Phenol transport in cellulose acetate membranes

Past detailed studies of solute transport through reverse-osmosis membranes have been conducted only with simple salts. The present work with phenol was undertaken largely because of the practical observation that the transport of low molecular weight organics is much more rapid than that of the salts. Studies of phenol sorption from dilute aqueous solution indicate that the diffusion coefficient for phenol in water-saturated 39.8 wt.-% acetyl cellulose acetate is 9.6 × 10^-10 cm.²/sec., and the equilibrium distribution coefficient between the acetate phase and water is 42. Thus, the diffusion coefficient is quite close to that measured for sodium chloride, and the higher permeability of the membranes to phenol can be attributed entirely to their greater sorption of this solute. In direct osmosis experiments performed with significant water flow a measurable interaction or positive coupling between water and phenol flows has been observed. Further evidence of flow coupling is derived from reverse osmosis experiments in which significant negative solute rejection is observed; i.e., the permeate is enriched in phenol by as much as 20%. It is shown that a solution-diffusion transport model is not adequate to rationalize the results, and a more complex transport model is apparently required.     

Reverse osmosis separation of phenols in aqueous solutions using porous cellulose acetate membranes

Reverse osmosis separations of phenol (9.4 to 108 ppm), p-cresol (108 ppm), and p-chlorophenol (129 ppm) were studied using Loeb-Sourirajan-type porous cellulose acetate membranes, and single-solute aqueous feed solutions at 500 psig and the indicated solute concentrations. It was found that, by dissociating the solute by changing the pH of the feed solution, all the above phenols could be separated by reverse osmosis. Solute separation increased with increase in the degree of dissociation of the solute in the feed solution; and, by the appropriate choice of pore size on the membrane surface, separations of phenol approaching the degree of dissociation of phenol in the feed solution could be obtained under the operating conditions used. Similar experiments using aniline (93 ppm) as the solute showed that dissociation of solute molecules in the feed solution could be a technique generally applicable for the reverse osmosis separation of nonionic solutes in aqueous solution. The effects of operating pressure in the range 250 to 1500 psig and pore size on the membrane surface on the separation of un-ionized phenol and p-chlorophenol showed that, with respect to single-solute aqueous feed solutions of phenols, the component whose relative acidity was greater was preferentially sorbed at the cellulose acetate membrane—aqueous solution interface, and the solute concentration in the membrane-permeated product solution was a function of the extent and mobility of each of the sorbed species.     

Solute–membrane interactions in hyperfiltration

The performances of several composite membranes (PEC-1000, Teijin, HR-95, HR-98) and one asymmetric membrane (Solrox SC-200) in hyperfiltration are compared at 25°C using different aqueous feed solutions (0.1M and 0.5M NaCl, 0.5M 1,3-and 1,4-dioxan, 0.1M benzyl alcohol and 2-methoxybenzyl alcohol, 1,2- and 1,4-butandiol, and Triton feed solution). The effects of solute dissociation, polarization, and hydrogen bonding ability on solute permeability are discussed; steric effects are also being considered. Strong solute–membrane interactions are exhibited in hyperfiltration by systems with distinct hydrogen bonding capabilities of the solute with functional sites of the membrane matrix. Knowledge of solute–membrane interactions can be useful for elaborating separation and transport mechanisms.     

The effect of chelation on the selective transport of alkaline-earth metal ions in asymmetric cellulose acetate hyperfiltration membranes

The rejection of calcium and/or magnesium ion by asymmetric cellulose acetate hyperfiltration membranes is increased significantly by formation of the corresponding alkaline-earth metal chelate. Typically solute fluxes are reduced by a factor of 5 consequent to chelation with ethylenediaminetetraacetic acid (EDTA) at pH 6.0. Selective chelation and, in turn, selective transport of magnesium is observed when equimolar solute mixtures corresponding to 1:1:1 magnesium:calcium:EDTA are hyperfiltered. Under these conditions, calcium successfully competes for the stoichiometrically limiting EDTA, and the rejection of magnesium is lower than the rejection observed for the hyperfiltration of the MgEDTA^2? complex in the absence of competitive calcium. Alternatively, the rejection of the CaEDTA^2? complex is increased under these identical conditions, presumably as a consequence of specific interactions between the available free magnesium and the cellulose acetate membrane. The effects reported here all seem to be related to reductions in solute diffusivity associated with the increased size of the alkaline-earth metal ion complex.     

