Preparation of hand-carry gravity-driven water filter with high throughput and water disinfection performance
11241660 · 2022-02-08
Assignee
Inventors
- Jianqiang Wang (Hong Kong, CN)
- Xiaonan Shi (Hong Kong, CN)
- Zhe Yang (Hong Kong, CN)
- Chuyang Tang (Hong Kong, CN)
Cpc classification
B01D67/0088
PERFORMING OPERATIONS; TRANSPORTING
B01D67/0079
PERFORMING OPERATIONS; TRANSPORTING
B01D69/02
PERFORMING OPERATIONS; TRANSPORTING
B01D69/125
PERFORMING OPERATIONS; TRANSPORTING
B01D71/42
PERFORMING OPERATIONS; TRANSPORTING
B01D67/0004
PERFORMING OPERATIONS; TRANSPORTING
B01D69/141
PERFORMING OPERATIONS; TRANSPORTING
B01D69/12
PERFORMING OPERATIONS; TRANSPORTING
C02F1/50
CHEMISTRY; METALLURGY
B01D69/10
PERFORMING OPERATIONS; TRANSPORTING
International classification
B01D69/12
PERFORMING OPERATIONS; TRANSPORTING
B01D69/02
PERFORMING OPERATIONS; TRANSPORTING
B01D67/00
PERFORMING OPERATIONS; TRANSPORTING
B01D71/42
PERFORMING OPERATIONS; TRANSPORTING
C02F1/50
CHEMISTRY; METALLURGY
Abstract
A hand-carry gravity-driven water filter with high throughput and water disinfection performance is formed. Membranes used for this water filter can be fabricated using electrospun method and non-solvent induced phase inversion method. A novel composite membrane structure (interwoven composite structure) was designed for further enhances water permeability and mechanical strength. The composite membrane can be composed of nanofibers with different diameter from the same polymer or different polymers. Membrane porosity and surface pore size can be controlled. Silver nanoparticles can be in-situ loaded on the surface of the membranes. The developed filter is effective for removal of a wide range of contaminants (e.g., pathogens, suspended solids and heavy metals). The purification process can be carried out under the drive of gravity (with an option for mechanically-enhanced filtration) without electricity.
Claims
1. A composite membrane, comprising: polymeric nanofibers, and a polydopamine layer that is a surface coating of polydopamine compounds, wherein the composite membrane has a composite structure including a first plurality of nanofibers having first diameters and a second plurality of nanofibers having second diameters that are different from the first diameters, the first plurality of nanofibers having a chemical composition different from that of the second plurality of nanofibers, the first plurality and second plurality of nanofibers together having an average diameter in a range of 100-1000 nm, and the polymeric nanofiber membrane having a porosity in a range of 75-95% and a mean pore size in a range of 10-1000 nm.
2. The composite membrane according to claim 1, wherein the composite membrane has a thickness of 50-500 μm.
3. The composite membrane according to claim 1, wherein the first plurality of nanofibers has diameters in a range of greater than 500 nm and smaller than 1000 nm and the second plurality of nanofibers has diameters in a range of 100-500 nm.
4. The composite membrane according to claim 1, wherein the polymeric nanofibers comprise hydrophobic polymeric nanofibers or hydrophilic polymeric nanofibers.
5. The composite membrane according to claim 1, wherein polymers forming the polymeric nanofibers are selected from a group consisting of poly(acrylonitrile) (PAN), poly(vinyl alcohol) (PVA), poly(vinyl fluoride) (PVDF), chitosan, polysulfone (PSf), polyethersulfone (PES), poly(methyl methacrylate) (PMMA) and poly(vinyl butyral) (PVB).
6. The composite membrane according to claim 1, further comprising nano-beads or microspheres disposed on surfaces of the composite structure.
7. The composite membrane according to claim 6, wherein the nano-beads or microspheres have an average diameter of 20-2000 nm.
8. The composite membrane according to claim 1, further comprising in-situ surface loaded silver nanoparticles disposed on surfaces of the composite membrane.
