Selective separation of n‐butanol from aqueous solutions by pervaporation using silicone rubber‐coated silicalite membranes

BACKGROUND: To use butanol as a liquid fuel and feedstock, it is necessary to establish processes for refining low‐concentration butanol solutions. Pervaporation (PV) employing hydrophobic silicalite membranes for selective recovery of butanol is a promising approach. In this study, the adsorption behavior of components present in clostridia fermentation broths on membrane material (silicalite powder) was investigated. The potential of PV using silicone rubber‐coated silicalite membranes for the selective separation of butanol from model acetone–butanol–ethanol (ABE) solutions was investigated. RESULTS: The equilibrium adsorbed amounts of ABE per gram of silicalite from aqueous solutions of binary mixtures at 30 °C increased as follows: ethanol (95 mg) < acetone (100 mg) < n‐butanol (120 mg). The amount of butanol adsorbed is decreased by the adsorption of acetone and butyric acid. In the separation of ternary butanol/water/acetone mixtures, the enrichment factor for acetone decreased, compared with that in binary acetone/water mixtures. In the separation of a model acetone–butanol–ethanol (ABE) fermentation broth containing butyric acid by PV using a silicone rubber‐coated silicalite membrane, the permeate butanol concentration was comparable with that obtained in the separation of a model ABE broth without butyric acid. The total flux decreased with decreasing feed solution pH. CONCLUSION: A silicone rubber‐coated silicalite membrane exhibited highly selective PV performance in the separation of a model ABE solution. It is very important to demonstrate the effectiveness of PV in the separation of actual clostridia fermentation broths, and to identify the factors affecting PV performance. Copyright © 2011 Society of Chemical Industry     

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     

Silicalite‐Filled PEBA Membranes for Recovering Ethanol from Aqueous Solution by Pervaporation

Pervaporation (PV) performances of silicalite‐filled polyether‐block‐amide (PEBA) membranes for separation of ethanol/water mixtures have been studied. The effects of silicalite content, ethanol concentration in feed, and feed temperature on the PV performances of the membranes have been investigated. It is found that addition of silicalite can improve PV performances of PEBA membranes. When the silicalite content is 2.0 wt %, both permeation flux and separation factor reach the maximum values, which are 833 g/m²h and 3.6, respectively. With increasing of ethanol in the feed and feed temperature, both separation factor and total flux increased. The higher permeation activation energy of ethanol (E_ethanol = 21.62 kJ/mol) compared to that of water (E_water = 18.33 kJ/mol) for the 2.0 wt% silicalite‐filled PEBA membrane accounts for the increase of the separation factor with feed temperature.     

Pervaporation study of water and tert‐butanol mixtures

The permeation behavior of water/tert‐butanol mixture through Sulzer Pervap2510 hydrophilic poly(vinyl alcohol) membranes was investigated and the effects of feed composition and temperature on separation efficiency of the membranes were studied. The pervaporation experiments were carried out with feed water content varying from 0 to 20 wt % according to the existing industrial needs and with the feed temperature from 60 to 100°C. Over this range, both water flux and separation factor increased with increasing water content and feed temperature. These phenomena may be attributed to (1) the strong interaction between water and the membrane, (2) the decoupling effect of the permeants and the membrane at elevated temperatures, and (3) the steric hindrance effect of branch chain alcohol. The permeability ratio (the ideal separation factor) of water to tert‐butanol across the membrane was calculated and found to follow the same relationship with increasing temperature and water content. Both flux and separation factor obtained from the Pervap2510 membrane in this study were much higher than previous reported values, possible causes for which were analyzed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 4082–4090, 2004     

交联壳聚糖膜对各种醇水体系分离特性的研究

壳聚糖（CS）膜对不同醇水混合物的分离性能与醇分子的体积相关,随醇分子体积的增加,膜的分离因子增加,而渗透通量下降。然而经戊二醛交联后的CS膜,在分离丙醇水体系时不但具有高的分离因子,还具有比乙醇水体系同的渗透通量。本文研究了在分离不同醇水体系时交联剂量对交联CS膜分离性能的影响,并就交联前后CS膜对醇水体系的分离性能发生变化的原因进行了探讨。     

