VOC removal from contaminated groundwater through membrane pervaporation. (Ⅱ): 1,1,1-trichloroethane-SDS surfactant solution system

The conventional “pump-and-treat' technology for subsurface remediation of groundwater contaminated with volatile organic compounds(VOCs) such as 1,1,1-trichloroethane(TCA), a common chlorinated organic solvent, has limitation of prohibitively long treatment time due to extremely low water solubility of the VOCs. Surfactant-based soil remediation has emerged as the effective technology that substantially reduces the treatment time. In order to make the whole process economical, the surfactant used in soil washing has to be recovered and reused. This study examined the recovery of anionic surfactant, sodium dodecyl sulfate(SDS), from soil remediation fluids containing TCA, using a bench-scale membrane pervaporation unit. The effects of high TCA concentration, surfactant dosage, and flow rate on permeation flux and selectivity(α value) of the process were evaluated. In general, higher surfactant concentration yielded lower TCA flux and constant water flux, resulting in declining α values; higher flow rate of TCA feed stream results in higher VOC flux and selectivity, an indication of the effect of concentration polarization; higher TCA feed concentration produces higher TCA permeation across the membrane, however, the selectivity was virtually unchanged unless the total TCA concentration exceeded 2000 ppm.

VOC removal from contaminated groundwater through membrane pervaporation. (Ⅰ): Water-1,1,1-trichloroethane system

trichloroethane(TCA), a common chlorinated organic solvent and volatile organic compound(VOC), was removed from contaminated groundwater by using a bench-scale membrane pervaporation unit. The effects of TCA concentration, temperature, and flow rate on permeation flux and selectivity(α value) of the process were evaluated. In general, higher temperature leads to higher VOC flux but lower selectivity; higher flow rate of TCA feed stream results in higher VOC flux and selectivity, an indication of the effect of concentration polarization; higher TCA feed concentration produces higher TCA permeation, however, the selectivity was virtually unchanged.

Hyperbranched polymer hollow-fiber-composite membranes for pervaporation separation of aromatic/aliphatic hydrocarbon mixtures

The separation of aromatic/aliphatic hydrocarbon mixtures is crucial in the petrochemical industry.Pervaporation is regarded as a promising approach for the separation of aromatic compounds from alkanes. Developing membrane materials with efficient separation performance is still the main task since the membrane should provide chemical stability, high permeation flux, and selectivity. In this study, the hyperbranched polymer(HBP) was deposited on the outer surface of a polyvinylidene fluoride(PVDF)hollow-fiber ultrafiltration membrane by a facile dip-coating method. The dip-coating rate, HBP concentration, and thermal cross-linking temperature were regulated to optimize the membrane structure.The obtained HBP/PVDF hollow-fiber-composite membrane had a good separation performance for aromatic/aliphatic hydrocarbon mixtures. For the 50%/50%(mass) toluene/n-heptane mixture, the permeation flux of optimized composite membranes could reach 1766 g·m^(-2)·h^(-1), with a separation factor of 4.1 at 60℃. Therefore, the HBP/PVDF hollow-fiber-composite membrane has great application prospects in the pervaporation separation of aromatic/aliphatic hydrocarbon mixtures.

Pervaporation performance and characterization of hydrophilic ZSM-5 zeolite membranes for high inorganic acid and inorganic salts

The hydrophilic ZSM-5 zeolite membranes are applied to separate the inorganic acid solutions and inorganic acid/inorganic salt mixtures by pervaporation,and the membrane presents good stability,dehydration,and desalination performance.Influences of inorganic acid type(H_(2)SO_(4),H_(3)PO_(4),HNO_(3),and HCl),H_(2)SO_(4)concentration(1-6 mol·L^(-1)),test temperature(60-90℃)and inorganic acid/inorganic salt type(2 mol·L^(-1)H_(2)SO_(4)and sulfate,2 mol·L^(-1)H3PO4 and phosphate)on the pervaporation performance are investigated in this work.Either for concentrating 3%(mass)H_(2)SO_(4)solution or consecutive dehydrating 20%(mass)H_(2)SO_(4)solution,the hydrophilic ZSM-5 zeolite membrane has a good dehydration performance and stability.Even though the H_(2)SO_(4)concentration and test temperature are increased to 6 M and 90℃,only H_(2)O molecules could pass through the membrane and pH value of the permeation is kept neutral.Besides,the membrane has good dehydration and desalination performance for H_(2)SO_(4)/sulfates and H_(3)PO_(4)/phosphate mixtures,and the rejection of natrium salt,molysite,and magnesium is almost 100%.

