超临界流体与膜过程的耦合技术

介绍了超临界流体与膜过程的耦合技术的研究进展和最新研究成果。将超临界CO_2萃取与纳滤过程相耦合,可以不经历压力、温度和相变循环而使CO_2循环利用,从而降低过程能耗、减小操作费用。将纳滤过程与超临界CO_2萃取相耦合,可以对萃取收率和选择性独立调控,使它们分别达到最佳值,从而实现对萃取物在高收率条件下达到精细分离的目的。将超临界CO_2引入高粘性液体的超滤过程,会在不提高温度和无需引入化学剂的情况下,大大降低流体粘度、增大透过流率、提高过滤效率、减小过程能耗,同时也有利于环境保护、提高产品质量。     

Electrochemical study of a hydrogen diffusion anode-membrane assembly for membrane electrolysis

The membrane electrode assembly (MEA) studied was constituted with a gas diffusion electrode (E-TEK) impregnated with Nafion^® solution which was assembled with a Nafion^® 117 cation exchange membrane under heat and pressure. The MEA was used as anode in a membrane electrolysis (ME) cell with the objective to regenerate HCl and NaOH from NaCl. Current efficiency for hydrogen oxidation was determined and its value is 100%, which indicates that the only reaction occurring at the anode is the oxidation of hydrogen. Current-potential curves, recorded in different conditions, showed a linear variation in the range 0-3000 A m⁻² when hydrochloric acid concentration is below 2 mol dm⁻³. In this case, the overvoltage was shown to be mainly due to the ohmic drop in the membrane and in the layer where Nafion^® impregnation was performed. MEA overvoltage necessary to reach 3000 A m⁻² current density was about 0.12 V. For high HCl concentration (6-8 mol dm⁻³), the MEA overvoltage increased sharply with current density due to the adsorption of chloride anions on platinum catalyst.     

Corrosion-resistant lightweight metallic bipolar plates for PEM fuel cells

Corrosion resistant treated metal bipolar plates with higher rigidity and electrical conductivity than graphite were developed and tested for PEM fuel cell applications. Six replicas of single cells were used three of which were made of graphite composites bipolar plates and the other three of the treated metallic plates. A Membrane Electrode Assembly (MEA) with 5.55 cm² active electrode areas, 0.3 mg cm^–2 Pt loading and Nafion membrane 115 was fitted to each cell and operated under identical conditions. The experimental testing was conducted at room temperature (20 °C). The average value of the data obtained for the three graphite cells was plotted. Similarly, the average value of the data obtained for the three treated metal cells was plotted on the same graph for comparison. Generally, the treated metal bipolar plate provided at least 12% saving in hydrogen consumption in comparison to graphite. This is attributed to the lower bulk and surface contact resistance of the metal used in this study in relation to graphite. The results of lifetime testing, conducted at room temperature under variable loading showed no indication of power degradation due to metal corrosion for at least 1500 hours.     

Permeation study on the hollow-fiber supported liquid membrane for the extraction of Cobalt(II)

The transport of Co(II) through hollow-fiber-supported liquid membrane containing di-(2-ethylhexyl) phosphoric acid (D2EHPA) diluted in kerosene was examined. The mass transfer rate, expressed as permeability, P, focused on diffusion through the aqueous layer in the feed solution, the organic layer and the aqueous layer in the stripping solution. Experiments were performed as a function of aqueous feed solution velocity (100-500 ml/min), carrier concentration (0.1-20% v/v), aqueous stripping solution velocity (100-1,000 ml/min) and feed concentration (100-1,000 ppm) with 0.1 M HCl in the product phase. pH of the feed solution was 5.0. The measured permeabilities were compared to generally accepted mass transfer correlations. The validity of the prediction was evaluated with the experimental data, and the data were found to tie in well with the theoretical values. The model is the reported describing that the rate limiting step in the transport of the ion was the diffusion through both aqueous films, feed and stripping, whereas the organic resistance of the membrane was negligible. From this study, the model has good potential for the prediction of permeability of Co(II).     