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     

Performance of Nanofiltration Membranes in Ethanol

Abstract

Several nanofiltration membranes were tested for flux and rejection of selected solutes in ethanol. The membranes were initially conditioned with pure solvent containing increasing concentrations of ethanol. Flux decreased with increase in ethanol concentration and increased at higher temperatures and pressures. The type of solute had an influence on membrane rejection profiles. The DK membrane showed increasing rejection of polyethylene glycols (PEG) dissolved in ethanol from 29% at a molecular weight (MW) of 200 to 80% at MW 1000. However, the MW of sugars and lipids had little or no effect on rejection with the DK membrane; their rejection averaged 87%. In contrast, the TFC‐SR1 membrane showed higher rejections with higher MW compounds: lipid rejection increased from 19% to 71%, sugars from 35% to 85%, and lipids from 77% to 89%. The TFC‐SR2 membrane was much more open and showed the lowest rejections of all these compounds. Flux generally showed opposite trends, with the DK showing the lowest flux and the SR2 the highest.     

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     

Removal of N‐butanol from aqueous solutions by ion–exchange membranes containing organic counterions

The pervaporation of aqueous butanol solutions was investigated using thin‐film composite membranes composed of a poly(vinylidene fluoride) substrate coated with a sulfonated poly(2,6‐dimethyl‐1,4‐phenelene oxide) polymer. The polymer was ion‐exchanged with quaternary ammonium cations having aliphatic substituents of various chain lengths. The pervaporation of aqueous n‐butanol solutions using these membranes gave a permeate more concentrated in n‐butanol; therefore, they were alcohol‐selective. The separation factor increased and the permeate flux decreased as the chain lengths of the aliphatic substituents were increased. Hence, the mass‐transport properties of such membranes can be controlled or altered to yield some desired permselectivity by the introduction of a proper counterion. It was observed that the n‐butanol flux was small relative to the total flux and, therefore, the water flux dominated the total permeate flux. The degree of swelling of the membranes and its effect on membrane performance was investigated as well. As the n‐butanol content was increased, the swelling of the membranes increased greatly. High membrane swelling caused a reduction in the separation factor. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 47–58, 1999     

Characterization of 2‐(2‐methoxyethoxy)ethanol‐substituted phosphazene polymers using pervaporation,solubility parameters,and sorption studies

Two linear phosphazene polymers were synthesized with differing amounts of hydrophilic 2‐(2‐methoxyethoxy)ethanol (MEE) and hydrophobic 4‐methoxyphenol (MEOP) substituted on the backbone. These high polymers were cast into membranes and their permeability to water, methanol, ethanol, and 2‐propanol was evaluated as a function of temperature. An additional polymer with a low content of MEE was studied for water permeation and was characterized by trace flux. At higher levels of MEE on the backbone, fluxes of all solvents increased. Solubility also was found to increase with increasing MEE content for all solvents except water. Unexpectedly, water was found to be less soluble in the higher MEE polymer, although higher membrane fluxes were observed. Diffusion coefficients showed the following trend: methanol ? 2‐propanol > ethanol ? water. Finally, the affinity of solvents and polymers was discussed in terms of Hansen solubility parameters. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 939–945, 2005     

Pervaporation for the Separation of Methyl Ethyl Ketone from Binary Process Mixtures

Abstract

The separation of methyl ethyl ketone (MEK) from binary process mixtures containing water and ethanol has been examined. These studies demonstrate the capability of pervaporation membranes to effectively separate MEK from various process streams in industry. Extensive organic permeation studies were performed using silicone composite membranes to evaluate the effect of temperature, permeate-side pressure, and feed concentration on flux and selectivity. Two organophilic membranes, a high selectivity low flux membrane and a low selectivity high flux membrane, were compared. Dehydration of a MEK-water mixture was also effectively performed with a polyvinyl alcohol composite membrane. MEK was separated only slightly from an ethanol mixture using a silicone membrane.     