Pervaporation of Toluene--n-Heptane Mixtures with Hybrid PVC Membranes Containing Inorganic Particles

The design and preparation of hybrid mixed matrix membranes based on PVC （polyvinylchloride） were studied for the separation of toluene--n-heptane mixtures by pervaporation. PVC was chosen as the starting organic matrix because it is an inexpensive polymer, possessing a very high selectivity for aromatics. This property is due to the polar macromolecular structure that can induce a specific transfer of aromatic species compared with aliphatic species. To improve the performance of the PVC glassy structure, lhe incorporation of several inorganic micro- and nanopartieles in the polymer matrix was performed to prepare mixed matrix membranes. The results reported were obtained using several types of clay, i.e., Maghnite, Wyoming, Kaolin and Nanocor, with the goal of improving membrane permeability due to the hybrid network. Our results show that the transport properties of the modified PVC network can be drastically modified by the type and amount of particles used,

Mass transfer model,preparation and applications of zeolite membranes for pervaporation dehydration:A review

Pervaporation(including vapor permeation) is a kind of new membrane separation technology, possessing the advantages of high efficiency, energy saving and convenient operation. It has promising application in the separation and purification of organic solvents. Dehydration is an important step in the production and recovery of organic solvents. Zeolite membranes have attracted wide attention for pervaporation dehydration due to their high separation performance and good thermal/chemical stability. So far, zeolite membranes have been preliminarily industrialized for dehydration of organic solvents. This paper reviews the recent development of zeolite membranes for pervaporation dehydration, including mass transfer models, preparation and applications of zeolite membranes. The review also discusses the current industrial applications of zeolite membranes and their future development in pervaporation.

Pervaporation Separation of Butanol-Water Mixtures Using Polydimethylsiloxane/Ceramic Composite Membrane

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 performance 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, respectively. The membrane with high flux is suitable for recovering butanol from ABE fermentation broth.

Manipulation of confined structure in alcohol-permselective pervaporation membranes

Alcohol-permselectivity pervaporation has been arousing increasingly more attention in bioalcohol production due to the advantages of environmental friendliness, low energy consumption and easy coupling with fermentation process. With the intrinsic feature of larger molecules preferentially permeating and the consequent inferiority in selective diffusion, the development of alcohol-permselective membrane is relatively retarded compared with water-permselective membrane. This review presents the prevalent membrane materials utilized for alcohol-permselective pervaporation and emphatically expatiates the representative and important developments in the past five years from the aspect of tuning confined structure in membranes. In particular, the diverse structure tuning methods are described with the classifications of physical structure and chemical structure. The corresponding structure-performance relationships in alcohol-permselective pervaporation membranes are also analyzed to identify the objective of structure optimization. Furthermore, the tentative perspective on the possible future directions of alcohol-permselective pervaporation membrane is briefly presented.

Pretreatment of Isopropanol Solution from Pharmaceutical Industry and Pervaporation Dehydration by NaA Zeolite Membranes

NaA zeolite membranes with 80 cm in length and 12.8 mm in outer diameter were prepared by our research group cooperating with Nanjing Jiusi Hi-Tech Co., China. The influence of dissolved inorganic salts and pH value in the feed of isopropanol （IPA） solution on NaA zeolite membranes was investigated. It was found that both factors exhibited strong influence on the stability of NaA zeolite membranes. A set of pretreatment steps such as pH adjustment and distillation of the IPA solution were proposed to improve stability for pervaporation dehydration. An industrial-scale pervaporation facility with 52 m2 membrane area was built to dehydrate IPA solution from industrial cephalosporin production. The facility was continuously operated at 368-378 K to dehydrate IPA solution from water mass content of 15%-20% to less than 2% with a feed flow rate of 400-500 L·h^-1 and an average water flux of 1-1.5 kg·m^-2·h-1. The successful application of this facility suggested a promising application of NaA zeolite mem-brane for IPA recovery from pharmaceutical production.

PERVAPORATION OF ETHANOL/WATER MIXTURES WITH HIGH FLUX BY ZEOLITE-FILLED PDMS/PVDF COMPOSITE MEMBRANES

Thin-film zeolite-filled silicone/PVDF composite membranes were fabricated by incorporating zeolite particles into PDMS(poly(dimethylsiloxane)) membranes.The morphology of zeolite particles and zeolite filled silicone composite membranes were characterized by SEM.The zeolite-filled PDMS/PVDF composite membranes were applied for the pervaporation of ethanol/water mixtures and showed higher flux compared with that reported in literatures.The effect of zeolite loading and Si/Al ratio of zeolite particles on pe...