9. The composite membrane according to claim 8, wherein the in-situ surface loaded silver nanoparticles are reduced by the polydopamine layer.
10. The composite membrane according to claim 8, wherein the in-situ surface loaded silver nanoparticles have a loading amount greater than zero and smaller than 5.0 wt. %.
11. The composite membrane according to claim 8, wherein the in-situ surface loaded silver nanoparticles have an average diameter greater than zero and smaller than 100 nm.
12. A gravity-driven nano-fibrous membrane filter comprising: a support structure forming an open top volume; and a composite membrane according to claim 1 on at least a bottom of the support structure, the composite membrane having a folded configuration, the filter accepting feed water at the open top volume and allowing cleaned water to exit below the composite membrane at the bottom.
13. The gravity-driven nano-fibrous membrane filter according to claim 12, further comprising a mechanically assisted vacuum system for drawing the feed water entered at top of the filter through the membrane.
14. The gravity-driven nano-fibrous membrane filter according to claim 13, wherein the mechanically assisted vacuum system comprises a piston located below the filter and a handle connected to the piston that allows the piston to be pulled down creating a vacuum on an opposite side of the membrane from the feed water.
15. The gravity-driven nano-fibrous membrane filter according to claim 12, wherein silver is loaded onto the composite membrane to provide water purification.
16. The composite membrane of claim 1, wherein the first plurality of nanofibers and the second plurality of nanofibers are interwoven into a single fiber layer.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The foregoing and other objects and advantages of the present invention will become more apparent when considered in connection with the following detailed description and appended drawings in which like designations denote like elements in the various views, and wherein:
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DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS OF THE INVENTION
(10) A hand-carry gravity-driven (or mechanically assisted) water filter with high throughput and water disinfection performance according to the present invention is fabricated in three steps: (1) membrane preparation; (2) membrane surface modification and (3) assembly.
(11) Membranes used in the water filter are prepared by an electrospun method or a non-solvent induced phase separation method (NIPS). The electrospun technology is used for the fabrication of nanofibrous membranes (a schematic diagram of the electrospun process is shown in
(12) A non-solvent induced phase separation (NIPS) process is commonly used for the preparation of separation membranes. The NIPS method helps fabrication of UF membranes. A schematic diagram of this process is shown in
(13) The present invention proposes a composite membrane nanofiber structures. In particular nanofibers with large-diameters of 200-1000 nm are used to provide a skeleton of the filter (to provide the required mechanical strength and permeability).
(14) The polymer used for the preparation of base nanofibrous membranes and UF membranes is selected from various polymeric materials, such as polyacrylonitrile (PAN), poly (vinyl alcohol) (PVA), poly (vinyl fluoride) (PVDF), chitosan, polysulfone (PSf), polyethersulfone (PES), poly (methyl methacrylate) (PMMA) and poly (vinyl butyral) (PVB), etc. The concentration of the polymer in the solution is from 1.0 to 30.0 wt. % (preferably 4.0 to 20.0 wt. %). Appropriate solvents include deionized water, 1-methyl-2-pyrrolidinone (NMP), dimethyl formamide (DMF), dimethyl-acetamide (DMAc), acetic acid (AA) and combination thereof. Macromolecule organics, small molecule organic and inorganic salts, such as polyvinyl pyrrolidone (PVP), polyethylene glycol (PEG), acetone, isopropanol, ethanol, lithium chloride (LiCl), etc. act as additives to adjust electrospun properties, membrane porosity and/or hydrophobicity-hydrophilicity, of which concentration in polymer solution was from 0.1 to 5.0 wt. % (preferably 0.2˜3.0 wt. %).
(15) The polymeric materials can be summarized in the following chart.
