Membranes Permasep

In 1971, E. I. Du Pont De Nemours Company, Inc. (DuPont) patented a linear aromatic polyamide with pendant sulfonic acid groups, which they commercialized as the Permasep B-9 and B-10 membranes (Permasep is a registered trademark of DuPont Company, Inc. Wilmington, DE). These membranes exhibited higher water flux at slightly lower operating pressures than cellulose acetate membranes. The membranes were cast as unique hollow fine fibers rather than in flat sheets or a tubes (see Chapter 4.3.4). 

Another important membrane useful for seawater, wastewater, nickel-plating rinse solutions, and other solutes is the synthetic aromatic polyamide membrane Permasep, made in the form of very fine hollow fibers (LI, P3). This type of membrane used industrially withstands continued operation at pH values of 10 to 11 (S4). Many other anisotropic membranes have also been synthesized of synthetic polymers, some of which can be used in organic solvents, at higher temperatures, and at high or low pH (M2, Rl). 

Fig. 13. A hoUow-fibet reverse osmosis membrane element. Courtesy of DuPont Permasep. In this twin design, the feedwater is fed under pressure into a central distributor tube where half the water is forced out tadiaUy through the first, ie, left-hand, fiber bundle and thus desalted. The remaining portion of the feedwater flows through the interconnector to an annular feed tube of the second, ie, right-hand, fiber bundle. As in the first bundle, the pressurized feedwater is forced out tadiaUy and desalted. The product water flows through the hoUow fibers, coUects at each end of the element, and exits there. The concentrated brine from both bundles flows through the concentric tube in the center of the second bundle and exits the element on the right.

In summary, we have demonstrated the successful operation of a "Permasep" RO pleint on biologically active feed waters by using the intermittent injection of iodine as a bacterial control measure. The use of this shock procedure allowed for steady, continuous performcince of the plant euid is expected to have significant impact on future applications of PA membranes to biological action as well as waste waters. 

Figure 19.5. The Permasep hollow fiber module for reverse osmosis, (a) Cutaway of a DuPont Permasep hollow fiber membrane module for reverse osmosis a unit 1 ft dia and 7 ft active length contains 15-30 million fibers with a surface area of 50,000-80,000 sqft fibers are 25-250 pm outside dia with wall thickness of 5-50pm (DuPont Co.), (b) The countercurrent flow pattern of a Permasep module.

Nonetheless a few commercially successful noncellulosic membrane materials were developed. Polyamide membranes in particular were developed by several groups. Aliphatic polyamides have low rejections and modest fluxes, but aromatic polyamide membranes were successfully developed by Toray [25], Chemstrad (Monsanto) [26] and Permasep (Du Pont) [27], all in hollow fiber form. These membranes have good seawater salt rejections of up to 99.5 %, but the fluxes are low, in the 1 to 3 gal/ft2 day range. The Permasep membrane, in hollow fine fiber form to overcome the low water permeability problems, was produced under the names B-10 and B-15 for seawater desalination plants until the year 2000. The structure of the Permasep B-15 polymer is shown in Figure 5.7. Polyamide membranes, like interfacial composite membranes, are susceptible to degradation by chlorine because of their amide bonds. 

As Figure 5.12 shows, Toray s PEC-1000 crosslinked furfuryl alcohol membrane has by far the best sodium chloride rejection combined with good fluxes. This explains the sustained interest in this membrane despite its extreme sensitivity to dissolved chlorine and oxygen in the feed water. Hollow fine fiber membranes made from cellulose triacetate by Toyobo or aromatic polyamides by Permasep (Du Pont) are also comfortably in the one-stage seawater desalination performance range, but the water fluxes of these membranes are low. However, because large-surface-area, hollow fine fiber reverse osmosis modules can be... 

