WO2010120325A1 - Improved tfc membranes with alkaline earth metal and other additives - Google Patents

Improved tfc membranes with alkaline earth metal and other additives Download PDF

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Publication number
WO2010120325A1
WO2010120325A1 PCT/US2009/060927 US2009060927W WO2010120325A1 WO 2010120325 A1 WO2010120325 A1 WO 2010120325A1 US 2009060927 W US2009060927 W US 2009060927W WO 2010120325 A1 WO2010120325 A1 WO 2010120325A1
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Prior art keywords
membrane
additives
flux
additive
tmc
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PCT/US2009/060927
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French (fr)
Inventor
Christopher James Kurth
Jeffrey Alan Koehler
Meijuan Zhou
Brett Anderson Holmberg
Robert Leon Burk
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Nanoh2O, Inc.
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Priority claimed from PCT/US2009/040732 external-priority patent/WO2009129354A2/en
Application filed by Nanoh2O, Inc. filed Critical Nanoh2O, Inc.
Priority to ES10800304T priority Critical patent/ES2715823T3/en
Priority to PCT/US2010/040417 priority patent/WO2011008549A2/en
Priority to AU2010273709A priority patent/AU2010273709B2/en
Priority to EP10800304.7A priority patent/EP2448657B1/en
Priority to JP2012518577A priority patent/JP5745512B2/en
Priority to US12/826,294 priority patent/US8567612B2/en
Priority to CA2766352A priority patent/CA2766352C/en
Publication of WO2010120325A1 publication Critical patent/WO2010120325A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002Organic membrane manufacture
    • B01D67/0006Organic membrane manufacture by chemical reactions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D61/00Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/002Forward osmosis or direct osmosis
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D61/00Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025Reverse osmosis; Hyperfiltration
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D63/00Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/10Spiral-wound membrane modules
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079Manufacture of membranes comprising organic and inorganic components
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079Manufacture of membranes comprising organic and inorganic components
    • B01D67/00791Different components in separate layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079Manufacture of membranes comprising organic and inorganic components
    • B01D67/00793Dispersing a component, e.g. as particles or powder, in another component
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12Composite membranes; Ultra-thin membranes
    • B01D69/125In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12Composite membranes; Ultra-thin membranes
    • B01D69/125In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • B01D69/1251In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14Dynamic membranes
    • B01D69/141Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14Dynamic membranes
    • B01D69/141Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B01D69/148Organic/inorganic mixed matrix membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/56Polyamides, e.g. polyester-amides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/58Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/60Polyamines
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/76Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/82Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2323/00Details relating to membrane preparation
    • B01D2323/36Introduction of specific chemical groups
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2325/00Details relating to properties of membranes
    • B01D2325/48Antimicrobial properties
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/445Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by forward osmosis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08Seawater, e.g. for desalination
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124Water desalination
    • Y02A20/131Reverse-osmosis

Definitions

  • This invention is related to thin film composite or TFC membranes including alkaline earth metal and/or other additives, and more particularly to such membranes useful for reverse or forward osmosis, for example to purify water.
  • Reverse osmosis membranes made by interfacial polymerization of a monomer in a nonpolar (e.g. organic) phase together with a monomer in a polar (e.g. aqueous) phase on a porous support membrane are known as TFC membranes and are used where flux and substantial rejection characteristics are required, for example in the purification of water.
  • TFC membranes Various materials have been added to TFC membranes in the hopes of increasing flux without reducing rejection characteristics and have met with limited success.
  • such membranes are subject to fouling resulting in reduced flux as contaminants, for example from the brackish or seawater to be purified, are believed to build up on the surface of the discrimination layer of the TFC membrane.
  • TFC membranes became available in about the 1970's and proved commercially successful for some RO tasks. Substantial further development has been done to improve the membranes operational characteristics, including permeability or flux, rejection and fouling resistance.
  • a polar aprotic solvent was said to be added to the aqueous solution prior to contacting with an acid halide solution for interfacial polymerization to enhance the operational characteristics of the resultant membrane.
  • catalysts were said to be added to the aqueous phase to accelerate interfacial polymerization, producing TFC membranes with a smoother surface.
  • TFC membranes have different membrane operational characteristics (such as flux, rejection, and fouling resistance) that make them more suitable for different tasks. These tasks are typically defined by the incoming water quality, plant design, and required product water quality, which together set the operational conditions of the plant (such as required applied pressure).
  • membranes for use in purifying brackish water are conventionally expected to encounter a substantially lower salinity - and be operated at substantially lower pressure - than a membrane useful for seawater desalination.
  • RO may require a minimum flux of at least 20 GFD (gallons per square foot per day of filtered liquid) with a minimum of 99.5% salt rejection when operated at a working pressure of about 220 psi on brackish water having an expected salinity of about 2000 ppm (parts per million) or less.
  • GFD gallate-dioxide
  • a typical specification for TFC membranes to be used for seawater RO may require a minimum flux of 20 GFD with a minimum of 99.5% salt rejection when operated at a working pressure of about 800 psi on seawater having an expected salinity of 32000 ppm or more.
  • TFC membranes suitable for brackish water use i.e., at low pressure and salt load, will typically not operate well when operated at the higher pressure and salinity used for seawater purification. There is no clear cut way to predict their performance under the salinity and operating conditions used for seawater exactly, however it can be said that such membranes typically lose permeability and salt rejection ability as the salinity increases.
  • micekols in example 35 discloses the use of a particular phosphorus compound additive which is said to produce a TFC membrane having membrane operation characteristics, including 19.5 GFD and 99.6% rejection when operated at 150 psi with salinity of 2000 ppm. Although these characteristics may be suitable for reverse osmosis of brackish water, there is no reasonable way to predict how to use such information in the formulation of a TFC membrane suitable for use under the conditions required for in seawater osmosis other than by preparing and testing it.
  • TFC membranes having properties suitable for reverse osmosis of seawater are conventionally made without the various additives discussed in the prior art, presumably because such additives tend to have deleterious action on TFC membranes rejection.
  • TFC membranes designed for seawater deslaination One common problem with conventional TFC membranes designed for seawater deslaination, is quality control and variability in product performance. That is, it is believed that fabricating TFC membranes with predictable flux, rejection and fouling resistance for seawater RO has been so difficult, that fabrication facilities are in some cases unable to prepare a specific product, or need to shift a product's formulation in order to maintain the required membrane properties.
  • Nanomaterials & Membrane Technology Research Laboratory determined that the addition of certain nanoparticles, such as LTA, and other materials could be used to improve TFC membrane operational characteristics at operating pressures, and expected salinities suitable for use in reverse osmosis of seawater.
  • TFC membranes in particular TFC membranes suitable for operation at the higher pressures and salinities required for reverse osmosis of seawater - which have higher flux than is achievable from TFC membranes made without such additives
  • Such desirable TFC membranes must also have a suitably high salt rejection, preferably on the order of about 99.5%. It would also be desirable to have increased fouling resistance - as well as higher flux and high rejection rates - when compared to a TFC membrane made the same way with the same chemistry but without the additives.
  • TFC membranes are also needed with such membrane operational characteristics for many other uses beyond seawater purification, including but not limited to brackish water purification, waste water reuse, ultrapure water generation, industrial water treatment, other RO tasks, forward osmosis and pressure retarded osmosis.
  • Fig. 1 is a block diagram illustrating layers used in the process of fabricating TFC membrane 10 in which additives 16 are present in aqueous phase 14.
  • Fig. 2 is a block diagram illustrating layers used in the process of fabricating TFC membrane 10 in which additives 16 are present in organic phase 18.
  • Fig. 3 is a block diagram illustrating layers used in the process of fabricating TFC membrane 10 in which additives 16 are present in both aqueous phase 14 and organic phase 18.
  • Fig. 4 is a block diagram illustrating layers used in the process of fabricating TFC membrane 10 in which additives 16 are present in organic solution 18 and in water solution 15 between porous support membrane 12 and aqueous phase 14.
  • FIG. 5 is a block diagram showing the use of a TFC membrane, having additives 16 in a layer discrimination layer 24, in a reverse osmosis process.
  • Fig. 6 is a block diagram showing the operation of TFC membrane
  • Fig. 7 is a block diagram showing the operation of TFC membrane 10 including hydrophilic layer 30, in which additives 16 were present during the interfacial polymerization of discrimination layer 24 and in the fabrication of support 12 and fabric 10, in a reverse osmosis process
  • Fig. 8 is an exploded view of membrane 10 in which additives 16, such as nanostructured additives, penetrate the upper and/or lower surfaces of discrimination membrane 24.
  • Fig. 9 is an exploded view of membrane 10 in which additives 16, such as nanostructured additives, are between discrimination membrane 24 and support 12.
  • Fig. 10 is a diagrammatic view of support membrane 12 during fabrication in which casting solution 13, including additives 16 such as nanoparticle additives, is coated on fabric 20 on glass plate 15.
  • Fig. 11 is the chemical structure of mono-hydrolyzed or mhTMC.
  • Fig. 12 is a graphic representing a 1 H-NMR analysis of the purity of synthesized mhTMC.
  • FIG. 13 is a graphical illustration of flux and rejection curves 32, 34 for increasing concentrations of additive 16, such as mhTMC lot 1 , indicating a range of preferred concentrations of mhTMC or other additives 16 - shaded area 45 - surrounding deflection axis A 44, in which one or more non-linearities or deflections appear to occur in flux growth and rejection decline as well as deflection axis B 46 indicating concentrations of additive 16 which appear to damage membrane 10.
  • additive 16 such as mhTMC lot 1
  • Fig. 14 is a graphical illustration of flux and rejection curves 36, 38 for increasing concentrations of additive 16, such as mhTMC lot 2, and of flux and rejection curves 40, 42 for increasing concentrations of additive 16, such as filtered mhTMC lot 2, indicating a range of preferred concentrations of additive 16 including deflection axis A 48 - shaded area 49 - in which one or more non-linearities or deflections appear to occur in flux growth and rejection decline.
  • Fig. 15 is a graphical comparison of the reduction in flux over time in membrane 10 with LTA additive 16, membrane 10 with another additive 16 and hybrid membrane 10 with additives 16 including the LTA and other additive used in the first two membranes 2 shown in this figure.
  • improved techniques for the use of alkaline earth additives in TFC membranes including combining one or more additives with either or both a polar liquid having a first monomer therein and a non-polar liquid having a second monomer therein and contacting the polar and non-polar liquids to form a selective membrane by interfacial polymerization, wherein at least one of the additives includes a complex including an alkaline earth metal.
  • a TFC membrane may be fabricated with an additive including a complex which includes an alkaline earth metal.
  • the complex may be a beta-diketonate complex such as acetylacetonate.
  • the complex may be present in a concentration in one of the liquids of from about 0.005 wt.% to about 5 wt.% and more preferably from about 0.05 wt.% to about 1 wt.%.
  • At least one of the additives includes a complex of magnesium, calcium, strontium or beryllium.
  • the polar liquid may include an amine monomer such as MPD.
  • the non-polar liquid may include TMC.
  • the ratio of MPD in the polar liquid to TMC in the non-polar liquid may be below 14 and may be low enough so that the resultant selective membrane has substantially higher flux than a control membrane.
  • the concentration of TMC in the non-polar liquid may high enough so that the resultant selective membrane has substantially higher flux than a control membrane made without the complex including an alkaline earth metal.
  • TFC membranes have been developed including the combined used of nanoparticles and/or nanotubes with alkaline earth metals, monohydrolyzed TMC and/or other molecular additives in hybrid nanocomposite TFC membranes with increased flux, rejection and anti-fouling characteristics.
  • the new hybrid nanocomposite TFC membranes together with more advantageous concentrations and ranges of TMC, MPD to TMC ratios as well as the discovery of deflection points in the concentrations of additives, such as monohydrolyzed TMC, make the design and fabrication of engineered nanocomposite TFC membranes with selected flux, rejection and antifouling characteristics possible.
  • some of the new additives particularly the alkaline earth metals and monohydrolyzed TMC, may be used for the design and fabrication of high flux, rejection and anti-fouling TFC membranes. These membranes may also advantageously use the advantageous concentrations and ranges of TMC, MPD to TMC ratios and deflection points in the concentrations of additives to provide optimum characteristics for particular circumstances.
  • a thin film composite membrane may be made by combining two or more additives with either or both a polar liquid having a first monomer therein and a non-polar liquid having a second monomer therein and contacting the polar and non-polar liquids to form a selective membrane by interfacial polymerization, wherein at least one of the two or more additives is a nanostructured additive.
  • the nanostructured additive may be a zeolite nanoparticle, such as
  • One of the additives may includes a predetermined concentration of mono-hydrolyzed TMC and/or di-hydrolyzed TMC in addition to the nanostructured additives.
  • a complex including an alkaline earth metal may also be included in addition to the nanostructured additives and/or a complex including an element selected from Groups 3 - 15, rows 3-6 of the Periodic Table (IUPAC) may be in addition to the nanostructured additives.
  • IUPAC Periodic Table
  • These additional additives may include aluminum, cadmium, chromium, cobalt, copper, gallium, hafnium, indium, iron, one of the lanthanoid elements, molybdenum, palladium, phosphorous, ruthenium, tin, vanadium or Zinc.
  • the polar liquid may include an amine, such as MPD, and the non- polar liquid may include TMC wherein ratio of MPD to TMC is below 14, low enough so that the resultant selective membrane has substantially higher flux than a control membrane.
  • the concentration of TMC may be high enough so that the effect of one or more of the additives, in the resultant selective membrane, is enhanced to produce a substantially higher flux than a control membrane.
  • Techniques are disclosed including an interfacial polymerization process for preparing a highly permeable RO membrane by contacting a first solution containing 1 ,3-diaminobenzene, and a second solution containing trimesoyl chloride, to fabricate a highly permeable RO membrane wherein at least one of the solutions contains well dispersed nanoparticles when contacted.
  • a first solution containing 1 ,3-diaminobenzene, and/or a second solution containing trimesoyl chloride may contain well dispersed nanoparticles and be contacted to form an RO membrane wherein at least 20% of the membrane surface area consists of nanoparticles.
  • a first solution containing polyamine monomer, and a second solution containing a polyfunctional acyl halide monomer, wherein a molecular additive compound is present in one or both solutions during the polymerization reaction may be used to fabricate a TFC membrane.
  • an interfacial polymerization process for preparing a low- fouling highly permeable RO membrane may include contacting on a porous support membrane, a first solution containing a polyamine monomer, and a second solution containing a polyfunctional acyl halide monomer, wherein aluminum ions are present in one or both solutions, during the polymerization reaction.
  • a low-fouling highly permeable RO membrane may be produced by an interfacial polymerization process by contacting on a porous support membrane, a first solution containing a polyamine monomer, and a second solution containing a polyfunctional acyl halide monomer , wherein aluminum ions are present in one or both solutions during the polymerization reaction.
  • Another process for preparing a highly permeable RO membrane may include contacting on a porous support membrane, an aqueous solution containing metaphenylenediamine (MPD), and an organic solution containing trimesoyl chloride (TMC) and a hydrolyzed TMC species.
  • MPD metaphenylenediamine
  • TMC trimesoyl chloride
  • Improved thin film composite or TFC membranes fabricated with additives for enhanced membrane performance are disclosed.
  • Techniques for improving membrane performance include dispersion and sizing of nanostructured additives, processing to enhance the performance of such additives in TFC membranes, selecting and processing such additives 16 to release soluble metal ions and/or adding additional additives 16 to fabricate hybrid TFC membranes.
  • Hybrid TFC membranes may include the following additives used in various combinations: nanoparticles, nanotubes, alkaline earth metal complexes, mono-and/or di-hydrolyzed TMC and/or other molecular additives such as elements selected from Groups 3 - 15 of the Periodic Table (IUPAC), particularly from Rows 3 - 6 of those groups.
  • TFC membranes may be fabricated without nanostructured additives.
  • Techniques for fabricating TFC membranes may include specific TMC concentrations and MPD/TMC ratios and selection of concentration or ranges of concentration by detection of deflections points - which may be non-linearities in the growth of flux, or decline in rejections, with increasing additive concentration - especially when such changes occur in both flux growth and rejection decline at the same levels of concentration of the additive(s).
  • Tables of examples are provided which illustrate these TMC concentrations and MPD/TMC ratios as well as the effects of using various additives in various combinations, in various locations including in the aqueous and/or organic phases contacted to cause interfacial polymerization of the discrimination layer or membrane in the TFC membranes fabricated in accordance with these examples.
  • the tables also illustrate the percentage of flux improvement of many of these TFC membranes compared to similar TFC membranes used as controls which were fabricated in the same way, but without such additives.
  • these tables illustrate the permeability or flux, and solute rejection rates, of the exemplar membranes.
  • the techniques used in the fabrication and testing of these membranes are also presented along with an outline of some of the advantages of the additives and combinations of additives used in the exemplars.
  • Section A Thin Film Composite (TFC) Membranes
  • Section B Specific Additive(s) 16 and Combinations thereof B.1. Nanostructured Additives 16
  • TFC Thin Film Composite
  • RO Reverse Osmosis
  • Fig.s 1-9 illustrate a first or aqueous 14 phase and a second or organic phase 18 in an exploded view for contact on support membrane 12 during fabrication for interfacial polymerization to form discrimination membrane 24 during the fabrication of TFC membrane 10.
  • One or more additive(s) 16 such as nanostructured materials, may be introduced into the interfacial polymerization between aqueous phase 14 and organic phase 18 before or at the beginning of the interfacial polymerization reaction to improve membrane characteristics.
  • FiQ- 1 indicates that additives 16 has been added to aqueous phase
  • Fig. 2 indicates that additives 16 has been added to organic phase 18.
  • Fig. 3 indicates that additives 16, has been added to both aqueous phase 14 and organic phase 18. The same or different additives 10 may be used in different locations.
  • Fig. 4 indicates that additives 16 has been added to both organic phase 18 as well as water solution 11 on the surface of support 12 before aqueous phase 14 is applied to support 12 followed by organic phase 18. It should be noted that in some embodiments, organic phase 18 may applied to support 12 before aqueous phase 14 is applied to organic phase 18.
  • Fig.s 5-7 illustrate TFC membranes 10 after fabrication, e.g., by the processes illustrated in Fig.s 1-4.
  • membrane 10 includes discrimination layer 24 formed by the interfacial polymerization of aqueous and organic phases 14 and 18 in the presence of one or more additive(s) 16.
  • TFC membrane 10 may conveniently be used for selective filtering, for example as RO TFC membrane 10, to purify saltwater 26 - applied under pressure to discrimination layer 24 - so that purified water 28 passes through discrimination layer 24, porous support membrane 12 and fabric layer 20, if present.
  • hydrophilic layer 30, such as a polyvinyl alcohol or PVA layer may be applied to discrimination layer 24 to the surface of membrane 10 in contact with the material to be filtered, e.g., seawater 26, to make that surface and therefore membrane 10 more hydrophilic, that is, to reduce the interfacial tension of the surface of membrane 10.
  • Improved hydrophilicity can be observed as a lower contact angle between seawater 26 and membrane 10. Improving the hydrophilicity of the upper or contact surface of membrane 10 is believed to reduce fouling and may improve flux flow.
  • Seawater 26 may be applied under pressure to TFC membrane 10 to produce purified water 28.
  • TFC membrane 10 may be synthesized using an interfacial polymerization process on a porous support, such as support membrane 12.
  • a porous support such as support membrane 12.
  • two immiscible solvents are used, one in aqueous phase 14 and the other in organic phase 18, so that a monomer in one solvent reacts with a monomer in the other solvent.
  • the interfacial polymerization reaction occurs at the interface between the two solutions when aqueous phase 14 and organic phase 18 are brought into contact with each other, to form a dense polymer matrix layer - discrimination layer 24 - on the surface of support membrane 12.
  • discrimination layer 24 is formed as a selective dense layer which is typically very thin and permeable to water, but relatively impermeable to dissolved, dispersed, or suspended solids, such as salts to be removed from sea or brackish water to produce purified water.
  • Resultant membrane 10 is conventionally described as a thin film composite (TFC) membrane.
  • the first monomer can be a dinucleophilic or a polynucleophilic monomer and the second monomer can be a dielectrophilic or a polyelectrophilic monomer. That is, each monomer can have two or more reactive (e.g., nucleophilic or electrophilic) groups. Both nucleophiles and electrophiles are well known in the art, and one of ordinary skill in the art can select suitable monomers for this use.
  • the first and second monomers are conventionally selected to react - when aqueous and organic phases 14 and 18 are brought into contact - by undergoing interfacial polymerization to form a three-dimensional polymer network, often called a polymer matrix.
  • the first and second monomers can also be chosen to be capable of undergoing a polymerization reaction when aqueous and organic phases 14 and 18 brought into contact to form a polymer product that is capable of subsequent crosslinking by, for example, exposure to heat, light, radiation, or a chemical crosslinking agent.
  • the first monomer can be selected to be soluble in a polar liquid, preferably water, to form a polar mixture, referred to herein as aqueous phase 14.
  • the difunctional or polyfunctional nucleophilic monomer can have primary or secondary amino groups and can be aromatic (e.g., a diaminobenzene, a triaminobenzene, m-phenylenediamine, p- phenyenediamine, 1 ,3,5-triaminobenzene, 1 ,3,4-triaminobenzene, 3,5- diaminobenzoic acid, 2,4-diaminotoluene, 2,4-diaminoanisole, and xylylenediamine) or aliphatic (e.g., ethylenediamine, propylenediamine, piperazine, and tris(2- diaminoethyl)amine).
  • aromatic e.g., a diaminobenzene, a triamin
  • Suitable amine species include primary aromatic amines having two or three amino groups, for example m-phenylenediamine, and secondary aliphatic amines having two amino groups, for example piperazine.
  • the amine can typically be applied to microporous support 12 as a solution in a polar liquid, for example water.
  • the resulting polar mixture typically includes in the range from about 1 to about 6 wt.% amine, preferably in the range of about 2 to about 4.0 wt.%, amine and most preferably about 3.0 wt.% amine.
  • the polar mixture need not be aqueous, but the polar liquid should be immiscible with the apolar liquid.
  • water is a preferred solvent
  • non-aqueous polar solvents can be utilized, such as acetonitrile and dimethylformamide (DMF) for aqueous phase 14.
  • Phase 14 can be called a polar phase or an aqueous phase because such mixtures typically use water as the polar solvent. We believe most practitioners in this art refer to phase 14 as the aqueous phase. To avoid any confusion, that convention will be followed herein so that the term "aqueous phase" 14 is intended to refer to all polar phase liquids, e. g. whether or not the polar liquid is water.
  • aqueous phase 14 may include one of the reactants, additive(s) such as nanostructured materials, e.g., nanoparticle additives 16, as well as processing aids such as surfactants, drying agents, catalysts, coreactants, cosolvents, etc.
  • additive(s) such as nanostructured materials, e.g., nanoparticle additives 16, as well as processing aids such as surfactants, drying agents, catalysts, coreactants, cosolvents, etc.
  • the polar mixture, aqueous phase 14 is typically applied to microporous support membrane 12 by dipping, immersing, slot die coating, spray coating, gravure coating or other well known techniques. Once coated on porous support membrane 12, excess polar mixture can be optionally removed by evaporation, drainage, air knife, rubber wiper blade, nip roller, sponge, or other devices or processes.
  • the monomer can be optionally delivered by vapor deposition from a vapor phase, or by heat, to support membrane 12.
  • the second monomer can be selected to be miscible with an apolar (organic) liquid, the mixture of which is shown in the figures as organic phase 18.
  • organic phase is intended to refer to any appropriate nonpolar mixture, e. g. organic phase 18.
  • the electrophilic monomer can be aromatic in nature and can contain two or more, for example three, electrophilic groups per molecule.
  • the second monomer can be a trimesoyl halide.
  • acyl chlorides are generally more suitable than the corresponding bromides or iodides because of the relatively lower cost and greater availability.
  • Suitable polyfunctional acyl halides include trimesoyl chloride (TMC), trimellitic acid chloride, isophthaloyl chloride, terephthaloyl chloride and similar compounds or blends of suitable acyl halides.
  • TMC trimesoyl chloride
  • trimellitic acid chloride trimellitic acid chloride
  • isophthaloyl chloride trimellitic acid chloride
  • terephthaloyl chloride trimellitic acid chloride
  • the second monomer can be a phthaloyl halide.
  • the polyfunctional acyl halide - e.g., TMC - can be dissolved in the apolar organic liquid, e.g., organic phase 18, in a range of, for example, from about 0.09 to about 1.0 wt.%, preferably from about 0.17 to about 0.3 wt.%. and most preferably in the range of about 0.3wt.% TMC.
  • Suitable apolar liquids are capable of dissolving the electrophilic monomers (e.g. polyfunctional acyl halides) and which are immiscible with a polar liquid (e.g., water) in aqueous phase 14.
  • suitable apolar liquids preferably include those which do not pose a threat to the ozone layer and yet are sufficiently safe in terms of their flashpoints and flammability to undergo routine processing without having to undertake extreme precautions.
  • These include C 5 - C 7 hydrocarbons and higher boiling hydrocarbons, i.e., those with boiling points greater than about 90° C, such as C 8 - C 24 hydrocarbons and mixtures thereof, which have more suitable flashpoints than their C 5 - C 7 counterparts, but are less volatile.
  • the apolar mixture - organic phase 18 - can typically be applied to contact aqueous phase 14 on microporous support membrane 12 by dipping, immersing, slot die coating, spray coating, gravure coating or other well known techniques.
  • Any excess apolar liquid can be removed by evaporation or mechanical removal. It is often convenient to remove the apolar liquid by evaporation at elevated temperatures, for instance in a drying oven. Preferred ovens include flotation ovens, IR dryers, and laboratory convection or gravity ovens. Control of both web temperature and evaporation rate may be used to alter structure and performance.
  • Organic phase 18 may also include one of the reactants, one or more additive(s) 16, and processing aids such as catalysts, co-reactants, co-solvents, etc. In some circumstances, organic phase 18 may be applied to support membrane 12 first and aqueous phase 14 may then be applied to contact organic phase 18 on support membrane 12.