(16) TABLE-US-00001 Polymeric materials Solvent Additives Polyarcylonitrile (PAN) Deionized water (DI water) Polyvinyl pyroolidone (PVP) Poly(vinyl alcohol) (PVA) 1-methyl-2- Polyethylene pyrrolidinone (NMP) glycol (PEG) Poly(vinyl fluorid) (PVDF) Dimethyl formamide (DMF) Acetone Chitosan Dimethyl-acetamide (DMAc) Isopropanol Polysulfone (PSf) Acetic acid (AA) Ethanol Polyethersulfone (PES) Combination of above Lithium Chloride (LiCl) Poly(vinyl butyral) (PVB)
(17) In order to make a filter according to the present invention, the membrane surfaces are modified in order to get high rejection for heavy metal ions (e.g., Pb.sup.2+, Cd.sup.2+, Ni.sup.2+ and Cr.sup.6+) and high water disinfection (pathogen removal and inactivation) power. The materials used for the modification of membranes include: dopamine hydrochloride (DOPA), 3-(3.4-dihydroxyphenyl)-L-alanine (L-DOPA) silver nitrate, tris (hydroxymethyl) aminomethane (Tris) buffer, polyamine (e.g., o-phenylenediamine (OPD), m-phenylenediamine (MPD), bisphenol A (BPA), trihydroxypropane and molecules with polychloride and polysulfonylchloride such as trimesoyl chloride (TMC) and 1, 5-naphthalene-bisulfonyl chloride, etc). Deionized (DI) water is used as a water phase solvent for dissolving polymers with polyamine, polyhydric alcohol and polyphenol groups. Hexane, cyclohexane, Isopar serials etc. and combinations thereof are used as oil solvents for dissolving polymers with polychlorde and polysulfonylchloride groups. They are hexane, cyclohexane, Isopar seials etc and combination thereof. Macromolecule organics, small molecule organics and surfactants, such as dimethyl sulfoxide (DMSO), ε-carprolactam (CL), triethylamine (TEA), camphorsulfonic acid (CSA), sodium dodecyl sulfate (SDS), and their combinations are used to increase the miscibility of two immiscible phases.
(18) Materials for modification of membranes can be summarized in the following chart.
(19) TABLE-US-00002 Materials Solvent Additives dopamine hydrochloride Deionized water (DI dimethyl sulfoxide (DOPA) water) (DMSO) 3-(3.4-dihydroxyphenyl)- tris (hydroxymethyl) ε-carprolactam L-alanine (L-DOPA) aminomethane (Tris) (CL) buffer silver nitrate Hexane,, triethylamine (TEA) o-phenylenediamine (OPD) cyclohexane camphorsulfonic acid (CSA) m-phenylenediamine Isopar sodium dodecyl (MPD) sulfate (SDS) bisphenol A (BPA) Combination of above Combination of above trihydroxypropane trimesoyl chloride (TMC) 1,5-naphthalene-bisulfonyl chloride
(20) During the preparation of a polymer solution for membrane fabrication, certain amounts of polymer and additives are mixed in organic solvent in a sealed container 20 at a certain temperature (preferably 50˜90° C.) until homogenous. See
(21) In the NIPS process, the casting solution 21 is directly cast with certain thickness onto a clean and smooth glass plate 22. See
(22) Prior to the interfacial polymerization, a uniform nanoparticle layer is deposited on the surface of a UF membrane. During the interfacial polymerization, a preformed membrane substrate is first poured with or soaked into a polyamine aqueous solution for 1˜1200 seconds (preferably 30˜600 seconds). Following this the excess polymer solution is removed from the surface, and is then immediately poured with or soaked into an acyl chloride n-hexane solution for 1˜600 seconds (preferably 10˜300 seconds). After the desired active layers has been formed, the membrane is rinsed thoroughly with hexane, and stored in 15-25° C. (preferably 20° C.) DI water before characterization.
(23) The prepared nanofibrous membrane is surface coated with branched polyethylenimine (PEI) by a simple filtration method. PEI is dissolved in water with a concentration of 0.1-5.0 wt. %, after that the coated membrane is cross-linked by glycerol diglycidyl ether or glutaraldehyde at a temperature of 40-60° C. The prepared nanofiber membrane coated by amine groups has a high rejection for heavy metal ions (shown in Table 3). In particular, Table 3 shows the results of the removal of heavy metal ions.
