Cellulose acetate membranes from water

Permeability constants for membranes must be determined experimentally for the particular type of membrane to be used. For cellulose acetate membranes, typical water permeability constants A , range from about 1 x 10to 5 X 10" kg solvents/s m -atm (Al, M3, Wl). Values for other types of membranes can differ widely. Generally, the water permeability constant for a particular membrane does not depend upon the solute present. For the solute permeability constants of cellulose acetate membranes, some relative typical values are as follows, assuming a value of = 4 X 10 m/s for NaCl 1.6 x 10 m/s (BaClz), 2.2 X 10" (MgClz), 2.4 x 10 (CaClj), 4.0 X 10 (Na2S04>, 6.0 x 10 (KCl), 6.0 x 10 (NH4CI) (Al). 

Fig. 9. SEM photographs of cellulose acetate membranes cast from a solution of acetone (volatile solvent) and 2-meth5l-2,4-pentanediol (nonvolatile solvent). The evaporation time before the stmcture is fixed by immersion ia water is shown (24).

The successful development of asymmetric cellulose acetate membranes by Loeb and Sourirajan in the early sixties, at the University of California, Los Angeles, has been primarily responsible for the rapid development of Reverse Osmosis (RO) technology for brack sh/sea water desalination. Reverse Osmosis approaches a reversible process when the pressure barely exceeds the osmotic pressure and hence the energy costs are quite low. Theenergy requirement to purify one litre of water by RO is only O.OO3 KW as against 0,7 KV required just to supply the vaporisation energy to change the phase of one litre of water from liquid to vapour by evaporation. Thus RO has an inherent capability to convert brackish water to potable water at economic cost and thus contribute effectively to the health and prosperity of all humanity. 

Results of this study confirm the expected improved recoveries of trace organics with membranes more selective and more highly cross-linked than the classical cellulose acetate membrane. Improved recoveries were predicted from literature data reported for similar membrane types. In light of these results, cellulose acetate should no longer be considered for applications such as these. Further improvements in recovery can be expected as developmental membranes with more highly selective barriers are brought into commercial use. Each new membrane type considered for use on disinfected waters should be evaluated for sensitivity to common disinfectants (oxidants). Both decreased selectivity and potentially troublesome chemical breakdown products should be considerations under these conditions. Although the cellulose acetate and FT-30 composite membranes did not prove to be particularly sensitive to chlorine, many commercially available... 

Wrasidlo 79) fabricated semipermeable poly(N-amide)imide (26) membrane from 3,3, 4,4 -benzophenonetetracarboxylic dianhydride (27) and isophthalic dihydrazide (28). The membrane with 28 i thickness had a water flux of 11401/m2 day-2000 A and salt rejection of 99.95%, while a 39.8% acetylated cellulose acetate membrane with 16 ji thickness had values of 118 1/m2 day and 99.35%. 

Figure 2.15 Measurements of Rosenbaum and Cotton [20] of the water concentration gradients in a laminated reverse osmosis cellulose acetate membrane under applied pressures of 68 and 136 atm. Reprinted from Steady-state Distribution of Water in Cellulose Acetate Membrane, S. Rosenbaum and O. Cotton, J. Polym. Sci. 7, 101 Copyright 1969. This material is used by permission of John Wiley Sons, Inc.

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... 

The salinity of brackish water is usually between 2000 and 10 000 mg/L. The World Health Organization (WHO) recommendation for potable water is 500 mg/L, so up to 90 % of the salt must be removed from these feeds. Early cellulose acetate membranes could achieve this removal easily, so treatment of brackish water was one of the first successful applications of reverse osmosis. Several plants were installed as early as the 1960s. 

Most gas separation processes require that the selective membrane layer be extremely thin to achieve economical fluxes. Typical membrane thicknesses are less than 0.5 xm and often less than 0.1 xm. Early gas separation membranes [22] were adapted from the cellulose acetate membranes produced for reverse osmosis by the Loeb-Sourirajan phase separation process. These membranes are produced by precipitation in water the water must be removed before the membranes can be used to separate gases. However, the capillary forces generated as the liquid evaporates cause collapse of the finely microporous substrate of the cellulose acetate membrane, destroying its usefulness. This problem has been overcome by a solvent exchange process in which the water is first exchanged for an alcohol, then for hexane. The surface tension forces generated as liquid hexane is evaporated are much reduced, and a dry membrane is produced. Membranes produced by this method have been widely used by Grace (now GMS, a division of Kvaemer) and Separex (now a division of UOP) to separate carbon dioxide from methane in natural gas. 

A continuous effect is the decrease in water content and void volume with Increasing temperature. Water is lost from the primary gel during annealing, both because of the formation of virtual crosslinks and because of the decrease in hydrogen bonding and cluster size in the water Itself. An example of a discontinuous effect is the dramatic increase in permselectivity (salt rejection) observed when cellulose acetate membranes are heated above the glass transition temperature 68.6 C. In fact, not one but two... 

A new cellulose acetate membrane for hemofiltration was developed by employing the mixtures of liquids of opposite properties for both solvent for cellulose diacetate and additive to the polymer solution. The additive was composed of water and organic solvents of limited water solubility. The role of the additive is likely to have somewhat different aspect from that of other additives known so far. 

It is to this topic of solute preferential sorption in reverse osmosis that this paper is dedicated. Specifically, this discussion will involve a description of solute preferential sorption, an overview of the literature in the area, and finally a presentation of some recent work on the removal of aromatic hydrocarbons from water. The significance of this work is at least two-fold. From a practical point of view the classes of solutes which demonstrate preferential attraction to the membrane material tend to be organic compounds and the removal and recovery of these solutes from water is environmentally and economically important. From a theoretical point of view an understanding of the phenomena involved is essential to the achievement of a fundamental description of the RO process. Although this paper deals solely with aqueous solutions and cellulose acetate membranes, it Is important to recognize that the concepts discussed can be extended to Include other membrane materials and non-aqueous systems. 

The functional stability of GOD membranes has also been enhanced by coupling with an asymmetric ultrafiltration membrane (Koyama et al., 1980). The GOD-cellulose acetate membrane used was prepared as follows 250 mg cellulose triacetate was dissolved in 5 ml dichloro-methane, the solution was mixed with 0.2 ml 50% glutaraldehyde and 1 ml l,8-diamino-4-amino methyl octane and sprayed onto a glass plate. After three days the membrane was removed from the support and immersed in 1% glutaraldehyde solution for 1 h at 35°C, rinsed with water and exposed for 2-3 h to phosphate buffer, pH 7.7, containing 1 mg/ml GOD. The membrane was then treated with sodium tetraborate, rinsed with water and stored at 4-lO°C until use. It was combined with the ultrafiltration membrane in the following way 20 mg cellulose diacetate was dissolved in 35 g formamide and 45 g acetone and cast on a glass plate. At room temperature the solvents evaporated within a few seconds and a membrane of about 30 pm thickness remained, which was kept in ice water for 1 h before application in the sensor. 

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