Swollen-Dry-Layer Model for the Pervaporation of Ethanol-Water Solution through Hydrophilic Membranes

Abstract

A swollen-dry-layer model is presented for the pervaporation of ethanol-water solution through hydrophilic polymer membranes: poly(vinyl alcohol) and carboxymethyl cellulose. Independent measurements were conducted of the sorption equilibrium, the hydraulic permeation rates through the swollen membranes, and the permeabilities of ethanol and water vapors. The hydraulic permeabilities were estimated from the mutual diffusion coefficients of solution in the swollen membrane. Sorption behavior and hydraulic permeabilities showed a dependence on feed concentration. Vapor permeabilities of water and ethanol through dry membranes differ by a factor of about 20. Comparisons between the experimental data from the pervaporation run and the results calculated from the model were made. The model offers a quantitative explanation for the dependency of selectivity and flux on feed concentration. The model explained that the flux dependency caused by a change in the swollen-dry-layer ratio, and that the selectivity is governed by vapor permeabilities through the dry layer.     

丙酮、乙醇对丁醇渗透汽化性能的影响

考察了全硅沸石silicalite-1对丁醇-水、丙酮-水、乙醇-水、丙酮-丁醇-水、乙醇-丁醇-水5种体系中各溶剂的吸附作用。采用自制的silicalite-1/硅橡胶杂化渗透汽化透醇膜,研究了温度对丙酮、丁醇、乙醇分离性能的影响以及不同分离温度下丙酮、乙醇的浓度对丁醇、水渗透汽化性能的影响,结果表明丙酮和乙醇的存在会促进丁醇的透膜性。     

Ceramic Membranes for Water Separation from Organic Solvents

Novel hydrophilic SiO_x modified alumina membranes with high separation factors and flux rates have been prepared for the separation of water from organic solvents. For the preparation of the membranes, SiO_x networks are deposited inside the γ‐Al₂O₃ layer of a commercial ultrafiltration membrane by hydrolysis of tetraethylorthosilicate in autoclaves at 250 °C. The transport resistances of the individual membrane layers for the permeation flux are described by a model. The membranes are stable towards solvents to temperatures of at least 150 °C. Pervaporation studies show that water can be separated from solvents such as acetonitrile, tetrahydrofurane, 2‐propanol, ethyl alcohol, dimethylsulfoxide, N, N‐dimethylformamide, and phenol. The separation performance of the membranes allows their use in technical separation processes, especially for the removal of water.     

Ethanol/water mixture pervaporation performance of b‐oriented silicalite‐1 membranes made by gel‐free secondary growth

b‐oriented silicalite‐1 membranes on porous silica supports were synthesized using gel‐free secondary growth. The porous silica supports were made by pressing crushed quartz fibers followed by sintering and polishing, and further modified by slip‐coating three layers of Stöber silica particles (1000, 350, and 50 nm). The b‐oriented seed layers were prepared by rubbing silicalite‐1 particles (2 μm × 0.8 μm × 3 μm along a‐, b‐, and c‐axis, respectively) after depositing a polymeric layer on the support. After silicalite‐1 seed deposition, a final coating of spherical silica particles was applied. Well‐intergrown, μm‐thick, b‐oriented membranes were obtained, which, after calcination, exhibited ethanol permselectivity in ethanol/water mixture pervaporation. At 60°C and for ～5 wt % ethanol/water mixtures, the best membrane exhibited overall pervaporation separation factor of 85 (corresponding to membrane intrinsic selectivity of 7.7) and total flux of 2.1 kg/(m²·h). This performance is comparable to the best performing MFI membranes reported in the literature. © 2015 American Institute of Chemical Engineers AIChE J, 62: 556–563, 2016     