  • Support membrane 12 is typically a polymeric microporous support membrane, which in turn is often supported by non-woven or woven fabrics, such as fabric 20, for mechanical strength.
  • Fabric 20 is preferably a polyester fabric having a basis weight of 60-120 grams per meter or gsm, and a thickness of 50- 200 microns.
  • Support membrane 12 may conventionally be made from polysulfone or other suitably porous membranes, such as polyethersulfone, poly(ether sulfone ketone), poly(ether ethyl ketone), poly(phthalazinone ether sulfone ketone), polyacrylonitrile, polypropylene, cellulose acetate, cellulose diacetate, or cellulose triacetate.
  • Microporous support membranes 12 may be 25-100 nm in thickness, preferably about 35 nm to about 75 nm and most preferably about 50 nm in thickness and may have the smallest pores located very near the upper surface. Porosity at the surface may be low, for instance from 5-15% of the total surface area.
  • Fig. 7 indicates that additives 16 were also added to support 12 and/or fabric 20 as well as to the interfacial polymerization of discrimination membrane 10.
  • Fig. 8 is an exploded view of membrane 10 and indicates that at least some of the particles in additive 16, such as nanostructured materials, may pierce the upper and/or lower surfaces of membrane 10.
  • Fig. 9 is an exploded view of membrane 10 and indicates that at least some portions of additive 16, may be at the intersection of discrimination membrane 24 and support 12 of membrane 10.
  • the preparation of support membrane 12 may begin, for example in a laboratory setting, with the addition of dimethylformamide (DMF) solvent (available from Acros Organics, USA) to a polysulfone polymer (such as Mn 26,000 available from Aldrich, USA) in transparent bead form in airtight glass bottles.
  • DMF dimethylformamide
  • NMP N-methyl pyrrolidone
  • Additive(s) 16 may be dispersed in the DMF before the DMF is added to the polysulfone polymer as discussed below in greater detail. The solution may then be agitated for several hours until complete dissolution is achieved, forming the dope or casting solution 13.
  • Casting solution 13 may then be cast or spread over non-woven fabric
  • glass plate 15 may then be immediately immersed into demineralized water, which had preferably been maintained at the desired temperature. Immediately, phase inversion begins and after several minutes, non-woven support fabric 20 supporting polysulfone membrane 12 may be separated from glass plate 15. Membrane 12 is then washed thoroughly with deionized water and stored in cold conditions until used. In a continuous coating process, glass plate 15 would not be required.
  • the presence of one or more additive(s) 16, such as nanoparticle additives, during the during the interfacial polymerization of discrimination membrane 24 may substantially improve the performance - for example by increasing the flux and/or resistance to fouling while maintaining a suitable rejection level - of TFC membrane 10 for a particular task such as purifying seawater by reverse osmosis to produce drinking water.
  • additive(s) 16 such as nanoparticle additives
  • Additive(s) 16 may be introduced into the interfacial polymerization reaction by adding them to aqueous phase 14, organic phase 18, water solution 11 , support membrane 12 and/or other by any other convenient mechanism.
  • additives 16 may be added to aqueous phase 14, organic phase 18 or both before these phases are put in contact with each other to begin the interfacial polymerization.
  • a relatively insoluble additive such as LTA nanoparticle additive 16 may be advantageously combined with one or more other additives 16, such as alkaline earth metals, mhTMC, soluble metal species and/or other additives 16, e.g., from Groups 3-15 of the periodic table, which in the presence of the interfacial polymerization provide substantially improved membrane characteristics such as increased flux at high rejection as shown and discussed below for example in the tables of examples.
  • additives 16 such as alkaline earth metals, mhTMC, soluble metal species and/or other additives 16 e.g., from Groups 3-15 of the periodic table, which in the presence of the interfacial polymerization provide substantially improved membrane characteristics such as increased flux at high rejection as shown and discussed below for example in the tables of examples.
  • Section B Specific Additive(s) 16 and Combinations thereof.
  • the introduction of one or more of the nanoparticle additives 16 into the interfacial polymerization between aqueous and organic phases 14 and 18 may provide substantially superior TFC membranes 10 for many selective filtering uses such forward osmosis (FO) and reverse osmosis (RO) for use, for example, in the purification of brackish water and seawater.
  • TFC membranes 10 may have improved flux performance and/or fouling resistance and retain suitably high rejection characteristics for various tasks.
  • nanostructured additives 16 such as nanoparticles
  • additional additives as discussed below
  • combinations of nanoparticles with more than one other additive may still further enhance membrane characteristics.
  • additives including nanoparticles and nanotubes in combination with alkaline earth metals, mhTMC, and selected other elements often in a complex with other materials have been tested as shown in the tables of examples below.
  • alkaline earth metals some other metallic species such as gold, silver, copper, zinc, titanium, iron, aluminum, zirconium, indium, tin, or an alloy thereof or an oxide thereof or a mixture thereof or a complex containing may be used as additives in addition to nanoparticle additives'! 6.
  • a nonmetallic species such as SisN 4 , SiC, BN, B 4 C, or an alloy thereof or a mixture thereof as well as a carbon-based species such as TiC, graphite, carbon glass, a carbon cluster of at least C 2 , buckminsterfullerene, a higher fullerene, a carbon nanotube, a carbon nanoparticle, or a mixture thereof may also be useful.
  • nanoparticles - or other nanostructured materials such as nanotubes and metal organic frameworks (MOF) - useful as additives 16 may include, but are not limited to:
  • Cu MOF A metal organic framework complex prepared from Cu and trimesic acid as described in Science 283, 1148 (1999); Stephen S.-Y. Chui, et al. "[Cu3(TMA)2(H2O)3]n A Chemically Functionalizable Nanoporous Material".
  • Nanostructured additives 16 may be especially beneficial when used in combination. Relatively insoluble nanostructured additives 16 may be used in combination with one or more additional additives 16 to form what may be called a "hybrid" TFC membrane 10. Nanostructured additives 16 may be considered to be relatively insoluble because, although primarily insoluble, we have discovered that some nanostructured additives may release a small amount of soluble metal ions into solution.
  • mhTMC one of the forms of hydrolyzed TMC that is sometimes present in commercial TMC.
  • impure TMC has been intentionally avoided in the fabrication of TFC membranes, that is, the purity of the TMC is conventionally thought to be of great importance.
  • commercial TMC is not always as pure as promised by the vendors.
  • TFC membranes made with such a controlled amount of some of these impurities may produce substantially better flux characteristics.
  • mhTMC as an additive in combination with nanoparticles to achieve membrane performance that conventional techniques have not been able to provide.
  • such other additives in addition to mhTMC - useful with nanostructured additives to produce a hybrid TFC membrane with improved operating characteristics - include alkaline earth metal complexes and selected other elemental complexes.
  • Aluminosilicate zeolites with a Si:AI ratio less than 1.5:1 may also be useful as nanostructured nanoparticle additives 16, especially if desired for their release of Al species in solution as part of additive 16.
  • Mordenite and ferrierite are examples of zeolites with calcium or magnesium exchangeable counterions that may be useful as nanoparticle additives 16, especially if desired for their release of alkaline earth metal species in solution.
  • additives 16 for relatively insoluble additives -such as nanoparticle additives 16 - may conveniently be described in terms of average hydrodynamic diameter, assuming a spherical shape of the particles.
  • Selected nanoparticle or other additives 16 can have an average hydrodynamic diameter of from about 10 nm to about 1000 nm, from about 12 nm to about 500 nm, and most preferably from about 50 nm to about 300 nm.
  • additives 16 e.g. additives having optimized size, shape, porosity, and/or surface chemistry
  • suitable process and preparation techniques can lead to well dispersed additive solutions which may result in the inclusion of a larger number of additives 16 in the final interfacially polymerized membrane being prepared.
  • Relatively insoluble additives such as nanoparticle additives 16 can exist either as isolated and individual species or as building blocks incorporated in larger aggregate structures when in solution. These aggregate structures can be fairly stable and unchanging such as those formed during synthesis (for instance during calcination of zeolites) or they can be transient structures arising from thermodynamics of the additives and solution.
  • Well-dispersed solutions that is solutions in which additives 16 are well-dispersed, primarily contain isolated and individual particles rather than aggregate structures of such particles. In particular, it may be preferable to use a solution containing primarily isolated and individual particles and very few larger structures such as aggregates. In this manner the largest number of isolated particles can be incorporated within the final membrane and/or serve to optimize the structure of the membrane.
  • polydispersity can be calculated by dividing the volume average particle diameter by the number average particle diameter. A polydispersity approaching 1 indicates a tight range of sizes, while a bigger number indicates a larger range of sizes. Preferred polydispersities are preferably in the range of about 1 to 20, and most preferably in the range of about 1 to 3.
  • centrifuge particles of larger mass have a faster settling velocity and form sediment at the bottom of a container while the remaining particles stay in solution. By removing the remaining liquid or the sediment both a different size and polydispersity can be obtained, e.g. particles having a smaller average size and as well as a smaller range of sizes.
  • microfluidization Another method of improving polydispersity is through the use of microfluidization. For example, using sonication alone on sample of 100nm LTA, may lead to a dispersion with a polydispersity of 62.4, while use of sonication followed by microfluidization using a Microfluidizer® process and centrifugation may lead to a polydispersity of 1.7. A separate sample of 400nm LTA after sonication and microfluidization had a polydispersity of 1.53. Microfluidizer® is a trademark of Microfluidics Corp. of Newton, MA.
  • nanotube additives 16 are provided in the presence of the interfacial polymerization reaction, it may be preferable to include surfactants such as: alkyl poly(ethylene oxide), copolymers of poly(ethylene oxide) and poly(propylene oxide) (commercially called Poloxamers or Poloxamines), alkyl polyglucosides including octyl glucoside or decyl maltoside, fatty alcohols including cetyl alcohol or oleyl alcohol, cocamide MEA, or cocamide DEA, to help disperse the nanotubes. These may also be chosen so as to help align nanotube additives 16 in a specific arrangement. It will be obvious to one skilled in the art to use other nonionic, cationic, anionic, or zwitterionic surfactants to aid in dispersing or aligning the nanotubes, or other relatively insoluble additives 16.
  • surfactants such as: alkyl poly(ethylene oxide), copolymers of poly(ethylene oxide) and poly(propylene oxide) (commercially
  • Nanotube additives 16 may be carbon nanotubes and/or may be made of FeC, titania, WS 2 , M0S 2 , boron nitride, silicon, Cu, Bi, ZnO, GaN, In 2 O 3 , vanadium oxide, or manganese oxide. When carbon nanotube additives 16 are used they may be single or multiwall, and may have a functionalized surface including derivitization with alcohol or carboxylic acid groups. Nanotube length may be from 100nm up to 50 microns, more preferably 100nm to 2 microns, and more preferably 0.5 microns to 2 microns. Nanotube diameter may be less than 50nm, preferably less than 25 nm and more preferably from 1-2nm.
  • Nanotube additives 16 may be thoroughly rinsed, or used as is. When used as is, trace impurities may be present including unreacted carbon precursors and/or carbon in other phases, oxidized materials, nanotube synthesis materials such as cobalt containing compounds, and/or other impurities. Nanotube additives 16 may also be processed before use to make them more beneficial for use in TFC membrane 10. For instance, laser ablation or treatment with a strong acid can be used to shorten the average length of the nanotubes. Ultra-high pressure homogenization, for instance by a Microfluidizer® process, may be used to break up nanotube bundles and to shorten average nanotube length. [000101] In some instances it may be preferred to align nanotube additives 16 within discrimination membrane 24.
  • nanotube additives 16 may be aligned normal to the superficial membrane surface. This can be used for example in situations where transport occurs through the interior of the nanotube and the smallest length of nanotube is desired to minimize resistance to transport. This can be accomplished by utilizing a magnetic catalyst that is incorporated with at least some, and preferably a plurality, of each of the nanotubes of nanotube additives 16. In this case, a magnetic field may be used during the interfacial polymerization to then trap nanotube additives 16 in this configuration. In a similar manner, surfactants may be used to align nanotube additives 16, particularly when used in aqueous phase 14.
  • Suitable surfactants include: alkyl poly(ethylene oxide),copolymers of poly(ethylene oxide) and poly(propylene oxide) (commercially called Poloxamers or Poloxamines), alkyl polyglucosides including octyl glucoside or decyl maltoside, fatty alcohols including cetyl alcohol or oleyl alcohol, cocamide MEA, or cocamide DEA. It may also be possible to use other nonionic, cationic, anionic, or zwitterionic surfactants to aid in aligning the nanoparticles.
  • the preferred alignment may be in the plane of membrane 10. This allows much longer nanotube additives 16 to be used that can impart improved mechanical properties to TFC membrane 10.
  • shear may be applied to the coating solution, for instance by application of the aqueous or organic phases 18 and 14 by a slot die coating method, or a dip coating process. Nanotube additives 16 may be aligned by this method in either the aqueous or organic solution.
  • TFC membranes 10 containing nanotube additives 16 can also have surprising biocidal activity. It appears, in some instances, that partially exposed nanotube additives 16 may be able to pierce, cut or otherwise interfere with the cell walls of microorganisms leading to cell death. In this way, the surface of TFC membrane 10 may exhibit antimicrobial activity.
  • alkaline earth metal additives 16 preferably magnesium (Mg), calcium (Ca), strontium (Sr) and/or beryllium (Be) typically in connection with a complex - e.g., beta-diketonate complexes such as acetylacetonate (acac) - have surprisingly proven very useful as additives 16 to increase flux of resultant TFC membrane 10.
  • Alkaline earth metals as a group provide other advantages because they can be safe, abundant, low cost, and easy to use in processing.
  • Members of this group - including magnesium, calcium, and strontium - are also environmentally benign and can be available as counter ions from zeolite nanoparticles.
  • TMC trimesic acid
  • TMC trimesic acid
  • mhTMC monohydrolyzed trimesoyl chloride - that is, mhTMC - is illustrated in a conventional manner.
  • This form of hydrolyzed TMC may be used directly as additive 16 and/or by the inclusion of partially hydrolyzed TMC in organic phase 18, or both, especially if care is taken to remove or otherwise limit the involvement of di- and/or tri-hydrolyzed TMC species by, for example, filtering organic phase 18 to selectively remove at least some of the aggregate structures formed thereby.
  • mhTMC is illustrated as a molecule of TMC in which one of the -Cl bonded groups has been replaced with a bonded OH group.
  • TMC mono-hydrolyzed TMC
  • mhTMC mono-hydrolyzed TMC
  • mhTMC di-hydrolyzed TMC
  • the ratio of mono and/or di-hydrolyzed TMC to TMC, e.g., in the organic phase layer 18, may preferably be in the range of on the order of about 1.0/100 to 100/100, more preferably from 1.667/100 to 33/100, and most preferably about 1.5/100 to 5/100. Further, the concentration of mhTMC in a mixture of mono- and di-hydrolyzed TMC used as additive 16 is preferably greater than 25%, more preferably at least 75% and most preferably near 100%.
  • a salt of mhTMC additive 16 may be used in place of the acid form.
  • Preferred salts may be those formed from substituted amines such as di-, tri-, or tetra-methyl, ethyl, propyl, or butyl derivatives.
  • Carbonyl chlorides of higher substitution than three may also be di- or higher hydrolyzed, as long as at least 2 carbonyl chloride groups remain allowing polymerization to occur.
  • Nonhydrolyzed variants of these additives may also be used as the reactant in organic phase 18.
  • Preferred concentrations of mhTMC additive 16 are in the ranges from about 0.0025% to 0.1 wt.% and more preferred from 0.005% to 0.1% by wt.%, in organic layer 18.
  • Preferred TMC/mhTMC ratios in organic phase 18 are preferably in the range of less than about 50:1 , more preferably less than about 25:1 , more preferably less than about 15:1 and most preferably less than about 1 :1.
  • cosolvents may also be useful to use cosolvents to better solvate the mhTMC additive.
  • Preferred cosolvents are those that are able to form clear solutions of the mhTMC before dilution.
  • aromatic solvents including benzene, toluene, xylene, mesitylene, or ethyl benzene. These cosolvents are preferably used at sufficiently low concentration to not negatively affect membrane formation or performance.
  • suitable additives 16 may include one or more of the transition metals or other inorganic additives - alone or in combination with nanostructured materials, alkaline earth metals or inorganic additives including hydrolyzed additives such as mhTMC - that are present as an at least partially soluble compound containing a central atom having a Pauling electronegativity of less than about 2.5.
  • hydrolyzed additives such as mhTMC - that are present as an at least partially soluble compound containing a central atom having a Pauling electronegativity of less than about 2.5.
  • suitable alternate additives 16 typically in a complex, e. g., with a beta-diketonate such as acetylacetonate (acac), include aluminum (Al), cadmium (Cd), chromium (Cr), cobalt (Co), copper (Cu), gallium (Ga), hafnium (Hf), indium (In), iron (Fe), at least some of the lanthanoid (Ln) elements, - e.g., praseodymium (Pd), erbium (Er) and ytterbium (Yb) -, molybdenum (Mo), palladium (Pd), phosphorous (P), ruthenium (Ru), Tin (Sn), vanadium (V), and Zinc (Zn).
  • a beta-diketonate such as acetylacetonate (acac
  • a beta-diketonate such as acetylacetonate (acac
  • concentrations of additive(s) 16 are from 0.005 wt.% to 5 wt.% by wt.% or more preferred from 0.05 wt.% to 1 wt.% in either aqueous layer 14 or organic layer 18 - or both.
  • concentration ranges for groups of additive(s) 16 also include from the lowest concentrations - plus or minus 20% - to the highest concentrations - plus or minus 20% - listed in the tables for groups of the same or similar examples where the increased flux is at least 25% and/or the rejection is at least 90%.
  • concentration ranges for groups of additive(s) 16 also include from the lowest concentrations - plus or minus 20% - to the highest concentrations - plus or minus 20% - listed in the tables for groups of the same or similar examples where the increased flux is at least 25% and/or the rejection is at least 90%.
  • Sonication may also serve to drive reactions that would otherwise require higher temperatures, catalysts, or initiators to occur. It may also be useful to apply cosolvents to better solvate the metal complex.
  • cosolvents are those that are able to form clear solutions of the additives 16 before dilution.
  • aromatic solvents including benzene, toluene, xylene, mesitylene, or ethyl benzene. These cosolvents are preferably used at sufficiently low concentration to not negatively affect membrane performance.
  • Suitable additives 16, in addition to nanoparticles or nanotubes, may include salts or compounds that are dissolvable to some extent in either aqueous phase layer 14 or organic phase layer 18 or both to make available the selected elements such as alkaline earth metals, mhTMC or the selected elements from Groups 3-15 of the Periodic Table (IUPAC) available during interfacial polymerization.
  • IUPAC Periodic Table
  • Different species may be dissolved in aqueous phase layer 14 and in organic phase layer 18.
  • Additives 16 may be added in a soluble form or as part of a complex, for example, with a beta-diketonate such as an acetoacetonate, e.g. acac complex.
  • the beta-diketonate may also be fluorinated for instance in hexafluoroacetylacetonate, or trifluoroacetylacetonate, or may include longer aliphatic chains such as in 2,2,6,6- tetramethyl-3,5-heptanedionate.
  • Other examples of appropriate beta-diketonates are well known in the art.
  • one or more additives 16 may be added during fabrication of membrane 10 by preferably being dispersed into aqueous phase 14 and/or organic phase 18 so that the one or more additives 16 present during the interfacial polymerization beneficially alter the polymer structure of the resultant discrimination membrane 24.
  • fabrication analysis of this TFC membrane 10, particularly of discrimination membrane 24 therein, may not be a reliable measure of the concentration or even existence of some additives 16 used in the fabrication of membrane 10.
  • additives 16 - such as nanostructured additives including LTA and other zeolites and nanotubes - are not particularly if at all soluble in aqueous phase 14 or organic phase 18 and are easily detected in the resultant membrane 10, typically in discrimination membrane 24. These additives may be considered detectable additives 16.
  • Alkaline earth metal - and other additive materials discussed herein - may be present during the interfacial polymerization whether added in the form of a complex, e.g., with acetylacetonate, or in a salt or other compound soluble in aqueous or organic phases 14 or 18.
  • alkaline earth metals may be added to organic phase 18 as additive(s) 16 in the form, for example, of Sr(F 6 acac 2 ), Ca(F 6 acac)2, Mg(F6acac)2 or Be(F 6 acac)2.
  • alkaline earth additives may therefore be considered to include Sr, Ca, Mg or Be additive 16 as well as, or as part of an (F 6 acac) or other acetylacetonate additive 16.
  • Sr, Ca, Mg or Be additive 16 as well as, or as part of an (F 6 acac) or other acetylacetonate additive 16.
  • such - perhaps relatively more soluble - additives 16 are often not present in membrane 10 at clearly detectable levels after fabrication. Although the reason is not clearly understood, it is believed that the presence of such undetectable additives 16 during fabrication alters the resultant polymer structure of discrimination membrane 10.
  • the undetectable additive 16 material may be at least partially washed away and/or partially otherwise rendered undetectable (or both) during fabrication processing after effecting the polymer, perhaps in the one or more washing steps.
  • post fabrication analysis may not accurately determine the concentration - or even the presence - of some of the additives 16 and may not be useful for fabrication or quality control purposes.
  • nanostructured materials such as nanoparticles may be combined with many types of other additives 16 including the alkaline earth metals discussed above and/or mhTMC, another undetectable additive.
  • Post-fabrication analysis of membranes 10 formed with such additives will likely detect the presence of the LTA additive 16 while not indicating the actual concentration - or likely not even detecting the presence - of the alkaline earth metal, acetylacetonate, mhTMC additives or another undetectable additive.
  • a zeolite or other nanostructured additive 16 -such as LTA - is selected and pre-processed in accordance with techniques disclosed herein and used as an additive in the fabrication of a membrane 10, the nanostructured additive may release an additional additive, such as a soluble metal species.
  • a soluble metal ion such as Al (or Ga) may be a useful additive 16 when added for example as sodium aluminate, aluminum chloride, aluminum citrate, in a complex with acac or when released for example from LTA and/or both as long as it is present in an appropriate concentration during the interfacial polymerization process.
  • a useful additive 16 when added for example as sodium aluminate, aluminum chloride, aluminum citrate, in a complex with acac or when released for example from LTA and/or both as long as it is present in an appropriate concentration during the interfacial polymerization process.
  • additives 16 including LTA, an alkaline earth metal complex and mhTMC only the LTA may be present in detectable quantities after fabrication. If any of the other additives 16 are detected at all, the detected concentration may well be inaccurate, typically much lower than actually used.
  • % Imp represents the percentage flux increase of membrane 10 made with additives 16 over the same membrane 10 made without additives.
  • Test procedures - such as the use of high purity TMC in organic phase 18 - were used to minimize the effects if any of impurities acting as additives.
  • example 1 represents the control membrane.
  • MPD/TMC Ratio 0.05% LTA was added to aqueous phase 14 and 0.058% Sr(F 6 acac) 2 was added to organic phase 18 as additives 16 and is recorded in the columns headed "Aqueous 14 Additive 16" and Organic 18 Additive 16". In this fabrication, no nanostructured material was added as additive 16 to organic phase 18 as recorded in the column headed Organic 18 Additive 16".
  • the percentage flux improvement for example 52 is not recorded, presumably because the test was used to determine the usefulness of a membrane with the noted additives fabricated with a slightly higher TMC concentration and therefore a resultant slightly lower MPD/TMC ratio.
  • a good approximation of the percentage flux improvement for example 52 can be made by making a control membrane in accordance with the parameters specified herein and, of course, good practice and recording the results.
  • the flux improvement percentage may then easily be determined. If the flux of the new membrane made in accordance with example 2 has a different flux value than as shown in the tables, it is reasonable to use the flux improvement ratio determined as above adjusted for the difference between the flux improvement shown in the tables and the flux improvement shown by the newly fabricated membranes.
  • the need for the use of the flux improvement ratio as a guide to determining the presence and concentration of one or more additives 16 which are not fully detectable by post fabrication analysis of membrane 10, as noted above, results from the fact that most if not all non-nanostructured additives 16 may not be easily, if at all, detected after fabrication.
  • the flux improvement guide may be the only current way to attempt to determine the presence and concentration of a suspected additive 16 in a unknown membrane.
  • the use of the preferred process parameters for making the control and test membrane provide the best current way to estimate the presence of a suspected additive as well as its approximate concentration.
  • Section C Process Techniques. C.1 Techniques for introducing additives 16
  • aqueous phase layer 14 is shown - with additive(s) 16 dispersed therein - on an upper surface of support membrane 12 when interfacial polymerization has - or is about to - occur as shown in Fig. 1.
  • additive(s) 16 are shown dispersed in organic phase layer 18.
  • additive(s) 16 may be included in both aqueous layer 14 and organic layer 18 as shown in Fig. 3.
  • concentrations of additive(s) 16 are from 0.025 wt.% to 0.25 wt.% by weight or more preferred from 0.024 wt.% to 0.18wt.%, or most preferably from 0.05% to 0.15% wt in either aqueous layer 14 or organic layer 18 - or both.
  • additive(s) 16 may also or alternately be introduced via water solution 11 on an upper surface of support 12, typically before contact between aqueous or organic phases 14, 18 in order to be present during the interfacial polymerization.
  • Water solution 11 may be, at least in part, a layer between aqueous phase 14 and support membrane 12 which may be in liquid communication with both aqueous layer 14 and the water wetted surface of support membrane 12.
  • Additives 16 may also be introduced, in order to be present during the interfacial polymerization, by any other convenient technique.
  • hydrolyzed additives may be introduced by direct addition to - or by using a compound including such hydrolyze additives 16 - as part of the fabrication process.
  • mono- and/or di-hydrolyzed TMC may be used in organic phase 18 to introduce hydrolyzed TMC additives 16 to the interfacial polymerization reaction.
