Gas injection membrane extraction for fast on-line analysis using GC detection

Membrane extraction has been interfaced with gas chromatography and mass spectroscopy for the analysis of volatile organics in water. The vacuum in a mass spectrometer provides fast mass transport. The time required to complete permeation in a GC interface can be fairly long, because the positive pressure of the carrier gas on the permeate side slows down the analyte permeation. The aqueous boundary layer formed on the membrane is considered to be the biggest contributor to the resistance to mass transfer. Another issue is the dispersion of analyte in the aqueous stream, which broadens the input pulse to the membrane. The overall effect of these two factors is to increase the analysis time. Gas injection of aqueous samples is presented in this paper to address these issues. Gas injection reduces the formation of boundary layer, and increases the overall diffusion coefficient seven times. Axial mixing of the sample with a gaseous eluent is minimal, and this eliminates the tailing in permeation profiles. The overall membrane extraction is found to be significantly faster when a gas is used to inject an aqueous sample. This method is also simpler in terms of instrumentation and operational procedures.     

膜蒸馏海水淡化用疏水性钇稳定氧化锆中空纤维膜的制备与表征

采用相转化/高温烧结技术方法制备了多孔钇稳定氧化锆(YSZ)中空纤维膜, 中空纤维膜的外径1.92 mm, 壁厚为0.21 mm。SEM分析表明: 纤维膜为典型的三明治结构, 靠近膜内外表面为指状孔, 中间区域为海绵状层。采用阿基米德法测得其孔隙率为54%。用泡点法测得其平均孔径为0.56 μm。通过表面接枝氟硅烷将其亲水性的表面改变为疏水性。真空式膜蒸馏实验表明YSZ中空纤维膜具有优异的盐水淡化性能。当膜的外侧与温度为80℃、浓度为4wt%的循环盐水接触, 膜的内侧用真空泵抽至4×10³ Pa时, 膜的水渗透通量高达48.3 L/(m²•h), 脱盐率大于99.7%。     

Simultaneous removal of nickel and cobalt from aqueous stream by cross flow micellar enhanced ultrafiltration

Nickel and cobalt were simultaneously removed from aqueous feed using cross flow micellar enhanced ultrafiltration. Twenty kiloDalton polysulfone membrane was used and the rejection more than 99% was obtained. The effect of operating variables like inlet flow rate, inlet pressure, feed metal ions concentration, surfactant to metal ion (S/M) ratio and pH on the rejection of metal ions was investigated. Gel layer formation and concentration polarization was insignificant under the present experimental condition. Presence of salt in the aqueous feed results in drop in rejection from 99% to 88%. The distribution coefficient of solutes in the micellar phase and aqueous phase was estimated from ultrafiltration data. The loading of micelles was also estimated for both the nickel and cobalt ions which confirmed the reproducibility of the micellar enhanced ultrafiltration (MEUF) experiments.     

超声波-减压膜蒸馏组合技术处理甲基橙溶液的研究

将超声波与减压膜蒸馏技术相结合,采用聚丙烯(PP)中空纤维膜,研究了超声波促进作用下减压膜蒸馏法处理高浓度甲基橙溶液的分离性能.实验结果表明,超声波有利于减轻减压膜蒸馏过程的膜污染,提高分离性能;进料甲基橙溶液浓度600 mg/L时,超声波提高减压膜蒸馏过程的膜通量达44.87%;同时,超声波-减压膜蒸馏组合技术较减压膜蒸馏过程有更大的COD去除率.     

膜蒸馏海水淡化过程研究:三种膜蒸馏过程的比较

采用聚偏氟乙烯(PVDF)中空纤维疏水微孔膜,以质量分数3.5%NaCl水溶液为模拟海水测试液,进行膜蒸馏脱盐实验.比较了真空(VMD)、气扫式(SGMD)和直接接触膜蒸馏(DCMD)过程的脱盐性能,考察了料液温度、流速、浓度以及冷侧冷凝条件等操作条件对过程性能的影响.结果表明:VMD过程的产水通量最高,达到21.8 L/(m2·h);DCMD次之,SGMD最小.三种MD过程的渗透通量均随料液温度的升高而增大,随料液浓度的增加而降低;SG-MD和VMD过程通量分别随冷侧气体流速和真空度增加而提高,而DCMD过程通量则几乎不随冷却水流速变化而改变.SGMD、DCMD和VMD过程的脱盐率分别为99.97%、99.98%和99.99%,几乎不随操作条件而改变.     

