Available online at www.sciencedirect.com ScienceDirect Hollow fiber membrane modules Norfamilabinti Che Mat, Yuecun Lou and G Glenn Lipscomb Hollow fiber membrane modules are used in a wide range of separation applications. Module design is critical to optimizing process performance. The state-of-the-art in fiber bundle and module manufacture is reviewed emphasizing industrial practice as reflected by the patent literature. Sources of nonideal module performance are identified that arise from nonuniform module flows. Efforts to quantify these effects and evaluate design alternatives to improve performance are reviewed. Despite this work, gaps in understanding the relationship between design and performance still exist. Addresses Chemical and Environmental Engineering Department, University of Toledo, 2801 West Bancroft Street, Toledo, OH 43606-3390, United States Corresponding author: Lipscomb, G Glenn ([email protected], [email protected]) Current Opinion in Chemical Engineering 2014, 4:18–24 This review comes from a themed issue on Separation engineering Edited by WS Winston Ho and Kang Li 2211-3398/$ – see front matter, # 2014 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.coche.2014.01.002 Introduction Global need for separation processes is increasing as society addresses grand challenges in providing water, energy, and health care sustainably. Membrane separation processes offer unique advantages over alternatives especially in terms of energy consumption and ability to handle labile components. The focus of this review is hollow fiber membrane modules and devices as illustrated in Figure 1. These devices are the mass transfer equivalent of a shell and tube heat exchanger. As such they consist of a tube bundle the ends of which are embedded in a tubesheet. The tubesheet is created to allow separate fluid communication with the fiber interior (lumens) and exterior (shell) spaces. The lumens are open along the tubesheet. Upon sealing the tubesheet to the case separate manifolds on the case exterior allow the introduction and removal of fluid streams to the lumen and shell spaces. The feed can be introduced to either the lumen or shell. A permeate sweep also may be fed to the module. The sweep mixes with the permeate and can dramatically improve module Current Opinion in Chemical Engineering 2014, 4:18–24 performance by increasing the chemical potential difference across the membrane. A baseline for process performance can be determined by assuming the fibers are uniform (identical inner and outer radii and permeances) and uniformly spaced. Additionally, baseline performance predictions assume the fluid distribution is uniform from the external ports on the case through the manifolds to the lumen and shell, that is, the flow rate inside and outside each fiber in the fiber bundle is identical. The performance of this ‘ideal’ device can be determined by analyzing the performance of a single fiber. Unfortunately, actual performance is poorer than ideal performance which has driven innovation in module design to improve performance. The differences are manifest in lower than expected process throughputs and higher energy consumption. For example, in nitrogen production from air, the retentate is the desired product and the nitrogen composition typically is specified. Nonideality leads to lower flow rates of the desired product and higher energy consumption. The higher energy consumption is due to a reduction in the fraction of the compressed air fed to the process that is recovered as the retentate product. This review focuses on the state of the art in module manufacture and module performance prediction. Note that the design of unconstrained hollow fiber bundles such as those used in membrane bioreactor applications are not covered here as these modules and applications possess unique features and operational characteristics not captured in the design of Figure 1. Module manufacture The earliest reports of hollow fiber module designs come from the patents of Dow [1] and DuPont [2]. Dow’s design drew most heavily on heat exchanger designs. Modules were formed by potting the ends of individual fibers or a small group of fibers (a fiber tow) in plugs. Subsequently, the plugs were placed in holes arranged in a regular array in two opposing metal plates. The fibers were held in slight tension between the two plates to allow uniform packing. The DuPont process represented a significant departure that facilitated the formation of larger bundles and was less labor intensive. Loops of fibers were formed by winding individual fibers or fiber tows around a rotating wheel and enclosed in multiple elastic socks. Tubesheets were formed by placing a mold over the end of the fiber www.sciencedirect.com Hollow fiber membrane modules Mat, Lou and Lipscomb 19 Figure 1 External case Permeate Permeate Sweep Tubesheet Fiber bundle Feed Retentate Lumen manifold bolted to case O-ring tubesheet-case seal Lumen distribution manifold Shell distribution manifold Current Opinion in Chemical Engineering Cut-away view of