Adsorbent filled membranes for gas separation. Part 1. Improvement of the gas separation properties of polymeric membranes by incorporation of microporous adsorbents

The effect of the introduction of specific adsorbents on the gas separation properties of polymeric membranes has been studied. For this purpose both carbon molecular sieves and zeolites are considered. The results show that zeolites such as silicate-1, 13X and KY improve to a large extent the separation properties of poorly selective rubbery polymers towards a mixture of carbon dioxide/methane. Some of the filled rubbery polymers achieve intrinsic separation properties comparable to cellulose acetate, polysulfone or polyethersulfone. However, zeolite 5A leads to a decrease in permeability and an unchanged selectivity. This is due to the impermeable character of these particles, i.e. carbon dioxide molecules cannot diffuse through the porous structure under the conditions applied. Using silicate-1 also results in an improvement of the oxygen/nitrogen separation properties which is mainly due to a kinetic effect. Carbon molecular sieves do not improve the separation performances or only to a very small extent. This is caused by a mainly dead-end (not interconnected) porous structure which is inherent to their manufacturing process

Phase separation phenomena in solutions of polysulfone in mixtures of a solvent and a nonsolvent: relationship with membrane formation

The phase separation phenomena in ternary solutions of polysulfone (PSf) in mixtures of a solvent and a nonsolvent (N,N-dimethylacetamide (DMAc) and water, in most cases) are investigated. The liquid-liquid demixing gap is determined and it is shown that its location in the ternary phase diagram is mainly determined by the PSf-nonsolvent interaction parameter. The critical point in the PSf/DMAc/water system lies at a high polymer concentration of about 8% by weight. Calorimetric measurements with very concentrated PSf/DMAc/water solutions (prepared through liquid-liquid demixing, polymer concentration of the polymer-rich phase up to 60%) showed no heat effects in the temperature range of −20°C to 50°C. It is suggested that gelation in PSf systems is completely amorphous. The results are incorporated into a discussion of the formation of polysulfone membranes

Competitive adsorption of plasma proteins at solid—liquid interfaces

The competitive adsorption of human serum albumin (HSA), human immuno-γ-globulin (HIgG) and human fibrinogen (HFb) onto polystyrene (PS) at 20° C and a pH of 7.35 (phosphate-buffered saline) was studied. Protein adsorption was studied using enzyme immunoassay. The results obtained with the immunoassay were compared with those obtained using radiolabelled proteins. Recent studies revealed that the adsorption behaviour of radiolabelled proteins onto surfaces differs from that of the non-labelled proteins, which may lead to misinterpretation of adsorption data. Differences in the adsorption behaviour of the labelled proteins as compared to non-labelled proteins can possibly be explained by the formation of modified proteins during the labelling procedure as shown by ion-exchange high-performance liquid chromatography (HPLC). The competitive adsorption of HSA, HIgG and HFb onto a PS latex was studied by measuring the depletion of proteins in solution. The decrease in protein concentration in solution was determined by HPLC techniques. A strong preferential adsorption of HFb was observed with maximum adsorption values of 0.6 μg/cm2

Preparation of zeolite filled glassy polymer membranes

The incorporation of zeolite particles in the micrometer range into polymeric matrices was investigated as a way to improve the gas separation properties of the polymer materials used in the form of membranes. The adhesion between the polymer phase and the external surface of the particles appeared to be a major problem in the preparation of such membranes when the polymer is in the glassy state at room temperature. Various methods were investigated to improve the internal membrane structure, that is, surface modification of the zeolite external surface, preparation above the glass-transition temperature, and heat treatment. Improved structures were obtained as observed by scanning electron microscopy, but the influence on the gas separation properties was not in agreement with the observed structural improvements

Ethanol-water separation by pervaporation

The separation of ethanol-water mixtures is of great importance for the production of ethanol from biomass. Both ultrafiltration and pervaporation processes can be used for the continuous processing of fermentation and separation, The removal of ethanol from the ultrafiltration permeate can be accomplished by pervaporation. Separation of ethanol-water mixtures by the pervaporation process has been investigated. Results are presented for membranes which are preferentially permeable for ethanol and for others which are preferentially water permeable. Details on the preparation of several membrane types (homogeneous, asymmetric and composite) are given. A schematic process diagram is given in which the fermentation of sugars to ethanol is membrane-controlled

