Membrane module composite membranes

In this chapter we have shown that the main trend in Pd-based membrane development is towards thinner membranes, particularly composite membranes. The relatively demanding operation conditions in many important applications require further work in terms of membrane development in combination with optimisation of reactor design and operation conditions. The encouraging industrial involvement in the development of the membrane, module and reactor technology is a key factor for successful implementation. Current state-of-the-art shows capability of small scale industrial membrane production of the most common Pd-based composite membranes. Their stability has been verified for thousands of hours under realistic conditions, but in processes free of some of the most hazardous components, e.g. sulfur. 

Hollow-fiber designs are being displaced by spiral-wound modules, which are inherently more fouling resistant, and require less feed pretreatment. Also, thin-film interfacial composite membranes, the best reverse osmosis membranes available, have not been fabricated in the form of hoUow-fine fibers. 

The first reverse osmosis modules made from cellulose diacetate had a salt rejection of approximately 97—98%. This was enough to produce potable water (ie, water containing less than 500 ppm salt) from brackish water sources, but was not enough to desalinate seawater efficiently. In the 1970s, interfacial composite membranes with salt rejections greater than 99.5% were developed, making seawater desalination possible (29,30) a number of large plants are in operation worldwide. 

The separation efficiency (e.g. permselectivity and permeability) of inorganic membranes depends, to a large extent, on the microstructural features of the membrane/support composites such as pore size and its distribution, pore shape, porosity and tortuosity. The microstructures (as a result of the various preparation methods and the processing conditions discussed in Chapter 2) and the membrane/support geometry will be described in some detail, particularly for commercial inorganic membranes. Other material-related membrane properties will be taken into consideration for specific separation applications. For example, the issues of chemical resistance and surface interaction of the membrane material and the physical nature of the module packing materials in relation to the membranes will be addressed. 

Albany International Research Co. has developed an advanced hollow fiber composite reverse osmosis membrane and module under the name of Quantro II . This composite membrane is comprised of a porous hollow fiber substrate on which has been deposited a rejection barrier capable of fluxes of commercial importance at high rejection of dissolved salts at elevated temperatures. Resistance to active chlorine has been demonstrated. Proprietary processes have been developed for spinning of the fiber, establishment of the rejection barrier and processing of the fiber to prepare modules of commercial size. Prototype modules are currently in field trials against brackish and seawater feed solutions. Applications under consideration for this membrane include brackish and seawater desalination as well as selected industrial concentration processes. 

Research effort at Albany International Research Co. has developed unit processes necessary for pilot scale production of several species of reverse osmosis hollow fiber composite membranes. These processes include spin-dope preparation, a proprietary apparatus for dry-jet wet-spinning of microporous polysul-fone hollow fibers, coating of these fibers with a variety of permselective materials, bundle winding using multifilament yarns and module assembly. Modules of the membrane identified as Quantro II are in field trial against brackish and seawater feeds. Brackish water rejections of 94+% at a flux of 5-7 gfd at 400 psi have been measured. Seawater rejections of 99+% at 1-2 gfd at 1000 psi have been measured. Membrane use requires sealing of some portion of the fiber bundle for installation in a pressure shell. Much effort has been devoted to identification of potting materials which exhibit satisfactory adhesion to the fiber while... 

Many aspects of the social behavior of cells are determined by the composition, arrangement, and interaction of cell-surface molecules. Therefore, changes in the composition and structure of plasma membranes appear to contribute to differences in such characteristics as cell adhesion, contact inhibition, and tumorogenicity of cells. Cell-surface glycoproteins, in particular, participate in a number of membrane-modulated phenomena, including responsiveness to hormones, agglutination by lectins, recognition by antibodies, or uptake of nutri-... 

The technology to fabricate ultrathin high-performance membranes into high-surface-area membrane modules has steadily improved during the modem membrane era. As a result the inflation-adjusted cost of membrane separation processes has decreased dramatically over the years. The first anisotropic membranes made by Loeb-Sourirajan processes had an effective thickness of 0.2-0.4 xm. Currently, various techniques are used to produce commercial membranes with a thickness of 0.1 i m or less. The permeability and selectivity of membrane materials have also increased two to three fold during the same period. As a result, today s membranes have 5 to 10 times the flux and better selectivity than membranes available 30 years ago. These trends are continuing. Membranes with an effective thickness of less than 0.05 xm have been made in the laboratory using advanced composite membrane preparation techniques or surface treatment methods. 

Currently, approximately one billion gal/day of water are desalted by reverse osmosis. Half of this capacity is installed in the United States, Europe, and Japan, principally to produce ultrapure industrial water. The remainder is installed in the Middle East and other desert regions to produce municipal drinking water from brackish groundwater or seawater. In recent years, the interfacial composite membrane has displaced the anisotropic cellulose acetate membrane in most applications. Interfacial composite membranes are supplied in spiral-wound module form the market share of hollow fiber membranes is now less than... 

A simplified flow scheme for a brackish water reverse osmosis plant is shown in Figure 5.24. In this example, it is assumed that the brackish water is heavily contaminated with suspended solids, so flocculation followed by a sand filter and a cartridge filter is used to remove particulates. The pH of the feed solution might be adjusted, followed by chlorination to sterilize the water to prevent bacterial growth on the membranes and addition of an anti-sealant to inhibit precipitation of multivalent salts on the membrane. Finally, if chlorine-sensitive interfacial composite membranes are used, sodium sulfite is added to remove excess chlorine before the water contacts the membrane. Generally, more pretreatment is required in plants using hollow fiber modules than in plants using spiral-wound modules. This is one reason why hollow fiber modules have been displaced by spiral-wound systems for most brackish water installations. 