  • membrane 10 may include additives 16, such as partially soluble nanostructured materials and the like, in discrimination membrane 24.
  • additives 16 such as partially soluble nanostructured materials and the like
  • discrimination membrane 24 is indicated as including additives 16, for convenience even though at least some of additives 16 may not be detectable in discrimination membrane 24 after fabrication.
  • additive 16 present during interfacial polymerization between organic and aqueous phases 18,14 may be removed- e.g., by washing or later processing - or may simply be present in quantities too small to detect with current techniques available to us - or may not be present at all.
  • Hydrolyzed additives 16, such as mhTMC are believed to be absorbed or converted to another molecule during inter
  • Fig. 8 illustrates the presence of additives 16 in membrane 24, which indicates at least that at least some additive 16 was present during interfacial polymerization.
  • additives 16 shown piercing or at the upper and lower surfaces of membrane 24 indicate additives 16 which are detectable at these locations.
  • Fig. 9 indicates the use of additives 16 during the fabrication of discrimination membrane 24 - some of which may or may not be detectable after production - as well as additives 16 present and detectable at the interface between membrane 24 and support membrane 12 after production.
  • FIG. 10 a technique is described which permits the fabrication of support 12, at least in a laboratory setting, which includes additives in this layer.
  • additives 16 may be detectable after fabrication in support layer 12 or not.
  • a similar technique may also be used to include additives 16 in fabric layer 20, depending upon the construction of fabric layer 20.
  • additives 16 such as nanostructured, alkaline earth, and other specific additives 16, described herein may also or alternately be incorporated into support membrane 12 by including such additives with casting solution 13 used to prepare support membrane 12 on fabric 20 on glass plate 15 - and/or by including additives 16 within the non-solvent, e.g., Dl water, used to induce phase inversion during fabrication of support membrane 12.
  • Glass plate 15 may conveniently be used in a laboratory setting but would likely not be used in a continuous coating process for fabricating support membrane 12.
  • Porous support membranes 12 are typically kept wet until use.
  • the amount of metal ion or other additives 16 introduced to the interfacial polymerization reaction between aqueous phase 14 and organic phase 18 may, in some cases, be increased by storing support membrane 12, e. g., in roll form, for a suitable time period such as at least one hour before fabrication of TFC membrane 10.
  • metal ion or other soluble additive 16 may also be important to allow sufficient time for metal ion or other soluble additive 16 to diffuse from a source such as support membrane 12 - e. g., into aqueous phase 14 - before or during interfacial polymerization.
  • a time of between 2 seconds and 5 minutes, and preferably between 10 seconds and 2 minutes is currently believed to be suitable for such diffusion so that metal ion additives 16 - for example from nanoparticle additives 16 - may be introduced to the interfacial polymerization reaction to impact the polymer structure of resultant discrimination layer 24 and improve performance of TFC membrane 10 by, for example, by increasing water flux there through for the same applied pressure.
  • Processing may include selecting nanostructured additives 16, such as other inorganic mineral compounds for other characteristics including solubility.
  • a nanostructured additive 16 may also be selected for its ability to release further additives 16 into solution, such as soluble metal species, based on the degree of crystallization of the additive.
  • Amorphous portions of nanoparticle additives 16 are typically more soluble than crystalline portions of the nanoparticle and processing can further increase solubility.
  • the amount of crystalline material can be determined through several techniques including x-ray crystallography.
  • nanoparticles or other additives 16 may be pre-process by using sonic energy from a sonic probe or sonic bath before incorporation thereof in support membrane 12 and/or further sonicate either aqueous phase 14, organic phase 18 or both just before or during interfacial polymerization.
  • Sonication of additives 16 may include immersing a sonic probe directly into casting solution 13 from which support membrane 12 is formed and/or placing solutions with additives 16 in a vessel and immersing the vessel in a sonic bath.
  • Solutions may be subjected to sufficient sonic energy from 10 to 60 minutes, more preferably about 30 minutes, to aid in the release for example of metal species additives 16, such as aluminum or alkaline earth metal ions 16, into the solution. Increased sonication time may release additional metal species additives 16 into solution up to some equilibrium limit.
  • Processing of selected nanoparticles or other additives 16 may also be accomplished using shear, cavitation, and impact forces generated by 1 to 60 minutes in a Microfluidizer® process. After processing, the solution may contains additional metal species that were dissolved, for example, from nanoparticles 16.
  • Processing of selected nanoparticle or other additives 16 may be also accomplished using a solution containing additive 16 in a vessel with a stir bar and using a stir plate to propel the stir bar in the solution or alternatively using a motorized propeller to stir the solution or alternatively using a laboratory tray shaker. Stirring or shaking may be most effective for nanoparticle or other additives 16 selected for high solubility in either the aqueous or the organic phases 14, 18 or both.
  • processing of selected nanoparticle or other additives 16 may also or solely be accomplished in a vessel containing a solution of additive 16 and adjusting the pH either lower than about 6 and more preferably lower than about 5 for at least 30 seconds, and/or to a pH greater than about 8 and more preferably greater than about 9 for at least 30 seconds. Whether pH is adjusted higher than about 8 or lower than about 6 may dependent on the solubility characteristics of the specific type of nanoparticle or other additive16.
  • Processing may assist in achieving the desired concentrations of additives 16 in solution.
  • additives 16 may have been broken or partially dissolved using shear, cavitation, or impact forces to maximize said soluble metal or other species introduced to the interfacial polymerization mixture.
  • Nanoparticles or other relatively insoluble additives 16 may be calcined for at least 1 hour at 200° C or more.
  • the processed additives can have been shaken in aqueous solution on a shaker table for at least 1 minute.
  • Nanoparticles or other relatively insoluble additives 16 may also have been processed with heat in a solution for at least 5 minutes at a temperature of 40 0 C or more. Nanoparticles or other relatively insoluble additives may have been processed with chelating agents in solution to bind soluble metal species or other atomic or molecular additives.
  • TMC purity of the TMC is supposed to be of paramount importance
  • TMC with a lower purity - e. g. partially hydrolyzed TMC - in organic phase 18 often has the beneficial effect of producing membranes, such as RO membranes 10, with substantially higher flux while maintaining rejection characteristics.
  • performance of TFC membrane 10 can also be improved by rinsing. This may be done in a high pH aqueous solution after TFC membrane 10 is formed.
  • membrane 10 can be rinsed in a sodium carbonate solution.
  • the pH may preferably be from 8-12, and exposure time may vary from 10 seconds to 30 minutes or more.
  • the rinse may alternately be at low pH to aid in removal of unreacted amine. This pH may, for example, be from pH 2 to pH 5.
  • the rinse may alternatively be at a neutral pH.
  • the rinse may alternatively be a hot water rinse with temperatures of 60°- 98° C.
  • the rinse may also include a chlorine species such as sodium hypochlorite at a concentration in the range of about 500 to about 2000 ppm.
  • the rinse may also include separate steps where combinations of the above rinse conditions are used sequentially. After rinsing the membrane may be dried, or may be left wet.
  • hydrophilic polymer layer 30 as shown in Fig. 6 may be applied to the surface of membrane 10.
  • a solution of polyvinyl alcohol in water may be applied to the surface of membrane 10 followed by a heat cure to produce layer 30.
  • the ratio of MPD to TMC may be another important factor in the preparation of high flux, high rejection, low fouling TFC membranes, particularly with additives 16, and combinations of additives 16, as described herein.
  • the preferred range is less than a ratio of about 35 for use in conjunction with the TMC concentrations discussed above, more preferably less than 25 and even more preferably less than about 15.
  • a most preferred ratio is about 13 for MPD/TMC on a wt% to wt% basis.
  • Fig. 12 after synthesis of purified mhTMC, the resultant product can be dissolved in deuterated toluene or deuterated acetone for further analysis.
  • the compound identity and purity of mhTMC can be verified through the use of 1 H-NMR as shown for example in this figure, which is a graphical representation of an analysis by this process of mhTMC.
  • the doublet at 8.6 ppm is believed to correspond to the two aromatic ring protons adjacent to both a carbonyl chloride and a carboxylic acid group.
  • the integrated area of this peak, 1.99, is twice that of the triplet at 8.4 ppm because there are two protons.
  • the triplet at 8.4 ppm corresponds to the single aromatic ring proton between two carbonyl chloride groups. Purity of this compound can be checked by comparing the integrated area of these protons versus those of the non-hydrolyzed TMC, di- hydrolyzed TMC, and trimesic acid compound identity and purity of the mhTMC was verified with 1 H-NMR of the isolated solid. The NMR process was run in deuterated toluene.
  • the purity of the synthesized mhTMC additive 16 may be estimated from the NMR spectra. Crude and purified mhTMC is dissolved in deuterated toluene for the NMR analysis. The purity calculation may be performed by looking at the relative quantities of trimesic acid, 1 ,3,5-Benzenetricarbonyl trichloride, monohydrolyzed TMC and di-hydrolyzed 1 ,3,5-Benzenetricarbonyl trichloride. These values may then be reduced by any extraneous NMR peaks which usually impurities from the synthesis.
  • Fig.s 13 and 14 membrane performance is illustrated graphically as a function of the concentration of mhTMC additive 16, adjusted for purity.
  • Examples 169-171 and 173-182 for mhTMC reflect the concentration of the synthesized mhTMC additive 16 used for these tests, and indicates the source of the mhTMC, i.e. synthesized lots 1 or 2.
  • lot 1 flux curve 32 illustrates the growth of flux for increasing concentrations of mhTMC additive 16, lot 1 , from 0%, representing the control membrane, to 0.025 wt%.
  • Lot 1 rejection curve 34 shows the corresponding rejection characteristics for the same concentrations.
  • Fig. 14 shows the most useful portion of the mhTMC concentration range shown in Fig. 13 - from 0% mhTMC to 0.015 wt% for mhTMC lot 2.
  • lot 2 flux curve 36 shows the growth of flux for membranes made with mhTMC lot 2
  • lot 2 rejection curve 38 illustrates the decrease in rejection over this range of concentrations.
  • the curves in Fig.s 13 and 14 have been adjusted for the purity of the synthesized mhTMC.
  • the data for lots 1 and 2 have been adjusted for the estimated concentrations of synthesized mhTMC based on an NMR assay, including simple percentage of materials dissolvable in toluene.
  • the purity was estimated to be about 80% pure mhTMC - the remaining 20% believed to be primarily di-hydrolyzed TMC - while in Fig. 14 for mhTMC lot 2, the purity was estimated to be about 25% pure mhTMC, the remaining 75% was believed to be primarily di-hydrolyzed TMC.
  • the curves have been scaled so that the curves for both lots 1 and 2 represent 100% pure mhTMC so they can be compared.
  • graph lines or curves 40 and 42 also represent the flux and rejection of membranes 10 for lot 2 mhTMC where organic phase 18 was filtered to remove larger contaminant structures believed to be the result of di-hydrolized TMC included with the mhTMC of lower purity. Any tri-hydrolized TMC present in either lot would likely have not been soluble and would have precipitated out of the mhTMC solution.
  • lot 1 flux curve 32 showed an increasing flux from 24 GFD at 0% concentration, i.e., at the control membrane concentration, to about 32.1 GFD at about 0.0075% concentration.
  • the rate of growth of flux decreased at the concentration which has been marked with line 44, vertical deflection axis A discussed below.
  • the flux continued to improve with increased concentration, but at a slightly slower rate, until the flux reached 39.7 GFD at the concentration which has been marked with line 44, vertical deflection axis B at about 0.0215% adjusted mhTMC concentration.
  • Further increased flux concentration beyond deflection axis B, line 46 caused dramatically increasing flux up to 45.1 GFD at 0.2050% adjusted concentration.
  • Deflection axes A and B are simply vertical lines drawn on the graph to indicated concentrations at which the effects of additive 16, in this case mhTMC additive 16, appear to change.
  • concentration of additive 16 in this case mhTMC additive 16 appear to change.
  • the flux for membranes 10 made with the indicated concentrations of additive 16 from 24 GFD to 32.1 GFD is shown as the concentration of additive grew is increased from 0 wt% (control membrane) to .005 wt%.
  • the rate of growth of flux in this area was therefore roughly (32.1-24)/.005 ⁇ 1 GFD per .001 wt% increase of additive 16.
  • points along membrane characteristic curves 32, 34, 36, 38, 40 and 42 which intersection lines 44, 46 and 48, deflection axes A and B, indicate that the rates of increase or decrease changed for both flux and rejection at these points, i.e., these deflection points are concentrations at which a feature, such as the second derivative of flux growth and rejection, changed. These deflection points may also be considered non-linearities.
  • the fact that both flux and rejection rates of growth changed in an unusual way at the same concentration points appears to be significant is likely an indication that there was a change in the effect of the presence of additive 16 e.g., mhTMC, on interfacial polymerization, at these concentrations.
  • additive 16 e.g., mhTMC
  • the rejection characteristics of the higher purity of mhTMC lot 1 were very good at the 0% concentration of the control membrane at 99.7% rejection.
  • the membrane rejection was still very good at about 99.60% for the membrane 10 fabricated with mhTMC additive 16 having about 0.0075% adjusted mhTMC concentration.
  • the rejection continued to decrease to 98.60% at 0.02125% at deflection point B along deflection axis B after which it decreased dramatically to 96.20% at about 0.0250% concentration.
  • a first major linearity e.g., in the rate of growth of flux with increasing concentrations of additive 16 occurred in range including axis A, line 44, indicated as area 25 in the figure.
  • This particular graph was drawn with limited data points, but the graph shown in Fig. 14 was drawn with additional data points to clarify this discussion.
  • the optimum point for the parameters of membrane 10 required for a particular task may have to be determined by experimentation and may depend on the proposed use for membrane 10. For example, if rejection lower than about 97.6% was acceptable for a particular filtering task, increased flux could be obtained by increasing the concentration of additive 16. Alternately, if higher rejection was required, the concentration could be lowered.
  • membrane 10 could be fabricated with 0.0050% additive mhTMC 16 to have a flux of about 30.0 GFD and a rejection over about 99.6% or at 0.01% adjusted concentration to have a flux of about 33.5 GFD with a rejection of about 99.35%.
  • Detection and analyses of the deflection points or non-linearities in the effect on increasing additive concentration may be useful in determining the value of a particular additive when such non-linearities occur generally at the same concentration levels, improvements for example in preprocessing of additives 16 which tend to reduce the impact of such non-linearities and of course the selection of an appropriate concentration level for a particular additive 16 - including combinations of additives - for a particular task.
  • concentration levels of additives 16 are found at which these non-linearities occur in both flux in rejection, and particularly at multiple levels of purity of additive 16, the materials included in additive 16 is a very likely a good candidate as an additive which can repeatably be used to fabricate membranes 10 with superior performance.
  • lot 2 flux curve 36 adjusted to reflect an estimated 25% concentration of pure mhTMC but not filtered, showed an increasing flux from the control membrane concentration of 0% mhTMC of 17.2 GFD, growing dramatically to about 36.2 GFD at about 0.00250% adjusted concentration and then growing to 35.5 GFD at which the rate of increase in flux growth leveled off, reaching about 36.4 GFD at lot 2, deflection axis A 48. Thereafter, the rate of flux increased and then slowly until flux reached about 38 GFD at about 0.0150% adjusted concentration.
  • filtered lot 2 flux curve 36 indicates that the flux increased linearly, from 17.2 GFD at 0% concentration, generally at the same rate of increase the resulted from increasing concentration of the higher purity of mhTMC from lot 1 to 26.4 GFD at deflection axis A of 0.0075% adjusted mhTMC concentration.
  • the increasing flux rose to substantially the same increasing flux shown by the graph line of lot 2, unfiltered, at about 31.9 GFD at 0.0150% adjusted concentration.
  • the fact that the lot 2 adjusted and filtered flux growth curves 36, 40 substantially join each other at a concentration of about 0.015% indicates good consistency in these test results.
  • deflection point A that is the point at which additional increases in additive 16 concentration produces a greater rate of loss in rejection characteristics - indicates a generally optimum concentration of additive 16, providing membrane 10 with both a high flux and a high rejection. Lower concentrations improve rejection at the cost of flux while higher concentrations improve flux at the cost of rejection.
  • Deflection point B the point at which increased concentration then produces an even greater rate of loss of rejection - indicates a possible defect in the polymer matrix structure of discrimination membrane 24 and should be avoided for most if not all applications of membrane 10.
  • deflection points A and B are believed to work the same way for other additives 16, not just mhTMC additive 16.
  • the unintentional use of additional, partially hydrolyzed TMC as a result of using less pure TMC for example in organic phase 18, may result in operation in contaminants area 50, along a line similar to flux curve 26 where the increased concentration of additive 16 does not produce a well controlled increase in flux.
  • This may be particularly unsatisfactory when the level of TMC contamination causes area 50 to include deflection point B. That is, when the contamination of TMC, i.e., with mhTMC or di-hydrolyzed mhTMC causes the concentration of additives 16 to exceed deflection point B so that damaged discrimination membranes 24 are produced.
  • Fig.s 13 and 14 illustrate our findings that the flux and rejection curves for concentrations of various useful additives 16 are typically relatively well behaved - that is, they change slowly and smoothly - from control membrane concentration (0%) to a concentration at which the polymeric structure of membrane 24 may have been damaged by the presence of too much additive 16 during interfacial polymerization.
  • Lot 2 flux and rejection curves 36 and 38 are shown at a series of concentrations to illustrate the fact that the rate of change of flux and growth -i.e., the 2 nd derivative of these membrane characteristic values - change at multiple concentrations within the range of concentration that may be used for fabricating membrane 10.
  • the concentrations used for flux and rejection for lot 1, and filtered lot 2 are only shown at a few points along flux and rejection curves 32, 34 and 40, 42 to illustrate the relatively smooth changes in the rates of growth and decrease of flux and rejection from additives 16 which are not substantially effected by contaminates. This relatively dramatic difference is very useful in selection of an appropriate concentration for additive 16 for commercial fabrication of membrane 10, that is, fabrication which will produce predictable and controllable membrane characteristics under a wide variety of environmental conditions encountered in a fabrication facility.
  • a concentration of additive 16 for use in a common task for membrane 10, e.g., for use in reverse osmosis (RO) of brackish or saltwater to produce pure or drinking water as shown above for example in Fig.s 5 and 6, would typically be a concentration at which the flux is higher than the flux of the control membrane which retains a rejection of perhaps 99.5%.
  • a concentration of perhaps 0.0025% would likely be selected which provides resultant membrane 10 with membrane characteristics of 32.6 GFD and 99.45%.
  • a fabrication facility may chose a concentration of 0.005% to get the benefit of the higher 35.5 GFD even though the slightly lower 99.24% rejection might not meet the desired water purity.
  • concentrations may be chosen from either of these concentrations, however, would likely encounter problems with repeatability and other fabrication limitations.
  • the fabricator By using the techniques described herein, namely determining the effect of contamination and identifying deflection point A, along axis line 48, the fabricator would have the ability to select the 0.0075% concentration for additive 16, and perhaps with contaminant removal, fabricate membrane 10 with membrane characteristics of 33.2 GFD and 99.56% rejection under a wide range of conditions.
  • insoluble additives such as nanostructured materials, e.g., nanoparticle or nanotube additives 16
  • insoluble nanostructured additives such as nanoparticles or nanotubes
  • the insoluble nanostructured additives, such as nanoparticles or nanotubes, are also believed to be primarily responsible for increased resistance to fouling because at least a detectable concentration of the nanoparticles remain in membrane 10 after fabrication while detectable levels of many if not all.
  • TMC mono- or di-hydrolyzed TMC
  • organic phase 18 may permit an increased membrane flux, perhaps at the loss of some control of the fabrication process unless filtered.
  • Additives 16 are believe to assist, template and or otherwise alter the formation of the polymer matrix during interfacial polymerization to achieve the desired membrane performance characteristics.
  • Some additives 16, such as nanoparticles and nanotubes are relatively insoluble materials and may alter the structure of the polymer matrix by physical interference, perhaps as the polymer matrix is formed around such insoluble materials to incorporate them in the matrix. This incorporation can lead to additional flow paths either through or around nanostructured materials or nanoparticle additives 16 leading to increased flux, or by other mechanisms increase the ability of the resultant polymer matrix film to permeate water and retain or reject solutes.
  • the diameter of such flow paths must be of kept of appropriate size to reject desired impurities.
  • the impact on the polymer structure of the incorporated additives 16 can occur in the area up to 10 nm, 1 micron, and even up to 100 microns from a particular nanoparticle additive 16. In such a way, dramatic increases in flux can be obtained by relatively few incorporated nanoparticle additives 16.
  • additives 16 such as relatively insoluble nanoparticles may be located at the interface between support membrane 12 and thin polymer film of discrimination layer 24 whether or not they are included in discrimination layer 24.
  • additives 16 such as relatively insoluble nanoparticles, can reduce the resistance of flow by creating channels and flow paths between discrimination layer 12 and the microporous pores at the surface of support membrane 12. Because of the relatively low density of pores at the surface of the microporous support membrane 12, reducing the resistance at this location can increase the membrane permeability of RO membrane 10 while maintaining the rejection characteristics.
  • additives 16 which may be detected in membrane 24 after fabrication may enhance fouling resistance. These relatively insoluble additives 16 may be useful by altering surface characteristics of resultant discrimination membrane 24, for example to make membrane 24 more hydrophilic than a corresponding control membrane made without such additives 16. This hydrophilicity may further be increased by the addition of hydrophilic polymer layer 30 shown in Fig. 6, for example, formed by a polymerized layer of polyvinyl-alcohol on the surface of membrane 24.
  • the area to the left of the concentration identified as deflection point A may be the range of concentrations in which additive(s) 16 disclosed herein promote increased flux while some remaining contaminants, such as hydrolyzed TMC - to the extent they effect the formation or structure of the interfacially polymerized discrimination membrane 24 - may serve to more or less increase flux without substantially reducing rejection.
  • This area may be called a "contaminant improved flux" zone.
  • the effect of such contaminants - if any - may have less beneficial effect on flux but begin to be more detrimental to the rejection characteristics of membrane 10 and called a "contaminant reduced rejection" zone.
  • a concentration level may be reached, shown in Fig. 13 as deflection point B at 0.02125% adjusted concentration and along flux and rejection curves 36, 38 for filtered lot 2 additive 16 at about 0.0115% concentration at which such contaminants increase the passage of both pure water and materials to be rejected indicating damage or other detriment to membrane 24.
  • mhTMC additive16 when used, in particular in organic phase 18, the mhTMC may react - e. g. with metaphenylene-diamine - during the interfacial polymerization to increase the hydrophilicity of resultant polymer discrimination layer 24. It is thought that mhTMC 16 may react with the polyfunctional nucleophilic monomer and may be incorporated along with non-hydrolyzed polyfunctional acyl halide. Either during the interfacial polymerization, or once the polymer matrix is formed, the hydrolyzed acid group present in this reactant may interact with terminal amine residuals on the polyfunctional amine reactant forming ionic cross-links.
  • Such ionic cross-links may increase the hydrophilicity of the polymer matrix relative to a polymer matrix containing amide cross-links exclusively, and thus promote increased water uptake and flux. At the same time, rejection may be maintained by virtue of the electrostatic interactions between the charged group, which is stabilized relative to normal electrostatic interactions, by the rigidity of the cross- linked aromatic backbone keeping the two charged centers close to each other.
  • the ionic crosslink may also allow a slight expansion of the matrix relative to a covalent bond increasing water uptake.
  • Aqueous Phase 14 An aqueous solution of MPD, 4.5 wt% of triethylammonium camphorsulfonate (TEACSA) and 0.06 wt% sodium lauryl sulfate (SLS) in Dl water was prepared.
  • TEACSA triethylammonium camphorsulfonate
  • SLS sodium lauryl sulfate
  • Organic Phase 18 An lsopar G® solution with TMC was also prepared and sonicated for 10 minutes, lsopar is a trademark of Exxon Corp.
  • Additive(s) 16 A homogenous solution of each of the additive(s) was added to - and/or dissolved in - either the aqueous phase, the organic phase or both.
  • aqueous phase additive(s) either the solid nanoparticle or an aqueous dispersion of nanoparticles, when used, was added to the aqueous phase.
  • organic phase additive(s) the additive was dissolved in an aromatic cosolvent e.g. xylene or mesitylene. Final concentration of the cosolvent was 4 wt% by wt. %.
  • mhTMC when used, was added to TMC in the organic phase and the lsopar solution was allowed to sit for 1 hour before use. Nanoparticles, when used, were added to the TMC and sonicated for 30 minutes.
  • Support membrane 12 A piece of wet polysulfone support was placed flat on a clean glass plate. An acrylic frame was then placed onto the membrane surface, leaving an area for the interfacial polymerization reaction to take place.
  • Discrimination membrane 24 Approximately 50 mL of the aqueous MPD solution was poured onto the framed membrane surface and remained for 1 min. The solution was drained by tilting the frame till no solution dripped from the frame. i) The frame was taken off, and was left horizontally for 1 minute. The membrane was then clamped with the glass plate in four corners. An air knife was used to finish drying the membrane surface. The membrane was reframed using another clean and dry acrylic frame and kept horizontally for 1 min. ii) Approximately 50 mL of the organic solution was poured onto the framed membrane surface and remained for 2 minutes. The solution was drained by tilting the frame (vertically) till no solution dripped from the frame. The acrylic frame was removed, and the membrane was kept horizontally for 1 minute. The membrane was then dried at 95° C for 6 minutes.
  • Membrane performance may be measured in a flat sheet cell test apparatus. Testing may be conducted at a Reynolds number of 2500, so that build up of rejected solutes at the membrane surface leads to a concentration preferably no more than 10% higher than that in the bulk. All testing may be performed on 32,000 ppm NaCI in tap, deionized (Dl) or RO water, at 25 0 C and 800 psi. Membranes may be run for 1 hour before performance characteristics (e.g. water flux and salt rejection) are measured.
