Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
  • B01D71/06—Organic material
  • B01D71/56—Polyamides, e.g. polyester-amides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
  • B01D61/002—Forward osmosis or direct osmosis
  • B01D61/0024—Controlling or regulating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
  • B01D67/0002—Organic membrane manufacture
  • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
  • B01D67/00091—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching by evaporation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
  • B01D67/0081—After-treatment of organic or inorganic membranes
  • B01D67/0086—Mechanical after-treatment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
  • B01D69/10—Supported membranes; Membrane supports
  • B01D69/105—Support pretreatment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
  • B01D69/12—Composite membranes; Ultra-thin membranes
  • B01D69/1213—Laminated layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
  • B01D69/12—Composite membranes; Ultra-thin membranes
  • B01D69/1216—Three or more layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
  • B01D71/06—Organic material
  • B01D71/54—Polyureas; Polyurethanes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
  • B01D71/06—Organic material
  • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
  • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
  • B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
  • B01D71/643—Polyether-imides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
  • B01D71/06—Organic material
  • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
  • B01D71/80—Block polymers
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F1/00—Treatment of water, waste water, or sewage
  • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
  • C02F1/445—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by forward osmosis
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2323/00—Details relating to membrane preparation
  • B01D2323/42—Details of membrane preparation apparatus
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2325/00—Details relating to properties of membranes
  • B01D2325/04—Characteristic thickness
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
  • C02F2103/08—Seawater, e.g. for desalination
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
  • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
  • Y02A20/124—Water desalination
  • Y02A20/131—Reverse-osmosis

Definitions

• One or more aspects relate generally to osmotic separation. More particularly, one or more aspects involve membranes that are useful in engineered osmotic separation processes.
• Semipermeable membranes are substantially permeable to a liquid and substantially impermeable to solutes based on the nature of their selective barrier.
• Osmotically driven membrane separation generally relies upon driving forces associated with the passage of draw solutes through one or more support layers of a membrane used in the separation process.
• TFC thin-film composite
• RO reverse osmosis
• F Forward osmosis
• a method of making a forward osmosis membrane may comprise providing a support structure including at least a first layer and a second layer, applying a material to a first layer of the support structure to form a membrane support layer, applying a barrier material to the membrane support layer to form the forward osmosis membrane, and releasing the forward osmosis membrane by separating the first layer of the support structure from the second layer of the support structure.
• the support structure may comprise a bilayer structure.
• the first layer of the support structure may have a Frazier air permeability of greater than about 50 cfm/ft 2 min.
• the material applied to the first layer of the support structure may be applied in a coating of between about 5 and 20 g/m 2 .
• the forward osmosis membrane may have an overall thickness of less than about 125 microns.
• the barrier material may comprise a semipermeable material.
• the barrier material may comprise a polymer.
• the barrier material may comprise a polyamide urea, polypiperazine, or a block co-polymer.
• the support structure may comprise a polymeric paper.
• the support structure may comprise PET or polypropylene.
• the method may further comprise rewetting the forward osmosis membrane.
• the method may also further comprise adding an additive to one or more layers of the membrane.
• the step of releasing the forward osmosis membrane by separating the first and second layers of the support structure may comprise modifying a pore structure in at least a section of the forward osmosis membrane.
• the method may further comprise reusing the second layer of the support structure.
• a method of making a forward osmosis membrane may comprise casting a paperless support structure on a fabrication belt or drum, depositing a barrier material on the paperless support structure, and delaminating the paperless support structure from the fabrication belt to form the forward osmosis membrane.
• the belt or drum may be constructed and arranged to provide a surface which retains a portion of the support structure. Retained support structure may be removed prior to full rotation of the belt or drum.
• a method of facilitating a forward osmosis separation operation may comprise providing a support structure, applying a material to the support structure to form a membrane support layer, applying a barrier layer to the membrane support layer to form a forward osmosis membrane, and configuring the forward osmosis membrane in a forward osmosis membrane module such that the support structure may provide a spacer or a flow channel for a draw solution or a feed solution supplied to the module during the forward osmosis separation operation.
• providing the support structure may comprise providing a bilayer structure.
• the method may further comprise providing a source of the draw solution.
• a forward osmosis membrane may comprise a fabric layer of less than about 75 microns, a support layer of less than about 50 microns applied on the fabric layer, and a barrier layer applied on the support layer.
• the forward osmosis membrane may have an overall thickness of less than about 125 microns.
• the barrier layer may comprise polyamide.
• the support layer may comprise PET.
• the support layer may contain less than about 30 g/m 2 of material overall.
• the supporting material may be applied in a coating of between about 8 and 17.5 g/m 2 .
• the combined weight of the support layer, support material, and barrier layer overall may be between about 20 and 40 g/m 2 .
• the support layer may be made in a wet laid process.
• a method may comprise rewetting a forward osmosis membrane by immersion in water containing a solute which enhances wetting.
• the solute may be a surfactant.
• the method may further comprise rewetting the membrane by immersion in water containing a low surface tension solvent.
• the solvent may comprise an alcohol.
• the solvent may comprise isopropyl alcohol, ethanol or methanol.
• the support structure is embedded within the hydrophilic material.
• the barrier material comprises polyamide.
• FIGS. 1 -6 present data referenced in the accompanying Example.
• Osmotic separation processes generally involve generating water flux across a semipermeable membrane based on osmotic pressure differentials. Solute may be rejected by the membrane and retained on either side due to the greater permeability of water than the solute with respect to the selective barrier of the membrane. Solutes may be undesirable and therefore removed from a process stream via membrane separation for purification, or desirable in which case they may be concentrated and collected via a membrane separation process.