The industry is extremely competitive, with the manufacturers producing similar products and competing mostly on price. Many incremental improvements have been made to membrane and module performance over the past 20 years, resulting in steadily decreasing water desalination costs in inflation-adjusted dollars. Some performance values taken from a paper by Furukawa are shown in Table 5.5. Since 1980, just after the introduction of the first interfacial composite membranes, the cost of spiral-wound membrane modules on a per square meter basis has decreased seven-fold. At the same time the water flux has doubled, and the salt permeability has decreased seven-fold. Taking these improvements into account, today s membranes are almost 100 times better than those of the 1980s. This type of incremental improvement is likely to continue for some time. 

Salts rejected by the membrane stay in the concentrating stream but are continuously disposed from the membrane module by fresh feed to maintain the separation. Continuous removal of the permeate product enables the production of freshwater. RO membrane-building materials are usually polymers, such as cellulose acetates, polyamides or polyimides. The membranes are semipermeable, made of thin 30-200 nanometer thick layers adhering to a thicker porous support layer. Several types exist, such as symmetric, asymmetric, and thin-film composite membranes, depending on the membrane structure. They are usually built as envelopes made of pairs of long sheets separated by spacers, and are spirally wound around the product tube. In some cases, tubular, capillary, and even hollow-fiber membranes are used. 

Figure 11.3 Partial fluxes of isoamyl alcohol, ethyl acetate, isoamyl acetate and ethyl hexanoate as a function of their feed crossflow velocity (bottom axis) and Reynolds number (top axis) in a singlechannel module, using a POMS-PEI composite membrane. Notice that external mass-transfer limitations are not fully overcome when soluteswith a high affinity towardsthe membrane are processed (Adapted from Ref. 32.)...

Most important for the regulation of the membrane architecture are membrane potential, intracellular Ca2+ concentration, pH, changes in lipid composition due to the action of phospholipases and cell-cell coupling as well as the coupling of the membrane to the cytoskeleton and the extracellular matrix. Membrane architecture is additionally modulated by ions, lipo- and amphiphilic hormones, metabolites, drugs, lipid-binding peptide hormones, and amphitropic proteins [44]. 

Figure 11.1 Model of a composite membrane, bending because of a stress in the thin layer deposited by plasma polymerization onto a flexible polymeric substrate layer and substrate have thickness d and D and Young s module e and E, respectively.

Processes for production of ethanol and acetone-butanol-ethanol mixture from fermentation products in membrane contactor devices were presented in Refs. [88,89]. Recovery of butanol from fermentation was reported in Ref. [90]. Use of composite membrane in a membrane reactor to separate and recover valuable biotechnology products was discussed in Refs. [91,92]. A case study on using membrane contactor modules to extract small molecular weight compounds of interest to pharmaceutical industry was shown in Ref. [93]. Extraction of protein and separation of racemic protein mixtures were discussed in Refs. [94,95]. Extractions of ethanol and lactic acid by membrane solvent extraction are reported in Refs. [96,97]. A membrane-based solvent extraction and stripping process was discussed in Ref. [98] for recovery of Phenylalanine. Extraction of aroma compounds from aqueous feed solutions into sunflower oil was investigated in Ref. [99]. 

Polymeric flat sheet membranes are easy to prepare, handle, and mount. For gas separation, the flat sheet membranes are composites with a selective polymer coated on a support. A commercial configuration that has been quite successful for hydrocarbon vapor recovery is the Borsig envelope type module (see Figure 4.19) [107]. Packing densities for flat sheet membranes may be in the range of 100 00 m /m [1]. 

Different supports are used, (see Section 10.6.4) with different geometry (discs or tubes), thickness, porosity, tortuosity, composition (alumina, stainless steel, silicon carbide, mullite, zirconia, titania, etc.), and symmetry or asymmetry in its stmcture. Tubular supports are preferable compared to flat supports because they are easier to scale-up (implemented as multichannel modules). However, in laboratory-scale synthesis, it is usually found that making good quality zeolite membranes on a tubular support is more difficult than on a porous plate. One obvious reason is the fact that the area is usually smaller in flat supports, which decreases the likelihood of defects. In Figure 10.1, two commercial tubular supports, one made of a-alumina (left side) and the other of stainless steel (right side) used in zeolite membrane synthesis, are shown. Both ends of the a-alumina support are glazed and both ends of the stainless steel support are welded with nonporous stainless steel to assure a correct sealing in the membrane module and prevent gas bypass. 

The specifications of the membrane module, which was supplied by the Desalination Division of the BARC (Mumbai), are listed in Table 33.2. The RO setup installed at the delay tank site is shown in Figure 33.3. The delay tank water composition is given in Table 33.1. The module was operated at a pressure of 15 bar, which was adjusted by a throttle valve placed on the reject line. The experiments were performed both in once-through and recirculation modes. The alpha and beta activities, and nitrate and TDS levels were periodically monitored by sampling the feed, permeate, and reject solutions using standard analytical methods. 

Typical membranes in NF are thin film composite membranes and their surface layers are mostly proprietary and not very easily identified by the user. Some industrial use of sulfonated polyethersulfone membranes has also been seen (see Section 35.6.2. Linpac recycle paper mill in Cowpens, South Carolina). Tubular and spiral wound modules are the dominating module type in NF and RO. Both membrane processes are used in industrial-scale applications in the pulp and paper industry (Table 35.1). When the membranes are installed in spiral wound modules, water pretreatment is often important to prevent plugging of the modules and fouling of the membranes. 

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