聚全氟乙丙烯中空纤维膜制备及其膜蒸馏过程*

以聚全氟乙丙烯(FEP)为成膜聚合物, 采用熔融纺丝-拉伸法制备FEP中空纤维膜, 研究了后拉伸倍数对FEP中空纤维膜结构与性能的影响。结果表明, 初生FEP中空纤维膜结构较为致密, 拉伸后出现微孔结构。随着拉伸倍数的提高膜的孔隙率和氮气通量明显增大, 而液体渗透压(LEP)有所降低。将所得FEP中空纤维膜用于减压膜蒸馏(VMD)研究, 并将其与常规熔融纺丝-拉伸法聚丙烯(PP)中空纤维膜比较。结果表明, 所得FEP中空纤维膜的疏水性能、液体渗透压力和力学强度均优于PP中空纤维膜。较强的疏水性能使其稳定运行而不被液体渗透, 脱盐率稳定在99%以上。同时, FEP中空纤维膜具有较大的内径(0.74 mm), 在保证较高脱盐率前提下可采用内压式减压膜蒸馏, 且真空膜蒸馏通量随着进料温度的升高显著增高。     

PVDF疏水中空纤维膜的膜蒸馏含盐废水处理性能研究

利用新型高通量聚偏氟乙烯(PVDF)中空纤维疏水膜,对石化企业废水经反渗透(RO)处理的浓排水进行减压膜蒸馏(VMD)处理实验.研究了RO浓排水流速、温度和冷侧真空度对VMD过程中PVDF膜性能的影响,考察了PVDF膜在VMD法RO浓水浓缩过程中的性能变化.结果表明,原液流速对膜性能无明显影响;原液温度或冷侧真空度提高都会使膜的产水通量明显上升,而产水电导保持稳定.在冷侧真空度为-0.095MPa、原液温度70℃、流速0.66m/s的条件下,经15.2h实验,将RO浓排水浓缩20倍,膜的产水通量从25.8L/(m2*h)降低至11.8L/(m2*h),产水电导低于4霺/cm,脱盐率高于99.99%,产水CODCr值约30mg/L.经过5次浓缩实验后,PVDF膜的通量和产水电导均保持稳定.     

中空纤维膜双向流(TWF)分离技术的研究

利用聚偏氟乙烯(PVDF)中空纤维膜,对比考察了双向流膜过滤工艺与普通膜过滤工艺.结果表明,中空纤维膜上下入口的周期性切换使得双向流工艺在过滤的同时进行冲刷清洗,大大提高了过滤效率以及膜的耐污染性.清洗实验同样表明,与普通过滤工艺相比,双向流工艺中膜污染后更易清洗,膜通量基本恢复.若干工程实例表明,双向流技术已得到广泛的应用并将对膜工艺优化设计产生重要的影响.     

膜蒸馏淡化处理油田高含盐废水的实验研究

采用减压膜蒸馏技术处理油田高含盐废水，研究了真空度、废水温度、流量以及废水含盐量对膜通量与截留率的影响。实验结果表明：随着膜下游真空度增加，膜通量先缓慢增大，当真空度超过某一临界值后，膜通量急剧增加；废水温度增加，膜通量增大，且真空度越高，膜通量随温度变化的曲线越陡；提高废水流量可增大膜通量；随着废水含盐量增加，膜通量减小，当废水含盐量大于220g／L时，馏出液电导率明显增加，但各次实验的截留率仍然接近100％，表明实验用聚丙烯中空纤维膜具有很好的疏水性。     

中空纤维封闭液膜用于乳酸分离

利用中空纤维封闭液膜技术对乳酸的分离进行了研究，采用三烷基胺（７３０１）＋正辛醇＋煤油混合溶剂为萃取剂，以水作为反萃剂，在聚砜中空纤维膜器中进行实验。研究结果表明，在中空纤维封闭液膜技术分离乳酸中，总传质阻力与料液相流速和反萃相流速的１／３次方均呈反比关系。实验研究了鼓泡技术对强化质的影响，在中空纤维膜器壳程中鼓入空气有利于提高传质系数。实验中还讨论了反萃液温度对过程的影响，传质阻力随着操作温度的     