Studies on the development of improved reverse osmosis membranes from cellulose acetate–acetone–formamide casting solutions

Improved membranes from cellulose acetate–acetone–formamide casting solutions have been prepared for low-pressure reverse osmosis applications. The film-casting details for one such type of membranes (Batch 400) are as follows. Casting solution composition: cellulose acetate (E-398-3), 17 wt-%, acetone, 56 wt-%, formamide, 27 wt-%; temperature of casting solution, 24°C; temperature of casting atmosphere, 24°C; casting atmosphere, ambient air in contact with 30 wt-% acetone in aqueous solution; solvent evaporation period, 30 sec; gelation medium, ice-cold water. Using aqueous feed solutions containing 3500 ppm of NaCl, the product rates obtained with the above membranes at 95, 90, and 60% levels of solute separation were 15.9, 22.1, and 58.7 gallons/(day ft²), respectively, at 250 psig under feed flow conditions corresponding to a mass transfer coefficient of 45 × 10^?4 cm/sec on the high-pressure side of the membrane. The effects of casting solution composition, presence of acetone in the casting atmosphere, evaporation period, evaporation rate constant, and the remoteness of casting solution composition from the corresponding phase boundary composition on membrane performance and shrinkage temperature profile were found to be similar to those reported earlier for membranes obtained from cellulose acetate–acetone–aqueous magnesium perchlorate casting solutions. The results illustrate the practical utility of the approach based on the solution structure–evaporation rate concept for creating more productive reverse osmosis membranes.     

Development and performance of some porous cellulose acetate membranes for reverse osmosis desalination

The effects of casting solution composition and evaporation period on the performance of resulting porous cellulose acetate membranes have been studied, and the results are discussed in terms of casting solution structure, solvent evaporation rate during film formation, and the film shrinkage temperature profile. The development of Batch 316-type porous cellulose acetate membranes is reported. At 90% level of solute separation and feed flow conditions corresponding to a mass transfer coefficient of 45 × 10^?4 cm/sec, the productivities of the above membranes are 21.5 gallons/day/ft² at 250 psig using 3500 ppm of NaCl in the feed, and 53.9 gallons/day/ft² at 600 psig using 5000 ppm of NaCl in the feed.     

Solution to the homogeneous surface diffusion model for batch adsorption systems using orthogonal collocation

A solution to the homogeneous surface diffusion model has been developed and incorporated into a batch adsorption model based on external boundary layer mass transport and homogeneous diffusion. The model has been extensively tested using three experimental adsorption systems, namely, phenol on carbon, basic yellow dye on carbon and basic blue dye on silica. The effect of initial solute concentration and adsorbent mass has been studied in 23 batch experiments, which have been modelled using the collocation solution method to solve the homogeneous surface diffusion equation. The theoretical concentration decay curves show a high degree of correlation with experimental data.     

Effect of ethanol–water mixture as gelation medium during formation of cellulose acetate reverse osmosis membranes

By using ethanol–water mixtures in a wide range of alcohol concentrations and temperatures, cellulose acetate membranes with a wide range of surface porosities can be obtained. Two different casting solution compositions were used, involving cellulose acetate, acetone, and aqueous magnesium perchlorate (composition I) or formamide (composition II). All reverse osmosis experiments were carried out at 250 psig using a 3500 ppm NaCl–H₂O feed solution at laboratory temperature. The effective area of film surface was 12 cm² in all cases. With composition I, with pure water gelation medium at 0°C, the resulting membrane gave a solute separation of 5% and product rate of 220 g/hr, whereas with 95% alcohol as gelation medium, the resulting membrane gave a solute separation of ～1% and product rate of 1240 g/hr under otherwise identical experimental conditions. With composition II membranes, the maximum product rate of 360 g/hr with the corresponding minimum solute separation of ～1% was obtained with 71.2% alcohol–water gelation medium at 0°C. Increase in the temperature of the gelation medium in the range 12° ?25°C tends to increase the average size of pores on the membrane surface. These results offer a basis for the development of cellulose acetate ultrafiltration membranes.     