a typical hollow fiber membrane module with a lumen feed and shell sweep operating in counter-current contacting mode. Key elements and flow paths are indicated: solid lines — lumen flow and dashed lines — shell flow. Note that the hidden portion of the module is a mirror image of that shown. bundle that possessed connections to introduce a tubesheet forming material (e.g. epoxy resin). The tubesheet material was introduced while the module rotated with its long axis parallel to the ground. The rotation kept the tubesheet material from wicking up into the fiber bundle due to centrifugal forces; wicking reduces the area available for mass transfer and weakens fibers. This technique is referred to as ‘centrifugal’ potting and produces the most uniform tubesheets among the currently available alternatives. A modern example of module formation is provided by Generon [3]. This process further reduces labor intensity while striving to improve uniformity of fiber packing. Individual fibers or fiber tows are removed from spools produced by the spinning process and woven to form a hollow fiber fabric. Weaving allows precise control of the spacing between the fibers or tows. This fabric is wound around a central tube to create a fiber bundle. The central tube serves several functions: firstly mechanical support of the fiber bundle, secondly contact points to facilitate module movement through the manufacturing process, and finally means to introduce or remove a fluid stream from the center of the fiber bundle. Tubesheets were formed by holding the module vertically, placing one end into a mold, and introducing the tubesheet material. This technique is referred to as ‘dunk’ potting and can suffer from undesirable wicking if formation conditions are not controlled carefully. Once rough tubesheets were formed on both ends of the bundle, machining yielded the desired final shape and opened fiber ends as in the DuPont process. Subsequent improvements to the process included introduction of permeate collection channels in the fiber bundle to reduce shell side permeate www.sciencedirect.com pressure drop in lumen-fed modules [4], vacuum assisted potting to improve tubesheet formation [5], and wrapping of fiber tows with a support thread to improve handling in the weaving process, in particular reduce splaying, and thereby improve uniformity of fiber packing [6]. Wrapping fibers with one or more support threads also is used to improve mechanical strength for high permeance fibers that otherwise would be damaged during module manufacture [7]. Many examples of helically winding fibers to form a structured bundle also exist. The earliest work dates back to the late 1960s [8–10]. Helically wound modules may be formed with a central core tube [11] or without [12,13]. The effect of wind angle on fiber length as the fiber bundle is formed must be considered to ensure fiber length and flow rate per fiber remain constant [14]. More recent work suggests varying the wind angle in the axial direction (in addition to changes with bundle diameter to maintain constant fiber length) can produce modules with improved flow distribution and reduced pressure drop in the shell by forming a tapered bundle [15]. Additionally, increasing the wind angle at the end of the bundle can improve tubesheet strength by reducing the diameter of the bundle and the amount of fiber enclosed in the tubesheet [16]; pressure drop and lost membrane area in the tubesheet are reduced as well. Note that the weaving process also can be modified to produce a hollow fiber fabric that will yield a tapered module [3]. Fiber bundles also can be produced from square or circular fiber disks (wafers). Such wafers can be stacked to form a stand-alone module [17–19] or used to produce a module that can be placed in-line in a piping system [20]. Current Opinion in Chemical Engineering 2014, 4:18–24 20 Separation engineering Significant effort has been devoted to adding module design features that facilitate flow distribution in the shell and improve mass transfer performance. These features include the introduction of baffles to improve flow uniformity in the shell region. The baffles may extend radially in the form of tori [21,22] or axially in the form of concentric sheets [23]. Flow distributors along the periphery of the fiber bundle near the shell inlet and outlet also are used to improve uniformity [24–27]. These distributors typically consist of collars that create a distribution manifold around the fiber bundle to improve uniformity of fluid flow from the external ports on the case into the shell region of the fiber bundle. Recent work describes the use of grooves and corrugated protrusions in the distribution collar to reduce pressure drop and reduce fiber blocking of the distribution holes in the collar [28]. Additional work describes modules possessing shell distribution manifolds that penetrate into the interior of the fiber bundle [29] and inserts that divide the bundle into uniform sections to facilitate fluid distribution from a central inlet tube and reduce