• Membranes may be used in various osmotically driven separation processes such as but not limited to desalination, wastewater purification and reuse, FO or PRO bioreactors, concentration or dewatering of various liquid streams, concentration in pharmaceutical and food- grade applications, PRO energy generation and energy generation via an osmotic heat engine.
• Polymeric membranes typically include a porous support structure that provides mechanical and structural support for a selective layer.
• Membranes may be formed in various shapes including spiral wound, hollow fiber, tubular and flat sheet depending on an intended application. Membrane characteristics should be customized to achieve ideal performance and may vary between specific applications. For example, in FO and PRO applications, the effectiveness of a separation process may be enhanced by reducing the thickness and tortuosity of the membrane, while increasing its porosity and hydrophilicity, without sacrificing strength, salt rejection and water permeability properties.
• the RO membrane industry has, to date, standardized on a polyethylene terephthalate (PET) support layer with a polysulfone active coating.
• PET polyethylene terephthalate
• the PET support layer is generally about four millimeters thick with a basis weight of approximately 80 g/m 2 and a Frazier air permeability of approximately four cfm/ft 2 /min.
• the PET material generally represents the most expensive raw material of the membrane and provides little to no benefit to the performance of the RO membrane.
• FO osmotic separation membranes
• PRO pressure retarded osmosis
• reducing the thickness of the support structure may be desirable.
• Attempting to reduce the thickness or weight of the support material may be associated with membrane processing problems, however, such as the inability to run the support material through a membrane fabrication line without creasing or wrinkling. In severe cases, membrane web breakage can occur which may result in significant costs to a manufacturer.
• the manufacture of membranes with reduced thickness for various engineered osmotic separation processes may be facilitated.
• the thickness of the membrane support structure may be reduced. Thinner support structures may be associated with reduced cost, enhanced mass transfer and higher flux within the membrane by reducing resistance to fluid flow and solute diffusion through the membrane support, and an increase in the amount of active membrane area which may be provided in a separation module. Furthermore, as water standards continue to become more stringent, reducing the thickness of the support structure may reduce the level of various residual chemicals of concern in the membranes, such as dimethylformamide and meta phenylene diamine.
• a bilayer substrate may be provided to facilitate membrane fabrication.
• a bilayer substrate may include a membrane support layer which will serve as the membrane support layer of a final membrane product.
• the membrane support layer of the bilayer substrate may be of reduced thickness compared to conventional membrane support layers while at the same time providing an overall thickness requisite for membrane manufacturing, including the application and processing of a selective layer upon the support layer.
• the bilayer support may include a removable backing layer in addition to the membrane support layer to provide the extra thickness. The removable backing layer may be intended to be separated from the support layer subsequent to membrane fabrication.
• the bilayer substrate may include a backing layer intended to remain intact subsequent to membrane fabrication.
• a bilayer substrate may include a membrane support layer generally affixed to a removable backing layer.
• the membrane support layer may be the support layer of a resultant membrane while the removable backing layer may be largely sacrificial, temporarily providing increased thickness to the support layer to facilitate membrane processing.
• the membrane support layer of the bilayer substrate may generally be a light basis weight layer of reduced thickness in comparison to a conventional membrane support layer.
• the support layer may be PET.
• the support layer and backing layer may be made of the same material. In other embodiments, they may be made of different materials.
• the bilayer substrate may be characterized by properties which allow the two layers together to perform similar to an existing standard PET support layer with respect to strength, resistance to creasing, and general processing in the membrane manufacturing process.
• the backing layer may typically be about two to about four mils in thickness with a Frazier air permeability of less than about 6 cfm/ft 2 min.
• the top layer which may ultimately be the membrane support structure as described herein, may typically be less than about 2 mils in thickness with a Frazier air permeability of greater than about 100 cfm/ft 2 min.
• the forward osmosis membrane may have an overall thickness of less than about 125 microns.
• the support layer may contain less than about 30 g/m 2 of material overall.
• the supporting material may be applied in a coating of between about 8 and 17.5 g/m 2 .
• the combined weight of the support layer, support material, and barrier layer overall may be between about 20 and 40 g m 2 .
• the top support layer may be made in a wet laid process, dry laid process, or a woven material. Alternately, the support layer may be made by deposition in the presence of an electrical field, such as in an electrospinning method. Materials may include PET or other polymers typically used in the fabrication of pressure driven membrane supports, and may additionally be designed to have a hydrophilic nature. In some embodiments, the support stracture may be a paper, such as a polymeric paper. In some nonlimiting embodiments, the support material may be made of PET, polypropylene, polysulfone, polyacrylonitrile, or other porous polymers suitable for creating a support for interfacial polymerization of a polyamide, polyamide urea, or similar type barrier layer.
• Hydrophilic additives may be introduced to the support material.
• a selective or otherwise active layer may be applied to the support material of the bilayer substrate during a membrane manufacturing process.
• a semipermeable layer may be applied as the active layer.
• the semipermeable layer may comprise a polymer.
• the semipermeable layer may comprise a polyamide, such as polyamide urea, a block co-polymer or polypiperazine.
• a polysulfone layer may be applied to a PET support layer of a bilayer substrate.
• Multi-layered substrates in accordance with one or more embodiments may be easier to coat than single layer since the substrate is sturdier and thicker and thereby less subject to wrinkling and tearing.
• the backing layer may then be separated and removed.
• a membrane with a support layer of reduced thickness may be produced using standard manufacturing equipment and techniques.
• the separation step may be performed prior to application of an active layer.
• disclosed methods may be characterized by minimal penetration of active material, such as polysulfone, into the backing layer which may facilitate separation and removal of the backing layer.
• active material such as polysulfone
• the use of multiple layers may mitigate the impact of strike- through by blocking excess coating material from penetrating the backing layer.
