Simon Shilton

Production of Super Selective Polysulfone Hollow Fiber Membranes for Gas Separation

Polysulfone gas separation hollow fiber membranes were manufactured using a dry/wet spinning process with forced convection in the dry gap. Hollow fibers were produced using two different bore coagulants: one pure water and one with reduced water activity. An optimized multi-component dope was used which proved to be a shear-thinning power-law fluid. For each bore system, membranes were spun at low and high dope extrusion rates (DERs) corresponding to shear rates of around 4000 s−1 and 10 000 s−1, respectively, at the outer spinneret wall. Plane polarized infrared spectroscopy was used to probe the membrane active layer. Pressure-normalized fluxes and selectivities were evaluated using pure carbon dioxide and methane. For the spinning conditions used here, the combination of reduced water activity in the bore and high DER produced highly selective membranes. Some selectivities reached about three times the recognized intrinsic value for the polymer.

Optimization of cellulose acetate hollow fiber reverse osmosis membrane production using Taguchi method

Cellulose acetate hollow fiber membranes for reverse osmosis (RO) were spun using a forced convection technique. In this study, a systematic experimental design based on Taguchis method (which is a fractional factorial method) has been employed for discussing the relationship between the rejection rate coefficient, permeation rate and the dry-wet spinning conditions for making cellulose acetate hollow fibers for RO. The factors considered in the experimental design included the polymer contents (PCs), the ratio of the solvent (acetone) to swelling agents (formamide) in the dope solution, the dope extrusion rate (DER), the type of bore fluid (BF), the residence time (RT) and the nitrogen gas flushing rate (GR). The results indicate that the BF and the DER are the two most important factors in determining the performance of the RO membranes.

A study of extrusion shear and forced convection residence time in the spinning of polysulfone hollow fiber membranes for gas separation

Polysulfone hollow fiber membranes for gas separation were spun using a forced convection technique. Experiments were designed to decouple the effect of extrusion shear from forced convection residence time in the dry gap allowing both factors to be investigated. The main objective was to study the pure influence of shear and its capacity to increase membrane selectivity. The results suggested that extrusion shear influences phase inversion dynamics. Increasing shear decreased active layer thickness and increased pressure-normalized flux. This was discussed in terms of thermodynamic instability and polymer precipitation/coalescence speed. Increasing shear was found to increase selectivity to levels greater than the intrinsic value for the amorphous membrane polymer. This may be as a result of induced molecular orientation in the active layer. However, a critical shear rate existed beyond which selectivity deteriorated. This was attributed to the development of surface pores as the active layer thins. Membranes spun at intermediate forced convection residence times exhibited the highest selectivities. Skin formation must be complete, but excessive residence time allows deleterious non-solvent encroachment from the lumen. The results indicate that if enhanced selectivity and high flux are to be achieved, membranes should be spun at a high shear rate and an optimized residence time in order to minimize surface defects, increase the critical shear rate, decrease active layer thickness and heighten molecular orientation.

Direct measurement of rheologically induced molecular orientation in gas separation hollow fibre membranes and effects on selectivity

Asymmetric polysulfone hollow fibre membranes for gas separation were spun using a dry/wet spinning process. An optimised four component dope solution was used: 22% (w/w) polysulfone, 31.8% (w/w) N,N-dimethylacetamide, 31.8% (w/ w) tetrahydrofuran and 14.4% (w/w) ethanol. Fibres were spun at low- and high-dope extrusion rates and hence at different levels of shear. Molecular orientation in the active layer of the membranes was measured by plane-polarised infrared spectroscopy. Gas permeation properties (permeability and selectivity) were evaluated using pure carbon dioxide and methane. The spectroscopy indicated that increased molecular orientation occurs in the high-shear membranes. The selectivities of these membranes were heightened and even surpassed the recognised intrinsic selectivity of the membrane polymer. The results suggest that increased shear during spinning increases molecular orientation and, in turn, enhances selectivity.

The rheology of fibre spinning and the properties of hollow-fibre membranes for gas separation

Abstract The effect of spinning rheology on gas-separation hollow-fibre membranes has been investigated. For polysulfone fibres, permeability decreased with increasing dope concentration. The lowest fibre selectivities occurred with the medium spinning-dope concentration, suggesting that both surface pore area and active layer thickness were high. Both permeability and selectivity increased with increasing dope extrusion rate, possibly due to enhanced orientation of the membrane skin. Permeability increased and selectivity decreased with increasing jet stretch. Polyacrylonitrile membranes, because of the low polymer permeability, proved insensitive to spinning conditions, showing no separation capability due to the dominating effect of surface pores.

