The product and methods disclosed herein are for use in water filtration. More particularly, the apparatus is a nanofiltration membrane used for water treatment or filtration in textile manufacturing.
Purification of industrial wastewater for re-use in industrial, agricultural or environmental use or human consumption is a global priority as water resources become more scarce. Membranous water filtrators have been known and commercialized. However, conventional phase-inversion or thin-film composite membranes have a low water flux rate, making them inefficient for high-volume industrial applications. The water flux rate is a measurement of permeation and volume flow rate of water through a membrane of a given cross-sectional area (i.e., the volume of water that can be filtered over a given time period). Membranes engineered on a nanoscale may increase the water flux rate, but they also can have high manufacturing and operational costs.
What is needed, then, is a nanoscale filtration membrane having a high flux rate and with a low manufacturing cost for mass production. The products and methods disclosed herein use nanofibers to fabricate a highly porous membrane with high flux rate and salt rejection.
An industrial wastewater filtration membrane and method for manufacture are disclosed herein. The membrane has at least three layers: a support layer of nonwoven fabric such as PET, a polysulfone nanofiber filtering membrane layer, and a nanoporous polyamide active separating layer. The polysulfone layer is electrospun onto the support layer. The very thin polyamide layer having a thickness of 10 to 100 nm is formed by contemporaneously electrospraying two reagent solutions onto the polysulfone layer. The resulting membrane has a pure water flux rate between 40-200 liters per square meter per hour when the pressure is between 0.4 to 0.8 MPa. The membrane shows a rejection rate of sodium chloride of 10-85% with inlet sodium chloride concentration of 2000 ppm, and a rejection rate of magnesium sulphate of 80-97% with inlet magnesium sulphate concentration of 2000 ppm. Differences in rejection rates are based on varying the composition and manufacturing methods as described herein. The membrane has industrial application for industrial water treatment or softening of hard water.
A method for manufacturing a nanofiltration membrane is disclosed having the steps of providing a support layer of nonwoven fabric; electrospinning a polysulfone filtering membrane layer onto the support layer; and electrospraying a nanoporous polyamide membrane active separating layer onto the filtering membrane layer, according to an embodiment of the invention.
A filtration membrane is disclosed having a support layer of nonwoven fabric, a nanofiber polysulfone filtering membrane layer applied to a surface of the support layer; and a nanoporous polyamide membrane active separating layer, according to an embodiment of the invention. The support layer may be a PET fabric. The filtering membrane layer may be formed of polyethylsulfone (PES) nanofibers. The active separating layer may be made by polymer condensation of molecules of DETA and/or TEGDA, and TMC.
Other characteristics or performance parameters of the disclosed membrane are provided herein.
Disclosed herein is a nanofiltration membrane for use in water filtration. The membrane is currently considered for water filtration in the textile manufacturing industry, however, it is possible the membrane may be used in other industries as well. The membrane filters and removes ions, particles, and impurities present in industrial water.
The membrane described herein has three primary layers. The first layer is a support layer. The second layer is a nanofibrous membrane applied during manufacture of the membrane to the underlying support layer. The third layer is an active separating layer. Other layers or filtration mechanisms may be applied without limiting the generality of the foregoing.
The first layer, the support layer, is a suitable non-woven fabric for supporting the second layer that is applied to it. In some embodiments, the non-woven fabric is a polyethylene terephthalate (PET or, more popularly, polyester). PET fabric is selected because of its water resistance, chemical resistance and high strength-to-weight ratio. Other fabrics having similar qualities may also be selected. The PET fabric may have a thickness between approximately 0.1 mm and 0.25 mm. The PET fabric may have a density between approximately 20 grams per square meter and 50 grams per square meter. The density and thickness of the PET fabric affect the strength of the resulting support layer.