• the backing layer may remain largely intact subsequent to separation, enabling reuse or recycling of the backing layer which may offer additional efficiencies and cost savings.
• the backing layer may be largely sacrificial.
• the backing layer may be recycled within the fabrication equipment itself, such as with a rotating belt or drum.
• the backing layer or belt may allow sufficient penetration of the support material so that upon removal of the backing material, beneficial disruption of the pore structure of the support material occurs. This may cause the base of the porous support material to have a more open and porous structure than it would have had without this disruption.
• Optimal backing layer characteristics may allow for slight penetration of the porous support material, without allowing complete penetration, or "strike through", such that when the backing layer is removed, the pore structure is opened up without causing defects in the barrier layer above it.
• One or more embodiments may find applicability in the manufacture of membranes for FO and PRO processes, as well as offer benefits for the manufacture of membranes used in pressure driven separations such as O, microfiltration (MF), ultrafiltration (UF) and nanofiltration (NF).
• pressure driven separations such as O, microfiltration (MF), ultrafiltration (UF) and nanofiltration (NF).
• a bilayer substrate may be formed by casting a support polymer on a substantially high release material such that after casting an active barrier layer on the support polymer, the support polymer may be peeled from the base material such that only support polymer and the active membrane coating remain.
• a bilayer material may be commercially purchased for use in a membrane manufacturing process.
• the removal of a sacrificial or recyclable backing layer may create a more open pore structure at a base region of the polymer support layer which previously interfaced with the backing layer prior to removal thereof. This may result in enhanced flux through the membrane.
• the tearing or other disruption of a relatively closed pore structure at the bottom-most section of the porous polymer support may produce a structure characterized by significantly enhancing the porosity and reducing the tortuosity of the support structure.
• the pore structure of such a polymeric support will be substantially open through most of its thickness, but become closed at the point where the polymer phase interacted with the base material. If some of the porous support penetrates into the base layer, removing this layer may expose a much more open structure as would be found throughout the porous layer, removing the tight layer at the base.
• a bilayer substrate may be implemented which is intended to wholly become part of a resultant membrane.
• a support polymer may be casted directly onto one or both sides of a tricot-type mesh support material.
• a polyurethane or other adhesive may be used to bind the support layer to the mesh layer.
• the support polymer may be PET in certain non-limiting embodiments.
• the mesh support such as a supporting tricot, may conduct fluid flow within a finished membrane module.
• a membrane barrier layer may then be applied on one or both of these support polymer coatings, forming a final single or double layer membrane with a water conducting mesh as its base or core.
• a tricot layer may be laminated to a thin PET layer to create a bilayer which may then be processed on existing membrane manufacturing machines.
• the strength of the tricot can be used to process the thin PET and the resulting bilayer material does not require separation in that the membrane including tricot may be incorporated directly into a membrane module to enhance module performance.
• the tricot backing may increase membrane production efficiency since it is relatively impervious to web breakage and has superior strength compared to the standard 4 millimeter PET. This may result in reduced creasing and wrinkling in the manufacturing process, increasing membrane performance and yields. Further production efficiencies may include reduction in fabrication steps by eliminating the need for producing leaf sets of tricot, flow spacers or permeate tubes which are traditionally separately incorporated into a completed membrane module.
• a bilayer substrate may be prewetted to improve mass transfer characteristics of the support polymer and polymer / fabric interface.
• a solvent such as with a solvent such as NMP, DMF, DMSO, triethyl phosphate, dimethyl acetamide, or a combination thereof may be used to prewet.
• Prewetting may create a more open pore structure, cause less occlusion of pores in the polymer support, enhance polymer porosity by encouraging macrovoid formation, improve pore structure and decrease tortuosity. These properties may be realized and even enhanced by separation of removable backing layer if used. These properties may be particularly desirable when using bilayer assemblies which are not intended to be separated, such as with supporting tricot mesh and PET fabric, for example, by preventing excessive penetration of the polymer into the supporting material.
• a process to manufacture a membrane for osmotically driven membrane processes may include the use of a drive system to transport a bilayer sheet of support material, for example two layers of PET paper, through a casting machine which may deposit a polymer in a solvent solution. Tensions may generally be maintained so as to reduce the possibility of creasing and wrinkling.
• the bilayer support material may be composed of two layers pressed together such that the bottom layer may be either subsequently removed or ultimately used as a membrane fluid channel spacer mesh.
• the bilayer support material may be conveyed to a polymer application device which applies a solution of polymer, for example polysulfone, in a solvent, for example
• the bilayer material may enter a quenching bath in which the polymer precipitates into the top layer of the bilayer material.
• the temperature of the quenching bath may vary and may impact one or more properties of a resultant membrane.
• improved properties of forward osmosis membranes may be associated with quenching bath temperature in the range of 100 °F to 110 °F.
• the bilayer top layer is designed to allow sufficient penetration of the solution to result in delamination pressures at which the precipitated polymer layer would disengage from the bilayer support material in excess of about ten psig.
• the backing layer of the bilayer material in contrast is designed to prevent polymer penetration to allow for the two support material layers to be separated after membrane manufacturing.
• the primary purpose of the backing layer is to prevent creasing and wrinkling of the top layer while processing by providing necessary strength to allow existing membrane machines to convey the very thin membrane required for forward osmosis membranes.
• the remainder of the membrane production is completed using standard rinsing and membrane casting equipment.
• any removable bilayer material implemented may be separated prior to or as part of module fabrication.
• the separation of the two layers can provide the additional benefit of opening the pore structure at the interface of the PET layers further enhancing separation properties.
• the bottom layer of the bilayer material may be integrated into the membrane module construction serving the role of the spacer mesh, for example tricot normally integrated between membrane layers as a fluid conveyance medium.