  • performance characteristics e.g. water flux and salt rejection
  • Contact angles may be those of Dl water at room temperature. Membranes may be thoroughly rinsed with water, and then allowed to dry in a vacuum desiccator to dryness. Membranes 10 may be dried in a vertical position to prevent redeposition of any extracted compounds that may impact contact angle. Due to the occasional variability in contact angle measurements, 12 angles may be measured with the high and low angles being excluded and the remaining angles averaged.
  • Flux Improvement The percentage of flux improvement may then calculated relative to a control membrane made with the same concentration of MPD and TMC, with no nanoparticles or additives, as the increase in GFD divided by the GFD of the control.
  • an aqueous dispersion of nanoparticle additive 16 including LTA having a nominal 150 nm diameter, was sonicated for 30 minutes and added to aqueous phase 14.
  • the resultant TFC membrane 10 provided an almost 80% increase in flux over the control membrane.
  • the aqueous dispersion of nanoparticle additive 16 including LTA having a nominal 300nm diameter, was added to aqueous phase 14 in a commercial continuous process system.
  • the final solution turbidity was 21 nephelometric turbidity units (NTU).
  • NTU nephelometric turbidity units
  • aqueous dispersion including 0.2 wt% of sodium lauryl sulfate (SLS) and nanoparticle additive 16 having 0.05% LTA with a nominal 80 nm diameter, was sonicated for 30 minutes and then added to aqueous phase 14.
  • Resultant TFC membrane 10 showed only a 9% improvement in flux over a control membrane.
  • an aqueous dispersion of LTA nanoparticles 16 was prepared by sonicating a 5% solution of LTA in water for 5 minutes, followed by 20 minutes of microfluidization, and stirring overnight. The dispersed LTA solution was then added to aqueous phase 14 having 0.2% SLS to produce TFC membrane 10 which showed a 40% increase of flux over a control membrane.
  • nanoparticle additive 16 in an aqueous dispersion in 500 ml of Dl water, were tested at room temperature of approximately 20 0 C for release of Al on a laboratory shaker table, as follows:
  • TFC membranes 10 were prepared with nanoparticle additives 16 - having differing Si:AI ratios - tested and yielded different flux performances. Each TFC membrane 10 was produced with an aqueous solution including 0.2 wt.% SLS in Dl water contained of zeolite nanoparticle additive 16 which had been sonicated for 30 minutes before use.
  • TFC membrane 10 made with a 0.25% Al (acac) 3 nanoparticle additive 16 dispersed in an lsopar G® solution with 0.3 wt% TMC in organic phase 18 which yielded a contact angle of 25.2° with Dl water, a substantial improvement over the 52.9° contact angle of a control membrane.
  • TFC membrane 10 was made with a 0.1% Al (acac) 3 additive 16, dispersion in an lsopar G® solution with 0.3 wt% TMC in organic phase 18 and was successfully tested in flat cells on pretreated seawater taken from the Pacific Ocean and yielded a 60% flux improvement over a similar control membrane.
  • citric acid was added to the amine in the sodium aluminate example 99 above to bring the pH to the range of 7.5-9.
  • Membrane 10 yielded a flux increase of 45%. The control did not require any acid addition.
  • organic phase 18 included a hexane solution with nanoparticle additive 16 - 0.3% AICI 3 - which was sonicated for 60 minutes before use in fabricating TFC membrane 10. A 15% flux improvement was noted.
  • RO membrane 10 was made in accordance with example 159, except that nanoparticle 16 included 0.2% Al (acac) 3 .
  • TFC membrane 10 was then rinsed in a 0.2% sodium carbonate solution before testing and yielded a flux improvement of 22% over its control membrane which was not rinsed in the sodium carbonate solution to evaluate the effect of this rinsing.
  • membrane 10 was fabricated in accordance with example 103, except organic phase 18 was only sonicated for 10 minutes. A flux improvement of 57% was noted.
  • membrane 10 was fabricated in accordance with example 159, except organic phase 18 was mechanically stirred for 60 minutes. A flux improvement of 20% was noted over its control membrane which was not stirred. A second control membrane was also made which was mechanically stirred for 60 minutes to test the benefits of stirring and a contact angle improvement from was noted over the first control membrane from 52.9° to 25.2°.
  • nanoparticle additive 16 e.g., template-free zeolite LTA nanoparticles in an aqueous dispersion - were found to have aluminum content after being subjected to impact, cavitation and shear forces in a microfluidizer.
  • the dispersion contained approximately 39 wt.% percent LTA made with double distilled water. When measured using ICP analysis, the solution had an aluminum content of 130.9 parts per million (ppm).
  • TFC membrane 10 was made in accordance with example 159 except that inorganic additive 16 - 0.075% Ga(acac) 3 - was used in organic phase 18. Contact time for aqueous and organic solutions were about 15 seconds. The flux improvement compared to the control was 43/22.7 or 89%.
  • example 184 is based on other experiments in which 0.1 % of nanoparticles zeolite LTA, was added to the organic phase before interfacial polymerization or IFP with an aqueous phase to produce a discrimination layer on a support layer and form a thin film nanocomposite or TFC membrane.
  • Membranes were prepared using general procedures. Membranes were run on a feed solution of Dl water with 32,000ppm of a salt blend formulated to simulate natural ocean water (Instant Ocean®). Temperature was maintained at 25° C and a pressure of 800 psi was used throughout testing. No filtration was used during this test allowing inorganic and organic colloids to recirculate through the system and biological material to grow. Performance data was taken 1 hr after testing began and again 47hrs later after continuous operation.
  • Example 183 shows that a particular additive 16, Ga(acac) 3 , provided a reasonable total flux of 30.8 GFD, which provided a flux improvement of about 36% over a control without additives and maintained a very good salt rejection of over 99.5%.
  • the Ga additive membrane showed a poor flux performance after 47 hours of fouling testing, losing almost half of its flux capacity.
  • Example 185 illustrates one of the benefits of a hybrid TFC membrane approach in which nanoparticles, such as LTA are combined with molecular additives, such as Ga(acac) 3l to form an improved hybrid TFC membrane with qualities superior than are provided by either additive separately.
  • the hybrid LTA Ga membrane provided 31.9 GFD flux, an improvement of about 41% more than the control with only slight loss in salt rejection.
  • the further increase in flux is on the order of an addition 14% when compared to the 36% flux increase of the Ga(acac) 3 additive.
  • the flux rate after the 47 hour test was 27.3 GFD, i.e. the flux loss was only 17% after the 47 hour test.
  • the hybrid TFC membrane has substantially the flux improvement of its soluble additive, in this case the Ga(acac) 3 , and the fouling resistance of the LTA nanoparticles.
  • Hybrid membranes that is, membranes with nanoparticles, and additives such as soluble ions, organometallic compounds, inorganic additives with or without ligands, and/or mhTMC enable a new degree of design flexibility to improve the overall flux, rejection, and fouling properties of membranes.
  • the several cases discussed below are meant to illustrate the range of benefits that can be realized through the application of hybrid membrane technology and are not meant to limit the scope of this application which is provided by the issued claims.
  • a hybrid membrane including both nanoparticles and other selected materials such as earth alkaline metal complex in additive 16 may provide a useful level of improvement of membrane operational characteristics, e.g., flux, rejection and flux improvement, over the use of a single material in additive 16.
  • a 0.05% concentration of LTA to the lsopar G® based organic phase before contact during IFP with the aqueous phase yields a nanocomposite TFC membrane with a 22.6 GFD flux, equal to that of the control membrane, but a salt rejection of 98.77%, lower than the 99.68% of the control membrane.
  • a membrane made with LTA and the Ca additive in the lsopar® based organic phase yields a nanocomposite hybrid TFC membrane having 34.4 GFD flux, a 52% flux increase over the control membrane without additives but with good salt rejection of 99.03%.
  • a nanocomposite TFC membrane with 0.05% LTA additive in the aqueous phase may yield a flux of 26.2 GFD, a 10% flux improvement over a control membrane without nanoparticle as well as a 99.17% salt rejection, below the 99.68% rejection of the control membrane
  • a TFC membrane with 0.02% mhTMC additive in the organic phase may yield a flux of 29.5 GFD having a 31 % flux improvement over a control membrane without additives as well as a 99.24% salt rejection, also below the rejection of the control membrane.
  • hybrid TFC membrane 10 with both the LTA and mhTMC additives may yield a flux of 30.7 GFD, yielding a better flux improvement of 36% and, perhaps more importantly, a substantially improved salt rejection of 99.63%, much closer to the 99.68% salt rejection of the control membrane.
  • a concentration of a particular nanoparticle in this case a 0.05% concentration of zeolite LTA, in aqueous phase 14 before contact with organic phase 18 for interfacial polymerization to form a nanocomposite TFC membrane providing 26.2 GFD at a 99.17% flux rejection.
  • the flux rate provides a 16% improvement over a control membrane made without the nanoparticle additives, which may be useful in some cases especially in light of the other benefits of nanoparticles. However, substantial further additional flux improvement is often desired.
  • an earth alkaline metal additive such as a 0.058% concentration of Sr(F 6 acac) 2 in organic phase 18, before contact with aqueous phase 14, may produce a TFC membrane yielding a 29.7 GFD flux rate, which at 31% has roughly double the 16% flux improvement of example 25 in the table, but provides only an additional 3.5GFD.
  • Including a combination of the LTA and strontium additives in additive 16 may yield a hybrid nanocomposite TFC membrane with improved membrane operation characteristics.
  • 0.05% LTA in additive 16 in aqueous phase 14 and 0.058% Sr(F 6 acac) 2 included in organic phase 18 yields membrane characteristics of 36.8 GFD flux rate - a 63% improvement over a control membrane - while providing an extremely good salt rejection of 99.57%.
  • the 36.8 GFD is a 10.6 or 3.8 GFD improvement over the examples described using only one additive material in additive 16. Further improvement in membrane characteristics made be found by selections of different additive materials and/or concentrations and/or use of specific additive materials in the aqueous or organic phases.
  • a nanocomposite TFC membrane with 0.05% LTA additive in the aqueous phase may yield a flux of 26.2 GFD, a 10% flux improvement over a control membrane without nanoparticle additives as well as a 99.17% salt rejection, below the 99.68% rejection of the control membrane.
  • membrane 10 made in accordance with this example may not meet the requirements for some tasks, such as single pass seawater desalination.
  • a TFC membrane with 0.02% mhTMC additive in the organic phase may yield a flux of 29.5 GFD having a 31% flux improvement over a control membrane without additives as well as a 99.24% salt rejection, also below the rejection of the control membrane.
  • a hybrid TFC membrane with both the LTA and mhTMC additives in organic phase 18 may yield a flux of 25.8 GFD and perhaps more importantly, a substantially improved salt rejection of 99.63%, above the 99.5% salt rejection level which may be required for reverse osmosis membranes.
  • a hybrid TFC membrane with both the LTA in aqueous phase 14 and mhTMC additive in organic phase 18 may yield a further improved flux of 30.7 GFD and a salt rejection of 99.63%, above the 99.5% salt rejection level which may be required for reverse osmosis membranes.
  • TFC membrane 10 may be used to desalinate waters containing materials which tend to accumulate on the membrane surface, decreasing the permeability of TFC membrane 10. This process is commonly called "fouling".
  • the fouling materials which accumulate on the membrane surface can include, but are not limited to, natural organic matter, partially insoluble inorganic materials, organic surfactants, silt, colloidal material, microbial species including biofilms, and organic materials either excreted or released from microbial species such as proteins, polysaccharides, nucleic acids, metabolites, and the like.
  • the drop in permeability is often smaller, that is, less fouling materials accumulate on the surface of TFC membrane 10 when nanoparticles are included in additive(s) 16.
  • This reduction in fouling, or improvement in fouling resistance, may - in part - be related to increased hydrophilicity of TFC membrane 10 when nanoparticles are included in additive(s) 16.
  • the hydrophilicity of TFC membrane 10 can be measured by measuring the equilibrium contact angle of the surface of membrane 10 with a drop of distilled water at a controlled temperature.
  • TFC membrane 10, when nanoparticles are included in additive(s) 16 can have a contact angle that is reduced by 5°, 10°, 15°, 25° or more, relative to a similarly prepared membrane without nanoparticles included in additive(s) 16.
  • the equilibrium contact angle can be less than 45°, less than 40°, than 37°, or even less than 25°.
  • Improved resistance to accumulation for TFC membranes can in part be related to increased hydrophilicity of these membranes.
  • the increased hydrophilicity can be measured by the equilibrium contact angle of the membrane surface with a drop of distilled water at a controlled temperature.
  • Membranes prepared with additive 16 present during polymerization can have a contact angle that is reduced by 5, 15, or even 25 or more degrees relative to a similarly prepared membrane without the additive.
  • the equilibrium contact angle can be less than 45°, less than 40°, or even less than 25°.
  • hybrid TFC membranes 10 may be used to desalinate waters that contain materials which have a tendency to accumulate on the membrane surface in contact with the contaminated water, decreasing the effective membrane permeability, e.g. decreasing membrane flux over time.
  • materials can include but are not limited to natural organic matter, partially insoluble inorganic materials, organic surfactants, silt, colloidal material, microbial species including biofilms, and organic materials either excreted or released from microbial species such as proteins, polysaccharides, nucleic acids, metabolites, and the like.
  • This drop in permeability or membrane flux is often smaller for membranes prepared as disclosed herein than for membranes prepared by conventional techniques due to a decreased amount, density, viability, thickness and/or nature of accumulated material.
  • Membrane surface properties such as hydrophilicity, charge, and roughness, often affect this accumulation and permeability change.
  • membranes with highly hydrophilic, negatively charged, and smooth surfaces yield good permeability, rejection, and fouling behavior.
  • nanoparticles such as zeolite LTA nanoparticles, have been shown to reduce roughness, increase negative charge without addition of carboxylate groups, and reduce contact angles.
  • Fig. 15 a simple graphical representation of the reduced loss of flux over time is shown in which the LTA alone shows low flux improvement with low flow loss due to fouling, the Ga(acac) 3 additive alone shows high flux improvement with substantial flux loss due to fouling while the hybrid shows the best of both additives, high flux improvement with low flux loss due to fouling.
  • the TFC membrane with the additive alone has a lower flux than the nanocomposite TFC membrane while the nanocomposite hybrid TFC membrane shows a flux improvement over the nanoparticle hybrid TFC membrane of about 21% in only 2 days.
  • the rate of flux drop tends to decrease in conventional membranes over time, but nanoparticle hybrid TFC membranes are expected to maintain an improvement of 20 to 100% above similar membranes with single additives or conventional membranes.
  • membrane 10 with 0.08% Ga(acac) 3 in organic phase 18 had a substantially improved flux of 30.9 GFD after 1 hour of operation under the same conditions, a substantial 37% flux improvement over its control membrane and the membrane of example 183.
  • the flux was reduced to 20.9 GFD after 2 days as a result of fouling. This represents an almost 50% flux loss due to fouling in just 2 days and unfortunately not that uncommon.
  • the complexes to be combined with nanostructured additives to substantially reduce fouling while maintaining high flux and rejection may include compounds with alkaline earth metals, Al, Fe, Ga, Sn, Co, Cu and Pr or phosphorous.
  • the combination of a nanostructured additive with mhTMC may also substantially reduce fouling.

Abstract

Thin film composite, TFC, membranes for use in forward and reverse osmosis may include earth alkaline metal complex additives and/or one or more other additives. Specific concentration and ratio ranges of components used for interfacial polymerization may be used to enhance the flux increase and/or limit the rejection decrease in these membranes and/or reduce fouling. Techniques are provided for determining the usefulness of particular additives and the best ranges of concentration for both membrane improvement and membrane fabrication repeatability based on non-linearities identified in the effects of the additives on flux and rejection.

Description

IMPROVED TFC MEMBRANES WITH ALKALINE EARTH METAL AND OTHER ADDITIVES
BACKGROUND OF THE INVENTION
Cross-reference to related U.S. applications:
[0001] This application claims benefit of U.S. Provisional Applications:
61/045,262, filed April 15, 2008; 61/045,234, filed April 15, 2008; 61/045,237, filed April 15, 2008; 61/045,247, filed April 15, 2008; 61/045,249, filed April 15, 2008; 61/045,252, filed April 15, 2008; 61/079,794, filed July 10, 2008; 61/088,666, filed August 13, 2008; 61/104,905, filed October 13, 2008; 61/122,341, filed Dec. 12, 2008; 61/112,342, filed Dec. 12, 2008; 61/122,343, filed Dec. 12, 2008; 61/122,344, filed Dec. 12, 2008; 61/122,345, filed Dec. 12, 2008; 61/122,346, filed Dec. 12, 2008; 61/122,347, filed Dec. 12, 2008; 61/122,348, filed Dec. 12, 2008; 61/122,350, filed Dec. 12, 2008; 61/122,351 , filed Dec. 12, 2008; 61/122,352, filed Dec. 12, 2008; 61/122,354, filed Dec. 12, 2008; 61/122,355, filed Dec. 12, 2008; 61/122,357, filed Dec. 13, 2008; 61/122,358, filed Dec. 13, 2008; 61/156,388, filed Feb. 27, 2009; 61/156,394, filed Feb. 27, 2009; 61/164,031 , filed March 27, 2009; and is a continuation-in-part of U. S. Pat. App. 12/424,533, filed April 15, 2009, all of which are incorporated by reference, in their entireties.
1. Field of the Invention:
[0002] This invention is related to thin film composite or TFC membranes including alkaline earth metal and/or other additives, and more particularly to such membranes useful for reverse or forward osmosis, for example to purify water.
2. Background of the Invention:
[0003] Reverse osmosis membranes, made by interfacial polymerization of a monomer in a nonpolar (e.g. organic) phase together with a monomer in a polar (e.g. aqueous) phase on a porous support membrane are known as TFC membranes and are used where flux and substantial rejection characteristics are required, for example in the purification of water. Various materials have been added to TFC membranes in the hopes of increasing flux without reducing rejection characteristics and have met with limited success. In addition, such membranes are subject to fouling resulting in reduced flux as contaminants, for example from the brackish or seawater to be purified, are believed to build up on the surface of the discrimination layer of the TFC membrane.
[0004] TFC membranes became available in about the 1970's and proved commercially successful for some RO tasks. Substantial further development has been done to improve the membranes operational characteristics, including permeability or flux, rejection and fouling resistance.
[0005] As shown for example in Chau U.S. Pat. No. 4,950,404, in the late
1980's, a polar aprotic solvent was said to be added to the aqueous solution prior to contacting with an acid halide solution for interfacial polymerization to enhance the operational characteristics of the resultant membrane.
[0006] As shown for example in Hirose, U.S. Pat. No. 5,989,426, in the mid
1990's, selected alcohols, ethers, ketones, esters, halogenated hydrocarbons, nitrogen-containing compounds and sulfur-containing compounds were said to be added prior to interfacial polymerization to improve membrane characteristics.
[0007] As shown for example in Costa, U. S. Pat. 5,693,227, in the mid
1990's, catalysts were said to be added to the aqueous phase to accelerate interfacial polymerization, producing TFC membranes with a smoother surface.
[0008] As shown for example in Mickols, U.S. Pat. 6,562,266, in about 2000, compounds including phosphorous or other materials were said to be added as a complexing agent to acyl halide before interfacial polymerization. A detectable quantity of the added material was said to be retained in the discrimination membrane as a result of the formation of a complex between the added material and the acyl halide.
[0009] The many, and varied, proposed formulations for TFC membranes in some instances have different membrane operational characteristics (such as flux, rejection, and fouling resistance) that make them more suitable for different tasks. These tasks are typically defined by the incoming water quality, plant design, and required product water quality, which together set the operational conditions of the plant (such as required applied pressure). For example, membranes for use in purifying brackish water are conventionally expected to encounter a substantially lower salinity - and be operated at substantially lower pressure - than a membrane useful for seawater desalination.
[00010] A typical specification for a TFC membrane used for brackish water
RO may require a minimum flux of at least 20 GFD (gallons per square foot per day of filtered liquid) with a minimum of 99.5% salt rejection when operated at a working pressure of about 220 psi on brackish water having an expected salinity of about 2000 ppm (parts per million) or less. On the other hand, a typical specification for TFC membranes to be used for seawater RO may require a minimum flux of 20 GFD with a minimum of 99.5% salt rejection when operated at a working pressure of about 800 psi on seawater having an expected salinity of 32000 ppm or more.
[00011] TFC membranes suitable for brackish water use, i.e., at low pressure and salt load, will typically not operate well when operated at the higher pressure and salinity used for seawater purification. There is no clear cut way to predict their performance under the salinity and operating conditions used for seawater exactly, however it can be said that such membranes typically lose permeability and salt rejection ability as the salinity increases.
[00012] As an example, Mickols in example 35 discloses the use of a particular phosphorus compound additive which is said to produce a TFC membrane having membrane operation characteristics, including 19.5 GFD and 99.6% rejection when operated at 150 psi with salinity of 2000 ppm. Although these characteristics may be suitable for reverse osmosis of brackish water, there is no reasonable way to predict how to use such information in the formulation of a TFC membrane suitable for use under the conditions required for in seawater osmosis other than by preparing and testing it.
[00013] Based on publicly available information, TFC membranes having properties suitable for reverse osmosis of seawater are conventionally made without the various additives discussed in the prior art, presumably because such additives tend to have deleterious action on TFC membranes rejection.
[00014] One common problem with conventional TFC membranes designed for seawater deslaination, is quality control and variability in product performance. That is, it is believed that fabricating TFC membranes with predictable flux, rejection and fouling resistance for seawater RO has been so difficult, that fabrication facilities are in some cases unable to prepare a specific product, or need to shift a product's formulation in order to maintain the required membrane properties.
[00015] Recently, as disclosed in Hoek et a!., ( ) UCLA's
Nanomaterials & Membrane Technology Research Laboratory determined that the addition of certain nanoparticles, such as LTA, and other materials could be used to improve TFC membrane operational characteristics at operating pressures, and expected salinities suitable for use in reverse osmosis of seawater.
[00016] What are needed are techniques for fabricating TFC membranes, in particular TFC membranes suitable for operation at the higher pressures and salinities required for reverse osmosis of seawater - which have higher flux than is achievable from TFC membranes made without such additives Such desirable TFC membranes must also have a suitably high salt rejection, preferably on the order of about 99.5%. It would also be desirable to have increased fouling resistance - as well as higher flux and high rejection rates - when compared to a TFC membrane made the same way with the same chemistry but without the additives.
[00017] Still further, it would be desirable to be able to produce such TFC membranes with predictable characteristics and yield on a continuous basis.
[00018] TFC membranes are also needed with such membrane operational characteristics for many other uses beyond seawater purification, including but not limited to brackish water purification, waste water reuse, ultrapure water generation, industrial water treatment, other RO tasks, forward osmosis and pressure retarded osmosis.
BRIEF DESCRIPTION OF THE DRAWINGS [00019] Fig. 1 is a block diagram illustrating layers used in the process of fabricating TFC membrane 10 in which additives 16 are present in aqueous phase 14.
[00020] Fig. 2 is a block diagram illustrating layers used in the process of fabricating TFC membrane 10 in which additives 16 are present in organic phase 18.
[00021] Fig. 3 is a block diagram illustrating layers used in the process of fabricating TFC membrane 10 in which additives 16 are present in both aqueous phase 14 and organic phase 18.
[00022] Fig. 4 is a block diagram illustrating layers used in the process of fabricating TFC membrane 10 in which additives 16 are present in organic solution 18 and in water solution 15 between porous support membrane 12 and aqueous phase 14.
[00023] Fig. 5 is a block diagram showing the use of a TFC membrane, having additives 16 in a layer discrimination layer 24, in a reverse osmosis process.
[00024] Fig. 6 is a block diagram showing the operation of TFC membrane
10, in which additives 16 were present during the interfacial polymerization of discrimination layer 24, in a reverse osmosis process.
[00025] Fig. 7 is a block diagram showing the operation of TFC membrane 10 including hydrophilic layer 30, in which additives 16 were present during the interfacial polymerization of discrimination layer 24 and in the fabrication of support 12 and fabric 10, in a reverse osmosis process
[00026] Fig. 8 is an exploded view of membrane 10 in which additives 16, such as nanostructured additives, penetrate the upper and/or lower surfaces of discrimination membrane 24.
[00027] Fig. 9 is an exploded view of membrane 10 in which additives 16, such as nanostructured additives, are between discrimination membrane 24 and support 12. [00028] Fig. 10 is a diagrammatic view of support membrane 12 during fabrication in which casting solution 13, including additives 16 such as nanoparticle additives, is coated on fabric 20 on glass plate 15.
[00029] Fig. 11 is the chemical structure of mono-hydrolyzed or mhTMC.
[00030] Fig. 12 is a graphic representing a 1H-NMR analysis of the purity of synthesized mhTMC.
[00031] Fig. 13 is a graphical illustration of flux and rejection curves 32, 34 for increasing concentrations of additive 16, such as mhTMC lot 1 , indicating a range of preferred concentrations of mhTMC or other additives 16 - shaded area 45 - surrounding deflection axis A 44, in which one or more non-linearities or deflections appear to occur in flux growth and rejection decline as well as deflection axis B 46 indicating concentrations of additive 16 which appear to damage membrane 10.
[00032] Fig. 14 is a graphical illustration of flux and rejection curves 36, 38 for increasing concentrations of additive 16, such as mhTMC lot 2, and of flux and rejection curves 40, 42 for increasing concentrations of additive 16, such as filtered mhTMC lot 2, indicating a range of preferred concentrations of additive 16 including deflection axis A 48 - shaded area 49 - in which one or more non-linearities or deflections appear to occur in flux growth and rejection decline.
[00033] Fig. 15 is a graphical comparison of the reduction in flux over time in membrane 10 with LTA additive 16, membrane 10 with another additive 16 and hybrid membrane 10 with additives 16 including the LTA and other additive used in the first two membranes 2 shown in this figure.
