogen and ethanol. The optimal conditions were determined to be 500 rpm, pH 6.4, 18.5 g/L crude glycerol (15 g/L glycerol) and 33% liquid recycling for a fresh feed rate of 0.44 mL/min. Using these optimized conditions, the process ran at a lower media cost than previous studies, was stable after 7 days without further inoculation and resulted in yields of 0.86 mol H₂/mol glycerol and 0.75 mol ethanol/mole glycerol.     

渗透汽化法从丙酮-丁醇-乙醇中分离浓缩丁醇

发酵法生产丁醇的产物质量浓度很低,为了实现丁醇的高效分离浓缩,文中采用渗透汽化膜分离技术对模型发酵液(丙酮、丁醇、乙醇混合溶液,ABE)进行浓缩实验。结果表明:随着温度、真空度、错流速度、料液质量浓度的增大,丁醇通量上升;渗透汽化膜对丁醇选择性在温度50℃时最佳,并随真空度的减小而减小,随料液质量浓度的增大而降低。实验证明,渗透汽化法能实现丁醇的高效分离浓缩,并且利用串联阻力溶解扩散模型可较好地预测ABE溶液体系中各组分的传质和分离效果。     

Preparation of novel ZSM‐5 zeolite‐filled chitosan membranes for pervaporation separation of dimethyl carbonate/methanol mixtures

Novel mixed matrix membranes were prepared by incorporating ZSM‐5 zeolite into chitosan polymer for the pervaporative separation of dimethyl carbonate (DMC) from methanol. These membranes were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and X‐ray diffraction (XRD) to assess their morphology, intermolecular interactions, and crystallinity. Sorption studies indicated that the degree of swelling for zeolite‐filled membranes increased with zeolite content in the membrane increasing and the separation selectivity of DMC/methanol was dominated by solubility selectivity rather than diffusivity selectivity. The characteristics of these membranes for separating DMC/methanol mixtures were investigated by varying zeolite content, feed composition, and operating temperature. The pervaporation separation index (PSI) showed that 5 wt % of ZSM‐5 zeolite‐filled membrane gave the optimum performance in the PV process. From the temperature‐dependent permeation values, the Arrhenius activation parameters were estimated. The resulting lower activation energy values obtained for zeolite‐filled membranes contribute to the framework of the zeolite. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007