PDMS/陶瓷复合膜用于正丁醇-水体系的渗透汽化分离

Pervaporation has attracted considerable interest owing to its potential application in recovering biobutanol from biomass acetone-butanol-ethanol (ABE) fermentation broth. In this study, butanol was recovered from its aqueous solution using a polydimethylsiloxane (PDMS)/ceramic composite pervaporation membrane. The effects of operating temperature, feed concentration, feed flow rate and operating time on the membrane pervaporation per-formance were investigated. It was found that with the increase of temperature or butanol concentration in the feed, the total flux through the membrane increased while the separation factor decreased slightly. As the feed flow rate increased, the total flux increased gradually while the separation factor changed little. At 40 C and 1% (by mass) butanol in the feed, the total flux and separation factor of the membrane reached 457.4 g•m2•h1 and 26.1, respec-tively. The membrane with high flux is suitable for recovering butanol from ABE fermentation broth.     

盐析萃取菊芋发酵液中的2,3-丁二醇(英文)

The removal of solid impurities and separation of target products from a fermentation broth is becoming more tedious with the utilization of lignocelluloses as source of substrate.2,3-Butanediol,an important chemical used widely is also a main product of sugar-based fermentation carried out by Klebsiella pneumoniae.In this study,we investigated the use of salting-out extraction(SOE) that employed a K2HPO4/ethanol system consisting of 21% ethanol and 17% K2HPO4(mass fraction) to separate 2,3-butanediol from the viscous Jerusalem artichoke-based fermentation broth.After SOE,about 98% of solid matters was removed,and the viscosity decreased from 72.5 mPa s in the original fermentation broth to 4.4 mPa s in the top phase.The partition coefficient and yield of 2,3-butanediol reached 13.4 and 99%,respectively,and 89% of soluble proteins was removed from the broth.The results showed that SOE is an efficient way for isolating 2,3-BD from a highly viscous fermentation broth by removing much of the solid matters within the broth.     

Purification of bioethanol fermentation broth using hydrophilic PVA crosslinked PVDF-GO/TiO2 membrane

The presence of impurities in the bioethanol fermentation broth should be removed to mitigate any possible ineffective refining processes as well as to enhance bioethanol production. In this study, a prefiltration process was carried out for separating fermentation yeast cells and residual substrates using a microfiltration membrane. Hydrophilic polyvinylidene fluoride-graphene oxide/titanium dioxide(PVDF-GO/TiO₂) membrane with polyvinyl alcohol(PVA) surface-coating modification was f...     

表面偏析法制备用于乙醇渗透蒸发脱水的整体PVA-PES复合膜(英文)

A facile surface segregation method was utilized to fabricate poly(vinyl alcohol)-polyethersulfone (PVA-PES) composite membranes. PVA and PES were first dissolved in dimethyl sulfoxide (DMSO), then casted on a glass plate and immersed in a coagulation bath. During the phase inversion process in coagulation bath, PVA spontaneously segregated to the polymer solution/coagulation bath interface. The enriched PVA on the surface was further crosslinked by glutaraldehyde. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and energy dispersive spectrometer (EDS) confirmed the integral and asymmetric membrane structure with a dense PVA-enriched surface and a porous PES-enriched support, as well as the surface enrichment of PVA. The coverage fraction of the membrane surface by PVA reached up to 86.8% when the PVA content in the membrane recipe was 16.7% (by mass). The water contact angle decreased with the increase of PVA content. The effect of co-agulation bath type on membrane structure was analyzed. The membrane pervaporation performance was evaluated by varying the PVA content, the annealing temperature, feed concentration and operation temperature. The mem-brane exhibited a fairly good ethanol dehydration capacity and long-term operational stability.     

REMOVAL OF ETHANOL FROM CONTINUOUS FERMENTATION BROTH BY PERVAPORATION

In the process of continuous fermentation with pervaporation(PVAP),ethanol can be removed and concentrated simultaneously from the broth. In this work, two kinds of modified PDMS (polydimethylsiloxane) membranes used for PVAP have been tested, the characteristics and kinetics of the process were investigated, and a set of kinetic equations has been derived along with the experimental results. The results show some major advantages of this process over that with ultrafiltration, more concentrated ethanol can be obtained from the broth directly; no appreciable fouling on the membrane and the process can be controlled steadily.     