Drastic improvement of bioethanol recovery using a pervaporation separation technique employing a silicone rubber‐coated silicalite membrane

A coupled fermentation/pervaporation process for reliable production of concentrated ethanol was studied using ethanol permselective silicalite membranes coated with two types of silicone rubber, KE‐45 and KE‐108, as a hydrophobic material. Ethanol recovery was greatly improved by using a membrane coated with KE‐45 silicone rubber. The recovered ethanol concentration in the permeate was 67% (w/w), and the amount of recovered ethanol from the broth was more than 10 times higher than that using a non‐coated membrane. Succinic acid and glycerol, by‐products created during fermentation, interfered with the pervaporation performance of the coated membrane when used to separate an ethanol/water solution. Copyright © 2003 Society of Chemical Industry     

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     

Tuning the framework polarity in MFI membranes by deboronation: Effect on mass transport

The polarity of a zeolite is an important parameter determining the transport and separation properties in zeolite packed beds and membranes. This study focuses on the systematic variation of the zeolite polarity for membrane applications by varying the amount of silanol groups within the framework of the MFI zeolite by deboronation and consecutive heat treatment from 9 to 4 silanol groups per unit cell. The decrease in the number of silanol groups after heat treatment is confirmed by diffuse reflection infrared Fourier transform (DRIFT) and ²⁹Si Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR). The permeation of pure water through the modified silicalite membranes is insensitive to the number of silanol groups, attributed to a decreased adsorption compensated by an increased diffusivity. The ethanol selectivity in water/ethanol mixtures shows an increase with decreasing amount of silanol groups. Residual boron in the zeolite may react with ethanol and decrease its adsorption capacity. A reduction in flux through the debronated MFI membranes was not observed after ethanol/water permeation.     

Poly(ether sulfone) supported hybrid poly(vinyl alcohol)–maleic acid–silicone dioxide membranes for the pervaporation separation of ethanol–water mixtures

Microporous poly(ether sulfone) (PES) supported hybrid polymer–inorganic membranes were prepared by the crosslinking of poly(vinyl alcohol) (PVA), maleic acid (MA), and SiO₂ via an aqueous sol–gel route and a solution‐casting method. The membrane performance was tested for the pervaporation separation of ethanol–water mixtures from 20 to 60 °C with a feed ethanol concentration of 96 wt %. The membrane characterization results reveal that different SiO₂ loadings affected the crystallinity and roughness of the membranes. The PVA–MA–SiO₂ membrane containing 10 wt % SiO₂ showed that SiO₂ nanoparticles were well dispersed within the polymer matrix; this resulted in significant enhancements in both the flux and selectivity. The membrane achieved a high water permeability of 1202 g·μm·m^?2 h^?1 kPa^?1 and a selectivity of 1027 for the separation of a 96 wt % ethanol‐containing aqueous solution. This enhanced membrane performance might have been due to the dense crosslinking membrane network, increased free volume, and uniform distribution of SiO₂ nanoparticles. Both the water and ethanol fluxes increased with the feed water concentration and temperature. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44839.     

Extraction of 1-butanol from aqueous solutions by pervaporation

The extraction of 1-butanol from fermentation broths by pervaporation offers potential for use in biotechnology. Various membrane materials have been screened for their suitability for this process. Polydimethylsiloxane (PDMS) membranes gave the best results in terms of flux and selectivity, with large variations depending on their nature and preparation. Selectivity was further increased by including either organophilic adorbents (cyclodextrins, zeolites), or oleyl alcohol in dense PDMS membranes. The predominance of driving force (i.e. activity gradient) on pervaporation extraction performances was shown by a comparative study on different binary aqueous solutions of alcohols. Water flux remained practically constant while the alcohol flux was linearly related to its feed concentration. The conclusions obtained with binary mixtures were consistent with those obtained with two model ternary solutions; the influence of salt on 1-butanol permeability was negligible, whereas ethanol had a strong effect.