solid accumulation on the membrane surface in filtration applications [30]. Module performance evaluation Fiber bundles may be formed from multiple fiber types to perform two separations simultaneously by spiral winding [31]. More recent work describes a module consisting of two concentric layers of fibers that perform the separations sequentially by controlling the shell and lumen flows between the two layers with proper tubesheet and internal baffle designs [32]. While these models can adequately capture real module performance, often significant deviations exist which are attributed to non-ideal flow behavior. This behavior can arise from fluid distribution from manifolds into the lumen or shell regions or from non-uniform flow within the lumen or shell as illustrated in Figure 2. The potential impact of these non-idealities was recognized in the earliest module fabrication patents [2]. The performance of a hollow fiber bundle most commonly is predicted assuming all fibers possess identical geometry and transport properties. Additionally, the lumen and shell flow rates are assumed to be identical for each fiber. If concentration and temperature polarization are not important, or correlations are known for fluid boundary layer resistances, mass balances for the retentate and permeate streams can be reduced to a set of ordinary differential equations in co-current or countercurrent contacting [37]. The correlations reported by Lipnizki and Field [38] commonly are used in these calculations. One can avoid the use of mass and heat transfer correlations by rigorously solving the two-dimensional conservation equations within a domain surrounding a single fiber. This domain can be constructed from an assumed regular square or triangular fiber arrangement [39] or by defining an equivalent axisymmetric free surface surrounding the fiber [40] based on Happel’s free surface model [41]. Although not practiced commercially, two novel module designs were proposed recently [33]. The first design wraps a woven hollow fiber fabric simultaneously with a commercial spiral wound module spacer to form a bundle consisting of alternating layers of fiber and spacer. The second design requires knitting hollow fibers within the mesh of the spacer; the fiber knitted spacer is wrapped to form the bundle. The performance of these novel designs was compared to a randomly packed fiber bundle, a woven fabric fiber bundle (with and without a central distribution tube), and a crimped (curly or wavy) fiber bundle in direct contact membrane distillation. The highest water fluxes were observed for the fiber knitted spacer bundle followed closely by the crimped fiber bundle. These results were attributed to a transverse flow component across curved fibers that is not present when fibers are substantially straight and parallel. Park and Chang [42] demonstrated that with conventional lumen headers the lumen flow rate is highest near the center of the bundle and then decreases rapidly, passing through a minimum, before increasing again at the bundle periphery. Similar observations were made recently for hemodialyzers possessing ports that direct flow normal to the tubesheet but flow distribution could be enhanced by directing the flow tangentially to the tubesheet surface [43]. Such a conclusion is consistent with previous work on the formation of crimped fiber bundles for dialysis applications [34–36]. This literature identifies specific design ranges for the amplitude and frequency (wavelength) of the wavy structure to optimize performance: amplitude = 20–200% of the fiber outer diameter and wavelength = 10–500 times the fiber outer diameter. Fluid distribution from the shell manifold into the shell space also is non-uniform. Concentration fields within an operating hemodialyzer determined using X-ray computed tomography are consistent with higher shell flows closer to the external port on the shell distribution manifold [44]. The flow distribution can be altered significantly by modifying the manifold to direct flow into the Current Opinion in Chemical Engineering 2014, 4:18–24 Fluid distribution from external manifolds into the fiber bundle is least well understood. Ideally, fluid is introduced and removed such that the pressure drop across the lumen of each fiber is the same and the pressure drop between any two points in the shell, at the same radial position on opposing tubesheets, is the same. Equal pressure drops lead to uniform flow rates. www.sciencedirect.com Hollow fiber membrane modules Mat, Lou and Lipscomb 21 Figure 2 (a) (b) (c) (d) ΔP ΔP Current Opinion in Chemical Engineering Sources of non-ideal flow distribution within hollow fiber modules: (a) flow distribution from the lumen manifold into the fiber lumens; (b) flow distribution from the shell manifold into the shell; (c) fiber inner diameter induced lumen flow variation; and (d) inter-fiber spacing induced shell flow variation. The length of the arrows indicates the relative magnitude of the flow rate variation anticipated for each source. (a) and (b) contain the