Purification and concentration of gluconic acid from an integrated fermentation and membrane process using response surface optimized conditions

A response surface method was used to optimize the purification and concentration of gluconic acid from fermentation broth using an integrated membrane system. Gluconobacter oxydans was used for the bioconversion of the glucose in sugarcane juice to gluconic acid (concentration 45 g·L^-1) with a yield of 0.9 g·g^-1. The optimum operating conditions, such as trans-membrane pressure (TMP), pH, cross-flow rate (CFR) and initial gluconic acid concentration, were determined using response surface methodology. Five different types of polyamide nanofiltration membranes were screened and the best performing one was then used for downstream purification of gluconic acid in a flat sheet cross-flow membrane module. Under the optimum conditions (TMP=12 bar and CFR=400 L·h^-1), this membrane retained more than 85% of the unconverted glucose from the fermentation broth and had a gluconic acid permeation rate of 88% with a flux of 161 L·m^-2·h^-1. Using response surface methods to optimize this green nanofiltration process is an effective way of controlling the production of gluconic acid so that an efficient separation with high flux is obtained.     

基于多场协同理论的渗透蒸发传质模型

Toprovide a theoretical basis for optimizing the pervaporation procedure, a mass transfer model for pervaporation for binary mixtures was developed basedon the multi-fields synergy theory. This model used the mechanism of sorption-diffusion-desorption and introduced a diffusion coefficient, which was dependent on the feed concentration and temperature. Regarding the strong coupling effect in the mass transfer, the concentration distribution in membrane was predicted using the Flory-Huggins thermodynamic theory. The batch experiments and other experiments with constant composition-were conducted-using a modified chitosan pervaporatioffmembrane to separate tert-butyl alcohol （TBA）-water mixtures. The parameters of the mass transfer model were obtained from the flux of the experiments with a constant composition and the activity coefficients available through phase equilibrium equation, using the Willson equation in the feed side and the Flory-Huggins thermodynamic theory within the membrane The simulation results of the experiments .are in good agreement with the results, of the experiments.     

硅橡胶复合膜用于渗透蒸发的膜传质动力学(Ⅱ)膜内的扩散传质

The pervaporation of organics from dilute aqueous solution through a novel plate composite silicone rubber membrane was investigated. The measured and derived data indicated that the composite membrane possessed very high permeation flux and stable selectivity for dilute organic aqueous solution. Based upon the well- known resistance-in- series model, diffusive mass transfer behavior in membrane was investigated by calculation from the measured data with different skin layer thickness of membranes. The experimental results showed that the diffusive mass transfer coefficient conformed to Arrhenius correlation with temperature and was independent of the flow status. The diffusivities of the given alcohols in membrane had an order of magnitude 10 m-10·s-1 at a wider range of temperature, which is similar to those reported in literatures.     

硅橡胶复合膜渗透汽化分离硫/汽油混合物

Worldwide environment has resulted in a limit on the sulfur content of gasoline. It is urgent to investigate the desulfurization of gasoline. The polydimethylsiloxane (PDMS)/polyetherimide (PEI) composite membranes were prepared by casting a PDMS solution onto porous PEI substrates and characterized by scanning electron microscope (SEM). The membranes were used for sulfur removal from gasoline by pervaporation. The effects of feed temperature, sulfur content in the feed and PDMS layer thickness on membrane performance were investigated, and an activation energy of permeation was obtained. Experimental results indicated that higher feed temperature yielded higher total flux and lower sulfur enrichment factor. The total flux varied little with the increase of sulfur content in the feed, but the sulfur enrichment factor first increased with the amount of thiophene added into the gasoline, and then the variation was little. The increase of PDMS layer thickness resulted in a smaller flux but a larger sulfur enrichment factor. The result indicates that the PDMS/PEI composite membranes are promising for desulfurization by pervaporation.     

丁酸在含氯化钙双水相体系中的有效分离(英文)

One of the bottlenecks for bioproduction of butyric acid as bulk chemical is the difficulty in separating butyric acid from the fermentation broth,compared with the petroleum-based chemical synthesis method.In the present work,a novel separation methodology was developed based on an aqueous two-phase system with inor-ganic salts.Calcium chloride was screened out for effective separation of butyric acid from butyric acid-water-salt systems.Within appropriate concentration range of butyric acid and salt,butyric acid was enriched in the upper phase and most of calcium ions remained in the lower phase.This"salting out"effect is very efficient to separate butyric acid from the simulated butyrate fermentation broth,which consists of butyric acid and acetic acid with concentration ratio of 4︰1,so that the final ratio of butyric acid/acetic acid in the upper phase is improved to 9.87. The aqueous two-phase system was used to separate butyric acid from the actual fermentation broth with satisfac-tory result.     

