Membranes with polydopamine coatings
View Patent ↗A membrane with rejection properties for mono and divalent-salts, BOD and COD good resistance to cleaning chemicals and maintaining high permeability for water. A polymeric coating prepared from polydopamine or hydroquinone or catechol or mixtures thereof, is deposited. In another embodiment, coating process steps and conditions are taught to achieve thickness control to tune the rejection properties of the membranes.
1. A method of improving membrane rejection properties by depositing a coating on one or more membranes, the method comprising:
(i) preparing a coating solution comprising one or more active agents, wherein said one or more active agents are polydopamine, hydroquinone, catechol, or a mixture thereof;
(ii) preparing a coated membrane by circulation of the coating solution through a membrane for a given duration of time while bubbling air or oxygen into the coating solution;
(iii) after completing step (ii), removing polymer particles formed in the coating solution using a 0.1-5 μm pore size filter to prepare a filtered coating solution;
(iv) reusing the filtered coating solution from step (iii) for a new set of membranes; and
(v) disposing of residual coating solution by
(a) storing the coating solution in a tank;
(b) bubbling oxygen or air through the tank for a period of 12-48 hrs to fully polymerize the one or more active agents;
(c) removing polymer particles from the coating solution; and
(d) adjusting the pH of the coating solution to neutral pH and adding 50-100 ppm bleach to oxidize any residual active agent;
wherein the pH of the coating solution is changed from basic to acidic between steps (iii) and (iv) to temporarily stop polymerization and preserve the coating solution.
2. The method of claim 1 , wherein the one or more membranes comprises an RO membrane, a UF membrane, an NF membrane, an MF membrane, or a combination thereof.
3. The method of claim 1 , wherein the % rejection improvements of one or more of the membranes after coating are between 0.5% and 200%.
4. The method of claim 1 , wherein the % loss of permeate flux of one or more of the membranes due to the coating process as described in claim 1 is between 0% and 50%.
5. The method of claim 1 , wherein the coated membranes as described in claim 1 have higher resistance to damage from cleaning chemicals and exposure to free chlorine.
6. The method of claim 1 , wherein coated Nanofiltration (NF) membranes after coating as described in claim 1 have greater than 96% rejection for monovalent ions and greater than 99% rejection for divalent ions.
7. The method of claim 1 , wherein coated Nanofiltration (NF) membranes after coating as described in claim 1 have more than 10% higher flux compared to extra low-energy (XLE) RO membranes while achieving >98% monovalent ion rejection and >99% divalent ion rejection.
8. The method of claim 1 , wherein the coated membrane as described in claim 1 comprises one or more of the following polymethyhnethacrylates , polystyrenes, polycarbonates, polyimides, epoxy resins, cyclic olefin copolymers, cyclic olefin polymers, acrylate polymers, polyethylene teraphthalate, polyphenylene vinylene, polyether ether ketone, poly(N-vinylcarbazole), acrylonitrile-styrene copolymer, or polyetherimide poly(phenylenevinylene)polysulfone, copolymer of styrene and acrylonitrile poly(arylene oxide), polycarbonate, cellulose acetate, polysulfones; poly(styrenes), styrene-containing copolymers, acrylonitrilestyrene copolymers, styrene-butadiene copolymers, styrene-vinylbenzylhalide copolymers;
polycarbonates;
cellulosic polymers, cellulose acetate-butyrate, cellulose propionate, ethyl cellulose, methyl cellulose, nitrocellulose, polyamides, polyimides, aryl polyamides, aryl polyimides, polyethers, poly(arylene oxides), poly(phenylene oxide), poly(xylene oxide);
poly(esteramide-diisocyanate), polyurethanes, polyesters (including polyarylates), poly(ethylene terephthalate), poly(alkyl methacrylates), poly(acrylates), poly (phenylene terephthalate), polysulfides, poly(ethylene), poly(propylene), poly(butene-1), poly(4-methyl pentene-1), polyvinyls, poly(vinyl chloride), poly(vinyl fluoride), poly(vinylidene chloride), poly(vinylidene fluoride), poly(vinyl alcohol), poly(vinyl esters), poly (vinyl acetate), poly(vinyl propionate), poly(vinyl pyridines), poly(vinyl pyrrolidones), poly(vinyl ethers), poly(vinyl ketones), poly(vinyl aldehydes), poly(vinyl formal), poly(vinyl butyral), poly(vinyl amides), poly(vinyl amines), poly(inyl urethanes), poly(vinyl ureas), poly(vinyl phosphates), poly(vinyl sulfates), polyallyls;
poly(benzobe117imidazole), polyhydrazides , polyoxadiazoles, polytriazoles, poly(benzimidazole), polycarbodiimides , polyphosphazines and combinations thereof.
9. The method of claim 1 , wherein additional dopamine, hydroquinone, catechol, or a mixture of any these is added between steps (iii) and (iv) to maintain a concentration of the one or more active agents.
10. The method of claim 1 , wherein a coated membrane as described in claim 1 is a flatsheet, or a hollow-fiber, or a porous block, or a rolled flatsheet with spacers.
11. The method of claim 1 , wherein for a porous membrane of claim 1 , only during the first 5-10 minutes of circulation in step (ii) a permeation is allowed through the porous membrane using pressure from a circulation pump or a height difference between a permeate port of the porous membrane and to allow penetration of the coating solution to a permeate side of the porous membrane.
12. A method of claim 1 , wherein a coated membrane as described in claim 1 has a higher rejection rate for salts and other impurities such as BOD, COD and harmful materials such as Boron and Arsenic than an uncoated membrane.