The XT-tube extractor: a hollow fiber-based supported liquid membrane extractor for bioanalytical sample preparation

A new supported liquid membrane extractor for bioanalytical sample preparation is presented. The extractor consists of a polypropylene hollow fiber mounted inside a PTFE tube by means of a cross-connector and a tee-connector. All parts are commercially available, inexpensive, and easily assembled. An organic solvent in the pores of the fiber forms a liquid membrane that separates the sample, which is pumped along the outside of the fiber, from the acceptor phase, which is pumped inside. The length of the hollow fiber may easily be varied to meet different demands on extractive surface and extract volumes. To test the system, the strongly acidic plasticizer/flame retardant metabolite diphenyl phosphate ester (DPhP), with a pKa value of 0.26, was extracted from urine. DPhP was protonated using 4 M hydrochloric acid and extracted into an acceptor phase at pH 9. Thirty extractions were made with the same liquid membrane without any decrease in extraction efficiency and with a relative standard deviation <7%. An analyte concentration enrichment of 5-10 times was achieved in the extraction step, giving a limit of detection (S/N = 3) of 0.014 microg/mL with LC/ESI-MS and 0.18 microg/mL with CE-UV. The effects on extraction efficiency using different sample pH, organic solvents, sample flow rates, and lengths of the fiber were evaluated.     

Kinetic model of membrane extraction with a sorbent interface

Membrane extraction with a sorbent interface (MESI) is an unique sample preparation alternative for trace organic analysis. The main features of MESI include its solvent-free nature, the rugged and simple design with no moving parts for long-term reliable performance, the fact that it is a single-step process which ensures good precision, its easy automation, and its feasibility for on-site operation. Among the available membrane extraction modules designed for the MESI system, the headspace configuration has continued to show its superior durability and versatility in membrane applications. The headspace membrane extraction configuration effectively eliminates the need for a sampling pump and flow metering and hence prevents the extraction system from plugging and greatly simplifies the extraction process. The module can be used for extraction of VOCs from gaseous, aqueous, or solid samples. A mathematical model has been developed for headspace membrane extraction of an aqueous sample, based on the assumption that the aqueous phase is perfectly stirred. The model is in good agreement with the experimental benzene extraction results obtained with an efficient agitation method such as high-speed magnetic stirring or sonication. The model has also been used to study the effects of various extraction parameters with respect to the sensitivity and response time of the MESI system. Sample agitation facilities analyte mass transport and hence improves both the system sensitivity and the response time. The sensitivity of the extraction method also increases with an increase of the extraction temperature.     

Membrane response model for ion-selective electrodes operated by controlled-potential thin-layer coulometry

The electrochemical response behavior of controlled-potential thin-layer coulometric sensors based on solvent polymeric membranes doped with ionophores is elucidated by numerical simulation. This treatment forms the theoretical basis for the design of potentially recalibration-free ion-selective chemical sensors that operate by exhaustive coulometry. Mass transport is assumed to occur primarily by diffusion in each bulk phase, and interfacial ion exchange with interfering ions is described with modern ion-selective electrode theory. The ion-selective membrane is assumed to contain an ion exchanger that can form concentration gradients as a result of transmembrane ion fluxes. It is shown that the diffusion of ions in the membrane phase will become rate limiting for membrane components with diffusion coefficients of 10(-8) cm(2) s(-1) that are typical for traditional ion-selective electrode formulations. This characteristic may be advantageous for sample thicknesses of 20 μm or less, where otherwise exhaustive depletion occurs too quickly to be distinguishable from nonfaradic processes. In most other cases, however, it will be necessary to formulate membrane materials that permit much faster diffusion characteristics. Indeed, the simulations give guidance on sensor design for sample concentrations that approach millimolar levels. The treatment also considers interferences from ions of the same charge sign as the analyte ion, and it is shown that the required selectivity for a given analysis must be about 1 order of magnitude higher than in direct potentiometry. This is because the coulometric exhaustive depletion process occurs only for the analyte ion, not for the interfering one, and to avoid interference, the required selectivity must be maintained even if the sample contains a fraction of the original analyte levels.     