• the selective barrier in the disclosed thin- film composite membranes may be a semipermeable three-dimensional polymer network, such as an aliphatic or aromatic polyamide, aromatic polyhydrazide, poly-bensimidazolone, polyepiamine/amide, polyepiamine/urea, polyethyleneimine/urea, sulfonated polyfurane, polybenzimidazole, polypiperazine isophtal amide, a polyether, a polyether-urea, apolyester, or a polyimide or a copolymer thereof or a mixture of any of them.
• a semipermeable three-dimensional polymer network such as an aliphatic or aromatic polyamide, aromatic polyhydrazide, poly-bensimidazolone, polyepiamine/amide, polyepiamine/urea, polyethyleneimine/urea, sulfonated polyfurane, polybenzimidazole, polypiperazine isophtal amide, a polyether,
• the selective barrier may be an aromatic or non-aromatic polyamide, such as residues of a phthaloyl (e.g., isophthaloyl or terephthaloyl) halide, a trimesyl halide, or a mixture thereof.
• the polyamide may be residues of diaminobenzene, triaminobenzene, polyetherimine, piperazine or poly-piperazine or residues of a trimesoyl halide and residues of a diaminobenzene.
• the selective barrier may also comprise residues of trimesoyl chloride and m-phenylenediamine.
• the selective barrier may be the reaction product of trimesoyl chloride and m- phenylenediamine.
• the selective barrier may be characterized by a thickness adequate to impart desired salt rejection and water permeability properties while generally minimizing overall membrane thickness.
• the selective barrier may have an average thickness from about 50 nm and about 200 nm.
• the thickness of the barrier layer is desired to be as limited as possible, but also thick enough to prevent defects in the coating surface.
• the practice of polyamide membrane formation for pressure driven semipermeable membranes may inform the selection of the appropriate barrier membrane thickness.
• the selective barrier may be formed on the surface of a porous support via polymerization, for example, via interfacial polymerization.
• Polymers that may be suitable for use as porous supports in accordance with one or more embodiments include polysulfone, polyethersulfone, poly( ether sulfone ketone), poly( ether ethyl ketone), poly(phthalazinone ether sulfone ketone), polyacrylonitrile, polypropylene, poly(vinyl fluoride), polyetherimide, cellulose acetate, cellulose diacetate, and cellulose triacetate polyacrylonitrile.
• the support layer may be characterized by a thickness adequate to provide support and structural stability to a membrane during
• the polymer support may have an average thickness from about 10 ⁇ and to about 75 ⁇ . It is generally desirable for the support to be as thin as possible without compromising the quality of the support surface for interfacial polymerization of the barrier layer. The smoother the support layer is, the less thickness of support material is generally required for this criterion, In at least some preferred embodiments, this layer is less than approximately 40 ⁇ .
• the porous support comprises a first side (active side) with a first plurality of pores, and a second side (support side) with a second plurality of pores. In certain embodiments, the first plurality of pores and the second plurality of pores are fluidly connected to each other.
• polymeric additives are dispersed within the porous support. Additives may enhance hydrophilicity, strength or other desirable properties.
• a thin-film composite membrane may include a porous support comprising a first side with a first plurality of pores, and a second side with a second plurality of pores, wherein the average diameter of substantially all of the first plurality of pores is between about 50 nm and about 500 nm, and the average diameter of substantially all of the second plurality of pores is between about 5 ⁇ and about 50 ⁇ .
• the purpose of the top layer is to allow for a high quality barrier to form by interfacial
• the purpose of the remainder of the support structure is to be as open and as minimally tortuous as possible, while being as thin as possible. Large pores towards the bottom may facilitate this purpose.
• a polymeric additive may be dispersed in the porous support. This addition may add strength, fouling resistance, hydrophilicity, or other desirable properties to the support porous structure and materials. In the case of hydrophilic additions, very small quantities may be added. By way of example, between 0.1-1% of PVP may be added to the polysulfone to enhance hydrophilicity in the structure. A semipermeable selective barrier may be applied on the first side of the porous support.
• the membrane flux may be between about 15 and about 25 gallons per square foot per day under operating conditions of 1.5 M NaCl draw solution and a DI feed solution at 25 °C.
• This high flux is an indication of the effectiveness of the thin, open, porous, and low tortuosity support layer in reducing resistance to diffusion of draw solutes into the membrane support structure to provide driving force for flux in the form of osmotic pressure.
• This high flux is due in part also to the water permeability of the barrier layer.
• a method of making a forward osmosis membrane may comprise providing a support structure including at least a first layer and a second layer, applying a material to a first layer of the support structure to form a membrane support layer, applying a barrier material to the membrane support layer to form the forward osmosis membrane, and releasing the forward osmosis membrane by separating the first layer of the support structure from the second layer of the support structure.
• a method of making a forward osmosis membrane may comprise providing a support structure including at least a thin support layer, adding a material to the support layer to form a membrane support structure, releasing the thin layer and material structure as one piece, and coating the membrane support structure with a barrier material to form the forward osmosis membrane.
• a method of facilitating a forward osmosis separation operation may comprise providing a support structure, applying a thin support layer to the support structure, applying a supporting material to the layer to form a porous membrane support structure, applying a barrier layer to the porous membrane support layer to form a forward osmosis membrane, and configuring the forward osmosis membrane in a forward osmosis membrane module such that the support structure may provide a turbulence spacer for a draw solution or a feed solution supplied to the module during the forward osmosis separation operation.