SUMMARY OF THE INVENTION
[00034] In one aspect, improved techniques for the use of alkaline earth additives in TFC membranes have been developed including combining one or more additives with either or both a polar liquid having a first monomer therein and a non-polar liquid having a second monomer therein and contacting the polar and non-polar liquids to form a selective membrane by interfacial polymerization, wherein at least one of the additives includes a complex including an alkaline earth metal.
[00035] In another aspect, a TFC membrane may be fabricated with an additive including a complex which includes an alkaline earth metal.
[00036] The complex may be a beta-diketonate complex such as acetylacetonate. The complex may be present in a concentration in one of the liquids of from about 0.005 wt.% to about 5 wt.% and more preferably from about 0.05 wt.% to about 1 wt.%. At least one of the additives includes a complex of magnesium, calcium, strontium or beryllium.
[00037] The polar liquid may include an amine monomer such as MPD. The non-polar liquid may include TMC. The ratio of MPD in the polar liquid to TMC in the non-polar liquid may be below 14 and may be low enough so that the resultant selective membrane has substantially higher flux than a control membrane. The concentration of TMC in the non-polar liquid may high enough so that the resultant selective membrane has substantially higher flux than a control membrane made without the complex including an alkaline earth metal.
[00038] In another aspect, improved techniques for the use of nanoparticles in
TFC membranes have been developed including the combined used of nanoparticles and/or nanotubes with alkaline earth metals, monohydrolyzed TMC and/or other molecular additives in hybrid nanocomposite TFC membranes with increased flux, rejection and anti-fouling characteristics.
[00039] In another aspect, the new hybrid nanocomposite TFC membranes, together with more advantageous concentrations and ranges of TMC, MPD to TMC ratios as well as the discovery of deflection points in the concentrations of additives, such as monohydrolyzed TMC, make the design and fabrication of engineered nanocomposite TFC membranes with selected flux, rejection and antifouling characteristics possible. [00040] In a further aspect, some of the new additives, particularly the alkaline earth metals and monohydrolyzed TMC, may be used for the design and fabrication of high flux, rejection and anti-fouling TFC membranes. These membranes may also advantageously use the advantageous concentrations and ranges of TMC, MPD to TMC ratios and deflection points in the concentrations of additives to provide optimum characteristics for particular circumstances.
[00041] A thin film composite membrane may be made by combining two or more additives with either or both a polar liquid having a first monomer therein and a non-polar liquid having a second monomer therein and contacting the polar and non-polar liquids to form a selective membrane by interfacial polymerization, wherein at least one of the two or more additives is a nanostructured additive.
[00042] The nanostructured additive may be a zeolite nanoparticle, such as
LTA, FAU and/or Zeolite Beta or an organometallic framework complex, such as CuMOF.
[00043] One of the additives may includes a predetermined concentration of mono-hydrolyzed TMC and/or di-hydrolyzed TMC in addition to the nanostructured additives. A complex including an alkaline earth metal may also be included in addition to the nanostructured additives and/or a complex including an element selected from Groups 3 - 15, rows 3-6 of the Periodic Table (IUPAC) may be in addition to the nanostructured additives. These additional additives may include aluminum, cadmium, chromium, cobalt, copper, gallium, hafnium, indium, iron, one of the lanthanoid elements, molybdenum, palladium, phosphorous, ruthenium, tin, vanadium or Zinc.
[00044] The polar liquid may include an amine, such as MPD, and the non- polar liquid may include TMC wherein ratio of MPD to TMC is below 14, low enough so that the resultant selective membrane has substantially higher flux than a control membrane. The concentration of TMC may be high enough so that the effect of one or more of the additives, in the resultant selective membrane, is enhanced to produce a substantially higher flux than a control membrane. [00045] Techniques are disclosed including an interfacial polymerization process for preparing a highly permeable RO membrane by contacting a first solution containing 1 ,3-diaminobenzene, and a second solution containing trimesoyl chloride, to fabricate a highly permeable RO membrane wherein at least one of the solutions contains well dispersed nanoparticles when contacted.
[00046] Similarly a first solution containing 1 ,3-diaminobenzene, and/or a second solution containing trimesoyl chloride, may contain well dispersed nanoparticles and be contacted to form an RO membrane wherein at least 20% of the membrane surface area consists of nanoparticles.
[00047] A first solution containing polyamine monomer, and a second solution containing a polyfunctional acyl halide monomer, wherein a molecular additive compound is present in one or both solutions during the polymerization reaction may be used to fabricate a TFC membrane.
[00048] Similarly an interfacial polymerization process for preparing a low- fouling highly permeable RO membrane may include contacting on a porous support membrane, a first solution containing a polyamine monomer, and a second solution containing a polyfunctional acyl halide monomer, wherein aluminum ions are present in one or both solutions, during the polymerization reaction.
[00049] A low-fouling highly permeable RO membrane may be produced by an interfacial polymerization process by contacting on a porous support membrane, a first solution containing a polyamine monomer, and a second solution containing a polyfunctional acyl halide monomer , wherein aluminum ions are present in one or both solutions during the polymerization reaction.
[00050] Another process for preparing a highly permeable RO membrane may include contacting on a porous support membrane, an aqueous solution containing metaphenylenediamine (MPD), and an organic solution containing trimesoyl chloride (TMC) and a hydrolyzed TMC species. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[00051] Improved thin film composite or TFC membranes fabricated with additives for enhanced membrane performance are disclosed. Techniques for improving membrane performance include dispersion and sizing of nanostructured additives, processing to enhance the performance of such additives in TFC membranes, selecting and processing such additives 16 to release soluble metal ions and/or adding additional additives 16 to fabricate hybrid TFC membranes.
[00052] Hybrid TFC membranes may include the following additives used in various combinations: nanoparticles, nanotubes, alkaline earth metal complexes, mono-and/or di-hydrolyzed TMC and/or other molecular additives such as elements selected from Groups 3 - 15 of the Periodic Table (IUPAC), particularly from Rows 3 - 6 of those groups. In some embodiments, TFC membranes may be fabricated without nanostructured additives.
[00053] Techniques for fabricating TFC membranes may include specific TMC concentrations and MPD/TMC ratios and selection of concentration or ranges of concentration by detection of deflections points - which may be non-linearities in the growth of flux, or decline in rejections, with increasing additive concentration - especially when such changes occur in both flux growth and rejection decline at the same levels of concentration of the additive(s).
[00054] Tables of examples are provided which illustrate these TMC concentrations and MPD/TMC ratios as well as the effects of using various additives in various combinations, in various locations including in the aqueous and/or organic phases contacted to cause interfacial polymerization of the discrimination layer or membrane in the TFC membranes fabricated in accordance with these examples. The tables also illustrate the percentage of flux improvement of many of these TFC membranes compared to similar TFC membranes used as controls which were fabricated in the same way, but without such additives. Finally, these tables illustrate the permeability or flux, and solute rejection rates, of the exemplar membranes. The techniques used in the fabrication and testing of these membranes are also presented along with an outline of some of the advantages of the additives and combinations of additives used in the exemplars.
[00055] For clarity, the present disclosure is divided into multiple sections, as follows:
Section A: Thin Film Composite (TFC) Membranes Section B: Specific Additive(s) 16 and Combinations thereof B.1. Nanostructured Additives 16
A. Nanoparticles
B. Particle Size
C. Dispersion
D. Nanotubes
B.2 Alkaline earth metal additives 16 B.3 mhTMC additive 16 B.4 Selected Other Additives 16 B.5 Additive characteristics B.6 Post-fabrication Analysis Section C: Process Techniques
C.1 Techniques for introducing additives 16
C.2 TMC Concentration and Purity
C.3 MPD/TMC Ratio
C.4 Preparation and purity of mhTMC additive 16
C.5 Theories
Section D: Tables of Examples D.1 Tables
Table 1: Improved TFC (control) Membrane w/o Additives
Table 2: Hybrid Membranes
Table 3: TFC Membranes with Nanostructured Additives
Table 4: TFC Membranes without Nanostructured Additives
Table 5. mhTMC Additive in TFC Membranes
Table 6. Fouling Tests D.2 Preparation Procedures
A. General Procedures
B. Specific Nanostructured Material Procedures
C. Specific Procedures for Fouling Tests Section E: Advantages
E.1 Increased Flux E.2 Improvement Ratio E.3 Improved Rejection E.4: Fouling Resistance
Section A: Thin Film Composite (TFC) Reverse Osmosis (RO) Membranes
[00056] The assignee of this application is the exclusive assignee of various applications and/or patents assigned to the Regents of the University of California related to the use of nanoparticles in TFC membranes to improve membrane performance characteristics and strength. In the course of further developing nanoparticle TFC membranes, we have substantially improved membrane performance by pre-processing nanoparticle additives and altering process conditions including reagent concentrations and ratios. We have also discovered specific additional additives - one or more of which -when combined with nanoparticles and our additive and membrane processing techniques permit substantial further performance and other improvements in nanoparticle TFC membranes. These new additives may also be used in combinations and/or as sole additives.
[00057] Referring now generally to Fig.s 1-9, which are not drawn to scale for clarity of the description, Fig.s 1-4 illustrate a first or aqueous 14 phase and a second or organic phase 18 in an exploded view for contact on support membrane 12 during fabrication for interfacial polymerization to form discrimination membrane 24 during the fabrication of TFC membrane 10. One or more additive(s) 16, such as nanostructured materials, may be introduced into the interfacial polymerization between aqueous phase 14 and organic phase 18 before or at the beginning of the interfacial polymerization reaction to improve membrane characteristics. [00058] FiQ- 1 indicates that additives 16 has been added to aqueous phase
14. Fig. 2 indicates that additives 16 has been added to organic phase 18. Fig. 3 indicates that additives 16, has been added to both aqueous phase 14 and organic phase 18. The same or different additives 10 may be used in different locations. Fig. 4 indicates that additives 16 has been added to both organic phase 18 as well as water solution 11 on the surface of support 12 before aqueous phase 14 is applied to support 12 followed by organic phase 18. It should be noted that in some embodiments, organic phase 18 may applied to support 12 before aqueous phase 14 is applied to organic phase 18.
[00059] Fig.s 5-7 illustrate TFC membranes 10 after fabrication, e.g., by the processes illustrated in Fig.s 1-4. As shown in Fig. 5, after fabrication, membrane 10 includes discrimination layer 24 formed by the interfacial polymerization of aqueous and organic phases 14 and 18 in the presence of one or more additive(s) 16. After fabrication, TFC membrane 10 may conveniently be used for selective filtering, for example as RO TFC membrane 10, to purify saltwater 26 - applied under pressure to discrimination layer 24 - so that purified water 28 passes through discrimination layer 24, porous support membrane 12 and fabric layer 20, if present.
[00060] Referring now in particular to Fig. 6, hydrophilic layer 30, such as a polyvinyl alcohol or PVA layer may be applied to discrimination layer 24 to the surface of membrane 10 in contact with the material to be filtered, e.g., seawater 26, to make that surface and therefore membrane 10 more hydrophilic, that is, to reduce the interfacial tension of the surface of membrane 10. Improved hydrophilicity can be observed as a lower contact angle between seawater 26 and membrane 10. Improving the hydrophilicity of the upper or contact surface of membrane 10 is believed to reduce fouling and may improve flux flow. Seawater 26 may be applied under pressure to TFC membrane 10 to produce purified water 28.
[00061] In general, TFC membrane 10 may be synthesized using an interfacial polymerization process on a porous support, such as support membrane 12. Conventionally, two immiscible solvents are used, one in aqueous phase 14 and the other in organic phase 18, so that a monomer in one solvent reacts with a monomer in the other solvent. The interfacial polymerization reaction occurs at the interface between the two solutions when aqueous phase 14 and organic phase 18 are brought into contact with each other, to form a dense polymer matrix layer - discrimination layer 24 - on the surface of support membrane 12.
[00062] The polymerization reactions are very fast and relatively high molecular weights for the resultant polymer matrix are obtained. Once formed, the dense polymer matrix - which becomes discrimination layer 24 - can advantageously act as a barrier to inhibit ongoing contact between the reactants in aqueous and organic phases 14 and 18 to slow the ongoing polymerization reaction. As a result, discrimination layer 24 is formed as a selective dense layer which is typically very thin and permeable to water, but relatively impermeable to dissolved, dispersed, or suspended solids, such as salts to be removed from sea or brackish water to produce purified water. Resultant membrane 10 is conventionally described as a thin film composite (TFC) membrane.
[00063] The first monomer can be a dinucleophilic or a polynucleophilic monomer and the second monomer can be a dielectrophilic or a polyelectrophilic monomer. That is, each monomer can have two or more reactive (e.g., nucleophilic or electrophilic) groups. Both nucleophiles and electrophiles are well known in the art, and one of ordinary skill in the art can select suitable monomers for this use. The first and second monomers are conventionally selected to react - when aqueous and organic phases 14 and 18 are brought into contact - by undergoing interfacial polymerization to form a three-dimensional polymer network, often called a polymer matrix.
[00064] The first and second monomers can also be chosen to be capable of undergoing a polymerization reaction when aqueous and organic phases 14 and 18 brought into contact to form a polymer product that is capable of subsequent crosslinking by, for example, exposure to heat, light, radiation, or a chemical crosslinking agent.
[00065] Regarding aqueous phase 14, the first monomer can be selected to be soluble in a polar liquid, preferably water, to form a polar mixture, referred to herein as aqueous phase 14. Generally, the difunctional or polyfunctional nucleophilic monomer can have primary or secondary amino groups and can be aromatic (e.g., a diaminobenzene, a triaminobenzene, m-phenylenediamine, p- phenyenediamine, 1 ,3,5-triaminobenzene, 1 ,3,4-triaminobenzene, 3,5- diaminobenzoic acid, 2,4-diaminotoluene, 2,4-diaminoanisole, and xylylenediamine) or aliphatic (e.g., ethylenediamine, propylenediamine, piperazine, and tris(2- diaminoethyl)amine).
[00066] Examples of suitable amine species include primary aromatic amines having two or three amino groups, for example m-phenylenediamine, and secondary aliphatic amines having two amino groups, for example piperazine. The amine can typically be applied to microporous support 12 as a solution in a polar liquid, for example water. The resulting polar mixture typically includes in the range from about 1 to about 6 wt.% amine, preferably in the range of about 2 to about 4.0 wt.%, amine and most preferably about 3.0 wt.% amine. The polar mixture need not be aqueous, but the polar liquid should be immiscible with the apolar liquid. Although water is a preferred solvent, non-aqueous polar solvents can be utilized, such as acetonitrile and dimethylformamide (DMF) for aqueous phase 14.
[00067] Phase 14 can be called a polar phase or an aqueous phase because such mixtures typically use water as the polar solvent. We believe most practitioners in this art refer to phase 14 as the aqueous phase. To avoid any confusion, that convention will be followed herein so that the term "aqueous phase" 14 is intended to refer to all polar phase liquids, e. g. whether or not the polar liquid is water.
[00068] During interfacial polymerization, aqueous phase 14 may include one of the reactants, additive(s) such as nanostructured materials, e.g., nanoparticle additives 16, as well as processing aids such as surfactants, drying agents, catalysts, coreactants, cosolvents, etc. The polar mixture, aqueous phase 14, is typically applied to microporous support membrane 12 by dipping, immersing, slot die coating, spray coating, gravure coating or other well known techniques. Once coated on porous support membrane 12, excess polar mixture can be optionally removed by evaporation, drainage, air knife, rubber wiper blade, nip roller, sponge, or other devices or processes.
[00069] For monomers having sufficient vapor pressure, the monomer can be optionally delivered by vapor deposition from a vapor phase, or by heat, to support membrane 12.
[00070] Regarding organic phase 18, the second monomer can be selected to be miscible with an apolar (organic) liquid, the mixture of which is shown in the figures as organic phase 18. Using the same convention discussed above with regard to aqueous phase 14, the typically used term "organic phase" is intended to refer to any appropriate nonpolar mixture, e. g. organic phase 18.
[00071] The electrophilic monomer can be aromatic in nature and can contain two or more, for example three, electrophilic groups per molecule. For example, the second monomer can be a trimesoyl halide. For the case of acyl halide electrophilic monomers, acyl chlorides are generally more suitable than the corresponding bromides or iodides because of the relatively lower cost and greater availability.
[00072] Suitable polyfunctional acyl halides include trimesoyl chloride (TMC), trimellitic acid chloride, isophthaloyl chloride, terephthaloyl chloride and similar compounds or blends of suitable acyl halides. As a further example, the second monomer can be a phthaloyl halide.
[00073] The polyfunctional acyl halide - e.g., TMC - can be dissolved in the apolar organic liquid, e.g., organic phase 18, in a range of, for example, from about 0.09 to about 1.0 wt.%, preferably from about 0.17 to about 0.3 wt.%. and most preferably in the range of about 0.3wt.% TMC. Suitable apolar liquids are capable of dissolving the electrophilic monomers (e.g. polyfunctional acyl halides) and which are immiscible with a polar liquid (e.g., water) in aqueous phase 14. In particular, suitable apolar liquids preferably include those which do not pose a threat to the ozone layer and yet are sufficiently safe in terms of their flashpoints and flammability to undergo routine processing without having to undertake extreme precautions. [00074] These include C5 - C7 hydrocarbons and higher boiling hydrocarbons, i.e., those with boiling points greater than about 90° C, such as C8 - C24 hydrocarbons and mixtures thereof, which have more suitable flashpoints than their C5 - C7 counterparts, but are less volatile. The apolar mixture - organic phase 18 - can typically be applied to contact aqueous phase 14 on microporous support membrane 12 by dipping, immersing, slot die coating, spray coating, gravure coating or other well known techniques. Any excess apolar liquid can be removed by evaporation or mechanical removal. It is often convenient to remove the apolar liquid by evaporation at elevated temperatures, for instance in a drying oven. Preferred ovens include flotation ovens, IR dryers, and laboratory convection or gravity ovens. Control of both web temperature and evaporation rate may be used to alter structure and performance.
[00075] Organic phase 18 may also include one of the reactants, one or more additive(s) 16, and processing aids such as catalysts, co-reactants, co-solvents, etc. In some circumstances, organic phase 18 may be applied to support membrane 12 first and aqueous phase 14 may then be applied to contact organic phase 18 on support membrane 12.
[00076] Support membrane 12 is typically a polymeric microporous support membrane, which in turn is often supported by non-woven or woven fabrics, such as fabric 20, for mechanical strength. Fabric 20 is preferably a polyester fabric having a basis weight of 60-120 grams per meter or gsm, and a thickness of 50- 200 microns. Support membrane 12 may conventionally be made from polysulfone or other suitably porous membranes, such as polyethersulfone, poly(ether sulfone ketone), poly(ether ethyl ketone), poly(phthalazinone ether sulfone ketone), polyacrylonitrile, polypropylene, cellulose acetate, cellulose diacetate, or cellulose triacetate. Microporous support membranes 12 may be 25-100 nm in thickness, preferably about 35 nm to about 75 nm and most preferably about 50 nm in thickness and may have the smallest pores located very near the upper surface. Porosity at the surface may be low, for instance from 5-15% of the total surface area. [00077] Referring now to Fig.s 7-9, Fig. 7 indicates that additives 16 were also added to support 12 and/or fabric 20 as well as to the interfacial polymerization of discrimination membrane 10. Fig. 8 is an exploded view of membrane 10 and indicates that at least some of the particles in additive 16, such as nanostructured materials, may pierce the upper and/or lower surfaces of membrane 10. Fig. 9 is an exploded view of membrane 10 and indicates that at least some portions of additive 16, may be at the intersection of discrimination membrane 24 and support 12 of membrane 10.
[00078] Referring now to Fig. 10, the preparation of support membrane 12 may begin, for example in a laboratory setting, with the addition of dimethylformamide (DMF) solvent (available from Acros Organics, USA) to a polysulfone polymer (such as Mn 26,000 available from Aldrich, USA) in transparent bead form in airtight glass bottles. Alternatively, N-methyl pyrrolidone (NMP) may be used as the solvent. Additive(s) 16 may be dispersed in the DMF before the DMF is added to the polysulfone polymer as discussed below in greater detail. The solution may then be agitated for several hours until complete dissolution is achieved, forming the dope or casting solution 13.
[00079] Casting solution 13 may then be cast or spread over non-woven fabric
20 attached to glass plate 15 via a knife-edge. Glass plate 15 may then be immediately immersed into demineralized water, which had preferably been maintained at the desired temperature. Immediately, phase inversion begins and after several minutes, non-woven support fabric 20 supporting polysulfone membrane 12 may be separated from glass plate 15. Membrane 12 is then washed thoroughly with deionized water and stored in cold conditions until used. In a continuous coating process, glass plate 15 would not be required.
[00080] The presence of one or more additive(s) 16, such as nanoparticle additives, during the during the interfacial polymerization of discrimination membrane 24 may substantially improve the performance - for example by increasing the flux and/or resistance to fouling while maintaining a suitable rejection level - of TFC membrane 10 for a particular task such as purifying seawater by reverse osmosis to produce drinking water.
[00081] Additive(s) 16 may be introduced into the interfacial polymerization reaction by adding them to aqueous phase 14, organic phase 18, water solution 11 , support membrane 12 and/or other by any other convenient mechanism. For example, additives 16 may be added to aqueous phase 14, organic phase 18 or both before these phases are put in contact with each other to begin the interfacial polymerization.
[00082] For example, in a preferred embodiment of TFC membrane 10, a relatively insoluble additive such as LTA nanoparticle additive 16 may be advantageously combined with one or more other additives 16, such as alkaline earth metals, mhTMC, soluble metal species and/or other additives 16, e.g., from Groups 3-15 of the periodic table, which in the presence of the interfacial polymerization provide substantially improved membrane characteristics such as increased flux at high rejection as shown and discussed below for example in the tables of examples.
Section B: Specific Additive(s) 16 and Combinations thereof.
[00083] Referring now generally to the figures and tables, the introduction of one or more of the nanoparticle additives 16 into the interfacial polymerization between aqueous and organic phases 14 and 18 may provide substantially superior TFC membranes 10 for many selective filtering uses such forward osmosis (FO) and reverse osmosis (RO) for use, for example, in the purification of brackish water and seawater. Such TFC membranes 10 may have improved flux performance and/or fouling resistance and retain suitably high rejection characteristics for various tasks.
[00084] Further, we have discovered that nanostructured additives 16 such as nanoparticles, when combined with additional additives as discussed below, may even further improve membrane flux and/or resistance to fouling. We have also discovered that combinations of nanoparticles with more than one other additive may still further enhance membrane characteristics.
[00085] Various additives including nanoparticles and nanotubes in combination with alkaline earth metals, mhTMC, and selected other elements often in a complex with other materials have been tested as shown in the tables of examples below. In addition to alkaline earth metals, some other metallic species such as gold, silver, copper, zinc, titanium, iron, aluminum, zirconium, indium, tin, or an alloy thereof or an oxide thereof or a mixture thereof or a complex containing may be used as additives in addition to nanoparticle additives'! 6. A nonmetallic species such as SisN4, SiC, BN, B4C, or an alloy thereof or a mixture thereof as well as a carbon-based species such as TiC, graphite, carbon glass, a carbon cluster of at least C2, buckminsterfullerene, a higher fullerene, a carbon nanotube, a carbon nanoparticle, or a mixture thereof may also be useful.
[00086] Still further, we were further surprised and pleased to discover that many of these additives are suitable for use even without nanoparticles, either alone or in various combinations with each other e.g., as shown below in the tables of examples.
B.1. Nanostructured Additives 16
A. Nanoparticles
[00087] As shown in the figures and tables below, nanoparticles - or other nanostructured materials such as nanotubes and metal organic frameworks (MOF) - useful as additives 16 may include, but are not limited to:
• Linde Type A (LTA) zeolites available freeze dried, 100nm diameter from Nanoscape AG, Am Klopferspitz 19, D-82152 Planegg, Germany,
• Linde Type Y (FAU) zeolites as described in MICROPOROUS AND MESOPOROUS MATERIALS Volume: 59 Issue: 1 Pages: 13-28 Published: APR 18 2003 by Holmberg BA, Wang HT, Norbeck JM, Yan YS, Zeolite Beta as described in MICROPOROUS AND MESOPOROUS MATERIALS Volume: 25 Issue: 1-3 Pages: 59-74 Published: DEC 9 1998 by Camblor MA, Corma A, Valencia S), and
• Cu MOF: A metal organic framework complex prepared from Cu and trimesic acid as described in Science 283, 1148 (1999); Stephen S.-Y. Chui, et al. "[Cu3(TMA)2(H2O)3]n A Chemically Functionalizable Nanoporous Material".
[00088] Nanostructured additives 16 may be especially beneficial when used in combination. Relatively insoluble nanostructured additives 16 may be used in combination with one or more additional additives 16 to form what may be called a "hybrid" TFC membrane 10. Nanostructured additives 16 may be considered to be relatively insoluble because, although primarily insoluble, we have discovered that some nanostructured additives may release a small amount of soluble metal ions into solution.
[00089] Conventional nanoparticle additives release only on the order of a few parts per million of the soluble metal or other species in solution as shown in the tables of examples below. These small amounts of soluble species are not typically sufficient, by themselves, to provide the benefits of the desired substantially improved membrane operational characteristics. We have discovered, however, that when certain other additives are also present in addition to the nanoparticle additives, such as the same or certain different soluble species, the desired membrane characteristics may be achieved.
[00090] One of the other additives which - when combined in appropriate quantities with a nanostructured additive - produces the desired characteristics is mhTMC, one of the forms of hydrolyzed TMC that is sometimes present in commercial TMC. Conventionally, impure TMC has been intentionally avoided in the fabrication of TFC membranes, that is, the purity of the TMC is conventionally thought to be of great importance. However, we expect that commercial TMC is not always as pure as promised by the vendors. We have discovered that TFC membranes made with such a controlled amount of some of these impurities may produce substantially better flux characteristics. In particular, we have successfully used mhTMC as an additive in combination with nanoparticles to achieve membrane performance that conventional techniques have not been able to provide.