Sorption, diffusion, and permeation of light olefins in poly(ether block amide) membranes

Sorption, diffusion, and permeation of three olefins (i.e., C₂H₄, C₃H₆, and C₄H₈) in poly(ether block amide) (PEBA 2533) membranes at different temperatures and pressures were investigated. This is pertinent to olefin recovery from resin off gas in polyolefin manufacturing. The relative contribution of solubility and diffusivity to the preferential permeability of olefins over nitrogen was elucidated. It was revealed that the favorable olefin/nitrogen permselectivity was primarily attributed to the solubility selectivity, whereas the diffusivity selectivity may affect the permselectivity negatively or positively, depending on the operating temperature and pressure. The olefin permeability is in the order of C₄H₈>C₃H₆>C₂H₄, the same order as their solubility in the membrane. In general, a low temperature favors both the permeability and selectivity. With an increase in pressure and/or a decrease in temperature, the sorption uptake of the olefin in the membrane increases progressively, and the diffusivity and hence the permeability are also enhanced because of the increased membrane plasticization/swelling caused by the penetrant sorbed in the membrane. At a given temperature, the pressure dependence of solubility and permeability could be described empirically by an exponential function. The limiting solubility at infinite dilution was correlated with the reduced temperature, and the hypothetical diffusivity at zero pressure was related to temperature by the Arrhenius equation.     

A glue method for fabricating membrane electrode assemblies for direct methanol fuel cells

We present a simple glue method for fabricating membrane electrode assemblies (MEA) for direct methanol fuel cells (DMFC). Rather than the conventional “dry” hot-pressing method that relies solely on hot-pressing at a high pressure and temperature to form a MEA, the “wet” method developed in this work introduces a binding agent, consisting of Nafion^® solution, between a polymer electrolyte membrane (PEM) and an anode/cathode. The introduced binding agent can provide a better adhesion and stronger binding force between a membrane and an electrode, thereby facilitating a better interfacial contact between the electrode and the Nafion^® membrane, which has been proved by scanning electron microscopy (SEM) analyses to the cross-sectional morphology of the MEA after long-term operation. The cell performance characterization showed the MEA fabricated by the glue method was more stable in cell performance than that fabricated by the conventional hot-pressing method. Cyclic voltammetry (CV) results also demonstrated the MEA fabricated by the glue method exhibited a higher electrochemical surface area (ESA) as a result of the improved interfacial contact between the Nafion^® membrane and the electrodes. Finally, the DMFC with the MEA fabricated by the glue method was characterized by the electrochemical impedance spectroscopy (EIS).     

高分子材料膜的污染和清洗

就高分子材料膜的污染、清洗及清洗过程的化学反应、清洗剂的选择和定性等问题进行了论述.力图全面而又简捷地对膜清洗做一综述.     

Gas-liquid mass transfer in a circulating jet-loop nitrifying MBR

Based on airlift configuration, a novel circulating jet-loop submerged membrane bioreactor (JLMBR) adapted to ammonium partial oxidation has been developed. Membrane technology and combined air and water forced circulation are adopted to obtain a high biomass retention time and to achieve a separate control of mixing and aeration. This study is intended to determine how gas-liquid mass transfer is affected by operating conditions. In a first approximation, liquid was assumed to be perfectly mixed. A classical non-steady state clean water test, known as the “gas out-gas in” method, was used to determine the gas-liquid mass transfer coefficient k_La. Air and recirculated liquid superficial velocities were gradually increased from 0.013 to and 0.0056 to , respectively. Subsequently, the gas-liquid mass transfer coefficient k_La varied from 0.01 to . It appears to be influenced by the combined action of air and recirculated liquid flowrates in the range and , respectively, for air and liquid. Correlations are proposed to describe this double influence. Experiments were performed on tap water and a culture medium used for the autotrophic growth of nitrifying bacteria, respectively. Oxygen transfer appeared to be not significantly affected by the mineral salt encountered in this medium.     

Chemical control of colloidal fouling of reverse osmosis systems

Fouling of membranes by colloidal organic and inorganic particles continues to be documented as the most common and challenging obstacle in attaining stable continuous operation of reverse osmosis (RO) and ultrafiltration (UF) systems. Much current research is being conducted on physical parameters to mitigate such fouling. The focus has been on membrane synthesis and element design; microfiltration and ultrafiltration pretreatment; electromagnetic devices; correlation with physical factors such as Silt Density Index, zeta potential and critical flux; technique of direct observation of fouling process through a membrane; and classification of macromolecular organics for correlation with fouling characteristics. We report initial successes with chemical control of colloidal fouling. Through screening with a large number of observable coagulations of natural colloids, we have developed a group of proprietary anticoagulants and dispersants that would, at less than 10 ppm dosage to the RO feedwater, control various classes of colloidal foulants. Case studies of the control of humic matter, elemental sulfur and colloidal silicate in problematic RO systems that became stabilized are briefly presented. We conclude that a great need and potential exists in economically controlling the myriads of fouling interactions of colloidal particles during concentration within the brine channels of RO membrane elements. Low dosages of antifoulants can in many cases obviate the need for installation and maintenance of pretreatment unit or operations designed to remove such colloidal foulants from the process stream.