The second layer of the filtration membrane is an electrospun nanofibrous filtering membrane. In some embodiments the filtering membrane is made of polyether sulfone (PES). Other polysulfones may be used as well. The nanofibers are spun directly onto the nonwoven fabric support layer. For the electrospinning process, the PES is dissolved in a dimethylformamide (DMF) or N,N-dimethylacetamide (DMAc) solution. The liquid solution is then electrostatically spun to apply nanofiber strands of PES to the nonwoven fabric layer. In some embodiments the PES nanofibers are fabricated by electrospinning a 20%-30% solution of PES in either DMF or DMAc, where the PES has a molecular weight of approximately 50,000 Da. The resulting nanofibers have a diameter between 100-2000 nm and form a PES layer having a thickness between 0.03-0.06 mm. In some embodiments the electrospinning working voltage for this application is in the range of about 40-50 kV. In some embodiments the working distance for this application is about 150-200 mm. The solution may be fed into the electrospinning machine nozzle at about 0.5-1 ml per hour.
The third layer of the filtration membrane is an active separating layer applied over the filtering membrane. The active separating layer is formed of amine and acyl chloride monomers that are condensed into a thin membrane or layer atop the filtering membrane. In some embodiments the amines selected are diethylenetriamine (DETA), 1,8-diamino-3,6-dioxaoctaine (TEGDA), or a combined mixture of DETA and TEGDA, provided in aqueous solution. Other amines may also be used. In some embodiments the acyl chloride is a hexane solution of trimesoyl chloride (TMC). Other acyl chlorides may also be used. The selected amine and acyl chloride solutions are then electrosprayed onto the filtering membrane, during which the solutions undergo polycondensation to solidify into the active separating layer. The electrospray may be performed by an electrospinning machine having multiple nozzles and syringe pumps. In some embodiments the working voltage of the electrospinning machine may be in the range between 40-50 kV. In some embodiments the working distance of the electrospinning machine may be in the range of about 200-300 mm. In some embodiments the solution flow rate of the amine and acyl chloride solutions may be in the range of about 30-40 ml per hour per nozzle. The resulting active separating layer may have a thickness from about 1 nm to 1000 nm. The active separating layer may have pores or channels in the layer having a diameter between about 0.1 nm and 10 nm.
Once the membrane is prepared, the membrane may be washed in de-ionized water and dried in an oven. The membrane may then be implemented in a water filtration system for use in filtering industrial wastewater, such as in textile manufacturing.
Applicant presents the following exemplary manufacturing methods and resulting embodiments.
A PES nanofiber membrane may be prepared on a PET supporting fabric. The PES is dissolved in DMF solution, wherein the PES is 20% by weight to 30% by weight of the solution. More specifically, in the imaging depicted in
A PES nanofiber membrane may be prepared on a PET supporting fabric. The PES is dissolved in DMAc solution, wherein the PES is 20% by weight to 30% by weight of the solution. More specifically, in the imaging depicted in
A nanoporous polyamide membrane for active separating may be prepared for application on a PES filtering membrane. A solution of 1.5% by weight TEGDA is dissolved in de-ionized water. A solution of 0.15% by weight TMC is dissolved in hexane. The aqueous and hexane solutions are loaded into an electrospinning machine in separate syringes for spinning by separate nozzles. The solutions are electrosprayed contemporaneously onto a PES filtering membrane and support fabric set to the following working parameters. The working range of the applied voltage for the electrospraying process was between 40-50 kV. The working range was a distance of 200-300 mm. The solution flow rate into the nozzles was in the range of 30-40 ml per hour per nozzle. In this process, two nozzles were used, one for the aqueous solution and one for the hexane solution. The resulting polyamide membrane is depicted in