• a method of facilitating a forward osmosis separation operation may comprise providing a support structure, applying a supporting material to the structure to form a porous membrane support structure, applying a barrier layer to the porous membrane support layer to form a forward osmosis membrane, and configuring the forward osmosis membrane in a forward osmosis membrane module such that the support structure may provide a turbulence spacer for a draw solution or a feed solution supplied to the module during the forward osmosis separation operation.
• a forward osmosis membrane may comprise a fabric layer of less than about 75 microns, a support layer of less than about 50 microns applied on the fabric layer, and a barrier layer applied on the support layer.
• the forward osmosis membrane may have an overall thickness of less than about 125 microns.
• the support layer may contain less than about 30 g/m 2 of material overall.
• the supporting material may be applied in a coating of between about 5 and 20 g/m 2 .
• the coating may be between about 8 and 17.5 g m 2 .
• the combined weight of the support layer, support material, and barrier layer overall may be between 20 and 40 g/m 2 .
• the support layer may be made in a wet laid process.
• the method may comprise rewetting the forward osmosis membrane by immersion in water containing a solute which enhances wetting.
• the solute may be a surfactant.
• the method may further comprise rewetting the membrane by immersion in water containing a low surface tension solvent.
• the solvent may comprise an alcohol.
• the solvent may comprise isopropyl alcohol, ethanol or methanol.
• the support structure is embedded within the hydrophilic material.
• the barrier material comprises polyamide.
• a forward osmosis membrane is disclosed.
• the membrane may be a composite, generally including an active layer in conjunction with a support layer. Other parameters such as the mass percent of polymer used, choice of solvent and/or bath temperature may impact the degree to which the support layer is rendered hydrophilic, open or porous.
• the active layer may generally include any material capable of rejecting or otherwise acting as a barrier to one or more target compounds present in a process stream brought into contact with the membrane.
• the active layer may comprise polyamide. Other materials commonly used as membrane active layers may also be implemented.
• a desired degree of cross-linking may be achieved within the active layer, such as to improve the barrier properties of the membrane. Inducing cross linking in the polyamide layer is generally desirable to improve salt rejection and overall performance.
• cross-linking is achieved in a manner such that the hydrophilic materials are not reduced in their performance, and are maintained in a wet state throughout the manufacturing and treatment process.
• hot water annealing may be used to facilitate cross-linking.
• heat treatment may occur in one or more of the immersion steps of the membrane fabrication process, during or after the active layer deposition or formation process.
• chemical treatment may be used.
• heat drying such as oven drying, is not used.
• the membranes will readily rewet by immersion in water, and in some embodiments, they will rewet by exposure to a wetting agent in conjunction with water, such that they will be substantially wet when ready for use.
• the membranes may be characterized as having a salt rejection of at least 99% or greater.
• the forward osmosis membranes may generally be relatively thin and characterized by high porosity, low tortuosity and high wettability.
• the membranes may find use in a variety of applications including osmotic-driven water purification and filtration, desalination of seawater, purification of contaminated aqueous waste streams, separation of various aqueous streams, osmotic power generation and the like.
• a polymer or other porous membrane material may be deposited via various known techniques, such as phase inversion, on a thin woven or non woven or inorganic substrate to give a forward osmosis membrane with a very thin support structure.
• the substrate used for membrane fabrication may include a multi-layered support.
• An ultrafiltration (UF) substrate may be placed on a multi-layer woven or non- woven support, such that one or more layers may be removable at the end of a membrane fabrication process prior to module construction.
• the size of the pores of the substrate material may be in the UF range, for example, about 100 nm to about 1 um diameter, to facilitate proper formation of an interfacial polymerization barrier layer on its surface.
• deposition may include phase inversion of polymers such as polysulfone or PAN.
• Layers which remain connected to the UF substrate may be optimized for desirable characteristics such as high porosity, low tortuosity, thinness or other properties which enhance diffusion to the UF layer.
• the materials may be but need not be generally hydrophilic.
• one or more layers may serve as a draw solution or feed solution spacer.
• a 100 nanometer layer of polyamide may be deposited on 0.5 mil layer of polysulfone on a 0.5 mil paper.
• a barrier coated UF material may be placed, such as with phase inversion of a polymer, followed by an interfacial polymerization of a barrier layer, on a woven or non-woven support such that after the manufacturing of the membrane, the support may be removed leaving only the UF and barrier material to be used in a module.
• a UF layer may be deposited then coated with a barrier layer such as polyamide or polyamide urea.
• the substrate may include an intentionally separable support.
• This support structure may be below the polymer, partially enclosed, or fully enclosed within it.
• interfacial polymerization or coating of a thin selecting layer which permits the passage of water but not salts may then be implemented.
• deposition of a porous support layer on a removable material such as
• delamination from a belt or other linear, mobile backing material that is used to enhance material handling in the fabrication equipment, but which is not intended to become part of the finished membrane product, may be used to create a very thin membrane support structure, such that it has no backing.
• a thin barrier layer may then be deposited on the surface of the paperless support.
• the barrier layer may be deposited on the support prior to the delamination of the support from the belt.
• a polymer may be coated on the surface of the support polymer, this top layer acting as the salt rejection layer, either with or without subsequent treatment.
• the support layer itself functions as the barrier layer, having sufficient salt rejection properties for the application to which it will be applied.
• a belt or drum may be used to facilitate casting upon thin supports.
• a belt such as a conveyor belt or like structure may be used as a substrate replacement that remains primarily within the scope of the membrane manufacturing equipment.
• the belt may provide support for the deposition of the support and barrier coating but may be retained and reused in the fabrication equipment rather than removed at the end and discarded or reused.
• the belt or drum may be designed to provide a surface which retains a portion of a porous support material.
• the base of a porous support structure may be disrupted when it is removed from the belt or drum due to retention of part of the porous support material. Such disruption may be beneficial.