乙醇发酵与渗透汽化在硅橡胶膜生物反应器中的耦合强化

用硅橡胶膜生物反应器(SMBR)实验研究了发酵-渗透汽化的耦合性能。发酵微生物采用酿酒活性干酵母,所用的碳源为工业级葡萄糖。间歇发酵过程由于产物抑制作用在乙醇浓度达到90g稬-1时就趋于停滞,而经耦合渗透汽化膜分离后,发酵罐内的乙醇浓度迅速降低并维持在40g稬-1,且发酵在此浓度下可以连续稳定地进行。 在SMBR运行达到稳态后,乙醇的体积产率为1.5gL-1h-1。SMBR中所用的聚二甲基硅氧烷(PDMS)复合膜由实验室自行制备,它能稳定分离含有酵母细胞的发酵液。当发酵液中乙醇浓度为92.7~49.5g稬-1时,PDMS复合膜的总通量为1490~1164g穖-2h-1,分离因子为6.9~7.8,与分离相同进料浓度的清洁模型溶液相比分别平均高出31%和14%。乙醇发酵和渗透汽化在硅橡胶膜生物反应器中能够相互耦合并得到强化。     

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     

硅橡胶膜生物反应器中乙醇发酵与渗透汽化的耦合

用硅橡胶膜生物反应器(SMBR)实验研究连续发酵-渗透汽化的耦合性能。发酵微生物采用酿酒干酵母,所用碳源为工业级葡萄糖。发酵过程由于产物抑制作用,在乙醇质量浓度达到73 g/L时趋于停滞,而耦合渗透汽化膜后,发酵罐内的乙醇质量浓度降低并维持在40 g/L,使发酵可以连续稳定地进行。在SMBR运行达到稳态后,乙醇的体积产率为4.02 g/(L.h)。发酵液中乙醇质量浓度维持在20~63 g/L,聚二甲基硅氧烷(PDMS)膜的总渗透通量为1 220~800 g/(m2.h),分离因子为5~9.2。与传统发酵和分离相同进料质量分数的乙醇溶液相比,乙醇发酵和渗透汽化在硅橡胶膜生物反应器中能相互耦合并得到强化。与较小规模耦合系统(发酵体积1 L和2 L)比较,性能稳定良好。     

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     

Mathematical modeling of fed-batch butanol fermentation with simultaneous pervaporation

A mathematical model was developed to describe a fed-batch acetone-butanol-ethanol (ABE) fermentation with simultaneous pervaporation. The model predicted satisfactorily batch or fed-batch fermentation with or without pervaporalion by introducing a parameter reflecting cell activity loss during fed-batch fermentation with pervaporation. The model also predicted the effect of membrane area, membrane thickness, and sweep air flow rate on glucose consumption rate and residual butanol concentration in the fermentation broth. Glucose consumption rate increased by 30% by either doubling the membrane area or decreasing membrane thickness by half.     

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     

硅橡胶膜生物反应器在苹果原汁发酵过程中的膜分离性能

利用硅橡胶膜生物反应器进行了苹果原汁发酵-渗透汽化分离实验,研究了苹果发酵液中的主要风味成分及其渗透汽化分离性能。发酵液中的主要芳香成分与传统苹果酒接近,但酯类物质的含量较低。硅橡胶膜对发酵液中的挥发性轻组分表现出良好的选择透过性,高级醇、酯类和醛类的分离率分别达到90%、76%和67%;而乳酸乙酯、β-苯乙醇和乙酸被不同程度地截留。非挥发性有机酸被截留在膜上游发酵液中。草酸、乙酸、柠檬酸和琥珀酸得到不同程度地浓缩;苹果酸、酒石酸和乳酸在分离过程中可能被微生物细胞所消耗,其含量有所降低。硅橡胶复合膜在选择性地分离挥发性轻组分的同时有效地保护了发酵液中的有机酸等非挥发性营养成分,研究结果进一步证明了采用硅橡胶膜生物反应器同时生产苹果白兰地和果汁发酵饮料的可行性。     

发酵-渗透汽化连续耦合生产ABE的动力学研究

采用PDMS膜生物反应器和丙酮丁醇梭菌进行了生产ABE的封闭循环连续发酵实验,研究了发酵和渗透汽化分离连续耦合条件下的发酵动力学行为。发酵-分离连续耦合实验运行持续时间长达 192 h。运行过程中,细胞浓度维持在 0.84~4.00 g/L,发酵液中ABE的总浓度为5.14~17.54 g/L,葡萄糖浓度大约为16.08~35.15 g/L,总体积产率为0.36 g/(L?h)。实验结果表明,膜生物反应器系统运行稳定,发酵-渗透汽化分离连续耦合生产ABE的操作模式具有可行性和优越性。     

发酵-渗透汽化连续耦合合成ABE的动力学

采用PDMS膜生物反应器和丙酮丁醇梭菌进行了生产ABE的封闭循环连续发酵实验,研究了发酵和渗透汽化分离连续耦合条件下的发酵动力学行为。发酵-分离连续耦合实验运行持续时间长达192 h。运行过程中,细胞质量浓度维持在0.84～4.00 g/L,发酵液中ABE的总质量浓度为5.14～17.54 g/L,葡萄糖质量浓度大约为16.08～35.15 g/L,总体积产率为0.36 g/(L.h)。结果表明,膜生物反应器系统运行稳定,发酵-渗透汽化分离连续耦合生产ABE的操作模式具有可行性和优越性。