NZ206386A - Anionic polysaccharide separation membranes; separation of water-organic compound mixtures - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £06386 2063 86 j Priority Date(s): Complete Specification Filed: Publication Date: NEW ZEALAND PATENTS ACT, 1953 No.: Date: COMPLETE SPECIFICATION ANIONIC POLYSACCHARIDE SEPARATION MEMBRANES i/We, THE DOW CHEMICAL COMPANY, of 2030 Dow Center/ Abbott Road, Midland, Michigan 48640, United States of America, a corporation organized and existing under the laws of the State of Delaware, United States of America, hereby declare the invention for which jt / we pray that a patent may be granted to titSt/us, and the method by which it is to be performed, to be particularly described in and by the following statement: - ' . 1 - s (followed by page la) -3ei~ Vj ANIONIC POLYSACCHARIDE SEPARATION MEMBRANES This invention relates to separation membranes and to methods for removing water from organic compounds using separation membranes.

The effective removal of water from organic 5 fluids is important in pollution control and in numerous industries such as in distilleries, the preparation of the anhydrous chemicals and the like. While such separations are comparatively simple when the organic compound is immiscible with water, many organic com-. 10 pounds are partially or completely soluble in water. Separation of such organic compounds from water is sometimes carried out by distilling the mixture but this process requires large amounts of energy. Moreover, some organic liquids which have boiling points close to 15 that of water or which form azeotropic mixtures with water cannot be readily separated using a distillation process.