• Retained porous support material may be removed prior to full rotation of the belt or drum to prevent accumulation of the material or inhibition of the effectiveness of the deposition and disruption process.
• phase inversion of a polymer coated on or around a material intended primarily to give the polymer resistance to deformation with strain may be used to create a membrane support.
• a very open and thin woven or non woven material may be surrounded by the polymer, rather than underneath it. Interfacial polymerization of a rejecting polymer may then be carried out on this support structure.
• a forward osmosis membrane may be a hydrophilic phase inversion membrane on a woven or non woven fabric.
• the hydrophilic material may be PAN in some non-limiting embodiments, alone or mixed with other monomers.
• the fabric layer may be of any desired thickness. In some non-limiting embodiments, the fabric may be about 25 micrometers in thickness.
• the forward osmosis membrane may be further characterized by polyamide interfacial polymerization on its surface. A polyamide active layer may be applied so as to result in a membrane of any desired thickness. In some non-limiting embodiments, the membrane may be approximately 25 micrometers thick.
• the active layer of the forward osmosis membrane may be modified to enhance rejection of draw solutes.
• the support film may be nonwoven and made of any material, but thinness, high porosity, low tortuosity, and hydrophilicity are generally desirable.
• the thickness of the support film may vary. In some embodiments, the support film may be less than about 100 micrometers, less than about 80 micrometers, less than about 50 micrometers or thinner. In at least one embodiment, a porous polyester nonwoven support film may be used as a substrate.
• a forward osmosis membrane may be formed by first creating a support layer. In some non-limiting embodiments, a thin fabric backing layer of less than about 30 micrometers may be coated with a polysulfone solution of about 12.5% in dimethylformamide.
• polysulfone thickness is illustrated in accompanying Figure 3.
• Lower concentrations of polysulfone may be used to further improve forward osmosis membrane properties, including flux, as evidenced by accompanying Figure 1.
• the amount of polysulfone coating may generally be less than about 16 g/m 2 to minimize the impact of the support layer on diffusion.
• the application of a support layer on a typical reverse osmosis fabric backing of about 3.9 mils in thickness may result in much less than optimal forward osmosis flux as evidenced by accompanying Figure 2.
• the resulting support layer precursor may then be immersed in room temperature water causing the phase inversion of the polymer. Immersion in temperatures greater than 90F may be used to improve the pore size characteristics of the support layer. This may produce a thin, microporous, open support structure with an embedded web giving the polymer strength for rolling and handling.
• the active layer may then be applied to the support structure.
• a non- limiting example of the coating of this support structure with the active layer would be the immersion of the support in a solution containing polyamide or other desired active material.
• the support structure may be immersed in a 3.4% solution of 1 -3 phenyl enediamine in room temperature water.
• the concentration of the solution may vary based on desired characteristics of the applied active layer.
• Duration of immersion may also vary. In some non-limiting embodiments, the duration may be less than about 5 minutes. In one specific embodiment, the duration of immersion may be about 2 minutes. Excess solution from the surface of the membrane may be removed, for example with a roller or air knife.
• the membrane may then be briefly immersed in another solution to induce the polymerization of the polyamide rejecting layer by combination of the diamine in the aqueous phase and, for example, acid chloride in the non-aqueous phase, at the surface of the support material where the phases meet.
• the membrane may be immersed in the solution for about 2 minutes.
• a 0.15% solution of 98% 3,5 benzenetricarbonyltri chloride in Isopar* C or G at room temperature may be used.
• the membrane may then removed and the Isopar* allowed to evaporate from the membrane for a period of time, for example less than about 5 minutes. In some embodiments, the duration of the evaporation step may be about 2 minutes.
• immersion may take the form of a dip coating process, such as one in which substantially only the surface of the membrane comes into contact with a solution.
• the entire membrane may be submerged in the bath.
• a combination of these techniques may be used, such as in a sequence of different immersion steps.
• a forward osmosis composite membrane may be heat treated to condition the rejecting layer so as to cause cross-linking, which may be referred to as annealing. Drying out the membrane, however, may in some cases cause detrimental shrinking of the void and pore structure.
• conditioning may be achieved by a wet annealing step, for example, immersion in a hot water immersion bath. Any temperature water bath may be used that is capable of resulting in a desired degree of cross-linking and desired membrane performance, for example in terms of salt rejection. In some embodiments, as low of a temperature as possible may be desirable. In some non-limiting embodiments, a water bath below about 100 °C may be used. In one specific non-limiting embodiment, a 95 °C water bath may be used. Duration in the water bath may also be in line with requirements to achieve the desired degree of cross-linking. In one specific embodiment, the hot water bath immersion occurs for 2 minutes.
• the heat treatment of the membrane may occur in any or several immersion steps intended for other purposes, such as during or after the active layer
• the heat treatment of the membrane may be done in a drying step, preceded by a solvent exchange involving a solvent with a lower surface tension than water being exchanged with water by immersion.
• the membrane properties may not be adversely affected and the membrane may retain the properties of being readily rewet.
• the treatment of the rejecting layer may be carried out by a chemical treatment rather than a heating step, in which case the membrane would be kept wet throughout the treatment process.
• treating the membrane support layer with the polyamide material to induce crosslinking in the polyamide layer to form the forward osmosis membrane comprises chemical treatment.
• the treatment step involves hot water immersion, and this may be referred to as wet annealing.
• the heat treatment occurs at any point during or after the polyamide phase inversion process, by maintaining a sufficient temperature in one or more immersion steps.
• the crosslinking is carried out by dry annealing, but this is done after a solvent exchange step, soaking the wet membrane in a solution comprising another solvent with a lower vapor pressure, so that "dry annealing" may be carried out without adversely affecting the membrane by such drying.