[00091J As described below, especially with regard to the tables of examples, such other additives in addition to mhTMC - useful with nanostructured additives to produce a hybrid TFC membrane with improved operating characteristics - include alkaline earth metal complexes and selected other elemental complexes.
[00092] Aluminosilicate zeolites with a Si:AI ratio less than 1.5:1 may also be useful as nanostructured nanoparticle additives 16, especially if desired for their release of Al species in solution as part of additive 16. Mordenite and ferrierite are examples of zeolites with calcium or magnesium exchangeable counterions that may be useful as nanoparticle additives 16, especially if desired for their release of alkaline earth metal species in solution.
B. Particle Size
[00093] The particle size of additives 16 for relatively insoluble additives -such as nanoparticle additives 16 - may conveniently be described in terms of average hydrodynamic diameter, assuming a spherical shape of the particles. Selected nanoparticle or other additives 16 can have an average hydrodynamic diameter of from about 10 nm to about 1000 nm, from about 12 nm to about 500 nm, and most preferably from about 50 nm to about 300 nm.
[00094] Inclusion of suitable relatively insoluble additives 16 (e.g. additives having optimized size, shape, porosity, and/or surface chemistry) appropriate process and preparation techniques, can lead to well dispersed additive solutions which may result in the inclusion of a larger number of additives 16 in the final interfacially polymerized membrane being prepared.
C. Dispersion [00095] Relatively insoluble additives, such as nanoparticle additives 16, can exist either as isolated and individual species or as building blocks incorporated in larger aggregate structures when in solution. These aggregate structures can be fairly stable and unchanging such as those formed during synthesis (for instance during calcination of zeolites) or they can be transient structures arising from thermodynamics of the additives and solution. Well-dispersed solutions, that is solutions in which additives 16 are well-dispersed, primarily contain isolated and individual particles rather than aggregate structures of such particles. In particular, it may be preferable to use a solution containing primarily isolated and individual particles and very few larger structures such as aggregates. In this manner the largest number of isolated particles can be incorporated within the final membrane and/or serve to optimize the structure of the membrane.
[00096] It can therefore be helpful, to aid in the dispersion of nanostructured additives 16, to use particles of a tighter size distribution by controlling what may be called polydispersity. Polydispersity can be calculated by dividing the volume average particle diameter by the number average particle diameter. A polydispersity approaching 1 indicates a tight range of sizes, while a bigger number indicates a larger range of sizes. Preferred polydispersities are preferably in the range of about 1 to 20, and most preferably in the range of about 1 to 3.
[00097] One means of doing this is through the use of a centrifuge. In a centrifuge, particles of larger mass have a faster settling velocity and form sediment at the bottom of a container while the remaining particles stay in solution. By removing the remaining liquid or the sediment both a different size and polydispersity can be obtained, e.g. particles having a smaller average size and as well as a smaller range of sizes.
[00098] Another method of improving polydispersity is through the use of microfluidization. For example, using sonication alone on sample of 100nm LTA, may lead to a dispersion with a polydispersity of 62.4, while use of sonication followed by microfluidization using a Microfluidizer® process and centrifugation may lead to a polydispersity of 1.7. A separate sample of 400nm LTA after sonication and microfluidization had a polydispersity of 1.53. Microfluidizer® is a trademark of Microfluidics Corp. of Newton, MA.
D. Nanotubes
[00099] When nanotube additives 16 are provided in the presence of the interfacial polymerization reaction, it may be preferable to include surfactants such as: alkyl poly(ethylene oxide), copolymers of poly(ethylene oxide) and poly(propylene oxide) (commercially called Poloxamers or Poloxamines), alkyl polyglucosides including octyl glucoside or decyl maltoside, fatty alcohols including cetyl alcohol or oleyl alcohol, cocamide MEA, or cocamide DEA, to help disperse the nanotubes. These may also be chosen so as to help align nanotube additives 16 in a specific arrangement. It will be obvious to one skilled in the art to use other nonionic, cationic, anionic, or zwitterionic surfactants to aid in dispersing or aligning the nanotubes, or other relatively insoluble additives 16.
[000100] Nanotube additives 16 may be carbon nanotubes and/or may be made of FeC, titania, WS2, M0S2, boron nitride, silicon, Cu, Bi, ZnO, GaN, In2O3, vanadium oxide, or manganese oxide. When carbon nanotube additives 16 are used they may be single or multiwall, and may have a functionalized surface including derivitization with alcohol or carboxylic acid groups. Nanotube length may be from 100nm up to 50 microns, more preferably 100nm to 2 microns, and more preferably 0.5 microns to 2 microns. Nanotube diameter may be less than 50nm, preferably less than 25 nm and more preferably from 1-2nm. Nanotube additives 16 may be thoroughly rinsed, or used as is. When used as is, trace impurities may be present including unreacted carbon precursors and/or carbon in other phases, oxidized materials, nanotube synthesis materials such as cobalt containing compounds, and/or other impurities. Nanotube additives 16 may also be processed before use to make them more beneficial for use in TFC membrane 10. For instance, laser ablation or treatment with a strong acid can be used to shorten the average length of the nanotubes. Ultra-high pressure homogenization, for instance by a Microfluidizer® process, may be used to break up nanotube bundles and to shorten average nanotube length. [000101] In some instances it may be preferred to align nanotube additives 16 within discrimination membrane 24. For example in some instances, it may preferred to align nanotube additives 16 normal to the superficial membrane surface. This can be used for example in situations where transport occurs through the interior of the nanotube and the smallest length of nanotube is desired to minimize resistance to transport. This can be accomplished by utilizing a magnetic catalyst that is incorporated with at least some, and preferably a plurality, of each of the nanotubes of nanotube additives 16. In this case, a magnetic field may be used during the interfacial polymerization to then trap nanotube additives 16 in this configuration. In a similar manner, surfactants may be used to align nanotube additives 16, particularly when used in aqueous phase 14. Suitable surfactants include: alkyl poly(ethylene oxide),copolymers of poly(ethylene oxide) and poly(propylene oxide) (commercially called Poloxamers or Poloxamines), alkyl polyglucosides including octyl glucoside or decyl maltoside, fatty alcohols including cetyl alcohol or oleyl alcohol, cocamide MEA, or cocamide DEA. It may also be possible to use other nonionic, cationic, anionic, or zwitterionic surfactants to aid in aligning the nanoparticles.
[000102] In other instances, the preferred alignment may be in the plane of membrane 10. This allows much longer nanotube additives 16 to be used that can impart improved mechanical properties to TFC membrane 10. To accomplish this, shear may be applied to the coating solution, for instance by application of the aqueous or organic phases 18 and 14 by a slot die coating method, or a dip coating process. Nanotube additives 16 may be aligned by this method in either the aqueous or organic solution.
[000103] TFC membranes 10 containing nanotube additives 16 can also have surprising biocidal activity. It appears, in some instances, that partially exposed nanotube additives 16 may be able to pierce, cut or otherwise interfere with the cell walls of microorganisms leading to cell death. In this way, the surface of TFC membrane 10 may exhibit antimicrobial activity.
B.2 Alkaline earth metal additives 16 [000104] As shown in the tables below - although to our knowledge, alkaline earth metals have not been used as additives in TFC membranes and were not expected to work - we surprisingly found that alkaline earth metal additives would in fact work extremely well at increasing membrane operational characteristics, e.g., permeability, In particular, alkaline earth metal additives 16, preferably magnesium (Mg), calcium (Ca), strontium (Sr) and/or beryllium (Be) typically in connection with a complex - e.g., beta-diketonate complexes such as acetylacetonate (acac) - have surprisingly proven very useful as additives 16 to increase flux of resultant TFC membrane 10. Alkaline earth metals as a group provide other advantages because they can be safe, abundant, low cost, and easy to use in processing. Members of this group - including magnesium, calcium, and strontium - are also environmentally benign and can be available as counter ions from zeolite nanoparticles.
B.3 mhTMC additive 16
[000105] We have discovered that the presence of mhTMC during interfacial polymerization has a strongly beneficial effect on membrane performance, especially by increasing flux, and that the presence of di-hydrolyzed TMC may also provide some benefits, especially in reduced concentration. Tri-hydrolyzed TMC, trimesic acid, may also be present in commercial batches of TMC, but it is believed not to be soluble in at least most formulations used in the fabrication of TMC membranes and therefore is typically not involved in the interfacial polymerization process. The effect of tri-hydrolyzed TMC on interfacial polymerization of TFC membranes, if any, is not currently known.
[000106] Referring now to Fig. 11 , monohydrolyzed trimesoyl chloride - that is, mhTMC - is illustrated in a conventional manner. This form of hydrolyzed TMC may be used directly as additive 16 and/or by the inclusion of partially hydrolyzed TMC in organic phase 18, or both, especially if care is taken to remove or otherwise limit the involvement of di- and/or tri-hydrolyzed TMC species by, for example, filtering organic phase 18 to selectively remove at least some of the aggregate structures formed thereby. In the figure, mhTMC is illustrated as a molecule of TMC in which one of the -Cl bonded groups has been replaced with a bonded OH group. [000107] Although conventionally it has been believed to be important to use relatively pure TMC in the fabrication of TFC membranes, we have discovered that it may be beneficial to have a small amount of mono-hydrolyzed TMC (1-carboxy- 3,5-dichloroformylbenzene or mhTMC) or di-hydrolyzed TMC (1 ,3-dicarboxy-5- chloroformylbenzene) present, e.g., in organic phase layer 18, during the interfacial polymerization reaction. The ratio of mono and/or di-hydrolyzed TMC to TMC, e.g., in the organic phase layer 18, may preferably be in the range of on the order of about 1.0/100 to 100/100, more preferably from 1.667/100 to 33/100, and most preferably about 1.5/100 to 5/100. Further, the concentration of mhTMC in a mixture of mono- and di-hydrolyzed TMC used as additive 16 is preferably greater than 25%, more preferably at least 75% and most preferably near 100%.
[000108] To alter performance or solubility, a salt of mhTMC additive 16 may be used in place of the acid form. Preferred salts may be those formed from substituted amines such as di-, tri-, or tetra-methyl, ethyl, propyl, or butyl derivatives.
[000109] In addition to mhTMC additives, other partially hydrolyzed reactants and/or additives 16 based thereon may also be effective at improving flux. For example, monohydrolyzed versions of 1 ,2,4-benzenetricarbonyl trichloride; 1 ,2,3- benzenetricarbonyl trichloride; and tricarbonyl chloride substituted naphthalene, anthracene, phenanthrene, biphenyl, or other aromatic rings may be used. Tricarbonyl chloride substituted cycloaliphatic rings, or bicycloaliphatics are also included. Carbonyl chlorides of higher substitution than three may also be di- or higher hydrolyzed, as long as at least 2 carbonyl chloride groups remain allowing polymerization to occur. Nonhydrolyzed variants of these additives may also be used as the reactant in organic phase 18.
[000110] Preferred concentrations of mhTMC additive 16 are in the ranges from about 0.0025% to 0.1 wt.% and more preferred from 0.005% to 0.1% by wt.%, in organic layer 18. Preferred TMC/mhTMC ratios in organic phase 18 are preferably in the range of less than about 50:1 , more preferably less than about 25:1 , more preferably less than about 15:1 and most preferably less than about 1 :1. [000111] It may also be beneficial to sonicate the solution. Sonication may serve to better disperse mhTMC additive 16 in organic solution 18. Sonication may also serve to drive reactions that would otherwise require higher temperatures, catalysts, or initiators to occur. It may also be useful to use cosolvents to better solvate the mhTMC additive. Preferred cosolvents are those that are able to form clear solutions of the mhTMC before dilution. Particularly preferred are aromatic solvents including benzene, toluene, xylene, mesitylene, or ethyl benzene. These cosolvents are preferably used at sufficiently low concentration to not negatively affect membrane formation or performance.
B.4 Selected Other Additives 16
[000112] Other suitable additives 16, may include one or more of the transition metals or other inorganic additives - alone or in combination with nanostructured materials, alkaline earth metals or inorganic additives including hydrolyzed additives such as mhTMC - that are present as an at least partially soluble compound containing a central atom having a Pauling electronegativity of less than about 2.5. Although there have been some published attempts to use some of these additives in TFC membranes, these prior attempts have generally been relatively ineffective at increasing membrane permeability.
[000113] We have found, however, that by adjusting the concentration of the reagents used to prepare TFC membrane 10 to specific ranges not previously identified, many of these alternate additives 16 can be made to work substantially more efficiently. More specifically, the concentration of TMC has been found to be very important in controlling the effectiveness of many of these alternate additives 16. Using concentrations of TMC 50% to 500% higher than commonly used in the industry (for example 0.1%) results in at least some of these alternate additives 16 giving a significantly larger increase in flux.
[000114] In general, in our work, we have discovered suitable alternate additives 16 that can advantageous be used in fabricating membranes 10 prepared in accordance with the concentration ranges of additives and reagents presented herein. In addition to the nanostructured materials, alkaline earth metals and mhTMC discussed above, we have successfully used other additives 16 in which the ligand is bound to an element selected from Groups 3 - 15 of the Periodic Table (IUPAC), particularly from Rows 3 - 6 of those groups.
[000115] As shown in the tables below, suitable alternate additives 16, typically in a complex, e. g., with a beta-diketonate such as acetylacetonate (acac), include aluminum (Al), cadmium (Cd), chromium (Cr), cobalt (Co), copper (Cu), gallium (Ga), hafnium (Hf), indium (In), iron (Fe), at least some of the lanthanoid (Ln) elements, - e.g., praseodymium (Pd), erbium (Er) and ytterbium (Yb) -, molybdenum (Mo), palladium (Pd), phosphorous (P), ruthenium (Ru), Tin (Sn), vanadium (V), and Zinc (Zn).
B.5 Additive characteristics
[000116] Generally preferred concentrations of additive(s) 16 are from 0.005 wt.% to 5 wt.% by wt.% or more preferred from 0.05 wt.% to 1 wt.% in either aqueous layer 14 or organic layer 18 - or both.
[000117] In addition, concentration ranges for groups of additive(s) 16 also include from the lowest concentrations - plus or minus 20% - to the highest concentrations - plus or minus 20% - listed in the tables for groups of the same or similar examples where the increased flux is at least 25% and/or the rejection is at least 90%. In addition, concentration ranges for groups of additive(s) 16 also include from the lowest concentrations - plus or minus 20% - to the highest concentrations - plus or minus 20% - listed in the tables for groups of the same or similar examples where the increased flux is at least 25% and/or the rejection is at least 90%.
[000118] Sonication may also serve to drive reactions that would otherwise require higher temperatures, catalysts, or initiators to occur. It may also be useful to apply cosolvents to better solvate the metal complex. Preferred cosolvents are those that are able to form clear solutions of the additives 16 before dilution. Particularly preferred are aromatic solvents including benzene, toluene, xylene, mesitylene, or ethyl benzene. These cosolvents are preferably used at sufficiently low concentration to not negatively affect membrane performance.
[000119] Suitable additives 16, in addition to nanoparticles or nanotubes, may include salts or compounds that are dissolvable to some extent in either aqueous phase layer 14 or organic phase layer 18 or both to make available the selected elements such as alkaline earth metals, mhTMC or the selected elements from Groups 3-15 of the Periodic Table (IUPAC) available during interfacial polymerization. Different species may be dissolved in aqueous phase layer 14 and in organic phase layer 18. Additives 16 may be added in a soluble form or as part of a complex, for example, with a beta-diketonate such as an acetoacetonate, e.g. acac complex. To improve effectiveness and solubility, the beta-diketonate may also be fluorinated for instance in hexafluoroacetylacetonate, or trifluoroacetylacetonate, or may include longer aliphatic chains such as in 2,2,6,6- tetramethyl-3,5-heptanedionate. Other examples of appropriate beta-diketonates are well known in the art.
B.6 Post-fabrication Analysis
[000120] As noted above, one or more additives 16 may be added during fabrication of membrane 10 by preferably being dispersed into aqueous phase 14 and/or organic phase 18 so that the one or more additives 16 present during the interfacial polymerization beneficially alter the polymer structure of the resultant discrimination membrane 24. However, fabrication analysis of this TFC membrane 10, particularly of discrimination membrane 24 therein, may not be a reliable measure of the concentration or even existence of some additives 16 used in the fabrication of membrane 10.
[000121] Some additives 16 - such as nanostructured additives including LTA and other zeolites and nanotubes - are not particularly if at all soluble in aqueous phase 14 or organic phase 18 and are easily detected in the resultant membrane 10, typically in discrimination membrane 24. These additives may be considered detectable additives 16. [000122] Alkaline earth metal - and other additive materials discussed herein - may be present during the interfacial polymerization whether added in the form of a complex, e.g., with acetylacetonate, or in a salt or other compound soluble in aqueous or organic phases 14 or 18. Further, these additives may be added by other means, such as in some other solvent or mechanism which makes the additive available during the interfacial polymerization process. As shown for example in examples 2-20 of the tables of examples included herein below, alkaline earth metals may be added to organic phase 18 as additive(s) 16 in the form, for example, of Sr(F6acac2), Ca(F6acac)2, Mg(F6acac)2 or Be(F6acac)2.
[000123] These alkaline earth additives may therefore be considered to include Sr, Ca, Mg or Be additive 16 as well as, or as part of an (F6acac) or other acetylacetonate additive 16. However, such - perhaps relatively more soluble - additives 16 are often not present in membrane 10 at clearly detectable levels after fabrication. Although the reason is not clearly understood, it is believed that the presence of such undetectable additives 16 during fabrication alters the resultant polymer structure of discrimination membrane 10. However, the undetectable additive 16 material may be at least partially washed away and/or partially otherwise rendered undetectable (or both) during fabrication processing after effecting the polymer, perhaps in the one or more washing steps.
[000124] The test results which indicate that TFC membranes 10 fabricated with nanoparticle additives 16 are more efficacious in resisting or reducing fouling strongly suggests that the presence of a detectable additive 16 - e.g., an additive 16 as discussed herein which is substantially retained in discrimination membrane 24, may be at least a major factor in the improvement of fouling resistance from nanoparticle additives 16, at least for membranes 10 fabricated in accordance with the processing steps and ranges described herein.
[000125] In any event, post fabrication analysis may not accurately determine the concentration - or even the presence - of some of the additives 16 and may not be useful for fabrication or quality control purposes. For example, as shown in Table 2, nanostructured materials such as nanoparticles may be combined with many types of other additives 16 including the alkaline earth metals discussed above and/or mhTMC, another undetectable additive. Post-fabrication analysis of membranes 10 formed with such additives will likely detect the presence of the LTA additive 16 while not indicating the actual concentration - or likely not even detecting the presence - of the alkaline earth metal, acetylacetonate, mhTMC additives or another undetectable additive.
[000126] Similarly, when a zeolite or other nanostructured additive 16 -such as LTA - is selected and pre-processed in accordance with techniques disclosed herein and used as an additive in the fabrication of a membrane 10, the nanostructured additive may release an additional additive, such as a soluble metal species.
[000127] For example, as shown in examples 2-4, 57-60 and 63-65, a soluble metal ion such as Al (or Ga) may be a useful additive 16 when added for example as sodium aluminate, aluminum chloride, aluminum citrate, in a complex with acac or when released for example from LTA and/or both as long as it is present in an appropriate concentration during the interfacial polymerization process. In the example of the membrane 10 above fabricated with additives 16 including LTA, an alkaline earth metal complex and mhTMC, only the LTA may be present in detectable quantities after fabrication. If any of the other additives 16 are detected at all, the detected concentration may well be inaccurate, typically much lower than actually used.
[000128] The only currently available technique we are aware of for determining the presence and concentration of the so-called "undetectable additives 16" in a TFC membrane is by comparison of flux and rejection characteristics of a membrane 10 made with such additives with an appropriate control membrane, made the same way, but without the inclusion of such additives.
[000129] In the tables of examples, the column heading "% Imp." represents the percentage flux increase of membrane 10 made with additives 16 over the same membrane 10 made without additives. Test procedures - such as the use of high purity TMC in organic phase 18 - were used to minimize the effects if any of impurities acting as additives.
[000130] In examples 2-83, example 1 represents the control membrane. Fabrication according to example 28 produced an exemplar membrane 10 using 4% MPD and 0.30% TMC. The recorded ratio of MPD to TMC, on a wt% to wt% percentage basis, is 4/0.3=13.33 and is recorded in the column headed "MPD/TMC Ratio". In example 28, 0.05% LTA was added to aqueous phase 14 and 0.058% Sr(F6acac)2 was added to organic phase 18 as additives 16 and is recorded in the columns headed "Aqueous 14 Additive 16" and Organic 18 Additive 16". In this fabrication, no nanostructured material was added as additive 16 to organic phase 18 as recorded in the column headed Organic 18 Additive 16".
[000131] The flux recorded by testing exemplar membrane 10 fabricated according to example 2 is recorded as 36.8 GFD. The rejection, e.g., of salts, was recorded as 99.57%. The control membrane fabricated for example 2 is shown in example 1. This same control membrane fabrication was used for most examples shown in these tables unless otherwise noted.
[000132] The fact that the same control membrane characteristics were consistently reproducible strongly indicates that the test procedures were consistent but even more importantly, indicates that the portion of the fabrication process - not including additives 16 - was a good process and under control. For example, the use of the recorded MPD and TMC concentrations and ratio were in the ranges discussed herein below as preferred and can be clearly be used to repeatably produce membranes to predetermined parameters.
[000133] In some examples, such as examples 52-55, no flux improvement was recorded because the examples were performed to verify the usefulness of fabrication parameters - such as MPD, TMC and MPD/TMC ranges - rather to determine flux improvement over a control membrane which may or may not have been fabricated at that time. However, if it is desirable to determine the flux improvement for an example in which the flux of the control membrane is not known or not recorded, this may be done to a reasonable accuracy by a relatively easy two-step process.
[000134] For example, the percentage flux improvement for example 52 is not recorded, presumably because the test was used to determine the usefulness of a membrane with the noted additives fabricated with a slightly higher TMC concentration and therefore a resultant slightly lower MPD/TMC ratio. A good approximation of the percentage flux improvement for example 52 can be made by making a control membrane in accordance with the parameters specified herein and, of course, good practice and recording the results.
[000135] The flux improvement percentage may then easily be determined. If the flux of the new membrane made in accordance with example 2 has a different flux value than as shown in the tables, it is reasonable to use the flux improvement ratio determined as above adjusted for the difference between the flux improvement shown in the tables and the flux improvement shown by the newly fabricated membranes.
[000136] The need for the use of the flux improvement ratio as a guide to determining the presence and concentration of one or more additives 16 which are not fully detectable by post fabrication analysis of membrane 10, as noted above, results from the fact that most if not all non-nanostructured additives 16 may not be easily, if at all, detected after fabrication. Further, the flux improvement guide may be the only current way to attempt to determine the presence and concentration of a suspected additive 16 in a unknown membrane. The use of the preferred process parameters for making the control and test membrane provide the best current way to estimate the presence of a suspected additive as well as its approximate concentration. The progress of technologies of analysis may improve with time so that the determination of the presence of the so-called "soluble" or non-detectable additives 16 may be possible in the future either by direct detection of the additive, or by measuring differences in the resulting membranes chemical structure or morphology.
Section C: Process Techniques. C.1 Techniques for introducing additives 16
[000137] Referring now again to Fig.s 1-9, aqueous phase layer 14 is shown - with additive(s) 16 dispersed therein - on an upper surface of support membrane 12 when interfacial polymerization has - or is about to - occur as shown in Fig. 1. In Fig. 2, additive(s) 16 are shown dispersed in organic phase layer 18. Similarly, additive(s) 16 may be included in both aqueous layer 14 and organic layer 18 as shown in Fig. 3.
[000138] Generally preferred concentrations of additive(s) 16 are from 0.025 wt.% to 0.25 wt.% by weight or more preferred from 0.024 wt.% to 0.18wt.%, or most preferably from 0.05% to 0.15% wt in either aqueous layer 14 or organic layer 18 - or both.
[000139] As shown in Fig. 4, additive(s) 16 may also or alternately be introduced via water solution 11 on an upper surface of support 12, typically before contact between aqueous or organic phases 14, 18 in order to be present during the interfacial polymerization. Water solution 11 may be, at least in part, a layer between aqueous phase 14 and support membrane 12 which may be in liquid communication with both aqueous layer 14 and the water wetted surface of support membrane 12. Additives 16 may also be introduced, in order to be present during the interfacial polymerization, by any other convenient technique. For example, hydrolyzed additives may be introduced by direct addition to - or by using a compound including such hydrolyze additives 16 - as part of the fabrication process. As one example, mono- and/or di-hydrolyzed TMC may be used in organic phase 18 to introduce hydrolyzed TMC additives 16 to the interfacial polymerization reaction.
[000140] Referring now in particular to Fig.s 5-7, after fabrication, membrane 10 may include additives 16, such as partially soluble nanostructured materials and the like, in discrimination membrane 24. In these figures, discrimination membrane 24 is indicated as including additives 16, for convenience even though at least some of additives 16 may not be detectable in discrimination membrane 24 after fabrication.
For example, some of additive 16 present during interfacial polymerization between organic and aqueous phases 18,14 may be removed- e.g., by washing or later processing - or may simply be present in quantities too small to detect with current techniques available to us - or may not be present at all. Hydrolyzed additives 16, such as mhTMC are believed to be absorbed or converted to another molecule during inter
[000141] Referring now also to Figs. 8 and 9, Fig. 8 illustrates the presence of additives 16 in membrane 24, which indicates at least that at least some additive 16 was present during interfacial polymerization. In Fig. 8, additives 16 shown piercing or at the upper and lower surfaces of membrane 24 indicate additives 16 which are detectable at these locations. Similarly, Fig. 9 indicates the use of additives 16 during the fabrication of discrimination membrane 24 - some of which may or may not be detectable after production - as well as additives 16 present and detectable at the interface between membrane 24 and support membrane 12 after production.