It has been found that certain materials, when formed into thin membranes, possess the capacity 20 to selectively permit water to pass therethrough while 3.0,662 F -1a* ;-2- ;2 ;preventing the passage of organic compounds. Thus, Binning et al. in U.S. Patent Nos. 2,953,502 and 3,035,060 teach the separation of ethanol from water . using cellulose acetate and hydrolyzed polyvinyl 5 acetate membranes. Chiang et al. in U.S. Patent Nos. 3,750,735; 3,950,247; 4,035,291 and 4,067,805 describe the separation of formaldehyde from water employing a variety of membranes. ;Unfortunately, previously known separation 10 membranes do not exhibit a selectivity as high as desired for many applications; that is, the water which permeates therethrough contains substantial amounts of organic compounds. Thus, it would be desirable to develop a separation membrane which more efficiently 15 separates water from organic compounds. ;The present invention particularly resides in a water-selective permeation membrane comprising a salt of a polysaccharide or polysaccharide derivative which bears a plurality of anionic groups derived from a 20 strong or weak acid, said anionic groups being present in an amount sufficient to allow the membrane to permeate water while substantially impeding the permeation of organic compounds therethrough. ;In another aspect, this invention is a 25 permeation membrane comprising a blend of the aforementioned salt of a polysaccharide or polysaccharide derivative with a salt of a non-cellulosic polymer having a plurality of anionic groups. The membranes of this invention exhibit surprisingly good selectivity 30 for water, i.e., when contacted on one side with a fluid mixture of an organic compound and water, they iW, 662-F -2- ;-3 ;2U6386 ;o allow water to permeate therethrough while substantially preventing the permeation of the organic materia: therethrough. ;In another aspect, the invention resides in 5 a process for separating mixtures of water and an ^ ~ s organic compound comprising v-' (a) contacting one side of a membrane com prising a salt of a polysaccharide or polysaccharide derivative having a 10 plurality of anionic groups derived from a strong or weak acid with a fluid feed mixture containing water and an organic compound, and (fa) withdrawing from the other side of said 15 membrane a permeate in vapor form, said permeate containing a. higher concentration of water than said feed mixture. ;According to the' method, surprisingly efficient separations of water and organic compounds can be 20 effected, with the permeate containing a higher concentration of water than permeates obtained using conven- -tional separation membranes. ;The polysaccharides or derivatives thereof suitably employed in this invention are those which 25 contain a plurality of pendant anionic groups. Said anionic groups are derived from strong or weak acids and include -S03~", -0S03~, -COO~, -As03~, -TeOg", -P03~, -HP03~ and the like, with sulfate, sulfonate and carboxylate groups being preferred. Exemplary polysac-30 charides and derivatives thereof include, but are not limited to, alginic acid salts, x an than gums and ;29,662-F -3- ;-4- ;2063 ;derivatives thereof, and salts of anionic cellulose derivatives such as carboxyalkyl cellulose, carboxy-alkylalkyl cellulose, sulfoalkyl cellulose, cellulose sulfate, cellulose phosphate, cellulose arsenate, 5 cellulose phosphinate, cellulose tellurate and the like. Also useful are salts of anionic derivatives of high molecular weight starches and gums such as tragacanth, karaya, guar and the like which by themselves or in blends can be formed into films of suf-10 ficient strength to operate as membranes. Of these, the diverse cellulose derivatives and alginic acid salts are preferred. Especially preferred are salts of carboxylate, sulfate or sulfonate-containing cellulose derivatives. Most preferred are salts of carboxymethyl 15 cellulose. ;Various polysaccharides such as alginic acid and xanthan gums contain anionic groups and do not need chemical modification to place anionic groups thereon. Other polysaccharides, notably cellulose, do not contain 20 anionic groups and must be modified to impart anionic groups thereto. Anionic groups are generally attached to polysaccharides by substitution of one or more of the hydroxyl groups on the anhydroglucose units of the polysaccharide molecule. Various methods for affixing 25 anionic groups to polysaccharide molecules are known in the art and are described, for example, in Bogan et al., "Cellulose Derivatives, Esters" and Greminger, "Cellulose Derivatives, Ethers," both in Kirk-Othmer Encyclopedia of Chemical Technology, 3d Ed., Vol. 5, John Wiley 30 and Sons, New York (1979). Carboxyalkyl groups, for example, can be attached to cellulose by the reaction of cellulose with a haloalkylcarboxylate. The alkyl group can contain up to five carbon atoms but because ;23,662 F ;4- ;2063 8 ;-5- ;the alkyl group tends to impart hydrophobic characteristics to the molecule, it is preferred that the alkyl group be methyl or ethyl- Cellulose sulfate can be prepared by reacting cellulose with mixtures of sulfuric acid and aliphatic alcohols, followed by neutralization with sodium hydroxide, or alternatively by reacting a dimethyl fonnamide-sul fur trioxide complex with cellulose using excess dimethylformamide as the solvent. It is noted that membranes prepared from cellulose sulfate are brittle when dry and are advantageously kept moist after their preparation and throughout the period of their use. Cellulose phosphate is advantageously prepared by reacting cellulose with phosphoric acid in molten urea, or with a mixture of phosphoric acid, phosphorus pentoxide and an alcohol diluent. ;In addition to the methods described hereinbefore, the hydroxymethyl groups of cellulose and like polysaccharides can be converted directly to carboxylate groups by oxidation and hydrolysis according to well-known processes. ;When a cellulose derivative is employed in the membrane, the amount of anionic substitution on a cellulose molecule is expressed as the average number of anionic groups per anhydroglucose unit of the molecule (degree of substitution (DS)). Since there are three hydroxyl groups per anhydroglucose unit of a cellulose molecule, the DS can range from 0 to 3. For the purpose of this invention, the anionic degree of substitution must be sufficiently high that the materials prepared therefrom will allow water to permeate therethrough while substantially impeding the permeation of organic compounds. Advantageously, the DS is ;5 ;o ;•6- ;in the range from 0.1 to 3.0, preferably from 0.3 to 1.5. In addition to the anionic substituent, the cellulose derivative can also contain other substitution, i.e., methyl, ethyl, hydroxyalkyl and the like 5 in an amount such that said substitution does not substantially increase the permeability of the cellulose to organic compounds. ;The anionic polysaccharide or polysaccharide derivative is in the salt form, the counterion being 10 any cation which forms an ionic bond with