A nanoporous polyamide membrane for active separating may be prepared for application on a PES filtering membrane. A solution of 1.5% by weight DETA is dissolved in de-ionized water. A solution of 0.15% by weight TMC is dissolved in hexane. The aqueous and hexane solutions are loaded into an electrospinning machine in separate syringes for spinning by separate nozzles. The solutions are electrosprayed contemporaneously onto a PES filtering membrane and support fabric set to the following working parameters. The working range of the applied voltage for the electrospraying process was between 40-50 kV. The working range was a distance of 200-300 mm. The solution flow rate into the nozzles was in the range of 30-40 ml per hour per nozzle. In this process, two nozzles were used, one for the aqueous solution and one for the hexane solution. The resulting polyamide membrane is depicted in
A nanoporous polyamide membrane for active separating may be prepared for application on a PES filtering membrane. A solution of 1.5% by weight of mixed DETA and TEGDA in a mix ratio of 4:6 is dissolved in de-ionized water. A solution of 0.15% by weight TMC is dissolved in hexane. The aqueous and hexane solutions are loaded into an electrospinning machine in separate syringes for spinning by separate nozzles. The solutions are electrosprayed contemporaneously onto a PES filtering membrane and support fabric set to the following working parameters. The working range of the applied voltage for the electrospraying process was between 40-50 kV. The working range was a distance of 200-300 mm. The solution flow rate into the nozzles was in the range of 30-40 ml per hour per nozzle. In this process, two nozzles were used, one for the aqueous solution and one for the hexane solution. The resulting polyamide membrane is depicted in
A nanoporous polyamide membrane for active separating may be prepared for application on a PES filtering membrane. A solution of 1.5% by weight of mixed DETA and TEGDA in a mix ratio of 3:7 is dissolved in de-ionized water. A solution of 0.15% by weight TMC is dissolved in hexane. The aqueous and hexane solutions are loaded into an electrospinning machine in separate syringes for spinning by separate nozzles. The solutions are electrosprayed contemporaneously onto a PES filtering membrane and support fabric set to the following working parameters. The working range of the applied voltage for the electrospraying process was between 40-50 kV. The working range was a distance of 200-300 mm. The solution flow rate into the nozzles was in the range of 30-40 ml per hour per nozzle. In this process, two nozzles were used, one for the aqueous solution and one for the hexane solution. The resulting polyamide membrane is depicted in
A nanoporous polyamide membrane for active separating may be prepared for application on a PES filtering membrane. A solution of 1.5% by weight of mixed DETA and TEGDA in a mix ratio of 2:8 is dissolved in de-ionized water. A solution of 0.15% by weight TMC is dissolved in hexane. The aqueous and hexane solutions are loaded into an electrospinning machine in separate syringes for spinning by separate nozzles. The solutions are electrosprayed contemporaneously onto a PES filtering membrane and support fabric set to the following working parameters. The working range of the applied voltage for the electrospraying process was between 40-50 kV. The working range was a distance of 200-300 mm. The solution flow rate into the nozzles was in the range of 30-40 ml per hour per nozzle. In this process, two nozzles were used, one for the aqueous solution and one for the hexane solution. The resulting polyamide membrane is depicted in
Combination of Layers
Based on the above processes and as shown in the exemplary embodiments, a resulting filtration membrane may be prepared having a nonwoven fabric support layer, a nanofibrous filtering membrane layer, and a nanoporous polyamide active separating layer. The various exemplary embodiments above may be combined to produce various resulting filtration membranes.
For example the process of exemplary embodiment 1A for preparing the PES membrane on PET may be combined with the process of exemplary embodiment 2A for preparing the polyamide membrane.
The process of exemplary embodiment 1A for preparing the PES membrane on PET may be combined with the process of exemplary embodiment 2B for preparing the polyamide membrane.
The process of exemplary embodiment 1A for preparing the PES membrane on PET may be combined with the process of exemplary embodiment 2C for preparing the polyamide membrane.
The process of exemplary embodiment 1A for preparing the PES membrane on PET may be combined with the process of exemplary embodiment 2D for preparing the polyamide membrane.
