Patent GB-1107066-A (GB)
Title: Improved process and apparatus for production of membranes
IPC: B29C67/20
Filed: 1966-07-01
Abstract: 1,107,066. Semi-permeable cellulose ester membranes. GENERAL DYNAMICS CORPORATION. 1 July, 1966 [6 July, 1965; 2 Sept., 1965], No. 29578/66. Heading B5B. In a method of making a non-uniform semi-permeable membrane having an active surface layer of a different composition from the remainder thereof, a film of a fluid cellulose ester membrane-forming solution containing an organic solvent is continuously cast upon a moving endless surface, the solvent evaporated from one surface of said cast film for a predetermined time, the film immersed after said evaporation in water at a temperature near its freezing point for a sufficient period to set-up the cast film into a semi-permeable membrane, and the set-up membrane removed from the endless surface to produce an endless length of semi-permeable membrane. In apparatus as shown, a casting solution is poured into the top of a D-shaped casting trough 17, the rear wall 61 of the trough having been previously adjusted to seat its lower edge in the groove 75 so as to close the bottom of the trough. The adjustable rear wall 61 is moved out of the groove 75 to provide a suitable gap at the bottom of the trough, downward flow of the casting solution begins and a thin coating of the casting solution is supplied uniformly across the major portion of the surface of the stainless steel casting drum 13. The cast solution is exposed to a flow of air under hood 23, supplied by blower 27, from the time it is cast until it becomes immersed in the reservoir 15 where it is contacted by distilled water. Immersion in the water at a suitable temperature e.g. about 1‹ C. completes the set-up of the non-uniform membrane and removes the remaining organic solvent and the swelling agent. The set-up membrane is then removed from the casting drum 13. Usually the first membrane produced is collected for about ten minutes, which is considered sufficient time to achieve uniformity of operation. This initial length of membrane is severed and discarded, and the sheet of membrane then being produced is wound on the take-up drum 19. The take-up drum 19 is allowed to accumulate about two hours worth of membrane and at the end of this time, the membrane is cut, the filled drum 19 removed, and a new drum 19 is inserted. After detachment of the membrane, the surface of drum 13 on emerging from the water in the reservoir passes below the squeegees 77 which remove any residual droplets therefrom so that the drum is relatively dry on passing again below trough 17. The membrane may then be transferred to a bath of circulating water at ambient temperature to remove solvent, swelling agent and other impurities and is finally rolled upon another spool. The preparation of semipermeable cellulose acetate membranes is particularly described. These may be made from a casting solution of cellulose acetate plus an aqueous solution of a swelling agent, such as magnesium perchlorate or zinc chloride, both of which have been dissolved in an organic solvent. A suitable casting solution comprises acetone 66À7%, cellulose acetate 22À2%, water 10À0% and magnesium perchlorate 1À1%. Preferably the " 2À5 " acetate is used. The reservoir 15 is filled with distilled water and the take-up drum 19 is driven so that its surface has a slightly higher linear speed than that of casting drum 13 to keep the membrane in tension during take-up. Belt 95 slips sufficiently in the groove on the surface of take-up drum 19 to prevent the membrane from tearing. Pump 103 and valves 107 and 109 are regulated to maintain a constant water level, and sufficient flow of a refrigerant is maintained through the cooling coils 39 to keep the temperature of the distilled water at about 1‹ C., the reservoir being suitably lagged to assist maintenance of the correct temperature. At the same time, sufficient circulation of distilled water is maintained during the casting operation so that any solids which might become entrained in the water are removed by filter 105 and so that there is a good flow of water past the membrane film which sets-up on the surface of casting drum 13. Complete removal of swelling agent and residual solvent from the film is effected, by adequate circulation of the water in the reservoir 15. Drain valve 107 is suitably set so that about 10% of the outlet flow of liquid from tank 33 is discharged to drain, and a like amount of water is returned to the circulation system 29 via the make-up valve 109. The make-up distilled water is pre-cooled to a temperature of about 1‹ C. before it is fed into circulation system 29. Blower 27 is activated to draw about 10 cubic feet of air per minute through hood 23. Although exposure for about a minute to a moving current of air is considered preferable, exposure to any suitable non- reactive gas for between about 30 seconds and about 5 minutes may be used. Trough 17 is filled to the desired level with the pre-cooled casting solution, suitably cooled to about - 8‹ C., although it may be used at temperatures between about 0‹ C. and about- 20‹ C. The temperature of the drum surface approximates that of reservoir 15, i.e. about 1‹ C. The cast solution is exposed to the flow of air under hood 23 for about one minute from the time it is cast until it becomes immersed in distilled water reservoir 15. The set-up membrane is then removed from casting drum 13. The rejection characteristic of the membrane produced may be altered and adapted for a high percentage of solute rejection, although at the same time accepting the decrease in flux, by heat treatment of the membrane. The entire roll of membrane is placed in a water bath which is maintained at about 80‹ C. and is held therein for about 30 minutes. Fig. 3 indicates a preferred alternative embodiment of a device for feeding a fluid casting solution for use in the apparatus of Fig. 2. The preferred feed device allows precise application of a thin film of casting solution and thus enables reproducable membranes readily to be produced. A cylindrical drum 113 is used and modified feed device 115 including a generally V-shaped casting trough 117 adjustably disposed above the top of rotatable drum 113 and serving to apply a thin film of casting solution thereto. The bottom of fixed rear wall 131 of the trough rides on the surface of casting drum 113, and to prevent leakage of casting solution rearward from trough 117 and to reduce the drag of the trough on drum 113, rear wall 131 includes a lower portion in the form of a wiper blade 141 made of a resilient material with low friction characteristics. The bottom edges of the side walls 133 are contoured to match the cylindrical surface of drum 113. The thickness of the film being cast is regulated by adjustable forward wall 135. Forward wall 135 is so supported that the bottom edge can be easily moved toward and away from the surface of casting drum 113 to adjust the distance therebetween to regulate the flow of the casting solution from trough 117 on to the rotating drum. Suitably, a pair of slotted guide ways are milled out of the inner surfaces of triangular side walls 133, and the lateral edges of forward wall 135 reside in these guide ways. The bottom surface 151 of front wall 135 is preferably smooth and located in converging relationship to drum 113, i.e. the distance between the rear edge of the bottom surface 151 and the drum 113 should be greater than the distance between the forward edge 153 of bottom surface 151 and the drum. (Fig. 4). Preferably, the flat bottom surface 151 is disposed horizontally on the uphill side of the crest of drum 113, so that a slight compressive action occurs in the upper region of the film as a point on the curved surface of rotating drum 113 moves under horizontal bottom surface 151. This compressive action combined with the use of the very smooth bottom surface 151 assists in establishing reproducability in the operating characteristics of the semi-permeable membranes. The trough may be covered with a transparent plastic cover 136.