Brodie crystallizer-purifier, 545, 547 Kureha purifier, 545,547 multistage, 543 MWB process, 543,545 Phillips process, 544-546 Schilaknecnt column, 543,544,546 TNO bouncing ball process 545.547 Melt purification. See Melt crystallization Membranes, 631,632,641 applications, 632 cellulose acetate, 635 equipment configurations, 632 gas permeation,633,644 hollow fiber, 632,633,641,643 performance, 646 Permasep, 641 olate and frame, 638 Prism, 633,643 properties, 635,636 structures, 632 tubular, 638,639 types, 635, 636... 

Fig. 15. A commercial cartridge containing hollow fiber membranes. This is a Permasep cartridge made by DuPont.

Membrane research and development started in Du Pont in 1962 and culminated in the introduction of the first B-9 Permasep permeator for desalination of brackish water by reverse osmosis (RO) in 1969. The membrane in this B-9 Permasep module consisted of aramid hollow fibers. In 1969, proponents of RO technology had ambitious dreams and hopes. Today, RO is a major desalination process used worldwide to provide potable water from brackish and seawater feeds. Du Font s membrane modules for RO are sold under the trademark Permasep permeators. The RO business is a virtually autonomous profit center that resides in the Polymer Products Department. The growth and success of the Permasep products business is a direct result of Du Font s sustained research and development commitment to polyamides, a commitment that dates back to the 1930 s and the classic polymer researches of Wallace H. Carothers. Since 1969, improved and new Permasep permeators have been introduced six times, as shown in Table I. 

Du Pont does not currently market Permasep permeators for gas separations. They did, however, in the B-1 Permasep permeator, introduce the first commercial, hollow fiber permeator for gas separations. This permeator employed hollow fibers of polyethylene terephthalate as the membrane. Later, permeators having aramid hollow fiber membranes were field tested for hydrogen separations. Du Pont is presently actively engaged in research for the development of membrane technology for a wide variety of applications. 

This brief historical summary of Permasep permeator developments introduces the subject of structure-property relationships for membranes from aromatic polyamides and derivatives. 

The membranes in Du Font s B-9 and B-10 Permasep permeators consist of bundles of aramid hollow fibers. A drawing illustrating the construction of B-9 and B-10 modules is shown in Figure 8 (23, 24). 

Specifications for B-9 and B-10 Permasep permeators are given in Du Font s PEM (Permasep Engineering Manual) (23) and in Du Font s Hollow Fiber Membranes (24). These references also... 

Some hydrolysis of the trimesoyl chloride takes place during membrane fabrication. ESCA studies indicated that approximately one-sixth of the carboxyl groups ere present as ionic carboxylate and five-sixths of the carboxyl groups are present as amides, leading to the above structure. The FT-30 barrier layer is insoluble in sulfuric acid and in all organic solvents, in agreement with the crosslinked nature indicated above. Its chemical structure is somewhat similar to the composition of the duPont Permasep B-9 hollow fiber polyamide, believed to be approximately as follows ... 

These organic rejections, while greatly exceeding the capabilities of cellulose acetate membranes, are not appreciably different than rejection levels exhibited by aromatic polyamide membranes (FT-30, Permasep B-9). Nor do they match the organic rejection characteristics of the PEC-1000 membrane. The Solrox membrane is not resistant to chlorine, and its water flux is somewhat low (about 25 gfd at 650 psi net driving pressure). Consequently, it has not become a significant competitive membrane in the world marketplace. 

In this context, only two polymers have ever been used on a large scale in asymmetric membranes cellulose acetate and Permasep B-9/B-10 aramids. The former polymer predates the era of reverse osmosis membranes. The latter polymer has been used in hollow fiber membranes for 15 years. Attempts to bring other new polymers into asymmetric membrane production have been few (PBIL, PBI, polypiperazineamides), generally without particular success. 

Mehta GD, Loeb S (1978) Performance of permasep B-9 and B-10 membranes in various osmotic regions and at high osmotic pressures. J Membr Sci 4 335-349... 

---