(24) Silver nanoparticles having an average diameter of 0-100 nm may be loaded in-situ on the surface of the membrane to provide for water disinfection. The loading amount can be 0 wt. %-5.0 wt. %.
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(26) The silver loaded nanofiber membrane has high water disinfection performance; the results are shown in Table 4. In particular, Table 4 shows the CFU data of nanofibrous membrane and NF membrane.
(27) A prototype is fabricated by mounting the prepared membranes on different surfaces of the filter. To increase the water throughput of this filter, the membranes are provided with a folded configuration when mounted in a filter body.
Example 1
(28) PAN (1.0-15.0 wt. %, preferably 4.0-8.0 wt. %) was dissolved in DMF at 40-80° C. (preferably 60° C.) to prepare the homogeneous and transparent electrospun polymer solution. The dope solution was cooled down to room temperature and then degassed statically in the same container. Conditions for electrospun were listed as follows: rate of feed solution: 0.5-2.0 mL/h (preferably 1.0-1.5 mL/h) applied voltage: 5-30 kV (preferably 10-20 kV) air gap (collection distance): 5-20 cm (preferably 10-15 cm) drum rotating speed: 10-200 rpm (preferably 50-100 rpm) electrospun period: 1-30 h (preferably 5-20 h)
The polymer used can be polyacrylonitrile (PAN), poly(vinyl alcohol) (PVA), chitosan, polysulfone (PSf), polyethersulfone (PES), and poly(vinyl butyral) (PVB), etc. The solvent included deionized water, 1-methyl-2-pyrrolidinone (NMP), dimethyl formamide (DMF), dimethyl-acetamide (DMAc), acetic acid (AA) and a combination thereof.
(29) The obtained electrospun membrane was hot pressed at 120-160° C. (preferably 140-150° C.) for 3 hours. Then the PAN nanofibrous membrane was immersed in dopamine Tris solution (0.5-5.0 g/L DOPA (preferably 1.0-3.0 g/L), 5-30 mM Tris-HCl (preferably 10-20 mM), pH 7.0-9.0 (preferably 7.5-8.5) under continuous shaking for 2-24 hours (preferably 10-20 h) at 25° C. The coated PAN membranes (cPAN) were rinsed using deionized water to remove the labile polydopamine (PDA) particles.
(30) Silver nanoparticles were immobilized onto the cPAN membranes through a spontaneous reduction of silver ions in-situ by the reductive catechol groups contained in PDA. Typically, a cPAN coupon (diameter of 7.6 cm) was immersed into a 0.5-10.0 g/L (preferably 2-5 g/L) silver nitrate solution for 0.5-10 hours (preferably 2-5 h). During the entire process, the solution was covered by aluminum foil and was shaken continuously. The resulting silver-loaded membranes were thoroughly rinsed with deionized water.
(31) The structure of the membranes could be a simple or symmetric structure as shown in
(32) Three prototypes were fabricated with different membrane configurations 60a-60c. In the first one, the membrane 60a (effective area is about 15.2 cm.sup.2) was mounted at the bottom of the filter support 62.
Example 2
(33) Prior to the electrospun of 1.0-4.0 wt. % PAN/DMF solution, an 8.0-15.0 wt. % PAN/DMF solution was first used for electrospun. Conditions for electrospun were listed as follows: rate of feed solution: 0.5-2.0 mL/h applied voltage: 5-30 kV air gap (collection distance): 5-20 cm (preferably 10-15 cm) drum rotating speed: 10-200 rpm (preferably 50-100 rpm) electrospun period: 1-30 h (preferably 5-20 h)
(34) A polymer used can be polyacrylonitrile (PAN), poly(vinyl alcohol) (PVA), chitosan, polysulfone (PSf), polyethersulfone (PES), and poly(vinyl butyral) (PVB), etc. The solvent can include deionized water, 1-methyl-2-pyrrolidinone (NMP), dimethyl formamide (DMF), dimethyl-acetamide (DMAc), acetic acid (AA) and combination of thereof.
(35) After that, the electrospun solution was changed to 1.0-4.0 wt. % PAN/DMF solution, and the electrospun process was continued for another 0-10 hours.