[000142] Referring now Fig. 10, a technique is described which permits the fabrication of support 12, at least in a laboratory setting, which includes additives in this layer. As noted above, additives 16 may be detectable after fabrication in support layer 12 or not. A similar technique may also be used to include additives 16 in fabric layer 20, depending upon the construction of fabric layer 20.
[000143] In Fig. 10, casting solution 13 on fabric 20 becomes support membrane 12 after processing. Additives 16, such as nanostructured, alkaline earth, and other specific additives 16, described herein may also or alternately be incorporated into support membrane 12 by including such additives with casting solution 13 used to prepare support membrane 12 on fabric 20 on glass plate 15 - and/or by including additives 16 within the non-solvent, e.g., Dl water, used to induce phase inversion during fabrication of support membrane 12. Glass plate 15 may conveniently be used in a laboratory setting but would likely not be used in a continuous coating process for fabricating support membrane 12.
[000144] Porous support membranes 12 are typically kept wet until use. The amount of metal ion or other additives 16 introduced to the interfacial polymerization reaction between aqueous phase 14 and organic phase 18 may, in some cases, be increased by storing support membrane 12, e. g., in roll form, for a suitable time period such as at least one hour before fabrication of TFC membrane 10.
[000145] It may also be important to allow sufficient time for metal ion or other soluble additive 16 to diffuse from a source such as support membrane 12 - e. g., into aqueous phase 14 - before or during interfacial polymerization. A time of between 2 seconds and 5 minutes, and preferably between 10 seconds and 2 minutes is currently believed to be suitable for such diffusion so that metal ion additives 16 - for example from nanoparticle additives 16 - may be introduced to the interfacial polymerization reaction to impact the polymer structure of resultant discrimination layer 24 and improve performance of TFC membrane 10 by, for example, by increasing water flux there through for the same applied pressure.
[000146] Processing may include selecting nanostructured additives 16, such as other inorganic mineral compounds for other characteristics including solubility. For example a nanostructured additive 16, may also be selected for its ability to release further additives 16 into solution, such as soluble metal species, based on the degree of crystallization of the additive. Amorphous portions of nanoparticle additives 16 are typically more soluble than crystalline portions of the nanoparticle and processing can further increase solubility. The amount of crystalline material can be determined through several techniques including x-ray crystallography.
[000147] For this and other reasons, it may be advantageous to pre-process nanoparticles or other additives 16 by using sonic energy from a sonic probe or sonic bath before incorporation thereof in support membrane 12 and/or further sonicate either aqueous phase 14, organic phase 18 or both just before or during interfacial polymerization. Sonication of additives 16 may include immersing a sonic probe directly into casting solution 13 from which support membrane 12 is formed and/or placing solutions with additives 16 in a vessel and immersing the vessel in a sonic bath. Solutions may be subjected to sufficient sonic energy from 10 to 60 minutes, more preferably about 30 minutes, to aid in the release for example of metal species additives 16, such as aluminum or alkaline earth metal ions 16, into the solution. Increased sonication time may release additional metal species additives 16 into solution up to some equilibrium limit.
[000148] Processing of selected nanoparticles or other additives 16 may also be accomplished using shear, cavitation, and impact forces generated by 1 to 60 minutes in a Microfluidizer® process. After processing, the solution may contains additional metal species that were dissolved, for example, from nanoparticles 16.
[000149] Processing of selected nanoparticle or other additives 16 may be also accomplished using a solution containing additive 16 in a vessel with a stir bar and using a stir plate to propel the stir bar in the solution or alternatively using a motorized propeller to stir the solution or alternatively using a laboratory tray shaker. Stirring or shaking may be most effective for nanoparticle or other additives 16 selected for high solubility in either the aqueous or the organic phases 14, 18 or both.
[000150] Similarly, processing of selected nanoparticle or other additives 16 may also or solely be accomplished in a vessel containing a solution of additive 16 and adjusting the pH either lower than about 6 and more preferably lower than about 5 for at least 30 seconds, and/or to a pH greater than about 8 and more preferably greater than about 9 for at least 30 seconds. Whether pH is adjusted higher than about 8 or lower than about 6 may dependent on the solubility characteristics of the specific type of nanoparticle or other additive16.
[000151] Processing may assist in achieving the desired concentrations of additives 16 in solution. In some embodiments, additives 16 may have been broken or partially dissolved using shear, cavitation, or impact forces to maximize said soluble metal or other species introduced to the interfacial polymerization mixture. Nanoparticles or other relatively insoluble additives 16 may be calcined for at least 1 hour at 200° C or more. The processed additives can have been shaken in aqueous solution on a shaker table for at least 1 minute.
[000152] Nanoparticles or other relatively insoluble additives 16 may also have been processed with heat in a solution for at least 5 minutes at a temperature of 40 0C or more. Nanoparticles or other relatively insoluble additives may have been processed with chelating agents in solution to bind soluble metal species or other atomic or molecular additives.
C.2 TMC Concentration and Purity
[000153] We have also determined that the addition of suitable additives 16 appear to require - or is at least appear most pronounced - when certain other conditions of the membrane fabrication process are modified from conventional membrane fabrication conditions. For example, we have found that by adjusting the concentration of the reagents used to prepare membrane 10 within specific ranges, additives 16 can be made to work more efficiently. That is, the concentration of TMC was clearly found to alter the effectiveness of additives 16. In particular, low concentrations of TMC was found, in some cases, to lower the effectiveness of specific additives - e.g., soluble metal ions, so much that the additives were not particularly useful in improving flow or rejection characteristics. Using high concentrations of TMC, typically much higher than conventionally used in the industry, results in such additives 16 causing a significantly larger increase in flux in TFC membrane 10.
[000154] Further, although conventional wisdom dictates that the purity of the TMC is supposed to be of paramount importance, we have also discovered that under some conditions, TMC with a lower purity - e. g. partially hydrolyzed TMC - in organic phase 18 often has the beneficial effect of producing membranes, such as RO membranes 10, with substantially higher flux while maintaining rejection characteristics.
[000155] In some cases, performance of TFC membrane 10 can also be improved by rinsing. This may be done in a high pH aqueous solution after TFC membrane 10 is formed. For example, membrane 10 can be rinsed in a sodium carbonate solution. The pH may preferably be from 8-12, and exposure time may vary from 10 seconds to 30 minutes or more. The rinse may alternately be at low pH to aid in removal of unreacted amine. This pH may, for example, be from pH 2 to pH 5. The rinse may alternatively be at a neutral pH. The rinse may alternatively be a hot water rinse with temperatures of 60°- 98° C. The rinse may also include a chlorine species such as sodium hypochlorite at a concentration in the range of about 500 to about 2000 ppm. The rinse may also include separate steps where combinations of the above rinse conditions are used sequentially. After rinsing the membrane may be dried, or may be left wet.
[000156] To prevent scratching of the surface of TFC membrane 10, or to alter the hydrophilicity of membrane 10, hydrophilic polymer layer 30 as shown in Fig. 6 may be applied to the surface of membrane 10. For example, a solution of polyvinyl alcohol in water may be applied to the surface of membrane 10 followed by a heat cure to produce layer 30.
C.3 MPDATMC Ratio
[000157] We have also discovered that the ratio of MPD to TMC may be another important factor in the preparation of high flux, high rejection, low fouling TFC membranes, particularly with additives 16, and combinations of additives 16, as described herein. The preferred range is less than a ratio of about 35 for use in conjunction with the TMC concentrations discussed above, more preferably less than 25 and even more preferably less than about 15. A most preferred ratio is about 13 for MPD/TMC on a wt% to wt% basis.
C.4 Preparation and purity of mhTMC additive 16
[000158] With respect now to Fig. 12, we have discovered from our experiments with mhTMC additive 16, synthesized from two lots of commercial TMC with different stated levels of purity, that the inclusion of di- and/or tri-hydrolyzed TMC contaminants has apparently predictable effects on flux improvement and on rejection characteristics of membranes 10 resulting there from. We have learned that concentrations of mhTMC additives 16 may depend in part on what other materials may included therewith. We have also discovered, based on our analysis of mhTMC additives 16, techniques for determining and/or selecting concentrations materials useful as superior additives 16. [000159] Relatively pure mhTMC was synthesized for the relevant examples described the tables below - in two lots, labeled lots 1 and 2 in the tables - as discussed in greater detail immediately below. Other monohydrolyzed polyhalides may be synthesized using similar methods for use in additives 16.
[000160] To prepare mhTMC, commercially available TMC was first purified by reflux in thionyl chloride with DMF as catalyst. Impurities were pulled off under vacuum. The purified TMC was then dissolved in methylene chloride and reacted with Wang Resin (a commercially available solid phase polymer with reactive hydroxy! groups) at 0° C. Dilute triethylamine was added drop-wise over 2 hours and the solution was then allowed to slowly warm up to room temperature overnight. Excess reagents were rinsed away with excess methylene chloride. Cleavage with trifluoroacetic acid lead to isolation of mhTMC.
[000161] Referring now to Fig. 12, after synthesis of purified mhTMC, the resultant product can be dissolved in deuterated toluene or deuterated acetone for further analysis. The compound identity and purity of mhTMC can be verified through the use of 1H-NMR as shown for example in this figure, which is a graphical representation of an analysis by this process of mhTMC. In the figure, the doublet at 8.6 ppm is believed to correspond to the two aromatic ring protons adjacent to both a carbonyl chloride and a carboxylic acid group. The integrated area of this peak, 1.99, is twice that of the triplet at 8.4 ppm because there are two protons. The triplet at 8.4 ppm corresponds to the single aromatic ring proton between two carbonyl chloride groups. Purity of this compound can be checked by comparing the integrated area of these protons versus those of the non-hydrolyzed TMC, di- hydrolyzed TMC, and trimesic acid compound identity and purity of the mhTMC was verified with 1H-NMR of the isolated solid. The NMR process was run in deuterated toluene.
[000162] The purity of the synthesized mhTMC additive 16 may be estimated from the NMR spectra. Crude and purified mhTMC is dissolved in deuterated toluene for the NMR analysis. The purity calculation may be performed by looking at the relative quantities of trimesic acid, 1 ,3,5-Benzenetricarbonyl trichloride, monohydrolyzed TMC and di-hydrolyzed 1 ,3,5-Benzenetricarbonyl trichloride. These values may then be reduced by any extraneous NMR peaks which usually impurities from the synthesis.
[000163] Referring now to Fig.s 13 and 14, membrane performance is illustrated graphically as a function of the concentration of mhTMC additive 16, adjusted for purity. Examples 169-171 and 173-182 for mhTMC reflect the concentration of the synthesized mhTMC additive 16 used for these tests, and indicates the source of the mhTMC, i.e. synthesized lots 1 or 2. In Fig. 13, lot 1 flux curve 32 illustrates the growth of flux for increasing concentrations of mhTMC additive 16, lot 1 , from 0%, representing the control membrane, to 0.025 wt%. Lot 1 rejection curve 34 shows the corresponding rejection characteristics for the same concentrations.
[000164] Fig. 14 shows the most useful portion of the mhTMC concentration range shown in Fig. 13 - from 0% mhTMC to 0.015 wt% for mhTMC lot 2. In particular, lot 2 flux curve 36 shows the growth of flux for membranes made with mhTMC lot 2, while lot 2 rejection curve 38 illustrates the decrease in rejection over this range of concentrations.
[000165] The curves in Fig.s 13 and 14 have been adjusted for the purity of the synthesized mhTMC. In particular, the data for lots 1 and 2 have been adjusted for the estimated concentrations of synthesized mhTMC based on an NMR assay, including simple percentage of materials dissolvable in toluene. In Fig. 13, for mhTMC lot 1 , the purity was estimated to be about 80% pure mhTMC - the remaining 20% believed to be primarily di-hydrolyzed TMC - while in Fig. 14 for mhTMC lot 2, the purity was estimated to be about 25% pure mhTMC, the remaining 75% was believed to be primarily di-hydrolyzed TMC. The curves have been scaled so that the curves for both lots 1 and 2 represent 100% pure mhTMC so they can be compared.
[000166] In Fig. 14, graph lines or curves 40 and 42 also represent the flux and rejection of membranes 10 for lot 2 mhTMC where organic phase 18 was filtered to remove larger contaminant structures believed to be the result of di-hydrolized TMC included with the mhTMC of lower purity. Any tri-hydrolized TMC present in either lot would likely have not been soluble and would have precipitated out of the mhTMC solution.
[000167] Regarding Fig. 13 in more detail, lot 1 flux curve 32 showed an increasing flux from 24 GFD at 0% concentration, i.e., at the control membrane concentration, to about 32.1 GFD at about 0.0075% concentration. The rate of growth of flux decreased at the concentration which has been marked with line 44, vertical deflection axis A discussed below. The flux continued to improve with increased concentration, but at a slightly slower rate, until the flux reached 39.7 GFD at the concentration which has been marked with line 44, vertical deflection axis B at about 0.0215% adjusted mhTMC concentration. Further increased flux concentration beyond deflection axis B, line 46, caused dramatically increasing flux up to 45.1 GFD at 0.2050% adjusted concentration.
[000168] Deflection axes A and B are simply vertical lines drawn on the graph to indicated concentrations at which the effects of additive 16, in this case mhTMC additive 16, appear to change. For example, for lot 1 , the flux for membranes 10 made with the indicated concentrations of additive 16, from 24 GFD to 32.1 GFD is shown as the concentration of additive grew is increased from 0 wt% (control membrane) to .005 wt%. The rate of growth of flux in this area was therefore roughly (32.1-24)/.005 ~ 1 GFD per .001 wt% increase of additive 16. However the flux increased at a lower rate from deflection axis A to deflection axis B, i.e., (39.7- 32.1)/(0.02125 - 0.005) ~ 0.5 GFD per .001% additive 16. The rate of increase of flux as a function of increasing concentration of additive 16 from deflection axis B with 39.7 GFD at .02125% to 45.1 GFD at .0250% is (5.4/0.0075) or 1.4 gfd per 0.001%.
[000169] In other words, points along membrane characteristic curves 32, 34, 36, 38, 40 and 42 which intersection lines 44, 46 and 48, deflection axes A and B, indicate that the rates of increase or decrease changed for both flux and rejection at these points, i.e., these deflection points are concentrations at which a feature, such as the second derivative of flux growth and rejection, changed. These deflection points may also be considered non-linearities. The fact that both flux and rejection rates of growth changed in an unusual way at the same concentration points appears to be significant is likely an indication that there was a change in the effect of the presence of additive 16 e.g., mhTMC, on interfacial polymerization, at these concentrations. Although the mechanisms are not understood, it is believed that at or about these "deflection point" concentrations, a non-linearity occurred in one or more mechanisms affecting the polymer structure being formed by interfacial polymerization due to the presence of additive 16.
[000170] In particular, as shown in Fig. 13, the rejection characteristics of the higher purity of mhTMC lot 1 were very good at the 0% concentration of the control membrane at 99.7% rejection. At deflection point A along deflection axis A, the membrane rejection was still very good at about 99.60% for the membrane 10 fabricated with mhTMC additive 16 having about 0.0075% adjusted mhTMC concentration. Thereafter, the rejection continued to decrease to 98.60% at 0.02125% at deflection point B along deflection axis B after which it decreased dramatically to 96.20% at about 0.0250% concentration.
[000171] Similarly, the addition of from 0% to perhaps 0.0150% adjusted concentration provided very useful performance of membrane 10, with concentrations of mhTMC as high as about 0.02% to about 0.02125% being useful at some conditions, but concentrations above that level, deflection axis B, line 46, suggest - together with the dramatically increased flux - probable damage to the polymer structure of discrimination membrane 24. The optimal point appears to be in the neighborhood of the deflection axis A, line 44 at about 0.0075% adjusted mhTMC additive 16 concentration for membrane 10 with about 32.1 GFD flux and 99.6% rejection.
[000172] In any event, a first major linearity, e.g., in the rate of growth of flux with increasing concentrations of additive 16 occurred in range including axis A, line 44, indicated as area 25 in the figure. This particular graph was drawn with limited data points, but the graph shown in Fig. 14 was drawn with additional data points to clarify this discussion. [000173] The optimum point for the parameters of membrane 10 required for a particular task may have to be determined by experimentation and may depend on the proposed use for membrane 10. For example, if rejection lower than about 97.6% was acceptable for a particular filtering task, increased flux could be obtained by increasing the concentration of additive 16. Alternately, if higher rejection was required, the concentration could be lowered. For example, membrane 10 could be fabricated with 0.0050% additive mhTMC 16 to have a flux of about 30.0 GFD and a rejection over about 99.6% or at 0.01% adjusted concentration to have a flux of about 33.5 GFD with a rejection of about 99.35%.
[000174] Detection and analyses of the deflection points or non-linearities in the effect on increasing additive concentration may be useful in determining the value of a particular additive when such non-linearities occur generally at the same concentration levels, improvements for example in preprocessing of additives 16 which tend to reduce the impact of such non-linearities and of course the selection of an appropriate concentration level for a particular additive 16 - including combinations of additives - for a particular task.
[000175] Referring now to Fig. 14, as will become apparent from the following more detailed discussion of the graphs and non-linearities of the effects of different concentrations of additive 16, this data provides the opportunity for much greater control of TFC membrane fabrication. In the particular example for mhTMC additive 16 concentrations, it is easy to conclude that after about .022%, the polymeric structure of the membrane has lost its selectivity and is probably damaged. The techniques presented in the following analysis of Fig. 14, especially when compared to Fig. 13, provide several very useful discoveries regarding fabrication of TFC membrane in general as well as TFC membranes with additives.
[000176] First is the identification of deflection points in the flux and rejection curves, that is detection of what appear to be non-linearities in the processes by which additives 16 alter the structure of the polymeric matrix formed by interfacial polymerization, /'. e., discrimination membrane 24. When concentration levels of additives 16 are found at which these non-linearities occur in both flux in rejection, and particularly at multiple levels of purity of additive 16, the materials included in additive 16 is a very likely a good candidate as an additive which can repeatably be used to fabricate membranes 10 with superior performance.
[000177] Further, comparison of such linearities for two very similar additive materials, e.g., as shown for lots 1 and 2 which differ by purity, permit a tradeoff between superior performance of one membrane characteristic with other membrane characteristics such as repeatable fabrication with predetermined flux and rejection characteristics. For example in Fig. 14, selection of concentration levels in area 49 permit fabrication of membranes using lot 2 additive 16 with a high flux in the range of 35.5 GFD at rejections of 99.24% to 99.05%. Analysis also indicates that preprocessing, e.g., by filtering lot 2 to remove larger structures - believed in this example to have resulted from the presence of di-hydrolyzed TMC in additive 16 - permits the selection of about a 0.0075% concentration of mhTMC of which can used to repeatably fabricate RO membranes 10 with relatively predictable flux and rejection performance.
[000178] That is, fabrication of membrane 10 using for example, filtered mhTMC as an additive, provides a slightly lower flux, say 33.2 GFD and a much better rejection rate, say 99.56%. This analysis makes it clear that selection of concentrations within area 49 will provide substantial fabrication repeatability. The identified non-linearities or deflection points in both Figs. 13 and 14 indicate a range of changes of concentration in which the effect on flux and rejection of a particular additive is limited. In particular, for each of lot 2 and filtered lot 2, area 49 represents low of at least predictable changes in flux together with low levels of change in rejection.
[000179] Now in greater detail with respect to Fig. 14, lot 2 flux curve 36, adjusted to reflect an estimated 25% concentration of pure mhTMC but not filtered, showed an increasing flux from the control membrane concentration of 0% mhTMC of 17.2 GFD, growing dramatically to about 36.2 GFD at about 0.00250% adjusted concentration and then growing to 35.5 GFD at which the rate of increase in flux growth leveled off, reaching about 36.4 GFD at lot 2, deflection axis A 48. Thereafter, the rate of flux increased and then slowly until flux reached about 38 GFD at about 0.0150% adjusted concentration.
[000180] However, filtered lot 2 flux curve 36 indicates that the flux increased linearly, from 17.2 GFD at 0% concentration, generally at the same rate of increase the resulted from increasing concentration of the higher purity of mhTMC from lot 1 to 26.4 GFD at deflection axis A of 0.0075% adjusted mhTMC concentration. The increasing flux rose to substantially the same increasing flux shown by the graph line of lot 2, unfiltered, at about 31.9 GFD at 0.0150% adjusted concentration. The fact that the lot 2 adjusted and filtered flux growth curves 36, 40 substantially join each other at a concentration of about 0.015% indicates good consistency in these test results.
[000181] The rejection characteristics shown along filtered lot 2 rejection curve 42, for membrane 10 made with mhTMC additives 16 from lot 2, adjusted and filtered, show little degradation of rejection from the control membrane value at 0% concentration to deflection point A along deflection axis A at about 0.0075% adjusted concentration.. The consistency between the deflections point and deflection axes indications in all three lots 1 , 2 and filtered 2 strongly suggest that the effects of the impurities are the same or similar in effect. These results suggest that effects - of the larger contaminants that were removed by filtering - are primarily on the rate of increase of flux with increasing concentration of additive 16, and less on rejection characteristics of membrane 10.
[000182] Although the concentration of mhTMC additive 16 in commercially available TMC- alone or together with other additives 16 such as nanoparticles, alkaline earth metals or other molecular additives - has not been determined, it is a matter of experimentation to determine the appropriate deflection point for optimal additive concentrations of the mhTMC and other additives, and combinations of additives, in accordance with the techniques as disclosed herein.
[000183] In particular, deflection point A - that is the point at which additional increases in additive 16 concentration produces a greater rate of loss in rejection characteristics - indicates a generally optimum concentration of additive 16, providing membrane 10 with both a high flux and a high rejection. Lower concentrations improve rejection at the cost of flux while higher concentrations improve flux at the cost of rejection. Deflection point B - the point at which increased concentration then produces an even greater rate of loss of rejection - indicates a possible defect in the polymer matrix structure of discrimination membrane 24 and should be avoided for most if not all applications of membrane 10.
[000184] It should be noted that, as shown in the graph of Fig. 14, when the results of lot 2 unfiltered were adjusted, a greater improvement in flux was achieved, for example just below and just above the concentrations at deflection axis A, presumably from the di- and/or tri-hydrolyzed or other contaminants which were not removed by filtering. The area between flux and rejection curves 36, 38 and 40, 42, for lot 2 and lot 2 filtered respectively- between 0% concentration and 0.02125% concentration, contaminant effected concentration zone 50 - therefore indicates the possibility of achieving a higher flux at a higher rejection without removing the larger contaminants by filtering, than can be obtained by the same purity mhTMC.
[000185] However, this anomaly - although it may be useful under some conditions - may be more difficult to control so that producing membranes 10, with a concentration in contaminant area 50, i.e., along flux curve 42, may be difficult to do commercially with consistent results.
[000186] The detection and use of deflection points A and B are believed to work the same way for other additives 16, not just mhTMC additive 16. However, when such other additives 16 are used, the unintentional use of additional, partially hydrolyzed TMC as a result of using less pure TMC for example in organic phase 18, may result in operation in contaminants area 50, along a line similar to flux curve 26 where the increased concentration of additive 16 does not produce a well controlled increase in flux. This may be particularly unsatisfactory when the level of TMC contamination causes area 50 to include deflection point B. That is, when the contamination of TMC, i.e., with mhTMC or di-hydrolyzed mhTMC causes the concentration of additives 16 to exceed deflection point B so that damaged discrimination membranes 24 are produced.
[000187] In summary, we believe we have discovered a very useful technique for determining appropriate concentration levels of additives 16, by identifying the deflection point of the curves at increasing flux above the level of the control membrane which allows us to knowingly choose concentrations of additives 16 appropriate for use in particular tasks for membrane 10 including the ability to select concentrations which may be more reproducible in commercial fabrication that merely picking the concentration at which the highest flux is achieved at an acceptable level of rejection. In particular, this technique permits the selection of a concentration and contamination levels which allows more consistent fabrication with a repeatable set of performance characteristics and obviates the need for altered formulations to combat such variability.
[000188] It is interesting to note that the rate of growth of flux as shown on lot 2 flux curve 36 changed at several different concentration levels. The same is true for the rate of decrease in rejection shown on lot 2 rejection curve 38. Based on these two curves alone, it would not have been easy to isolate 0.0075% mhTMC concentration as the deflection point to be selected, but the use of curves 32 and 40, showing relatively pure mhTMC with at least the largest contaminant structures removed, reflects the same concentration as the concentration to be selected.
[000189] Fig.s 13 and 14 illustrate our findings that the flux and rejection curves for concentrations of various useful additives 16 are typically relatively well behaved - that is, they change slowly and smoothly - from control membrane concentration (0%) to a concentration at which the polymeric structure of membrane 24 may have been damaged by the presence of too much additive 16 during interfacial polymerization. We have investigated the effects of contaminants in mhTMC in detail because di- and tri-hydrolyzed TMC contaminants are potentially present in any interfacial polymerization in which TMC is used in organic phase 18.
[000190] Lot 2 flux and rejection curves 36 and 38 are shown at a series of concentrations to illustrate the fact that the rate of change of flux and growth -i.e., the 2nd derivative of these membrane characteristic values - change at multiple concentrations within the range of concentration that may be used for fabricating membrane 10. The concentrations used for flux and rejection for lot 1, and filtered lot 2, are only shown at a few points along flux and rejection curves 32, 34 and 40, 42 to illustrate the relatively smooth changes in the rates of growth and decrease of flux and rejection from additives 16 which are not substantially effected by contaminates. This relatively dramatic difference is very useful in selection of an appropriate concentration for additive 16 for commercial fabrication of membrane 10, that is, fabrication which will produce predictable and controllable membrane characteristics under a wide variety of environmental conditions encountered in a fabrication facility.