the anionic groups of the polymers. Said cations generally include alkali metals, alkaline earth metals, transition metals, as well as ammonium ions of the form, R^N+, where each R is hydrogen or methyl. Because of their relative 15 ease in preparation and improved selectivity, the counterion is preferably an alkali metal. It has been found that the selectivity and the permeation rate, i.e., the rate at which water permeates the membrane, are dependent on the choice of the counterion. For 20 alkali metals, the selectivity of the membrane generally decreases slightly as the counterion is changed from sodium to potassium to cesium while the permeation rate increases as the counterion is varied in the same sequence. However, the selectivities of the membranes 25 of the invention are superior to those of conventional separation membranes even when cesium is employed as the counterion. ;The anionic polysaccharide or polysaccharide derivative is advantageously converted to salt form by 30 contacting said derivative with a dilute solution of the hydroxide of the desired counterion. Generally, ;29,002-F ;-6' ;-7- ;the salt can be formed in this manner at ambient condi-tions using relatively dilute, i.e., 0.02 to 1 molar solutions of the desired hydroxide. When the cationic species form an insoluble hydroxide, a solution of a 5 soluble salt of said cation is contacted with the anionic polysaccharide in order to convert said anionic polysaccharide to the desired salt form through an ion exchange process. ;In a preferred embodiment of this invention, 10 the anionic polysaccharide or polysaccharide derivative is blended with a salt of a polyanion which is not a 3 polysaccharide having a plurality of groups derived from strong or weak acids such as are described hereinbefore. In general, the polyanion is chosen such that 15 it forms solutions which are sufficiently compatible with solutions of the anionic polysaccharide or polysaccharide derivative such that blends can be produced therefrom. The polyanion is employed in the salt form, with the counterions being those described hereinbefore. 20 The polyanion can be a homopolymer containing repeating anionic units such as polyacrylic acid or poly (sodium vinylsulfonate), or may be a copolymer having repeating anionic units and repeating nonionic units such as a styrene/sodium vinylsulfonate copolymer or sodium 25 acrylate/alkyl acrylate copolymers. The polyanion has a molecular weight sufficiently high that films prepared therefrom do not rapidly dissolve or become distorted in the presence of the water/organic mixture to be contacted therewith. Preferably, the polyanion is a 30 homopolymer of an ethylenically unsaturated sulfonate or carboxylate with sodium polyacrylate, sodium polyvinyl sulfonate) and sodium poly(styrene sulfonate) being preferred. ;■o o ;2-9 ,002 F ;-7- ;2© ;-8- ;The polyanion is employed in amounts sufficient to increase the charge density on the membrane but in amounts less than that which causes substantial incompatability with the anionic polysaccharide deriva-5 tive in the preparation of the membrane. Generally, such substantial incompatibility is evidenced by the separation of a solution containing these components into distinct phases. Said phase separation makes it difficult to prepare a film which is a blend of the 10 polyanion and the polysaccharide. In general, the polyanion will comprise up to about 70 weight percent, preferably less than 50 weight percent, more preferably less than 30 weight percent of the membrane. ;The membranes of this invention are advanta-15 geously formed into the desired shape by casting films of the membrane onto a suitable surface and removing the solvent therefrom. Said films may be, for example, flat, concave, convex, or in the form of hollow fibers. Preferably, the membrane is cast from an aqueous solu-20 tion. The solvent is generally removed by evaporation at ambient conditions or at elevated temperatures, low pressures, or by other suitable techniques. Membranes which are blends of an anionic polysaccharide or polysaccharide derivative and a polyanion are generally 25 formed in the manner described hereinbefore by casting a film from the solution containing both materials. Solutions containing both the anionic polysaccharide derivative and the polyanion are advantageously prepared by mixing solutions of the anionic polysaccharide 30 derivative with a solution of the polyanion or by mixing finely divided portions of each material and dissolving the mixture into a suitable solvent. ;2-9/6G2 F ;8 ;I ;' O ;__ te? ■ ^ ;-9- ;The anionic polysaccharide derivative and the polyanion described hereinbefore are generally soluble in water and the use thereof is generally restricted to feed mixtures having relatively low concentrations of 5 water, i.e., less than 50 weight percent water. Accordingly, it is highly preferred to crosslink the membranes in order to render them insoluble in water. Cross-'"■■■Jj linking of polysaccharides is known in the art and can be accomplished, for example, by reacting said polysac-10 charide with glyoxal or epihalohydrin ammonium hydroxide. When a blend of a polysaccharide and a polyanion is employed, crosslinks may be formed between the polysac-3 charide and the polyanion, solely between the polysac charide, or solely between the polyanion. ;15 The crosslinking agent is employed in an amount sufficient to render the membrane essentially insoluble in water. The crosslinking agent advantageously comprises from 1 to 30 weight percent of the membrane. The crosslinked membranes of this invention 20 can be effectively employed using feed compositions containing even very high, i.e., 90 weight percent or more, concentrations of water. ;In the preparation of crosslinked membranes, the crosslinking agent is advantageously added to a — 25 solution of the polysaccharide, and the membrane formed w into the desired shape. The membrane is cured after the removal of the solvent therefrom to crosslink the membrane. The particular means employed for curing the membrane will depend on a variety of factors including 30 the particular polymers and crosslinkers employed. ^ Generally, known procedures for curing crosslinked polymers, such as heating, irradiation and the like, ;£9,602 F- ;-9- ;-10- ;2 063 86 ;are advantageously employed to crosslink the membranes of the invention. ;The membrane has a minimum thickness such that it is essentially continuous, i.e., there are essentially no pinholes or other leakage passages therein. However, the rate at which water permeates the membranes of this invention is inversely proportional to the thickness of the membrane. Accordingly, it is preferred to prepare a membrane as thin as possible in order to maximize the permeation rate while ensuring the integrity of the membrane. The thickness of the membrane is advantageously in the range from about 0.1 to 250 microns, preferably from about 10 to about 50 microns. Mechanical strength can be imparted to the membrane by affixing the membrane to a porous supporting