Water and solute transport across cellulose acetate membranes in the treatment of soybean whey by reverse osmosis

In processing full-fat soy flour to produce an acid-precipitated lipid protein concentrate, there results a by-product whey fraction which, because of its high biological oxygen demand, represents a serious disposal problem. Processing of food waste streams by reverse osmosis has received considerable attention because of its low theoretical energy requirement, since no phase change is involved. A series of statistically designed and analyzed experiments were conducted on a pilot-plant reverse osmosis unit to study the effect of the operating parameters on solute and solvent transport in cellulose acetate membranes. Sucrose and sodium chloride solutions were tested in addition to soybean whey to relate the mixed solute system in whey to that of single-solute organic and inorganic feed solutions. Water flux was shown to have an Arrhenius dependency on temperature, and some membrane compaction was observed with the more porous membrane. Concentration polarization for sucrose and sodium chloride solutions increased linearly with water flux. Solute flux for soybean whey solutions decreased with molarity and was independent of pressure, whereas solute rejection increased with temperature and pressure and was independent of molarity. Good agreement was obtained using the derived parameters A, B, and τ for soy whey in the diffusion transport model when compared to the observed experimental values.     

Performance of cellulose acetate butyrate membranes in hyperfiltration of sodium chloride and urea feed solution

Cellulose acetate butyrate (CAB) membranes gave high salt and urea rejection with a water flux of about 3 gfd (gallons/ft² · day) during hyperfiltration at 600 psig. Evidence was obtained which indicated that the CAB membranes used in this work were asymmetric. Membrane heat treatment increased urea rejection significantly while salt rejection was invariant, and water flux decreased. An increase in feed solution temperature caused a significant increase in water flux and a small decrease in urea and salt rejection. Increasing the pressure increased water flux and urea and salt rejection. During a 400-hr life test, the water flux decreased by about 25% while urea rejection increased and salt rejection was invariant. The influence of pressure, membrane heat treatment, and compaction during CAB membranes life testing on urea and salt rejection provided evidence that these two solutes were rejected by somewhat different mechanisms. Salt rejection was consistent with a solution–diffusion mechanism for membrane transport and uncoupled flow while changes in urea rejection with pressure, membrane heat treatment, and compaction during life testing suggested that urea was at least partially rejected by membrane exclusion resulting from geometric factors.     

Development and characterization of cellulose acetate benzoate flat osmotic membranes

Different parameters of casting solutions and casting conditions were studied for the development of cellulose acetate benzoate flat osmotic membranes. Casting solutions were prepared with different concentrations of the polymer, the additive, and the solvent; viscosity of the casting solution; and the thickness of the membrane developed. The membranes were given different evaporation periods and annealing temperatures under different RH. Different annealing baths were also used. Based on these, conditions were optimized for the development of cellulose acetate benzoate flat osmotic membranes. These membranes were characterized with respect to bound water content, specific water content, transport properties by direct osmosis, salt intake by direct immersion, water permeability coefficient of the dense membrane, diffusion coefficient, salt permeability, and salt distribution by electrical conductivity. Also, cellulose acetate benzoate membranes were compared with conventionally used cellulose acetate membranes. © 1994 John Wiley & Sons, Inc.     

Preparation of ultrathin reverse osmosis membranes and the attainment of theoretical salt rejection

Cellulose acetate reverse osmosis membranes, 600–2800 A. thick, have been prepared on glass surfaces by dipping a clean glass plate into a dilute solution of cellulose acetate. After drying, the membranes are floated of onto a water surface and placed on molecular filter supports. Theoretical salt rejections, as calculated from the solution-diffusion model of membrane transport for cellulose acetate, were obtained with imperfection-free membranes.     