Molecular orientation and the performance of synthetic polymeric membranes for gas separation

Asymmetric polysulfone and polyacrylonitrile flat sheet membranes have been produced by a simple dry-wet casting technique. Both membrane types were cast at low and high shear rate. Molecular orientation in the membranes was determined using polarized reflection i.r. spectroscopy. Gas permeation properties were examined using carbon dioxide and methane as test gases. I.r. dichroism was detected in all samples, the extent being greater in the high shear membranes for both polysulfone and polyacrylonitrile. The effects, however, were more intense in the polyacrylonitrile samples. Gas permeation tests showed that for both polymer types, the high shear membranes exhibited greater selectivity (CO2/CH4). Selectivities were greater and permeabilities lower for the polysulfone samples. The results show (i) that polarized reflection i.r. spectroscopy can be used to determine—at least qualitatively—the degree of molecular orientation in sheared polymers, (ii) that molecular orientation is enhanced by shear during casting, and (iii) that this has a favourable effect on membrane selectivity. In the examples chosen molecular orientation was more pronounced in the polyacrylonitrile membranes, but with these the potential for high selectivity was thwarted by the poor intrinsic permeability of the polymer which causes flow through pores or imperfections to dominate.

Polysulfone Hollow Fiber Gas Separation Membranes Filled with Submicron Particles

Abstract: Three different fillers, carbon black (CB), vapor grown carbon fibers (VGCF), and TiO2, were incorporated into polysulfone spinning solutions with the intention of producing highly selective membranes with enhanced mechanical strength. The effect of filler presence on gas permeation characteristics, mechanical strength (bursting pressure), and morphology was investigated and compared to unfilled membranes. As well as studying filler types, the influence of CB filler concentration on membrane performance was also examined. For all filler types (at a concentration of 5%w/w), the pressure‐normalized flux of O2, N2, and CH4 was greater in the composite than in the unfilled membranes. The CO2 pressure‐normalized flux was only greater in the TiO2 composite membranes. For CB and VGCF, the CO2 pressure‐normalized flux was reduced compared with unfilled membranes. Three CB concentrations were investigated (2, 5, and 10%w/w). For O2, N2, and CH4, pressure‐normalized flux peaked at 5%w/w CB. CO2 exhibited the opposite trend, showing a minimum pressure‐normalized flux at 5%w/w. Considering O2/N2 and CO2/CH4 gas pairs and the various filled membrane categories, only the O2/N2 selectivity of the 2%w/w CB filled membranes was higher than that of the unfilled fibers—all other selectivities were lower. In terms of CB concentration, selectivity was a minimum at the intermediate concentration of 5%w/w. All the filled membrane types exhibited greater mechanical strength (bursting pressure) than unfilled fibers apart from the 5%w/w VGCF composites. The 2%w/w CB composites were the strongest. Electron microscopy showed no visible differences in general morphology between the various filled and unfilled membranes.

Study of shear rate influence on the performance of cellulose acetate reverse osmosis hollow fiber membranes

The effect of shear rate on the separation performance of reverse osmosis hollow fiber membrane is discussed. Experiments involving six different dope extrusion rates (DERs) (ranging 2.5-5 ml/min) are performed with the other process factors set at the optimum conditions determined by the Taguchi analysis. This will enable an assessment to be made on the relationship between the DER and the rejection rate. The regression method is used to analyse the experimental results and an empirical model has been developed. Simultaneously, it is found that there is a fairly strong correlation between extrusion shear rate and the rejection rate of the membranes, whereby as the shear rate increases, the rejection rate increases until a critical level of shear is achieved, beyond which reverse osmosis membrane performance deteriorates, suggesting that there exists an optimum shear rate which yields optimal membrane morphology for reverse osmosis hollow fiber membranes.

The deduction of fine structural details of gas separation hollow fibre membranes using resistance modelling of gas permeation

Gas transfer through asymmetric polysulfone hollow fibre membranes has been modelled, allowing fine details of fibre structure to be deduced from gas permeation characteristics. The structural information is used to interpret the relationship between spinning conditions and fibre properties. Dope concentration determines the general morphology of the fibre, such as the porosity (voidage fraction), thickness of the active layer and order of magnitude of surface porosity (fraction of surface area that is pores), and thus it sets the permeability and level of selectivity that are likely to be achieved on coating. The selectivity of the solid polymer (the maximum selectivity achievable by any membrane if coating is highly effective or if no surface pores are present) was found to increase with increasing dope extrusion rate. The elevated levels of shear in the spinneret may enhance the orientation of polymer molecules. Increasing the jet stretch ratio during spinning had a detrimental effect on solid polymer selectivity. Increased elongational strain possibly results in an unfavourable polymer structure.

Flow profile induced in spinneret during hollow fiber membrane spinning

A methodology is presented to establish the flow profile induced in a spinneret during the spinning of hollow fiber membranes. The flow equations are derived for a power law fluid passing through a concentric annulus. The pressure drop, the velocity profile, the shear stress profile, and the shear rate profile induced during spinning can then be determined. This type of rheological knowledge is useful if membrane structure and properties are to be related to the flow conditions experienced in the spinneret.