material. Particularly thin membranes can be formed by casting the membrane directly onto the porous supporting material. ;Separation of water from organic compounds is effected with the membranes of this invention using general procedures described in U.S. Patent Nos. 3,950,247 and 4,035,291 to Chiang et al. in general, the separation process comprises contacting one side of the membranes of this invention with the fluid mixture containing an organic compound and water and withdrawing from the other side of the membrane a mixture containing a substantially higher concentration of water. The feed mixture can be a mixture of gaseous and liquid components. The permeate side of the membrane is maintained at a pressure less than the vapor pressure of water and is advantageously as low as about 0.1 mm of mercury. Superatmospheric pressure may also be exerted on the ;2$r&62«r- ;-10- ;2063 86 ;-li- ;feed side of the membrane. The temperature at which the separations are conducted affects both the selectivity and the permeation rate. As the temperature increases, the permeation rate rapidly increases, while selectivity decreases slightly. The increase in rate, however, may be compensated for by the increase in energy needed to maintain the system at an elevated temperature. In general, the temperature is sufficiently high that the water has a substantial vapor pressure at the pressures at which the separation is effected, and is sufficiently low that the membrane remains stable. Advantageously, the temperature is from -10°C to 95°C. ;The membranes of this invention are most useful in separating water from organic compounds which are miscible with water. Exemplary water-miscible compounds include, but are not limited to, aliphatic alcohols such as methanol, ethanol, propanol, hexanol and the like; ketones such as ethyl methyl ketone, ;acetone, diethyl ketone and the like; aldehydes such as formaldehyde, acetaldehyde and the like; alkyl esters of organic acids such as ethyl acetate, methylpropio-nate and the like; p-dioxane, alkyl and cycloalkyl amines and other water-miscible organic compounds which do not chemically react with or dissolve the membranes of this invention. In addition, the organic compound may be one in which water has a limited solubility, ;such as the chlorinated alkanes like chloroform and carbon tetrachloride. Preferably, the organic compound is an aliphatic alcohol, a ketone, or an aldehyde, with lower alcohols, especially ethanol, being preferred. ;The ability of a membrane to selectively permeate one component of a multi-component mixture is ;11- ;-12- ;2063 86 ;expressed as the separation factor a which is defined as wt % A/wt % B in permeate aA/B = wt % A/wt % B in feed wherein A and B represent the components to be separated. For the purposes of this invention, A will represent water. ;The separation factor or is dependent on the type and concentrations of the components in the feed mixture as well as the relative concentrations thereof in the feed. Accordingly, it is also advantageous to express the efficiency of the separation membrane in terms of the composition of the permeate. The separation membranes of this invention will generally have separation factors for water/ethanol mixtures of at least 50, preferably at least 100, more preferably at least 500 and often will have separation factors of 2500 or more. The permeates obtained with the use of the separation membranes of this invention to separate ethanol/water mixtures will generally contain at least 90 weight percent, preferably at least 98 weight percent, more preferably at least 99.5 weight percent water. ;The separation membranes of this invention are especially useful in the preparation of anhydrous organic compounds, particularly when said compound forms an azeotropic mixture with water. In such systems, the membranes of this invention present an economical alternative to azeotropic distillation. The membranes of this invention can also be used in conjunction with ;2&,662-F ;-12 ;2063 ;-13- ;distillation processes to effect rapid, efficient removal of water from organic compounds. ;The following examples are intended to illustrate the invention but not to limit the scope thereof. ;5 All parts and percentages are by weight unless otherwise indicated. ;Example 1 ;Membrane Sample No. 1 is prepared from an aqueous solution containing 4.25 percent sodium carboxy-10 methylcellulose. The carboxymethylcellulose has a carboxymethyl degree of substitution of about 0.9. The membranes are prepared by casting an excess of the solution onto a glass plate and allowing the water to evaporate, thereby yielding a film having a thickness 15 of about 19.8 microns (0.78-mil). ;The following apparatus is used to evaluate membrane Sample No. 1 and the samples in all subsequent examples. The membrane is placed into a Gelman in-line stainless steel filter holder which is modified so that 20 a 14.19 cm2 section of the membrane is open to the feed solution. The membrane is supported with cellulosic filter paper and a porous metal disk. The permeate side of the filter holder is connected to a vacuum pump with two cold traps placed in line to collect the 25 permeate by condensation. The membrane and holder are then immersed in a closed flask containing the mixture to be separated. The flask is equipped with a thermocouple or thermometer for measuring temperature and a reflux condenser to prevent feed loss due to evaporation. ;2 063 86 ;-14- ;Separation is effected by pulling a vacuum of about 0.1 mm/Hg on the permeate side of the membrane and collecting the permeate in the cold traps. The temperature of the feed solution is as indicated in the individual examples. The permeation rate is calculated by periodically weighing the collected permeate. The permeate composition is determined by gas chromatography analysis using a Hewlett Packard 5840A gas chromatograph equipped with a thermal conductivity detector. The column is a 1.83 met x 0.32 cm (6 ft x 1/8 inch inside diameter) in Poropak QS column. ;Sample No. 1 is evaluated according to the foregoing procedure using various ethanol/water mixtures as the feed composition. Each separation is effected at 25°C until a steady state condition is obtained, i.e., until the permeation rate and permeate content are nearly constant over time. Once a steady state is reached, the content of the permeate and permeation rate are determined. The respective concentrations of water in the feeds, concentrations of water in the permeates, separation factors and permeation rates are as reported in Table I following. ;TABLE I ;Separa- Permeation ;% HoO % H-0 tion Rate in Feed in Permeate Factor (q-mil/m2-hr) ;5.68 99.36 1 2578 12.2 ;9.93 99.25 1200 37.8 ;18.19 99.49 877 126.5 ;20.10 99.62 1042 128 ;29-r*2-f -14- o 2063 86 r\ It is seen from the foregoing Table I that the separation membranes made from sodium carboxymethyl-cellulose exhibit excellent selectivity for water/ethanol mixtures as expressed in terms of the separation factor 5 or as expressed as the composition of the permeate.

