Cellulose acetate membranes plasticization

In 1966, Cadotte developed a method for casting mlcroporous support film from polysulfone, polycarbonate, and polyphenylene oxide plastics ( ). Of these, polysulfone (Union Carbide Corporation, Udel P-3500) proved to have the best combination of compaction resistance and surface microporosity. Use of the mlcroporous sheet as a support for ultrathin cellulose acetate membranes produced fluxes of 10 to 15 gfd, an increase of about five-fold over that of the original mlcroporous asymmetric cellulose acetate support. Since that time, mlcroporous polysulfone has been widely adopted as the material of choice for the support film in composite membranes, while finding use itself in many ultrafiltration processes. 

The process shown in Figure 9.21 was first developed by Separex, using cellulose acetate membranes. The separation factor for methanol from MTBE is high (>1000) because the membrane material, cellulose acetate, is relatively glassy and hydrophilic. Thus, both the mobility selectivity term and the sorption term in Equation (9.5) significantly favor permeation of the smaller molecule, methanol, because methanol is more polar than MTBE or isobutene, the other feed components. These membranes are reported to work well for feed methanol concentrations up to 6%. Above this concentration, the membrane is plasticized, and selectivity is lost. More recently, Sulzer (GFT) has also studied this separation using their plasma-polymerized membrane [56],... 

A decade after Dr. Hassler s efforts, Sidney Loeb and Srinivasa Sourirajan at UCLA attempted an approach to osmosis and reverse osmosis that differed from that of Dr. Hassler. Their approach consisted of pressurizing a solution directly against a flat, plastic film.3 Their work led to the development of the first asymmetric cellulose acetate membrane in 1960 (see Chapter 4.2.1).2 This membrane made RO a commercial viability due to the significantly... 

Meier, M. M., Kanis, L. A., and Soldi, V. (2004), Characterization and drug-permeation profiles of microporous and dense cellulose acetate membranes Influence of plasticizer and pore forming agent, Int. J. Pharm., 278, 99-110. 

Another industrial application of gas-separation membranes is the removal of carbon dioxide from natural gas. The CO2/CH4, selectivity is about 20 to 30 for polycarbonate, polysulfone, and cellulose acetate membranes at 35°C and 40 atm. A selectivity of over 60 can be obtained with Kapton , but this polymer is much less permeable than the others. Increasing the temperature raises the permeability of most polymers but generally causes a. slight decrease in selectivity. The operating temperature is chosen to be somewhat above the dew point of the residue gas. There is considerable COj absorbed in the membranes at high CO2 partial pressures, and the plasticization effect of CO2 increases the effective diffusion coefficients for all gases and makes the selectivity less than that based on pure-gas data. Methods of allowing for such nonlinear effects have been presented. ... 

In this type of module a number of membranes of tubular shape are encased in a container. For example, 18 tubes are connected in scries by headers at both ends of the Nitto NTR-1500-PI 8A module. Figures 7.9 and 7.10 show the structure of the module. Cellulose acetate membranes are formed in the internal wall of the support tube of 12-mm internal diameter The tubular membranes so prepared are inserted into plastic tubes with many holes, which are mounted in a module container. The feed liquid flows inside the tube, and the permeate flows from the inside to the outside of the membrane tube and is collected at the permeate outlet. There are also tubular modules in which the feed is supplied to the outside of the membrane tube. The main features of the tubular module are... 

A decade after Dr. Hassler s efforts, Sidney Loeb and Srinivasa Sourirajan at UCLA attempted an approach to osmosis and reverse osmosis that differed from that of Dr. Hassler. Iheir approach consisted of pressurizing a solution directly against a flat, plastic film. Their work led to the development of the first asymmetric cellulose acetate membrane in 1960 (see Chapter 4.2.1). This membrane made RO a commercial viability due to the significantly improved flux, which was 10 times that of other known membrane materials at the time (such as Reid and Breton s membranes). These membranes were first cast by hand as flat sheets. Continued development in this area led to casting of tubular membranes. Figure 1.3 is a schematic of the tubular casting equipment used by Loeb and Sourirajan. Figure 1.4 shows the capped, in-floor immersion well that was used by Loeb and students and is still located in Boelter Hall at UCLA. 

Traditionally, ultrafilters have been manufactured from cellulose acetate or cellulose nitrate. Several other materials, such as polyvinyl chloride and polycarbonate, are now also used in membrane manufacture. Such plastic-type membranes exhibit enhanced chemical and physical stability when compared with cellulose-based ultrafiltration membranes. An important prerequisite in manufacturing ultrafilters is that the material utilized exhibits low protein adsorptive properties. 

Filtration can remove fine suspended solids and microorganisms, and microfiltration membranes of cellulose acetate or polyamides are available that have pores 0.1-20 /xm in diameter. Clogging of such fine filters is an ever-present problem, and it is usual to pass the water through a coarser conventional filter first. Ultrafiltration with membranes having pores smaller than 0.1 fim requires application of pressures of a few bars to keep the membrane surface free of deposits, water flows parallel to the membrane surfaces, with only a small fraction passing through the membrane. The membranes typically consist of bundles of hollow cellulose acetate or polyamide fibers set in a plastic matrix. Ultrafiltration bears some resemblance to reverse osmosis technology, described in Section 14.4, with the major difference that reverse osmosis can remove dissolved matter, whereas ultrafiltration cannot. 

Polybenzimidazolone membrane 21 developed by Teijin Ltd. had the following permeative characteristics Water permeation, 840 1/m2 - day salt rejection, 99.5% (1% NaCl aqueous solution, 80 kg/cm2)69). The membrane was less sensitive to plasticization with water than cellulose acetate and aromatic polyamide membranes... 

The discussion directly following Eq (6) provides a simple, physically reasonable explanation for the preceding observations of marked concentration dependence of Deff(C) at relatively low concentrations. Clearly, at some point, the assumption of concentration independence of Dp and in Eq (6) will fail however, for our work with "conditioned" polymers at CO2 pressures below 300 psi, such effects appear to be negligible. Due to the concave shape of the sorption isotherm, even at a CO2 pressure of 10 atm, there will still be less than one CO2 molecule per twenty PET repeat units at 35°C. Stern (26) has described a generalized form of the dual mode transport model that permits handling situations in which non-constancy of Dp and Dh manifest themselves. It is reasonable to assume that the next generation of gas separation membrane polymers will be even more resistant to plasticization than polysulfone, and cellulose acetate, so the assumption of constancy of these transport parameters will be even more firmly justified. 

Other system variables that will have an effect on the separation process are temperature and relative humidity of the gas. Increasing the temperature raises most permeabilities by about 10 to 15% per 10°C and has little effect on separation factors. The effect of relative humidity is variable depending upon the membrane used. High relative humidities, greater than 95%, are generally detrimental due to membrane plasticization. Contamination with liquid water has been found to dramatically reduce membrane performance for cellulose acetate ... 

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