• a method of making a forward osmosis membrane may comprise providing a thin woven or non- woven fabric backing of less than about 50 micrometers in thickness.
• a support layer and a barrier layer may be applied to the fabric backing.
• the thin woven or non-woven fabric support layer (top layer) may be characterized by a Frazier air penneability of greater than about 100 ft 3 /ft 2 /min.
• the thin woven or non-woven fabric backing layer (bottom layer) may be characterized by a Frazier air permeability of less than about 10 ft 3 /ft 2 /min.
• a Frazier air permeability of about 5 ft 3 /ft 2 /min for the bottom layer may be desirable.
• the thin woven or non-woven fabric backing may be of less than about 30 g/m 2 basis weight.
• the support layer applied to the fabric backing may be less than about 40 micrometers in thickness.
• the barrier layer may be applied to the polymeric support layer.
• a fabric backing layer and a support layer may be provided using a polysulfone concentration of less than about 13%.
• the support structure may be modified with a process quench temperature greater than about 95 °F.
• the support layer of the forward osmosis membrane may also be modified using a solution with a hydrophilic agent, for example, polyvinylpyrrolidone.
• a forward osmosis membrane may comprise a fabric backing, a support layer of less than about 16 g/m 2 of polysulfone or polyacrilonitrile, and a barrier layer.
• a forward osmosis membrane may be characterized by a flux of greater than about 20 gfd using 1.5M NaCl draw solution and deionized feed water at 25 °C.
• a forward osmosis membrane may be characterized by a salt rejection of greater than about 99% using 1.5M NaCl draw solution and deionized feed water.
• a polysulfone solution ofless that about 13% may be applied to enhance one or more properties of a forward osmosis membrane.
• less than about 16 g m 2 of polysulfone may be applied on a fabric backing layer of a forward osmosis membrane.
• a method of making a forward osmosis membrane may comprise providing a support structure, applying a hydrophilic material to the support structure to form a membrane support layer, applying a polyamide material to the membrane support layer, immersing the membrane support layer with the applied polyamide material in water, carrying out a solvent exchange by immersion of the membrane, and dry annealing the membrane support layer with the polyamide material to form the forward osmosis membrane.
• a forward osmosis membrane may be processed on production lines currently used in the manufacture of reverse osmosis, membranes.
• the method by which a thin forward osmosis membrane is processed may include the use of an integrated drive system to control tension in discrete sections of a machine. Supplemental manual or automated web steering devices may also be implemented.
• machine design may allow for no more than about a 10% tension drop per zone to reduce over tensioning of the membrane which may lead to creasing and folding over of the membrane. Membrane tensions of less than about 1 pound per linear inch may prevent creasing of the membrane.
• the design of the machine may also generally limit the free span of unsupported membrane to less than one half the web width in areas in which the membrane is submersed.
• machine design may also include optical alignment at a tolerance of about 0.001 inches per linear foot of roller width to prevent creasing and folding over of the membrane.
• various techniques disclosed herein may be used to make membranes for forward osmosis applications.
• various techniques disclosed herein may also be used to make membranes for applications involving pressure retarded osmosis.
• pressure retarded osmosis may generally relate to deriving osmotic power or salinity gradient energy from a salt concentration difference between two solutions, such as a concentrated draw solution and a dilute working fluid.
• a draw solution may be introduced into a pressure chamber on a first side of a membrane.
• the draw solution may be pressurized based on an osmotic pressure difference between the draw solution and a dilute working fluid.
• the dilute working fluid may be introduced on a second side of the membrane.
• the dilute working fluid may generally move across the membrane via osmosis, thus increasing the volume on the pressurized draw solution side of the membrane.
• a turbine may be spun to generate electricity.
• a resulting dilute draw solution may then be processed, such as separated, for reuse.
• a lower-temperature heat source such as industrial waste heat may be used in or facilitate a pressure retarded osmosis system or process.
• Gen 1 Techniques using a single layer support are generally referred to herein as Gen 1
• Gen 2 techniques using a bilayer approach are generally referred to herein as Gen 2.
• FIG. 1 presents flux data as a function of polysulfone concentration. Flux was measured at various polysulfone concentrations with other parameters remaining constant. In accordance with a substantially inverse relationship, flux increased as polysulfone concentration decreased. Experimental data has shown improved forward osmosis membrane flux with polysulfone concentrations in the range of about 9% to about 13%. Membranes used were Gen 1 , but with a thicker 4 mil PET.
• FIG. 2 presents data indicating an inverse relationship between membrane thickness and flux. Flux decreased with increasing membrane thickness, generally indicating the desirability of thin membranes. Other parameters were kept constant. Flux was also measured for various polysulfone loadings with other parameters remaining constant. Membranes used were Gen 1.
• FIG. 3, consistent with FIG. 1 indicates that flux decreased with increasing polysulfone loading.
• Membranes used were Gen 1.
• FIG. 4 depicts flux data collected using two membranes, depicted as Gen 2A and Gen 2B, both manufactured in accordance with the decreased PS (polysulfone) concentration, decreased PS loading, increased porosity, and bilayer approach disclosed herein, in comparison to flux data collected from a membrane made with a single supporting layer depicted as Gen 1 , where only the benefits of decreased PS concentration, decreased PS loading, and increased porosity were employed, but no bilayer manufacturing technique.
• the test method involved using 1.5M NaCl draw solution on the supporting side of the membrane and either deionized water or 0.5 M NaCl solution on the feed side.
• membranes in this experiment produced less than 1 GFD of flux.
• FIG. 5 depicts the flux results of a membrane made in accordance with the bilayer technique described herein in comparison to a membrane made with a single supporting layer.
• the membrane which produced the highest flux was manufactured by first combining two layers of PET.