Example 2 A 4.25 percent solids solution containing 77 weight percent of the sodium carboxymethylcellulose having a degree of substitution of 0.85 and 23 weight 10 percent sodium polyacrylate (based on the total solids weight) is prepared by mixing separate solutions of the sodium carboxymethylcellulose and the sodium polyacrylate. Membrane Sample No. 2 with an area of 14.19 cm2 and a thi'ckness of 15.2 microns (0.6 mil) is prepared 15 as described in Example I. This membrane is used to separate several ethanol/water mixtures at 25°C with the results given in Table II following.

TABLE II vJ % h20 in Feed % h2o in Permeal Separation te Factor Permeation ■ Rate (a-mil/m2-hr) 4.4 99.6 3200 - 1 -2 ' 16.1 99.8 2600 103 19.7 99.7 1355 161 24.1 99.3 447 308 At all feed compositions, the permeate is essentially free of ethanol when a sodium carboxymethyl- cellulose/sodium polyacrylate membrane is employed to separate ethanol and water mixtures « 2 2 063 86 Example 3 Membrane Sample No. 3 comprising. 78.5 percent sodium carboxymethylcellulose having a degree of substitution of 0.9 and 21.5 weight percent polysodiumvinyl 5 sulfonate is prepared according to the methods described in Example 1. The membrane is 12.7 microns (0.5 mil) thick and is evaluated with various ethanol/water mixtures at 25°C with the results as given in Table III following.