Improvement of porous cellulose acetate reverse osmosis membranes by change of casting conditions

The effects of temperature of casting solution in the range ?10° to 15°C, that of casting atmosphere in the range 10° to 30°C, relative humidity of casting atmosphere in the range 35% to 75%, and solvent evaporation period in the range 0.5 to 3 min were studied on shrinkage temperatures, solute separations, and product rates of Loeb-Sourirajan-type cellulose acetate membranes in reverse osmosis experiments. The composition of casting solution used was as follows: cellulose acetate, 17; acetone, 69.2; magnesium perchlorate, 1.45; and water, 12.35 wt-%. Best performance was obtained with membranes cast under the following conditions: temperature of casting solution, 10°C; temperature of casting atmosphere, 30°C; relative humidity of casting atmosphere, 65%; and solvent evaporation period, 1 min. For a 90% level of solute separation, the productivities of the above type of membranes were 22.9, 61.4, and 64.5 gallons/day-ft² at 250, 600, and 1500 psig using 3500 ppm NaCl–H₂O, 5000 ppm NaCl–H₂O, and 28395 ppm NaCl–H₂O feed solutions, respectively. In all cases, the feed flow rates corresponded to a mass transfer coefficient of 45 × 10^?4 cm/sec on the high-pressure side of the membrane. The general specifications of the above type of membranes are given for the operating pressures of 250, 600, and 1500 psig. The effects of the above casting condition variables on the surface pore structure during film formation are discussed.     

Studies on syntheses and permeabilities of special polymer membranes. X. Effects of conditions of membrane preparation on permeation characteristics of cellulose acetate membranes in separation of aqueous polymer solutions

The effects of casting solvents, dissolution temperature of casting solution, and pH and temperature of gelation solution, etc. on the permeation characteristics of cellulose acetate membranes in the separation of polymers from their aqueous solutions were investigated, using aqueous solutions of poly(ethylene glycol) and poly(vinyl alcohol) as feed. The permeation characteristics were influenced significantly by the conditions of membrane preparation and of the permeation. It was found that a concentration polarization at the membrane surface occurred with poly(vinyl alcohol) molecules, but it was very small with poly(ethylene glycol). The above results were discussed in detail from points of view of structure of the resulting membranes and the interactions between the solvent, the solute in the feed and the cellulose acetate molecules.     

Some transport characteristics of aromatic polyamide membranes in reverse osmosis

The effects of solute concentration in the range of 0.0013 to 1.051 molality in the feed solution and operating pressure in the range of 100 to 900 psig on solute transport parameter D_AM/Kδ in reverse osmosis have been studied for a class of laboratory-made aromatic polyamide membranes and aqueous sodium chloride feed solutions. The results showed that D_AM/Kδ for NaCl increased both with increase in operating pressure and solute concentration in the concentrated boundary solution on the high-pressure side of the membrane. A general expression for D_AM/Kδ for NaCl including the effects of both the above operating variables is given. These results are different from the corresponding results obtained for cellulose acetate membranes.     

Dynamic deposition of polyacids on porous membrane supports

Poly(acrylic acids), poly(styrenesulfonic acid), and their block and random copolymers were tested for their ability to form dynamic membranes on partially cured asymmetric cellulose acetate. Chemically modified porous polypropylene (Celgard) was also used as a support for poly(acrylic acid). Salt rejections, water fluxes, and streaming potentials of membranes were tested under hyperfiltration conditions. Sorption of the polyelectrolytes by the cellulose acetate supports was studied using spectrophotometric, ²²Na tracer, and electron microscopy techniques. The dynamic membrane formation was noted only for poly(acrylic acid) and for its 1:4:1 block copolymer with poly(styrenesulfonic acid). The uneffectiveness of other polyelectrolytes was discussed in terms of a negative zeta potential of cellulose acetate. The increase in salt rejection (R) due to the polyelectrolyte is strongly dependent on the initial R_i of the support. Sharp maxima in the ΔR -versus-R_i curves have been noted for R_i in the range of 40–55%. The most significant improvement in the hyperfiltration characteristics of cellulose acetate was attained with the 1:4:1 block copolymer. Flux of 17 gfd at 350 psi and R = 93% was obtained in short-term tests for a 0.1N feed solution. Long-term tests did not reveal any flux or salt rejection decline for membranes in which poly(acrylic acid) was complexed with phosphoramidic groups grafted onto Celgard.     