(36) The modification processes for the asymmetric nanofibrous membrane were the same as Example 1.
Example 3
(37) 1.0-4.0 wt. % and 8.0-12.0 wt. % PAN/DMF solutions were electrospun together. Conditions for the electrospun were as follows: rate of feed solution: 0.5-2.0 mL/h (preferably 1.0-1.5 mL/h) applied voltage: 5-30 kV (preferably 10-20 kV) air gap (collection distance): 5-20 cm (preferably 10-15 cm) drum rotating speed: 10-200 rpm (preferably 50-100 rpm) electrospun period: 1-30 h (preferably 5-20 h)
(38) Three syringes with metal needles were used in the electrospun process. PAN/DMF solutions with higher concentration were filled in either two or one of the three syringes. The polymer used can be polyacrylonitrile (PAN), poly(vinyl alcohol) (PVA), chitosan, polysulfone (PSf), polyethersulfone (PES), and poly(vinyl butyral) (PVB), etc. The solvent can include deionized water, 1-methyl-2-pyrrolidinone (NMP), dimethyl formamide (DMF), dimethyl-acetamide (DMAc), acetic acid (AA) and combination of thereof.
(39) The modification processes for the asymmetric nanofibrous membrane were the same as in Example 1. The prototype fabrication process was the same as Example 1.
Example 4
(40) 1.0-4.0 wt. % PAN/DMF solutions (to prepare nanofibers with small diameter) and 8.0-30.0 wt. % PVDF/DMF (to prepare nanofibers with large diameter) solutions were electrospun together. Conditions for the electrospun were listed as follows: rate of feed solution: 0.5-2.0 mL/h (preferably 1.0-1.5 mL/h) applied voltage: 5-30 kV (preferably 10-20 kV) air gap (collection distance): 5-20 cm (preferably 10-15 cm) drum rotating speed: 10-200 rpm (preferably 50-100 rpm) electrospun period: 1-30 h (preferably 5-20 h)
(41) Three syringes with metal needle were used in the electrospun process. polymer/DMF solutions with higher concentration were filled in either two or one of the three syringes.
(42) Polymers used for the preparation of nanofibers with small diameter can be polyacrylonitrile (PAN), poly(vinyl alcohol) (PVA), chitosan, polysulfone (PSf), polyethersulfone (PES), and poly(vinyl butyral) (PVB), etc. Polymers used for the preparation of nanofibers with large diameter can be poly(vinyl alcohol) (PVA), chitosan, polysulfone (PSf), polyethersulfone (PES), and poly(vinyl butyral) (PVB), etc. Solvents can include deionized water, 1-methyl-2-pyrrolidinone (NMP), dimethyl formamide (DMF), dimethyl-acetamide (DMAc), acetic acid (AA) and combination of thereof.
(43) The modification processes for the asymmetric nanofibrous membrane structures (
Example 5
(44) A polymer solution, which is made from PSf beads (15.0 wt. %) dissolved in DMF at 50° C. until homogeneous and transparent, was used as casting solution. The casting solution was cooled down to room temperature and then degassed statically in the same container. The casting solution was spread directly onto a smooth and clean glass plate. The glass plate with the whole composite was then immediately immersed in a coagulant bath containing room temperature tap water for at least 5 min to finish the phase inversion.
(45) To fabricate nanofiltration membranes, Dopamine hydrochloride powder (0.4 g) was dissolved in 200 ml of a 10 mM Tris-HCl buffer solution with the pH adjusted to 8.5. The PDA coating solution was placed in a reservoir exposed to the active layer of the PSf membrane. Two electrical motor-driven stirring paddles (See
(46) Table 1 shows the properties of a PAN nanofibrous membrane and a PAN ultrafiltration membrane.