PERVAPORATION PROPERTIES OF PDMS MEMBRANES CURED WITH DIFFERENT CROSS-LINKING REAGENTS FOR ETHANOL CONCENTRATION FROM AQUEOUS SOLUTIONS

Ethanol perm-selective PDMS/PVDF composite membranes were prepared by curing polydimethylsiloxane (PDMS) with various cross-linking reagents,such as tetraethoxylsilane(TEOS),γ-aminopropyltriethoxylsilane(APTEOS), phenyltrimethoxylsilane(PTMOS) and octyltrimethoxylsilane(OTMOS) as well.The cross-linking density and surface properties of the PDMS active layer were adjusted by varying cross-linking reagents.The pervaporation performance of PDMS membranes cured with different cross-linking reagents was investig...

Polymer/Ceramic Composite Membranes and Their Application in Pervaporation Process

Pervaporation(PV),as an environmental friendly and energy-saving separation technology,has been received increasing attention in recent years.This article reviews the preparation and application of macroporous ceramic-supported polymer composite pervaporation membranes.The separation materials of polymer/ceramic composite membranes presented here include hydrophobic polydimethylsiloxane(PDMS) and hydrophilic poly(vinyl alcohol)(PVA),chitosan(CS) and polyelectrolytes.The effects of ceramic support treatment,polymer solution properties,interfacial adhesion and incorporating or blending modification on the membrane structure and PV performance are discussed.Two in-situ characterization methods developed for polymer/ceramic composite membranes are also covered in the discussion.The applications of these composite membranes in pervaporation process are summarized as well,which contain the bio-fuels recovery,gasoline desulfuration and PV coupled proc-ess using PDMS/ceramic composite membrane,and dehydration of alcohols and esters using ceramic-supported PVA or PVA-CS composite membrane.Finally,a brief conclusion remark on polymer/ceramic composite mem-branes is given and possible future research is outlined.

Fabrication of high-performance PVA/PAN composite pervaporation membranes crosslinked by PMDA for wastewater desalination

The pyromellitic dianhydride（PMDA） crosslinked poly（vinyl alcohol）（PVA） was coated on top of the PAN ultrafiltration membrane to form a PVA/PAN composite PV membranes for wastewater desalination. The composite membranes have high application value in industrial wastewater treatment. By varying the membrane fabrication parameters including the weight percent（wt%） of the PMDA, the crosslink temperature and duration, membrane with the best desalination performance was obtained. The composite membrane with a 2-lm-thick PVA selective layer containing 20 wt% of PMDA and being crosslinked at 100 °C for 2 h showed the highest Na Cl rejection of 99.98% with a water flux of 32.26 L/（m^2 h）at 70 °C using the 35,000 ppm Na Cl aqueous solution as feed. FTIR spectroscopy, wide-angle X-ray diffraction, thermogravimetric analysis and scanning electron microscope have been used to characterize the structures and properties of both the crosslinked PVA dense films and PVA/PAN composite membranes. The effects of the concentrations of PMDA,the crosslinking time and temperature to the membrane water contact angle, swelling degree, salt rejection and water flux were systematically studied.

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.

Modeling investigation of geometric size effect on pervaporation dehydration through scaled-up hollow fiber NaA zeolite membranes

A mass transfer model in consideration of multi-layer resistances through NaA zeolite membrane and lumen pressure drop in the permeate side was developed to describe pervaporation dehydration through scaled-up hollow fiber supported NaA zeolite membrane. It was found that the transfer resistance in the lumen of the permeate side is strongly related with geometric size of hollow fiber zeolite membrane, which could not he neglected. The effect of geometric size on pervaporation dehydration could be more significant under higher vacuum pressure in the permeate side. The transfer resistance in the lumen increases with the hollow fiber length but decreases with lumen diameter. The geometric structure could be optimized in terms of the ratio of lumen diameter to membrane length. A critical value of d1/L （Rc） to achieve high permeation flux was empirically correlated with extraction pressure in the permeate side. Typically, for a hollow fiber supported NaA zeolite membrane with length of 0.40 m, the lumen diameter should be larger than 2.0 mm under the extraction pressure of 1500 Pa.