Synthesis and evaluation of aromatic polyamide membranes for desalination in reverse-osmosis technique

Reverse-osmosis membrane-grade aromatic polyamides have been synthesized by reacting 3,5-diaminobenzoic acid separately with three different acylchlorides, viz. isophthaloyl chloride, terephthaloyl chloride, and 4,4′-diphenyldicarboxylic acid chloride. Using these polyamides, asymmetric membranes were developed and characterized for various physical parameters, such as Staverman coefficient, membrane potential, and percent salt rejection using sodium chloride solution under high pressure. The effects of pressure, feed concentration, and feed flow rate have been studied on membrane transport parameters, viz. pure water permeability constant, product rate, solute transport parameter, and separation factor. The effects of annealing temperature and solvent evaporation time on the performance of the membranes were also studied. The analysis of the reverse-osmosis data revealed that the membranes prepared from the 3,5-diaminobenzoic acid and 4,4′-diphenyldicarboxylic acid chloride are superior to the membranes prepared from other polymeric materials. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 643–653, 1997     

Negative Rejection of Group Ib Metal Cyanide Complexes in the Hyperfiltration by Cellulose Acetate Membranes. Donnan Membrane Effect

Abstract

Anionic cyanide complexes of Group Ib family metal ions, Cu^ICN)^? ₂, Ag^ICN)^? ₂ and Au^ICN)^? ₂, showed negative rejection in hyperfiltration through cellulose acetate membranes when the feed solution contained such polyvalent anions as succinate, tartrate, aspartate, ethylenediaminetetraacetate, polyacrylate, polyvinylsulfonate, phosphate, and sulfate in a substantial concentration. The dicyanometal complex anions are essentially membrane permeable, while the polyvalent anions are essentially membrane impermeable. Both types of anions combined with the membrane permeable countercations form an ionic ternary system in which the Donnan membrane effect operates to enhance the diffusion of the permeable salt through the membrane, resulting in its enrichment in the permeate solution. By taking advantage of this phenomenon, a selective enrichment of dicyanoargentite in the permeate and its separation from the coexisting transition metals were achieved. Based on this principle, a new hyperfiltration-ultrafiltration technique was proposed for the ion-selective separation of salts.     

Development of a Mixed-Matrix Membrane for Pervaporation

Abstract

In the production of pure alcohol, pervaporation is developing into an important technology. In this study, in order to improve the performance of the pervaporation process, a mixed-matrix polymer-zeolite membrane is developed. In the preparation of these membranes, cellulose acetate as base polymer, acetone or DMF as solvent, and 13X or 4A zeolites as fillers were used. To test the performance of homogeneous and mixed-matrix membranes, a laboratory-scale pervaporation setup was constructed. The effect of the following experimental parameters on the selectivity and flux were experimentally studied to determine the optimum values of operating conditions and to understand the separation mechanism in the indicated ranges: feed concentration, 70–90 wt%; feed temperature, 30–70°C; feed flow rate, 32–76 L/h. It was observed that the addition of zeolite to the membrane matrix improves the flux value twofold with respect to its homogeneous membranes with some loss in their selectivity. For example, for a feed concentration of 74 wt% EtOH at 50°C and 1 mmHg, the flux value for the unfilled membrane is 0.6 L/m²·h, and for a 30% zeolite-filled membrane, the flux is increased to 1.33. For these cases, the selectivities are 7.76 and 5.0 for the unfilled and filled membranes, respectively. TEM micrographs of the mixed-matrix membranes show a homogeneous distribution of zeolite particles which produce a cavelike porous structure in the matrix. The combined effect of this modified morphology and zeolite selectivity is the possible reason for the observed pervaporation performances of mixed-matrix membranes.     

Effect of casting conditions on the performance of porous cellulose acetate membranes in reverse osmosis

Several sets of porous cellulose acetate membranes were made using the same casting solution composition and gelation conditions but varying the casting solution temperature and solvent evaporation conditions. The films were tested in reverse osmosis experiments at 250 psig using aqueous feed solutions containing 3500 ppm NaCl. The results show that the product rate obtained at a given level of solute separation is independent of evaporation time in the range tested and, for a given casting solution composition, the temperature of the casting solution and conditions of solvent evaporation during film formation together constitute an important interconnected variable governing the porous structure of the resulting membranes. These results offer a new approach to the problem of developing more productive reverse osmosis membranes and have led to a new class of porous cellulose acetate membranes capable of giving product rates 100% to 150% higher than those of the best membranes reported, at any given level of solute separation under the experimental conditions used. These results are of practical importance in low-pressure reverse osmosis applications.