Solvent bar microextraction

In this work, a new and simple microextraction method termed solvent bar microextraction (SBME) was developed. In this method, the organic extractant solvent (1-octanol) was confined within a short length of a hollow fiber membrane (sealed at both ends) that was placed in a stirred aqueous sample solution. Tumbling of the extraction device within the sample solution facilitated extraction. Pentachlorobenzene (PCB) and hexachlorobenzene (HCB) were used as model compounds to investigate the extraction performance. Analysis was carried out by gas chromatography/electron capture detection. This new method provided very high enrichment (approximately 110-fold for PCB and approximately 70-fold for HCB) in 10 min and good reproducibility (<4%, n = 6). Since the hollow fiber membrane was sealed, it could be used for extraction from "dirty" samples, such soil slurries. This novel microextraction method was compared with single-drop microextraction and static hollow fiber membrane microextraction in which the extractant solvent was also held within a hollow fiber but with the latter fixed to a syringe needle (i.e., there was no tumbling effect). Comparison between SBME and conventional solid-phase microextraction in a soil slurry sample was also investigated.     

Application of vacuum membrane distillation to lithium bromide absorption refrigeration system

Conventional generator in lithium bromide absorption refrigeration system is too bulky and heavy to be fitted into small scale device, and the temperature of the driving heater in the generator seems much higher than low grade energy such as regenerative energy or waste heat energy. In this paper, desorption of aqueous lithium bromide solution by vacuum membrane distillation process was presented. Hollow fiber membrane module made by polyvinylidene fluoride was used as desorption device of aqueous lithium bromide solution. Influencing factors of feed flux, feed temperature in lumen side and vacuum pressure in shell side were tested and analyzed with orthogonal test. The results showed that permeation flux of water vapor increased with the feed temperature increasing and the feed flux increasing in lumen side, and the permeation flux also went up along with absolute pressure drop in shell side. Feasibility and potential application analysis shows that the temperature of the driving heat was low and the volume and weight of the desorption device was light. In this study, vacuum membrane distillation to the lithium bromide absorption refrigeration system has proved to be an efficient and cheap desorption mode.     

Immunologic trapping in supported liquid membrane extraction

To obtain a high degree of selectivity in sample preparation, supported liquid membrane (SLM) extraction was combined with immunologic recognition. The SLM employs a hydrophobic polymer for supporting the immobilization of an organic solvent, thus forming a nonporous membrane. Said membrane separates the aqueous sample on one side (donor) from a receiving aqueous phase on the other (acceptor). The extraction involves the partitioning of neutral compounds between the sample solution, continuously pumped alongside the membrane, and the membrane. From the membrane, reextraction takes place into a second aqueous phase containing antibodies specific for the target compound(s). Hence, there is a formation of an antibody-antigen complex at the heart of the sample preparation (ImmunoSLM). When the immunocomplex forms, the antigen can no longer redissolve in the organic membrane, thus being trapped in the acceptor. Consequently, the concentration gradient of free antigen over the membrane is ideally unaffected, this being the driving force for the process. With a surplus of antibody, the concentration of analyte in the receiving phase will easily exceed the initial sample concentration. In this work, the so formed immunocomplex was quantified on-line, using a fluorescein flow immunoassay in a sequential injection analysis (SIA) setup. The outlined ImmunoSLM-SIA scheme was successfully applied for the extraction of 4-nitrophenol from spiked water solutions as well as from a spiked wastewater sample, indicating that the immunoextraction can be suitable when dealing with difficult matrixes.     

PVDF hollow fiber and nanofiber membranes for fresh water reclamation using membrane distillation

Polyvinylidene fluoride hollow fiber and nanofibrous membranes are engineered and successfully fabricated using dry-jet wet spinning and electrospinning techniques, respectively. Fabricated membranes are characterized for their morphology, average pore size, pore size distribution, nanofiber diameter distribution, thickness, and water contact angle. Direct contact membrane distillation (DCMD) performances of the fabricated membranes have been investigated using a locally designed and fabricated, fully automated MD bench scale unit and DCMD module. Electrospun nanofibrous membranes showed a water flux as high as 36 L m^?2 h^?1 whereas hollow fiber membranes showed a water flux of 31.6 L m^?2 h^?1, at a feed inlet temperature of 80 °C and at a permeate inlet temperature of 20 °C.     