TABLE III Separa- Permeation % H,0 % H-0 tion Rate in Feed in Permeate Factor (q-mil/m2-hr) .6 99.3 2391 4.6 14.5 99.9 5891 56 19.1 99.9 4231 114 This membrane exhibits very high separation factors at all feed compositions evaluated, with the permeate in each instance comprising almost entirely 20 water.

Example 4 An aqueous solution of the sodium salt of cellulose sulfate having a sulfate degree of substitution of 2.5 is prepared.

A 1.5-mil membrane is prepared in the manner described in Example 1. The membrane is evaluated for 96.25 hours at 25°C with results as reported in Table IV.

Z9-, 662-F- 16- TABLE IV Separa- Permeation Time % H,0 % H20 tion Rate (hr) in Feed in Permeate Factor (g-mil/m2-hr) 0.75 20.20 98.68 295 440.9 _ 6.79 19.79 99.64 1122 413.2 23.63 18.57 99.68 1366 372.8 96.25 14.57 99.85 3903 261.6 As can be seen from Table IV, excellent ^ 10 separations are obtained using the cellulose sulfate membrane.

Example 5 A 19 micron (0.75 mil) thick film of alginic acid, sodium salt, prepared according to the general 15 procedures described in Example 1, is used to separate an ethanol/water mixture. After 47 hours of operation, the average permeation rate is 163 g-mil/m2 hr. The feed mixture comprises 19.2 percent by weight water and 80.8 percent by weight ethanol. The permeate contains • 20 99.5 percent water. The separation factor is 837.

Example 6 ^_j) To demonstrate the effect of the counterion on selectivity and permeation rate, a membrane is prepared from 80 percent sodium carboxymethylcellulose 25 having a degree of substitution of 0.9 and 20 percent sodium polyacrylate. This membrane is converted to the ^2) hydrogen form by soaking the membrane in a 0.4 M HC1 solution in 90 percent ethanol and 10 percent water. 206386 Conversion to acid form is confirmed from the IR spectrum. The membrane is then soaked in a fresh 90 percent ethanol, 10 percent water solution and evaluated for the separation of ethanol/water solution as described in Example 1. The feed composition initially contains 10.1 percent of water. After 52 hours of operation, the permeate contains 69.8 percent of water yielding a separation factor of 21. The permeation rate is 93 g-mil/m2-hr (2.36 g-mm/m2-hr).

The membrane is then converted to potassium form by soaking in a 0.5 M potassium hydroxide solution and 90 percent ethanol, 10 percent water for 3.75 hours. The membrane is then soaked in fresh 90 percent ethanol, 10 percent water solution for 16 hours and dried. The conversion to potassium form is confirmed by IR spectrum. The membrane is then evaluated using an ethanol/water feed containing 20 percent water. When the water content of the feed is reduced to 19.2 percent, the separation factor is 697. When the water content of the feed is reduced to 13.9 percent, the separation factor is 6188. At feed water content of 10.2 percent, the separation factor is 8795. In all cases, the permeate contains over 99 percent water. In addition to the greatly improved separation factor, the permeation rate increases when the membrane is converted to potassium form from about 93 g-mil/m2-hr (2.36 g-mm/m2-hr) to as much as 595 g-mil/m2-hr (14.8 g-mm/m2-hr).

Example 7 Membrane Nos. VIIA-VIIF, having thicknesses as noted in Table V, are prepared from a 4.25 percent solids aqueous solution containing 80 percent sodium- 29-r6r62=F" 2 063 86 carboxymethylcellulose and 20 percent sodium polyacrylate, said percentages being based on the weight of the solids. The membrane is used to separate, at 25°C, mixtures containing 11 weight percent water and 89 weight percent of the organic compounds noted in Table V following. The permeate composition, selectivity factor a, and permeation rates for each separation are as reported in Table V following. 2 9j£&2-F G & O O o 0 K 1 I to © I Membrane No.