• the top layer of PET was 1.5 mils in thickness with a basis weight of 15 grams per square meter and was combined with a backing PET with a thickness of 2.3 mils and a basis weight of 49 grams per square meter.
• the top thinner layer of PET was coated with a 12.5% solution of polysulfone and dimetylformamide resulting is a polysulfone coating weight of 21 grams per square meter.
• the described support was then processed using membrane chemistry of an acid chloride and amine to produce the forward osmosis polyamide membrane. Following the membrane formation, the bottom PET layer was removed prior to module construction.
• the resultant membrane and support had a basis weight of approximately 35 grams per square meter and a total thickness of 95 microns.
• the test method was to use 6 M ammonium salt draw solution on the supporting side of the membrane and varying concentrations of NaCl solution on the feed side at a temperature of 50 °C. Flux was measured as the mass change in the draw solution over time.
• the disclosed bilayer technique was associated with superior flux results due to the reduced thickness and other parameters and characteristics associated with the bilayer technique disclosed herein. Particularly, this illustrates the capability of treating very high salinity feeds using membranes in a way that has not in the past been possible due to the benefits of the membrane manufacturing techniques described herein.
• the data points presented for 0.5M feed are experimental, and the remaining data represents an extrapolation using accepted modeling techniques. Not shown is the very low flux that is produced by using a membrane made by techniques used in pressure driven semi-permeable membrane manufacturing. Conventional RO membranes would produce negligible flux in the high salinity feed scenarios.
• FIG. 6 presents an SEM image of a membrane manufactured in accordance with one or more bilayer techniques described herein.
• the pore structure is substantially open at a base region of the polymer support layer which previously interfaced with the backing layer prior to removal thereof.
• the polyamide barrier layer, the porous support layer, the topmost PET and backing PET are all shown.
• the term “plurality” refers to two or more items or components.
• the tenns “comprising,” “including,” “carrying,” “having,” “containing,” and “involving,” whether in the written description or the claims and the like, are open-ended terms, i.e., to mean “including but not limited to.” Thus, the use of such tenns is meant to encompass the items listed thereafter, and equivalents thereof, as well as additional items. Only the transitional phrases “consisting of and “consisting essentially of,” are closed or semi-closed transitional phrases, respectively, with respect to the claims.
• ordinal tenns such as “first,” “second,” “third,” and the like in the claims to modify a claim element does not by itself connote any priority, precedence, or order of one claim element over another or the temporal order in which acts of a method are performed, but are used merely as labels to distinguish one claim element having a certain name from another element having a same name (but for use of the ordinal tenn) to distinguish the claim elements.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Water Supply & Treatment (AREA)
• Manufacturing & Machinery (AREA)
• Dispersion Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Hydrology & Water Resources (AREA)
• Environmental & Geological Engineering (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Separation Using Semi-Permeable Membranes (AREA)

Priority Applications (14)

Applications Claiming Priority (6)

Publications (2)

Family

ID=43649894

Family Applications (1)

Country Status (16)

Cited By (18)

Families Citing this family (47)

Family Cites Families (71)

• 2010
  • 2010-08-24 WO PCT/US2010/046521 patent/WO2011028541A2/en not_active Ceased
  • 2010-08-24 CN CN201080048101.6A patent/CN102574071B/zh not_active Expired - Fee Related
  • 2010-08-24 EA EA201270314A patent/EA026762B1/ru not_active IP Right Cessation
  • 2010-08-24 IN IN2582DEN2012 patent/IN2012DN02582A/en unknown
  • 2010-08-24 CN CN201510306013.6A patent/CN105032201B/zh not_active Expired - Fee Related
  • 2010-08-24 MX MX2012002393A patent/MX2012002393A/es active IP Right Grant
  • 2010-08-24 SG SG2012011649A patent/SG178507A1/en unknown
  • 2010-08-24 US US12/862,584 patent/US8181794B2/en not_active Expired - Fee Related
  • 2010-08-24 EP EP10814254.8A patent/EP2470292A4/en not_active Withdrawn
  • 2010-08-24 BR BR112012004100A patent/BR112012004100A2/pt not_active Application Discontinuation
  • 2010-08-24 JP JP2012526925A patent/JP5873019B2/ja not_active Expired - Fee Related
  • 2010-08-24 KR KR1020127007350A patent/KR101817611B1/ko not_active Expired - Fee Related
  • 2010-08-24 MX MX2014012281A patent/MX345000B/es unknown
  • 2010-08-24 SG SG10201403279SA patent/SG10201403279SA/en unknown
  • 2010-08-24 CA CA2771902A patent/CA2771902C/en not_active Expired - Fee Related
  • 2010-08-24 AU AU2010289795A patent/AU2010289795B2/en not_active Ceased
• 2012
  • 2012-02-16 IL IL218142A patent/IL218142A/en not_active IP Right Cessation
  • 2012-02-24 CL CL2012000492A patent/CL2012000492A1/es unknown
  • 2012-03-21 MA MA34710A patent/MA33599B1/fr unknown
  • 2012-04-17 US US13/448,962 patent/US8460554B2/en not_active Expired - Fee Related
• 2013
  • 2013-03-12 US US13/797,166 patent/US9463422B2/en not_active Expired - Fee Related
• 2016
  • 2016-01-14 JP JP2016004841A patent/JP6155347B2/ja not_active Expired - Fee Related
  • 2016-06-29 US US15/196,680 patent/US20170113192A1/en not_active Abandoned
  • 2016-12-01 CL CL2016003089A patent/CL2016003089A1/es unknown
• 2018
  • 2018-04-30 US US15/966,194 patent/US20180345228A1/en not_active Abandoned

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events