Sample preparation using a miniaturized supported liquid membrane device connected on-line to packed capillary liquid chromatography

A miniaturized supported liquid membrane device has been developed for sample preparation and connected on-line to a packed capillary liquid chromatograph. The device consists of hydrophobic polypropylene hollow fiber, inserted and fastened in a cylindrical channel in a Kel-F piece. The pores of the fiber are filled with an organic solvent, in this study 6-undecanone, thus forming a liquid membrane. The sample is pumped on the outside of the hollow fiber (donor), and the analytes are selectively enriched and trapped in the fiber lumen (acceptor). With this approach, the volume of the acceptor solution can be kept as low as 1-2 μL. This stagnant acceptor solution is then transferred through capillaries attached to the fiber ends to the LC system. The system was tested with a secondary amine (bambuterol), as a model substance in aqueous standard solutions as well as in plasma. The best extraction efficiency in aqueous solution, with an acceptor volume of 1.9 μL, was 32.5% at a donor flow rate of 2.5 μL/min. At flow rates above 20 μL/min, the concentration enrichment per time unit was approximately constant, at 0.9 times/min, i.e., 9 times enrichment in about 10 min. The overall repeatability (RSD) for spiked plasma samples was ～4% (n = 12). Linear calibration curves of peak area versus bambuterol concentration were obtained for both aqueous standard solutions and spiked plasma samples. The detection limit for bambuterol in plasma, after 10 min of extraction at a flow rate of 24 μL/min, was 80 nM.     

Liquid-liquid-liquid microextraction for sample preparation of biological fluids prior to capillary electrophoresis.

Methamphetamine as a model compound was extracted from 2.5-mL aqueous samples adjusted to pH 13 (donor solution) through a thin phase of 1-octanol inside the pores of a polypropylene hollow fiber and finally into a 25-microL acidic acceptor solution inside the hollow fiber. Following this liquid-liquid-liquid microextraction (LLLME), the acceptor solutions were analyzed by capillary zone electrophoresis (CE). Extractions were performed in simple disposable devices each consisting of a conventional 4-mL sample vial, two needles for introduction and collection of the acceptor solution, and a 8-cm piece of a porous polypropylene hollow fiber. From 5 to 20 different samples were extracted in parallel for 45 min, providing a high sample capacity. Methamphetamine was preconcentrated by a factor of 75 from aqueous standard solutions, human urine, and human plasma utilizing 10(-1) M HCl as the acceptor phase and 10(-1) M NaOH in the donor solution. In addition to preconcentration, LLLME also served as a technique for sample cleanup since large molecules, acidic compounds, and neutral components were not extracted into the acceptor phase. Utilizing diphenhydramine hydrochloride as internal standard, repetitive extractions varied less than 5.2% RSD (n = 6), while the calibration curve for methamphetamine was linear within the range 20 ng/microL to 10 micrograms/mL (r = 0.9983). The detection limit of methamphetamine utilizing LLLME/CE was 5 ng/mL (S/N = 3) in both human urine and plasma.     

中空纤维反渗透复合膜的制备及分离性能研究

通过间苯二胺水溶液和均苯三甲酰氯的正己烷溶液的界面缩聚反应,以聚砜中空纤维超滤膜为基膜,制备了聚芳香酰胺反渗透复合膜.用扫描电镜对复合膜的表面及断面进行表征,探索了复合膜在不同操作条件以及进液性质下的分离性能.研究结果表明:中空纤维反渗透复合膜具有良好的耐压密性和稳定性,在0.7MPa下具有良好的分离性能.此复合膜对NaCl、KCl、CaCl2、MgCl2、MgSO4、Na2SO4等无机盐水溶液的脱盐率不低于93.5%,通量大于21L/(m2·h);对天津市大港、小站两地的苦成水具有优异的淡化性能;对天津市自来水中的盐分也有良好的去除率.