VIIA VI IB VIIC VI ID VI IE VI IF Thickness u (mill (1.18) 19.3 (0.76) 32 (1,27) 31 (1.21) 21 (0.82) 23 (0.90) TABLE V Organic Compound ethanol 2-propanol t-butanol 1-propanol 1-butanol acetone % H00 in 99.7 >99,99 (1) >99.99 (1) 99.997 98.8 99.853 Separation Factor 2,700 800,000 800,000 270,000 730 ,500 Permeation Rate (g-mil/m2-hr) 50 155 224 250 412 424 (1) No detectable organic found in permeate.

Claims (22)

£063 86 As can be seen from the foregoing table, the membranes of this invention can be used to perform very efficient separations of water from a variety of organic compounds. '-ft 'SiC fi -22- WHAT^WE CLAIM IS? WHftT-lb L'LAlMliJJ ii!-

1. A water-selective permeation membrane comprising a salt of a polysaccharide or polysaccharide (^) derivative having a plurality of anionic groups derived from a strong or weak acid, said anionic groups being present in an amount sufficient to allow the membrane to permeate water while substantially impeding the permeation of organic compounds therethrough.

2. The membrane of Claim 1 wherein the polysaccharide or polysaccharide derivative is alginic acid, carboxyalkylcellulose, cellulose sulfate, cellulose phosphate, carboxyalkylalkylcellulose or sulfo-alkylcellulose.

3. The membrane of Claim 1 wherein the polysaccharide or polysaccharide derivative contains a ^ plurality of sulfate, sulfonate or carboxylate groups.

4. The membrane of Claim 2 wherein said polysaccharide derivative is a cellulose derivative containing from.0.1 to 3.0 anionic groups per anhydroglucose unit of the cellulose molecule. G 29-; 062 "F" 22- -23 206336

5. The membrane" of Claim 4 wherein the cellulose derivative is carboxymethylcellulose.

6. The membrane of any one of Claims 1 to 5 furthe oarprising a salt of a polymer which is not a polysaccharide having a plurality of anionic groups derived from a strong or weak acid in an amount sufficient to increase the charge density on said membrane.

7. The membrane of Claim 6 wherein the polymer which is not a polysaccharide is a polymer of acrylic acid, vinylsulfonic acid or styrene sulfonic acid.

8. The membrane of any one of Claims 1 to 7 wherein said salt of the polysaccharide or polysaccharide derivative is an alkali metal salt thereof.

9. The membrane of Claim 8 wherein the alkali metal salt is a cesium salt.

10. The membrane of Claim 6 wherein the polymer which is not"a polysaccharide comprises from 1 to 70 weight percent of said membrane.

11. The membrane of Claim 1 or 6 which is crosslinked to a degree sufficient to render the membrane insoluble in water.

12. A process for separating mixtures of water and an organic compound comprising (a) contacting one side of a membrane comprising a salt of a polysaccharide or polysaccharide derivative having a 29,662-F -23 -24- 206386 plurality of anionic groups derived from a strong or weak acid with a fluid feed mixture containing water and an organic compound, and (b) withdrawing from the other side of said membrane a permeate in vapor form, said permeate containing a higher concentration of water than said feed mixture.

13. The process of Claim 12 wherein said polysaccharide derivative is a cellulose derivative.

14. The process of Claim 13 wherein said cellulose derivative is carboxymethyl cellulose, cellulose sulfate, or sulfoethylcellulose.

15. The process of any one of Claims 12 to 14 wherein said membrane further ccxnprises a salt of a polymer which is not a polysaccharide having a plurality of anionic groups derived from a strong or weak acid.

16. The process of any one of Claims 12 to 15 wherein the membrane is rendered insoluble in water by cross-linking.

17. The process of any one of Claims 12 to 16 vdierein the organic compound is an aliphatic alcohol.

18. The process of Claim 17 wherein the aliphatic alcohol is ethanol.

19. The process of aiy one of Claims 12 to 18 wherein the permeate comprises at least 95 weight percent water. ■' ' r~:~ 29,662-F -24- -25- 206386

20. The process of Claim 19 wherein the permeate comprises at least 98 weight percent water.

21. The process of any one of Claims 12 to 20 wherein the counterion is an aitcaU metal.

22. The process of Claim 21 wherein the counterion is cesium. oated THIS * J DAY OF ^7*^ „ € 7 A. J. PARK & SON PER AGENTS FOR THE APPLICANTS