(47) TABLE-US-00003 TABLE 1 Properties of a PAN nanofibrous membrane and a PAN ultrafiltration membrane. Porosity BET surface area Mean pore size (%) (m.sup.2/g) (nm) PAN nanofibrous 89.6% 24.5 190 membrane PAN ultrafiltration 76.7% 19.3 15 membrane
(48) In further embodiments, the porosity of the PAN nanofibrous or ultrafitration membrane can be 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94% and 95%. In further embodiments, the mean pore size of the PAN nanofibrous or ultrafitration membrane can be 10 nm, 50 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, 550 nm, 600 nm, 650 nm, 700 nm, 750 nm, 800 nm, 850 nm, 900 nm, 950 nm and 1000 nm.
(49) Table 2 shows the water permeability properties of different membranes.
(50) TABLE-US-00004 TABLE 2 Water permeability at different water head and different monomer concentration Water permeability Membranes (Lm.sup.−2h.sup.−1bar.sup.−1) Nanofiber membranes 15460 ± 44~71193 ± 2524 Nanofiltration membrane 13.1 ± 0.3 PIP (0.5 wt. %) Nanofiltration membrane 10.2 ± 0.7 PIP (1.0 wt. %) Nanofiltration membrane 6.4 ± 0.6 PIP (2.0 wt. %)
(51) Table 3 shows the results of heavy metal ion removal.
(52) TABLE-US-00005 TABLE 3 Results of heavy metal ions removal. Pb.sup.2+ Cd.sup.2+ Ni.sup.2+ Cr.sup.6+ Initial Concentration 165 161 162 163 (μg/L) Detection limit 1.0 0.1 0.5 0.2 (μg/L) Rejection * 99.4% 99.9% 99.7% 99.9% * Rejection results are calculated based on the detection limit, because no metal ions can be detected in permeates.
(53) Table 4 shows the colony-forming unit (CFU) data of a nano-fibrous membrane and a nano-filtration (NF) membrane. A (CFU) is a unit used to estimate the number of viable bacteria or fungal cells in a sample. Table 4 particularly shows the effect of a silver loaded membrane.
(54) TABLE-US-00006 TABLE 4 CFU data of nanofibrous membranes and nanofiltration membranes. Control Pristine Silver loaded sample membrane membrane Nano- CFU E. coli 1.18 × 10.sup.8 ± 1.00 × 10.sup.8 ± 325 ± 263 fibrous (cells/ 2.36 × 10.sup.7 3.58 × 10.sup.7 membrane mL) B. 1.37 × 10.sup.7 ± 8.67 × 10.sup.6 ± <10 subtilis 2.52 × 10.sup.6 2.73 × 10.sup.6 Nano- CFU E. coli 1.18 × 10.sup.8 ± 1.05 × 10.sup.8 ± 6.67 × 10.sup.7 ± filtra- (cells/ 2.31 × 10.sup.7 3.39 × 10.sup.7 1.51 × 10.sup.7 tion mL) B. 1.08 × 10.sup.7 ± 8.67 × 10.sup.6 ± 1.10 × 10.sup.6 ± membrane subtilis 1.72 × 10.sup.6 2.42 × 10.sup.6 6.63 × 10.sup.5
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(56) The water filter of the present invention can remove unwanted particles (e.g. suspended inorganic particles and organic particles), biological entities (e.g. pathogen and bacteria), and heavy metal ions (e.g. Pb.sup.2+, Cd.sup.2+, Ni.sup.2+ and Cr.sup.6+). With good permeability, the nanofibrous membrane in this invention can be used as a water filtration system. In addition, with silver loading of silver nanoparticles in-situ on the surface of the membrane the filter is provided with water disinfection properties.
(57) The advantages of the present water filter invention are a) light-weight, b) high water throughput (orders of magnitude higher than the commercial MF and UF membranes), c) driven by gravity directly or by mechanical assist, so no electricity is needed, d) high disinfection power and e) antifouling and anti-bacterial effects. In addition, the water filter product of the present invention enjoys several advantages compared to the existing commercial products as follows: f) can be used as a portable water purification device, g) is disposable and different types are available for different treatment applications, h) low cost, i) water permeability can be further improved through a mechanical-assist system and j) operation is very simple, no need for complex instructions.
(58) While the present invention has been particularly shown and described with reference to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.