A rationale for the preparation of asymmetric pervaporation membranes

Pervaporation is carried out primarily with homogeneous membranes. An improvement in permeation rate can be achieved by using asymmetric or composite membranes. In order to maintain a high selectivity, very dense top layers are needed. The formation of asymmetric pervaporation membranes will be discussed in terms of the model proposed by our group: formation of the top layer by gelation; formation of the porous sublayer by liquid-liquid phase separation followed by gelation of the concentrated polymer phase. To obtain very dense top layers the following factors are important: the ratio of nonsolvent inflow and solvent outflow, polymer concentration, location of the liquid-liquid demixing gap, and location of the gel region. Asymmetric membranes have been prepared by varying these factors, and the obtained membranes have been tested on ethanol/water mixtures

Modelling of the diffusion of carbon dioxide in polyimide matrices by computer simulation

Computer aided molecular modelling is used to visualize the motion of CO2 gas molecules inside a polyimide polymer matrix. The polymers simulated are two 6FDA-bases polyimides, 6FDA-4PDA and 6FDA-44ODA. These polymers have also been synthesized in our laboratory, and thus the simulated properties could directly be compared with “real-world” data. The simulation experiments have been performed using the GROMOS1 package. The polymer boxes were created using the soft-core method, with short (11 segments) chains. This results in highly relaxed and totally amorphous polyimide matrices. The motion of randomly placed CO2 molecules in the boxes during molecular dynamics runs was followed, revealing three types of motion: jumping, continuous- and trapped motion. The calculated diffusivities are unrealistic, but possible shortcomings in our model are given

The resistance towards gas transport of a sublayer of asymmetric PPO hollow fiber membranes determined by plasma-etching

Plasma-etching is a powerful tool in the determination of the resistance of the sublayer of skinned asymmetric hollow fiber membranes of poly (2,6-dimethyl-l,4-phenylene oxide). Using a resistance model and data provided by etched hollow PPO fiber membranes it is possible to predict the ultimate selectivity of the total membrane for helium over nitrogen and oxygen over nitrogen. From this model and from permeability measurements it is shown that the gas resistance of the sublayer of asymmetric membranes with a selective layer has a large effect on the ultimate overall selectivity of the membranes. In order to improve the membrane performance the resistance of the sublayer has to be minimized. Etching experiments were performed on follow fiber membranes spun from PPO-types with different intrinsic viscosities. The resistance of the sublayer decreased markedly with increasing intrinsic viscosity of the PPO. To a lesser extent the membrane preparation (the length of the air gap) influences the gas resistance of the sublayer

Fluidized beds as turbulence promoters in the concentration of food liquids by reverse osmosis

Fluidized beds offer a potential improvement of reverse osmosis processes for food liquids, less fouling of the membrane, and reduced energy consumption. Our experiments were concerned with tubular systems in which fluidized beds of glass, steel, and lead beads were used. Glass beads appeared to be preferable, since they caused little damage to the membrane. Only with the larger glass beads (3 mm) did the membrane skin become corrugated, so that the rejection decreased. The permeate flux for Gouda cheese whey was almost equal to that of an empty tube for which the velocity was about thirty times higher. The erosive action of the glass beads on the fouling layer was partially responsible for this effect. For reverse osmosis of skim milk and potato fruit water the bed did not reduce the fouling layer to a sufficient extent and, therefore, had a lower permeate flux than an empty tube

Diffusion of solvent from a cast cellulose acetate solution during the formation of skinned membranes

The transport of solvent out of a cast cellulose acetate (CA) solution into the coagulation bath during membrane formation is treated as a diffusion process. From the increase of solvent concentration in the bath with time (solvent leaching experiments) an overall solvent diffusion coefficient has been calculated. In size these coefficients compare well to mutual pseudo-binary solvent-non-solvent diffusion coefficients determined by means of a classical boundary broadening method applied to ternary solutions with fixed CA concentration, but with a gradient in solvent-nonsolvent composition. Since binary polymer-solvent interdiffusion coefficients are at least one order of magnitude lower, it is concluded that the diffusion of solvent into the coagulation bath is essentially a pseudo-binary solvent-non-solvent diffusion process. Combination of experimental results with model calculations for the effect of a thin dense skin on the diffusion of solvent out of the sublayer shows that the casting-leaching diffusion coefficient can be used to describe the out-diffusion of solvent from the layer under the skin provided that the relative skin resistance is not too high, or that the skin thickness is small