The potential of pervaporation for biofuel recovery from fermentation:An energy consumption point of view

Recovering alcohols from dilute fermentation broth is an emergent task in bio-fuel production process. Since they are primary planned for fuels, energy required to separate these alcohols should be considered in evaluating the potential of a separation technology. A membrane-based process, pervaporation, is of special interest because of its environmental friendliness and easy integrating character. This review probes into the fundamentals of pervaporation especially in terms of the heat required for evaporation. Meanwhile, the separation data of the most representative alcohol-selective pervaporation membranes reported in the literatures are collected and compared with the vapor–liquid equilibrium curve, which represents the distillation selectivity. They include:inorganic membranes, silicon rubber based membranes, Mixed Matrix Membranes and some other special materials. By doing so, the status of alcohol recovery via pervaporation would be more clear for researchers.For ethanol recovery, it is selectivity rather than flux that is in urgent need of solution. While for butanol recovery,membranes with satisfactory selectivity have been developed, increasing the separation capacity would be more pressing.

Hybrid Process of Reactive Distillation and Pervaporation for the Production of Tert-amyl Ethyl Ether

In this study, a reactive distillation column in which chemical reaction and separation occur simultaneously is applied for the synthesis of tert-amyl ethyl ether （TAEE） from ethanol （EtOH） and tert-amyl alcohol （TAA）. Pervaporation, an efficient membrane separation technique, is integrated with the reactive distillation for enhancing the efficiency of TAEE production. A user-defined Fortran subroutine of a pervaporation unit is developed, allowing the design and simulation of the hybrid process of reactive distillation and pervaporation in Aspen Plus simulator. The performance of such a hybrid process is analyzed and the results indicate that the integration of the reactive distillation with the pervaporation increases the conversion of TAA and the purity of TAEE product, compared with the conventional reactive distillation.

PDMS/ZIF-8 coating polymeric hollow fiber substrate for alcohol permselective pervaporation membranes

In order to develop high performance composite membranes for alcohol permselective pervaporation(PV),poly(dimethylsiloxane)/ZIF-8(PDMS/ZIF-8)coated polymeric hollow fiber membranes were studied in this research.First,PDMS was used for the active layer,and Torlon?,PVDF,Ultem?,and Matrimid?with different porosity were used as support layer for fabrication of hollow fiber composite membranes.The performance of the membranes varied with different hollow fiber substrates was investigated.Pure gas permeance of the hollow fiber was tested to investigate the pore size of all fibers.The effect of support layer on the mass transfer in hydrophobic PV composite membrane was investigated.The results show that proper porosity and pore diameter of the support are demanded to minimize the Knudsen effect.Based on the result,ZIF-8 was introduced to prepare more selective separation layer,in order to improve the PV performance.The PDMS/ZIF-8/Torlon?membrane had a separation factor of 8.9 and a total flux of 847 g·m-2·h-1.This hollow fiber PDMS/ZIF-8/Torlon?composite membrane has a great potential in the industrial application.

PERVAPORATION SEPARATION FOR TOLUENE/n-HEPTANE MIXTURE BY POLYIMIDE MEMBRANES CONTAINING FLUORINE

Five kinds of polyimides were synthesized using five dianhydrides (including 2,2-bis[4-(3,4-dicarboxyphenoxy)- phenyl] propane dianhydride (BPADA),3,3 ,4,4 -diphenylsulfone-tetracarboxylic dianhydride (DSDA),4,4 - (hexafluoroisopropylidene)-diphthalic anhydride (6FDA),1,4-bis(3,4-dicarboxyphenoxy) benzene dianhydride (HQDPA), and 4,4 -oxydiphthlic dianhydride (ODPA)) and 2,2-bis[4-(4-aminophenoxy)phenyl] hexafluoropropane (BDAF) via the two- step method that included polyaddition to form the polyamic acid a...

Breakthroughs on tailoring membrane materials for ethanol recovery by pervaporation

Bioethanol, as a clean and renewable fuel, has gained increasing attention due to its major environmental benefits. Pervaporation(PV) is a promising and competitive technique for the recovery of ethanol from bioethanol fermentation systems due to the advantages of environmental friendliness, low energy consumption and easy coupling with fermentation process. The main challenge for the industrial application of ethanol perm-selective membranes is to break the trade-off effect between permeability and selectivity. As membrane is the heart of the pervaporation separation process, this article attempts to provide a comprehensive survey on the breakthroughs of ethanol perm-selective PV membranes from the perspectives of tailoring membrane materials to enhance PV separation performance. The research and development of polymeric and organic/inorganic hybrid membranes are reviewed to explore the fundamental structure-property-performance relationships. It is found that mixed matrix membranes with welldesigned membrane structures offer the hope of better control overphysi-/chemical microenvironment and cavity/pore size as well as size distribution, which may provide both high permeability and membrane selectivity to break the trade-off effect. The tentative perspective on the possible future directions of ethanol perm-selective membranes is also briefly discussed, which may provide some insights in developing a new generation of high-performance PV membranes for ethanol recovery.