This invention relates to a membrane arrangement for use in the osmotic concentration of aqueous solutions.

One use for osmotic concentration of aqueous solutions is in the concentration of juices and beverages.

A desirable membrane structure for use in the osmotic concentration of aqueous solutions via osmotic transfer of water to concentrated aqueous saline solutions, is a microporous, non-water-wettable membrane, contacted on its opposite surfaces by the solution to be concentrated and the brine into which the water is to be transferred. The membrane operates such that the pores thereof are filled only with water vapour, and water transport occurs only by molecular transport through the vapour phase. Membranes of such properties are well-known to those skilled in the membrane art, and include microporous structures fabricated from poly tetrafluorethylene, for example GORE-TEX (trade mark of W.L. Gore & Associates, Inc.), from polypropylene, for example CELGARD (Registered Trade Mark), ACCUREL (Registered Trade Mark) and the like.

In many instances, however, the proper functioning of such a membrane is prevented by the presence of contaminants or other components of the feed liquid which promote wetting of the membrane by that solution, and the subsequent penetration of the membrane pores by the wetting liquid. In such a situation, there may be leakage of the feed liquid into the brine-compartment, or of brine into the feed liquid.

Contaminants or other components present in the feed liquid which are likely to cause this problem include emulsified oil droplets, colloidal hydrogel particles, proteins and other biological macromolecules, and surface active agents. These components are, for the most part, non-volatile under the conditions of osmotic concentration, with the result that they remain behind in the feed liquid and may preferentially and adversely accumulate at the upstream membrane surface.

Components of solutions used to clean membrane devices often contain surface active agents, and that residual from these solutions, rather than feed components, might also promote membrane wetting.

It is an object of the invention to provide an improved membrane structure for osmotic concentration.

The invention provides a membrane structure for use in the osmotic concentration of liquids, said structure including a water-permeable sheet attached to a non-water-

wettable, microporous membrane.

The invention also provides a membrane structure for use in the osmotic concentration of liquids, wherein the feed liquid contains volatile and/or fragrance and/or flavour components, said structure including a liquid impermeable but vapour permeable sheet or film associated with a non-wettable membrane, said sheet separating said feed liquid from said membrane.

The invention further provides an osmotic concentration method, using the membrane structure of either of the two preceding paragraphs.

Embodiments of the invention, which may be preferred, will be described in detail hereinafter.

The previously-described problem, of the proper function of the membrane used in osmotic concentration being prevented by wetting of the membrane taking place, is believed to be overcome by the present invention.

In one general embodiment, it is suggested to impose, between the feed liquid and the microporous hydrophobic membrane described herein above, a barrier film which is substantially freely permeable to water (and which may be permeable also to other microsolutes present), but which is essentially impermeable to macrosolutes and colloids. If such a barrier were deposited on the feed-liquid side of the membrane, then none of the wettabilϊty-altering components of the feed solution would contact the membrane surface, but water transporting across that barrier would be free to evaporate and migrate through the vapour-filled membrane pores and condense in the brine on the opposite surface.

Any (non-volatile) microsolutes, such as sugar, which can migrate into the barrier layer, will be concentrated at the layer/membrane boundary, and must then migrate by molecular diffusion back through the barrier into the feed solution. In order to minimize the additional resistance to water transport imposed by this back-transport of solutes (so called solute-polarization), it is desirable that this barrier film be as thin as possible, commensurate with the rate of transport of water from the feed liquid into the brine.

In one particular embodiment, the membrane structure could be a laminate comprising the microporous membrane described hereinabove with a thin, hydrophilic gel- type membrane of high intrinsic water-permeability but very low permeability to macrosolutes. One such likely candidate for this laminate is dialysis grade cellophane or CUPROPHAN (Registered Trade Mark) as is used in the fabrication of hemodialyzers. This film might simply be laid on the surface of the microporous membrane, and the

assembly mounted in the same module as is currently used for osmotic concentration. Cellophane membranes as thin as 12.5 microns (0.5 mil) are commercially available, and would probably be suitable for this purpose. To be functional for this embodiment, it is essential that the hydrogel-film-side of the laminate be in contact with the feed liquid or solution to be concentrated. Any other hydrophilic polymer film of adequately high intrinsic water permeability and virtual impermeability to macrosolutes and colloids, which can be fabricated in sufficient thinness, is suitable for this purpose, such films including (but not limited to) those comprised of esters and ethers of cellulose; crosslinked gelatin; gelatinized starch; chitin; agar; alginic acid; crosslinked polyacrylamide; poly (hydroxyethyl) methacrylate; crosslinked polyvinyl alcohol; and the like.

In another embodiment, as an alternative to a hydrogel film for fabrication of such a laminate, is an asymmetric, ultramicroporous, water-wettable membrane, such as an ultrafiltration membrane, the pore size of which is too small to admit the objectionable macrosolutes or colloids. In this case also (since such membranes are permeable to microsolutes), the film should be as thin as possible to minimise polarization within the film, and consequent impedance to water transport. A number of commercially available asymmetric ultrafiltration membranes are useful for this purpose, including (but not limited to) those comprised of cellulose acetate, polyacrylonitrile, Dynel (trade mark), polycarbonate, polyamide, polysulfone, polyolefin, and polyvinylidene difluoride.

Yet another embodiment of such a laminate, involves coating the microporous membrane with a solution of a highly water-permeable polymer in a volatile, non-wetting solvent which, upon evaporation, leaves a very thin (but defect-free) coating of that polymer on the membrane. One class of polymers useful for this purpose are the hydrophilic thermoplastic polyurethanes, for example, ESTANE (Registered Trade Mark) which are soluble in such solvents as tetrahydrofuran, DMF, and N-methyl pyrrolidone, from which thin films are easily cast.

Other film-forming coating formulations suitable for this purpose include (but are not limited to) (1) aqueous solutions of thermally curable or cross-linkable polymers such as polyvinyl alcohol/glyoxal; ammonium carboxymethylcellulose; zinc ammonium alginate; gelatin/formaldehyde; chitosan formate; (2) alcohol or acetone solutions of hydroxyethylated or hydroxypropylated cellulose esters or ethers; (3) alcohol solutions of polyhydroxyethyl methacrylate; and the like.

It can be seen that the membrane structure of this invention is an improvement on

existing osmotic concentration structures, which will permit direct osmotic concentration processing of juices and beverages, with or without pulp, and without pretreatment.

The invention is considered to be additionally suitable for the processing of aqueous solution of surface active solutes which are volatile, such as ethyl alcohol, and flavor and fragrance components such as aliphatic and aromatic esters, ethers, ketone, alcohols, and aldehydes. These components, if present in solution in the liquid feed contacting the non- water-wettable membrane, will tend to promote wetting and liquid penetration. On the other hand, if a liquid impermeable but vapor permeable film separates the feed liquid from the membrane, then none of the surface active components will be present as a liquid phase in the membrane, and wetting will not occur. This particular situation is likely to be encountered in osmotic concentration of alcoholic beverages, or of fruit or vegetable extracts rich in flavor/fragrance components. So long as the brine into which these volatiles will condense is sufficiently rich in salt, the brine phase will not be capable of wetting the pores of the membrane, and establishing a liquid pathway for transport.