The process of exemplary embodiment 1A for preparing the PES membrane on PET may be combined with the process of exemplary embodiment 2E for preparing the polyamide membrane.
The process of exemplary embodiment 1B for preparing the PES membrane on PET may be combined with the process of exemplary embodiment 2A for preparing the polyamide membrane.
The process of exemplary embodiment 1B for preparing the PES membrane on PET may be combined with the process of exemplary embodiment 2B for preparing the polyamide membrane.
The process of exemplary embodiment 1B for preparing the PES membrane on PET may be combined with the process of exemplary embodiment 2C for preparing the polyamide membrane.
The process of exemplary embodiment 1B for preparing the PES membrane on PET may be combined with the process of exemplary embodiment 2D for preparing the polyamide membrane.
The process of exemplary embodiment 1B for preparing the PES membrane on PET may be combined with the process of exemplary embodiment 2E for preparing the polyamide membrane.
Manufacture of Membrane
The nanofiber filtering membrane and active separating layer are each applied as described above using electrospraying and electrospinning fabrication techniques. These are related techniques performed using the same basic equipment. An equipment schematic is provided as
Controlling Hydrophilicity of Polyamide Membrane Layer
The polyamide membrane active separating layer is hydrophilic. The polyamide membrane layer may be modified in its composition or surface roughness to select a variable hydrophilicity. For example, the use of DETA and/or TEGDA, or the mix ratio of those two solutes, may be modified to change the hydrophilicity of the membrane as desired. The hydrophilicity of the polyamide membrane layer may be measured with a contact angle goniometer applying a water droplet as small as 1 microliter on the membrane surface using the sessile drop technique. A high-resolution camera may then capture an image of the water droplet and the contact angle may be measured. For clarity, a surface is hydrophilic if the contact angle is less than 90 degrees. The image shown in
Permeability of Membrane
The three-layer membrane disclosed herein has a high water flux rate. For testing permeability, a chamber having an opening to a graduated cylinder was provided, with the membrane cut and sized to cover the opening. A sealing O-ring sealed the chamber and opening. The membrane was positioned and oriented such that the side having the polyamide membrane faced into the chamber. Pure water was pumped into the testing chamber with the pressure at 0 MPa. Water filled the chamber and flowed through the membrane for a period of 10 minutes at zero pressure to stability flow through the membrane. Then the pressure was set to 0.48 MPa. The volume of water forced through the membrane over a set time was then determined. Using this standard, the pure water flux rate for the membrane described herein was measured to be 40-200 liters per square meter per hour, depending on the fabrication of the membrane using different reagent solutions as described above.
Membrane Performance
Membranes prepared as described above have a rejection rate of sodium chloride at the value range between 10-85%, depending on the fabrication of the membrane using different reagent solutions as described above, with inlet sodium chloride concentration of 2000 ppm. Membranes further have a rejection rate of magnesium sulphate at the value range between 80-97% with inlet magnesium sulphate concentration of 2000 ppm, depending on the fabrication of the membrane using different reagent solutions as described above.
It is to be noted here that the present products and methods are not limited to the preceding exemplary embodiments or products having the tested parameters or characteristics described above, and various changes and modifications can be made within the scope not departing from the gist of the present teachings. The description of exemplary embodiments is provided to enable a person skilled in the art to make and use the present product. Moreover, various modifications to these exemplary embodiments will be readily apparent to those skilled in the art, and the generic principles and specific examples defined herein may be applied to other embodiments without the use of inventive faculty. Therefore, the present claimed invention is not intended to be limited to the exemplary embodiments described herein but is to be accorded the widest scope as defined by the limitations of the claims and equivalents. Further, it is noted that the inventors' intent is to retain all equivalents of the claimed invention even if the claims are amended during prosecution.
This application claims the benefit of filing of U.S. Provisional Patent App. No. 62/830,970 filed on Apr. 8, 2019.
Number | Date | Country | |
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62830970 | Apr 2019 | US |