module elements indicated in Figure 1 while (c) and (d) are abstracted pictorial illustrations of a bundle axial cross-section. fiber bundle as well as around the fiber bundle using a porous distribution collar or tab [45]. Non-uniform fiber properties (e.g. size and transport properties) can lead to flow maldistribution in the lumen even with uniform pressure drop across each fiber. A fiber inner diameter variation leads to a flow rate variation that can dramatically reduce module performance, especially in the well-developed mass transfer limit (i.e. low feed flow rates) [46–48]. Analyses of gas separation modules indicate variability in fiber size has a much greater effect on performance than transport properties due to the dependence of flow rate on the fourth power of the inner diameter [49–51]. For sufficiently broad fiber size variations, a limit on the maximum gas purity achievable may exist but this effect can be mitigated by module staging [52]. Few comparisons between experiment and theory exist for commercial size modules, but a recent study indicates that the inclusion of the actual fiber size distribution in predictions of gas separation performance could www.sciencedirect.com not account for the performance reductions observed experimentally relative to a module with ideal flows [53]; the differences were attributed to poor shell flow distribution as discussed here. Non-uniform fiber packing affects module performance in a manner analogous to the effect of fiber inner diameter. Variation in the shell space between fibers will lead to flow rate variation that can be detrimental to performance. The variation may be so large that fluid effectively bypasses the fiber bundle as first noted by Noda et al. [54]. Chen and Hlavacek describe an algorithm for representing the variation in shell void volume for randomly packed parallel fiber bundles using Voronoi tessellation [55]. The flow through a cross-section of the bundle can be calculated from the hydraulic diameter of each tessellated cell and an appropriate friction factor relationship. This algorithm has been used to evaluate overall effective mass transfer coefficients by flow rate averaging individual cell mass transfer coefficients Current Opinion in Chemical Engineering 2014, 4:18–24 22 Separation engineering [56,57]. Mass transfer coefficients for each cell are determined from the hydraulic diameter of the cell and an appropriate mass transfer coefficient correlation. An alternative algorithm represents the variation in shell void volume by surrounding a representative distribution of fibers with a Happel free surface of varying radius [58]. The detrimental effect of random packing in parallel fiber bundles has been reported for a variety of membrane separations including membrane distillation [59], membrane extraction [60], and gas–liquid contactors [61,62]. The effects of a simultaneous variation in fiber outer radius [63] and a fractal distribution of shell void volumes [64] also have been investigated. Reported agreement between experiment and theory generally is good using one or more of the shell mass transfer coefficient correlations available in the literature. Differences between theory and experiment typically are attributed to poor flow distribution from the shell manifold into the shell region. Use of Voronoi tessellation or the free surface model can be avoided through the use of a periodic cell containing a finite number of randomly packed fibers to represent an infinite fiber bundle [65]. The periodic cell must contain a sufficiently large number of fibers to provide an accurate representation but the number required can be determined by increasing the cell size until the results are independent of number. The computational demand of the simulation can be reduced in the entry [66] and well developed [67] mass transfer limits where partial analytical solutions for the concentration field are available. Comparisons of results obtained with the periodic cell and either Voronoi tessellation or the free surface model are limited but the periodic cell appears to predict slightly lower values for effective mass transfer coefficient [63]. Fluid distribution from the shell manifold across the fiber bundle represents an additional source of flow maldistribution in the shell. Fluid must flow from the shell inlet distribution manifold across the fiber bundle before it can flow along the fiber bundle toward the outlet; likewise, the fluid also must flow across the fiber bundle at the outlet end before it can be collected in the outlet manifold. This flow introduces a cross-flow component to the nominally counter-current flow as well as a residence time distribution due to different flow path lengths between the inlet and outlet distribution manifolds; the paths near the shell outlet are illustrated in Figure 1. Attempts to evaluate fluid distribution have relied on approximating the shell region as a porous media within which Darcy’s law provides the relationship between volume-average pressure and velocity [68,69]. This work demonstrates the residence time distribution and its effect on overall shellside mass transfer coefficient depends on the product of the radial to axial Darcy permeability ratio and the square of the module aspect ratio (length to radius ratio). Darcy’s Current Opinion in Chemical Engineering 2014, 4:18–24 law has been used to describe flow in the lumen as well as the shell to evaluate the effect of shell-side flow distribution on gas separation [70] and hemodialysis [71]. The results indicate that the residence time distribution can lead to large concentration gradients at the lumen and shell outlets but these gradients have surprisingly little effect on module performance. Recent work on shellswept modules for gas dehydration is consistent with these observations in that large concentration gradients exist within the module but have minimal impact on performance [72]. Recent attempts to reduce concentration polarization in the shell region rely on novel fiber shapes. Fibers with a corrugated or convoluted circumference can increase the membrane area available per unit module volume as well as enhance fluid mixing and thereby reduce concentration polarization [73,74,75]. Recent work also demonstrates that use of elliptical fibers can improve performance [76] as well as introducing baffles around individual fibers [77]. Future challenges and conclusions The patent literature describing the formation of large hollow fiber bundles and modules dates back nearly 50 years. Industry currently favors the manufacture of structured bundles using hollow fiber fabrics or spiral winding techniques that offer better shell flow distribution and lower mass transfer resistance. Fiber crimping also has been introduced to reduce mass transfer resistances. The introduction of fluid into the shell region of these devices has received significant attention as it can impact performance significantly. The analysis of hollow fiber membrane module performance most commonly relies on assuming all fibers are identical and the flow rates in the fiber lumen and shell region surrounding each fiber are identical. However, variability in fiber size and packing can reduce module performance dramatically. Well-developed algorithms exist to assess the uniformity of shell and lumen flows and their effect on performance. The effect of fluid distribution into the lumen and shell regions of the fiber bundle through external ports and manifolds has received less attention. The impact of the lumen manifold on lumen flow uniformity appears to be less significant than the effect of the shell manifold on shell flow uniformity. However, additional work is required to clarify the influence of both, especially distribution from the shell manifold which has been invoked as the source of unexplained performance deviations. Theoretical analyses of modern fiber bundle designs that utilize fiber fabrics and crimped fibers have lagged commercial implementation. The availability of simulation tools would help guide the evolution of these designs and foster future innovations. www.sciencedirect.com Hollow fiber membrane modules Mat, Lou and Lipscomb 23 Comparisons of theoretical performance predictions to experimental measurements for commercial scale units are limited. Comparisons to hand-made, lab-scale units can help assess simulation fidelity. However, conclusions drawn from these units may not be applicable to larger commercial modules due to manufacturing expertise that leads to improved fiber and fiber bundle uniformity as well as differences in module scale, for example, fluid distribution from the shell manifold into the shell region is expected to depend on the ratio of fiber outer diameter to bundle diameter for sufficiently small bundles. As higher performance membrane materials become available with greatly enhanced permeances, concentration polarization and pressure drops will become more important considerations in module design. Emerging applications in forward osmosis are especially sensitive to concentration polarization while carbon dioxide capture applications require low pressure drop designs. References and recommended reading Papers of particular interest, published within the period of review, have been highlighted as: of special interest of outstanding interest 1. Mahon HI: Permeability Separatory Apparatus, Permeability Separatory Membrane Element, Method of Making the Same and Process Utilizing the Same, US Patent 3,228,876; 1966. 2. Maxwell JM, Moore WE, Rego RD: Fluid Separation Process and Apparatus, US Patent 3,339,341; 1967 This patent clearly identifies the key issues in module manufacture and the sources of non-ideal behavior early in the history of the field — a must read for those interested in module design. 3. Alei PE, Schletz JC, Jensvold JA, Tegrotenhuis WE, Allen W, Coan FL, Skala KL, Clark DO, Wait HV: Loom Processing of Hollow Fiber Membranes, US Patent 5,598,874; 1997. 15. Giglia S, Bikson B: Hollow Fiber Membrane Separation Apparatus, US Patent 5,837,033; 1998. 16. 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