[000191] In particular, referring to lot 2 flux and rejection curves 36 and 38 in Fig. 13, a concentration of additive 16 for use in a common task for membrane 10, e.g., for use in reverse osmosis (RO) of brackish or saltwater to produce pure or drinking water as shown above for example in Fig.s 5 and 6, would typically be a concentration at which the flux is higher than the flux of the control membrane which retains a rejection of perhaps 99.5%. A concentration of perhaps 0.0025% would likely be selected which provides resultant membrane 10 with membrane characteristics of 32.6 GFD and 99.45%. In some cases, a fabrication facility may chose a concentration of 0.005% to get the benefit of the higher 35.5 GFD even though the slightly lower 99.24% rejection might not meet the desired water purity. The selection of either of these concentrations, however, would likely encounter problems with repeatability and other fabrication limitations.
[000192] By using the techniques described herein, namely determining the effect of contamination and identifying deflection point A, along axis line 48, the fabricator would have the ability to select the 0.0075% concentration for additive 16, and perhaps with contaminant removal, fabricate membrane 10 with membrane characteristics of 33.2 GFD and 99.56% rejection under a wide range of conditions.
C.5 Theories [000193] Although not willing to be limited to our current hypotheses, the hybrid membranes described are believe to achieve better membrane performance because of the differing or cumulative effects of the relatively insoluble additive which typically remains in discrimination membrane 24 and the one or more other additives 16 which may not.
[000194] We believe that the introduction of one or more suitable additive(s) 16 into the interfacial polymerization of aqueous phase 14 and organic phase 18 ma have the effect of altering the polymer matrix of discrimination membrane 24 formed thereby so that substantial flux improvement may be achieved when compared to the flux of a control membrane made the same way but without the introduction of such addϊtive(s) 16 thereto.
[000195] The use of insoluble additives, such as nanostructured materials, e.g., nanoparticle or nanotube additives 16, seems to increase membrane flux performance - perhaps by modifying, interfering with and/or being included within the polymer matrix being formed - and the introduction of other, perhaps more soluble additives 16 seems to further increase flux performance by also interfering with and/or otherwise modifying the polymer matrix being formed. The insoluble nanostructured additives, such as nanoparticles or nanotubes, are also believed to be primarily responsible for increased resistance to fouling because at least a detectable concentration of the nanoparticles remain in membrane 10 after fabrication while detectable levels of many if not all.
[000196] The inclusion of at least some mono- or di-hydrolyzed TMC in organic phase 18 may permit an increased membrane flux, perhaps at the loss of some control of the fabrication process unless filtered.
[000197] Additives 16 are believe to assist, template and or otherwise alter the formation of the polymer matrix during interfacial polymerization to achieve the desired membrane performance characteristics. Some additives 16, such as nanoparticles and nanotubes are relatively insoluble materials and may alter the structure of the polymer matrix by physical interference, perhaps as the polymer matrix is formed around such insoluble materials to incorporate them in the matrix. This incorporation can lead to additional flow paths either through or around nanostructured materials or nanoparticle additives 16 leading to increased flux, or by other mechanisms increase the ability of the resultant polymer matrix film to permeate water and retain or reject solutes. For nanoparticles incorporating additional flow paths, the diameter of such flow paths must be of kept of appropriate size to reject desired impurities. The impact on the polymer structure of the incorporated additives 16 can occur in the area up to 10 nm, 1 micron, and even up to 100 microns from a particular nanoparticle additive 16. In such a way, dramatic increases in flux can be obtained by relatively few incorporated nanoparticle additives 16.
[000198] Referring now to Figs. 8 and 9, in some instances some additives 16 such as relatively insoluble nanoparticles may be located at the interface between support membrane 12 and thin polymer film of discrimination layer 24 whether or not they are included in discrimination layer 24. At this location at the surface of membrane 12, additives 16 such as relatively insoluble nanoparticles, can reduce the resistance of flow by creating channels and flow paths between discrimination layer 12 and the microporous pores at the surface of support membrane 12. Because of the relatively low density of pores at the surface of the microporous support membrane 12, reducing the resistance at this location can increase the membrane permeability of RO membrane 10 while maintaining the rejection characteristics.
[000199] Further, the use of additives 16 which may be detected in membrane 24 after fabrication may enhance fouling resistance. These relatively insoluble additives 16 may be useful by altering surface characteristics of resultant discrimination membrane 24, for example to make membrane 24 more hydrophilic than a corresponding control membrane made without such additives 16. This hydrophilicity may further be increased by the addition of hydrophilic polymer layer 30 shown in Fig. 6, for example, formed by a polymerized layer of polyvinyl-alcohol on the surface of membrane 24. [000200] Regarding Fig.s 13 -14 and the related discussion above, it is believed that the area to the left of the concentration identified as deflection point A, may be the range of concentrations in which additive(s) 16 disclosed herein promote increased flux while some remaining contaminants, such as hydrolyzed TMC - to the extent they effect the formation or structure of the interfacially polymerized discrimination membrane 24 - may serve to more or less increase flux without substantially reducing rejection. This area may be called a "contaminant improved flux" zone. At increased concentrations after deflection point A, the effect of such contaminants - if any - may have less beneficial effect on flux but begin to be more detrimental to the rejection characteristics of membrane 10 and called a "contaminant reduced rejection" zone. As the impact of the contaminants continues to increase with increasing concentration of additive(s) 16, a concentration level may be reached, shown in Fig. 13 as deflection point B at 0.02125% adjusted concentration and along flux and rejection curves 36, 38 for filtered lot 2 additive 16 at about 0.0115% concentration at which such contaminants increase the passage of both pure water and materials to be rejected indicating damage or other detriment to membrane 24.
[000201] When mhTMC additive16 is used, in particular in organic phase 18, the mhTMC may react - e. g. with metaphenylene-diamine - during the interfacial polymerization to increase the hydrophilicity of resultant polymer discrimination layer 24. It is thought that mhTMC 16 may react with the polyfunctional nucleophilic monomer and may be incorporated along with non-hydrolyzed polyfunctional acyl halide. Either during the interfacial polymerization, or once the polymer matrix is formed, the hydrolyzed acid group present in this reactant may interact with terminal amine residuals on the polyfunctional amine reactant forming ionic cross-links. Such ionic cross-links may increase the hydrophilicity of the polymer matrix relative to a polymer matrix containing amide cross-links exclusively, and thus promote increased water uptake and flux. At the same time, rejection may be maintained by virtue of the electrostatic interactions between the charged group, which is stabilized relative to normal electrostatic interactions, by the rigidity of the cross- linked aromatic backbone keeping the two charged centers close to each other. The ionic crosslink may also allow a slight expansion of the matrix relative to a covalent bond increasing water uptake.
[000202] The following tables of examples represent pertinent experiments and the membrane characteristics of resultant membranes 10 so far found to be useful. Some of the experiments indicate the results of changes in concentration and/or ranges and ratios which indicate which such changes produce more - or less - useful membranes. Data for control membranes, and therefore for flux improvement there over, may not have been made or not shown.
Section D: Tables of Examples D.1 Tables
[000203] Table 1: Improved TFC (control) Membrane w/o Additives
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
[000206] Table 4: TFC Membranes without Nanostructured Additives
Figure imgf000061_0002
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
[000207] Table 5. mhTMC Additive in TFC MEMBRANES
Figure imgf000065_0002
Figure imgf000066_0001
[000208] Table 6. FOULING TESTS
Figure imgf000067_0001
D.2 Preparation Procedures
A. General Procedures
[000209] The general procedure for the preparation of a flat cell test membrane, using the concentrations shown in the tables, was to prepare aqueous and organic phases, add the desired additives to one or both of these phases, apply the aqueous phase to a wet polysulphone membrane support on a glass plate and then apply the organic phase to the aqueous phase on the membrane support as described in more detail immediately below. Control membranes were made in a similar way, except without the additive(s). All performance data unless otherwise noted was obtained from flat sheet testing on NaCI (32,000 ppm) in Dl water tested at 800 psi after 1 hour of running.
[000210] Aqueous Phase 14: An aqueous solution of MPD, 4.5 wt% of triethylammonium camphorsulfonate (TEACSA) and 0.06 wt% sodium lauryl sulfate (SLS) in Dl water was prepared.
[000211] Organic Phase 18: An lsopar G® solution with TMC was also prepared and sonicated for 10 minutes, lsopar is a trademark of Exxon Corp.
[000212] Additive(s) 16: A homogenous solution of each of the additive(s) was added to - and/or dissolved in - either the aqueous phase, the organic phase or both. i) For aqueous phase additive(s), either the solid nanoparticle or an aqueous dispersion of nanoparticles, when used, was added to the aqueous phase. ii) For organic phase additive(s), the additive was dissolved in an aromatic cosolvent e.g. xylene or mesitylene. Final concentration of the cosolvent was 4 wt% by wt. %. mhTMC, when used, was added to TMC in the organic phase and the lsopar solution was allowed to sit for 1 hour before use. Nanoparticles, when used, were added to the TMC and sonicated for 30 minutes.
[000213] Support membrane 12: A piece of wet polysulfone support was placed flat on a clean glass plate. An acrylic frame was then placed onto the membrane surface, leaving an area for the interfacial polymerization reaction to take place.
[000214] Discrimination membrane 24: Approximately 50 mL of the aqueous MPD solution was poured onto the framed membrane surface and remained for 1 min. The solution was drained by tilting the frame till no solution dripped from the frame. i) The frame was taken off, and was left horizontally for 1 minute. The membrane was then clamped with the glass plate in four corners. An air knife was used to finish drying the membrane surface. The membrane was reframed using another clean and dry acrylic frame and kept horizontally for 1 min. ii) Approximately 50 mL of the organic solution was poured onto the framed membrane surface and remained for 2 minutes. The solution was drained by tilting the frame (vertically) till no solution dripped from the frame. The acrylic frame was removed, and the membrane was kept horizontally for 1 minute. The membrane was then dried at 95° C for 6 minutes.
[000215] Testing: All performance data unless otherwise noted were obtained from flat sheet testing on NaCI (32,000 ppm) in Dl water tested at 800 psi after 1 hour of running.
[000216] Separation Efficacy: Membrane performance may be measured in a flat sheet cell test apparatus. Testing may be conducted at a Reynolds number of 2500, so that build up of rejected solutes at the membrane surface leads to a concentration preferably no more than 10% higher than that in the bulk. All testing may be performed on 32,000 ppm NaCI in tap, deionized (Dl) or RO water, at 25 0C and 800 psi. Membranes may be run for 1 hour before performance characteristics (e.g. water flux and salt rejection) are measured.
[000217] Contact angle: Contact angles may be those of Dl water at room temperature. Membranes may be thoroughly rinsed with water, and then allowed to dry in a vacuum desiccator to dryness. Membranes 10 may be dried in a vertical position to prevent redeposition of any extracted compounds that may impact contact angle. Due to the occasional variability in contact angle measurements, 12 angles may be measured with the high and low angles being excluded and the remaining angles averaged.
[000218] Flux Improvement: The percentage of flux improvement may then calculated relative to a control membrane made with the same concentration of MPD and TMC, with no nanoparticles or additives, as the increase in GFD divided by the GFD of the control.
B. Specific Nanostructured Material Procedures.
[000219] The following examples use the same procedures as discussed above, except where noted.
[000220] With regard now to example 59, an aqueous dispersion of nanoparticle additive 16, including LTA having a nominal 150 nm diameter, was sonicated for 30 minutes and added to aqueous phase 14. The resultant TFC membrane 10 provided an almost 80% increase in flux over the control membrane.
[000221] With regard to example 50, the aqueous dispersion of nanoparticle additive 16, including LTA having a nominal 300nm diameter, was added to aqueous phase 14 in a commercial continuous process system. The final solution turbidity was 21 nephelometric turbidity units (NTU). This continuous process included a brief application of a vacuum, which led to a concentration of nanoparticle additives 16, i.e. LTA nanoparticles, at the surface of discrimination member 24. The contact angle in resultant TFC membrane 10 decreased from 50.7° in the control membrane to 37.6° in membrane with nanoparticles.
[000222] With regard to example 57, an aqueous dispersion including 0.2 wt% of sodium lauryl sulfate (SLS) and nanoparticle additive 16 having 0.05% LTA with a nominal 80 nm diameter, was sonicated for 30 minutes and then added to aqueous phase 14. Resultant TFC membrane 10 showed only a 9% improvement in flux over a control membrane.
[000223] Regarding example 58, in a continuous coating process, an aqueous dispersion of LTA nanoparticles 16 was prepared by sonicating a 5% solution of LTA in water for 5 minutes, followed by 20 minutes of microfluidization, and stirring overnight. The dispersed LTA solution was then added to aqueous phase 14 having 0.2% SLS to produce TFC membrane 10 which showed a 40% increase of flux over a control membrane.
[000224] Various forms of nanoparticle additives 16 were tested to determine the concentration of soluble metal ions released thereby.
1 ) Approximately 39 wt.% of template-free zeolite LTA nanoparticle additive 16, in an aqueous dispersion in deionized water (Dl) yielded an aluminum content of 130.9 ppm after being subjected to impact, cavitation and shear forces in a microfluidizer. A similar dispersion of templated zeolite LTA nanoparticles (5%) showed an aluminum content of only 2.9 ppm.
[000225] Various other forms of nanoparticle additive 16, in an aqueous dispersion in 500 ml of Dl water, were tested at room temperature of approximately 200C for release of Al on a laboratory shaker table, as follows:
2) 0.05% free zeolite LTA having a 1 :1 Si:AI ratio yielded 35.90 parts per million (ppm) based on an average of 77 to 160 day data.
3) 0.05% templated zeolite LTA having a 1.5:1 Si:AI ratio yielded less than 0.1 ppm based on an average of 1 to 84 day data.
4) 0.05% zeolite FAU having about a 2.5:1 Si:AI ratio also yielded less than 0.1 ppm based on 2 day data. [000226] TFC membranes 10 were prepared with nanoparticle additives 16 - having differing Si:AI ratios - tested and yielded different flux performances. Each TFC membrane 10 was produced with an aqueous solution including 0.2 wt.% SLS in Dl water contained of zeolite nanoparticle additive 16 which had been sonicated for 30 minutes before use. The test results, expressing flux in gallons per square foot of membrane per day (gfd), were as follows:
5) 0.05 wt.% template free zeolite LTA having a 1 :1 ShAI ratio yielded a 13% flux improvement over the control membrane.
6) 0.05 wt.% templated zeolite LTA with a 1.5:1 Si:AI ratio yielded only a 9% flux improvement.
7) 0.05 wt.% zeolite KFI with a 2.2:1 Si:AI ratio yielded no flux improvement.
8) 0.1 wt% template-free zeolite LTA having a 1 :1 Si:AI ratio yielded a 50% flux improvement over the control membrane under similar conditions.
[000227] Regarding example 159, TFC membrane 10 made with a 0.25% Al (acac)3 nanoparticle additive 16 dispersed in an lsopar G® solution with 0.3 wt% TMC in organic phase 18 which yielded a contact angle of 25.2° with Dl water, a substantial improvement over the 52.9° contact angle of a control membrane.
[000228] With regard to example 166, TFC membrane 10 was made with a 0.1% Al (acac)3 additive 16, dispersion in an lsopar G® solution with 0.3 wt% TMC in organic phase 18 and was successfully tested in flat cells on pretreated seawater taken from the Pacific Ocean and yielded a 60% flux improvement over a similar control membrane.
[000229] With regard to example 161 , 0.5% sodium aluminate additive 16, was used in aqueous phase 14 with Hexane as the solvent in organic phase 18 to fabricate TFC membrane 10. A 53% flux improvement over a similar control membrane was noted. This example illustrates the beneficial effects on resultant membrane 10 of the presence of soluble aluminum species in the aqueous phase during interfacial polymerization, whether added as additive 16 and/or released from nanoparticle additive 16 - in appropriate concentrations - as discussed.
[000230] With regard now to example 162, citric acid was added to the amine in the sodium aluminate example 99 above to bring the pH to the range of 7.5-9. Membrane 10 yielded a flux increase of 45%. The control did not require any acid addition.
[000231] With regard to example 163, camphorsulfonic acid was added to aqueous phase 14 of another TFC membrane 10 prepared in accordance with example J 99 above to bring the pH to the range of 7.5-9. The insoluble precipitate that formed was filtered before use. Membrane 10 yielded a 42% flux increase compared to its control membrane which did not require any acid addition.
[000232] With regard to example 160, organic phase 18 included a hexane solution with nanoparticle additive 16 - 0.3% AICI3 - which was sonicated for 60 minutes before use in fabricating TFC membrane 10. A 15% flux improvement was noted.
[000233] With regard to example 156, RO membrane 10 was made in accordance with example 159, except that nanoparticle 16 included 0.2% Al (acac)3. TFC membrane 10 was then rinsed in a 0.2% sodium carbonate solution before testing and yielded a flux improvement of 22% over its control membrane which was not rinsed in the sodium carbonate solution to evaluate the effect of this rinsing.
[000234] With regard to example 157, membrane 10 was fabricated in accordance with example 103, except organic phase 18 was only sonicated for 10 minutes. A flux improvement of 57% was noted.
[000235] With regard to example 158, membrane 10 was fabricated in accordance with example 159, except organic phase 18 was mechanically stirred for 60 minutes. A flux improvement of 20% was noted over its control membrane which was not stirred. A second control membrane was also made which was mechanically stirred for 60 minutes to test the benefits of stirring and a contact angle improvement from was noted over the first control membrane from 52.9° to 25.2°.
[000236] With regard to nanoparticle additive 16, - e.g., template-free zeolite LTA nanoparticles in an aqueous dispersion - were found to have aluminum content after being subjected to impact, cavitation and shear forces in a microfluidizer. The dispersion contained approximately 39 wt.% percent LTA made with double distilled water. When measured using ICP analysis, the solution had an aluminum content of 130.9 parts per million (ppm).
[000237] With regard to example 116, in a continuous coating process, TFC membrane 10 was made in accordance with example 159 except that inorganic additive 16 - 0.075% Ga(acac)3 - was used in organic phase 18. Contact time for aqueous and organic solutions were about 15 seconds. The flux improvement compared to the control was 43/22.7 or 89%.
[000238] With regard to examples 164 and 165, two membranes were fabricated in accordance with example 161 above, a first one using a first lot of TMC which was approximately 99.5% pure, the a second one using a second lot of TMC other about 98.5% pure (purity from vendor) with trace amounts of mono-, di-, and tri-hydrolyzed TMC. The control membranes with either TMC lot gave similar performance and were averaged for the "control" data (18.3gfd and 98.85%). . TFC membrane 10 using lot 2 provided an 81% flux improvement over the control, while TFC membrane 10 using lot 1 provided only a 12% flux improvement.
C. Specific Procedures for Fouling Tests
[000239] Referring now in particular to Table 9, FOULING TEST, example 184 is based on other experiments in which 0.1 % of nanoparticles zeolite LTA, was added to the organic phase before interfacial polymerization or IFP with an aqueous phase to produce a discrimination layer on a support layer and form a thin film nanocomposite or TFC membrane.
[000240] Membranes were prepared using general procedures. Membranes were run on a feed solution of Dl water with 32,000ppm of a salt blend formulated to simulate natural ocean water (Instant Ocean®). Temperature was maintained at 25° C and a pressure of 800 psi was used throughout testing. No filtration was used during this test allowing inorganic and organic colloids to recirculate through the system and biological material to grow. Performance data was taken 1 hr after testing began and again 47hrs later after continuous operation.
[000241] Example 183 shows that a particular additive 16, Ga(acac)3, provided a reasonable total flux of 30.8 GFD, which provided a flux improvement of about 36% over a control without additives and maintained a very good salt rejection of over 99.5%. However, the Ga additive membrane showed a poor flux performance after 47 hours of fouling testing, losing almost half of its flux capacity.
[000242] Example 185 illustrates one of the benefits of a hybrid TFC membrane approach in which nanoparticles, such as LTA are combined with molecular additives, such as Ga(acac)3l to form an improved hybrid TFC membrane with qualities superior than are provided by either additive separately. In particular, the hybrid LTA Ga membrane provided 31.9 GFD flux, an improvement of about 41% more than the control with only slight loss in salt rejection. The further increase in flux is on the order of an addition 14% when compared to the 36% flux increase of the Ga(acac)3 additive. Perhaps even more importantly, the flux rate after the 47 hour test was 27.3 GFD, i.e. the flux loss was only 17% after the 47 hour test. As a result, the hybrid TFC membrane has substantially the flux improvement of its soluble additive, in this case the Ga(acac)3, and the fouling resistance of the LTA nanoparticles.
Section E: ADVANTAGES
[000243] Hybrid membranes, that is, membranes with nanoparticles, and additives such as soluble ions, organometallic compounds, inorganic additives with or without ligands, and/or mhTMC enable a new degree of design flexibility to improve the overall flux, rejection, and fouling properties of membranes. The several cases discussed below are meant to illustrate the range of benefits that can be realized through the application of hybrid membrane technology and are not meant to limit the scope of this application which is provided by the issued claims. E.1 Increased Flux
[000244] Regarding increased flux compared to membranes with the individual additives, and referring now in particular to Tables 2, 2.1 and 2.2, a hybrid membrane including both nanoparticles and other selected materials such as earth alkaline metal complex in additive 16 may provide a useful level of improvement of membrane operational characteristics, e.g., flux, rejection and flux improvement, over the use of a single material in additive 16.
[000245] As can be seen from an inspection of the tables of examples, some nanostructured and other additives do not provide an obvious or substantial improvement in performance when used alone. However, combinations of nanoparticles and additives have proven to be substantially useful by providing flux increases when incorporated into hybrid TFC membranes.
[000246] As shown in example 63, a 0.05% concentration of LTA to the lsopar G® based organic phase before contact during IFP with the aqueous phase yields a nanocomposite TFC membrane with a 22.6 GFD flux, equal to that of the control membrane, but a salt rejection of 98.77%, lower than the 99.68% of the control membrane.
[000247] As shown in example 135, a 0.09% Ca(F6acac)2 additive to the lsopar G® based organic phase yields a TFC membrane with 24.8 GFD flux having about a 10% flux increase over the control membrane without additives, with a good salt rejection of 99.63%.
[000248] Referring now to example 68, a membrane made with LTA and the Ca additive in the lsopar® based organic phase yields a nanocomposite hybrid TFC membrane having 34.4 GFD flux, a 52% flux increase over the control membrane without additives but with good salt rejection of 99.03%.
[000249] As can be seen by inspection of the tables, some additives may have acceptable flux increases but decreased rejection when used alone. However, some combinations of such additives produce hybrid TFC membranes can be made that have the same or similar flux responses, but with improved rejection relative to either additive alone.
[000250] Referring now to example 4, a nanocomposite TFC membrane with 0.05% LTA additive in the aqueous phase may yield a flux of 26.2 GFD, a 10% flux improvement over a control membrane without nanoparticle as well as a 99.17% salt rejection, below the 99.68% rejection of the control membrane
[000251] Referring now to example 175, a TFC membrane with 0.02% mhTMC additive in the organic phase may yield a flux of 29.5 GFD having a 31 % flux improvement over a control membrane without additives as well as a 99.24% salt rejection, also below the rejection of the control membrane.
[000252] Referring now to another example, not shown in the tables, hybrid TFC membrane 10 with both the LTA and mhTMC additives may yield a flux of 30.7 GFD, yielding a better flux improvement of 36% and, perhaps more importantly, a substantially improved salt rejection of 99.63%, much closer to the 99.68% salt rejection of the control membrane.
[000253] Referring now to example 4, the use is illustrated of a concentration of a particular nanoparticle, in this case a 0.05% concentration of zeolite LTA, in aqueous phase 14 before contact with organic phase 18 for interfacial polymerization to form a nanocomposite TFC membrane providing 26.2 GFD at a 99.17% flux rejection. The flux rate provides a 16% improvement over a control membrane made without the nanoparticle additives, which may be useful in some cases especially in light of the other benefits of nanoparticles. However, substantial further additional flux improvement is often desired.
[000254] Referring now to example 104, the use of an earth alkaline metal additive, such as a 0.058% concentration of Sr(F6acac)2 in organic phase 18, before contact with aqueous phase 14, may produce a TFC membrane yielding a 29.7 GFD flux rate, which at 31% has roughly double the 16% flux improvement of example 25 in the table, but provides only an additional 3.5GFD. [000255] Including a combination of the LTA and strontium additives in additive 16 may yield a hybrid nanocomposite TFC membrane with improved membrane operation characteristics. As shown in example 28, 0.05% LTA in additive 16 in aqueous phase 14 and 0.058% Sr(F6acac)2 included in organic phase 18 yields membrane characteristics of 36.8 GFD flux rate - a 63% improvement over a control membrane - while providing an extremely good salt rejection of 99.57%. The 36.8 GFD is a 10.6 or 3.8 GFD improvement over the examples described using only one additive material in additive 16. Further improvement in membrane characteristics made be found by selections of different additive materials and/or concentrations and/or use of specific additive materials in the aqueous or organic phases.
E.2 Improvement Ratio
[000256] Previous uses of additive materials showed little promise because the total flux flow through membrane 10 was relatively low, with an acceptable or even low level of rejection, and the percent of flux improvement compared to a control membrane was so low - that use and/or further experimentation with such additives was unlikely. However, the use of selected processing parameters, such as the MPD, TMC and/or MPD/TMC ratios as discussed herein vastly improves both the total flux available from a particular membrane at a high rejection rate on the order of 99.5%. These process parameters also provide substantial advantages when additive materials - including the previous known additives - are included in additive 16 alone or in combination with other such materials.
[000257] In particular, as shown in example 15, the inclusion of 0.05% LTA in additive 16 in aqueous phase 14, together with 0.04% Al(acac)3 in organic phase 18 produces a commercially useful membrane using a 13.3 MPD/TMC ratio fabrication process having more than a 50% flux improvement at a flux of more than 35 GFD with 99.44% rejection. This membrane 10 is a vast improvement over previously known membranes which included Al because it is a commercially viable membrane for many uses where a membrane have substantially lower membrane performance characteristics remains merely a laboratory curiosity. [000258] Further, as shown in example 68, the inclusion of 0.05% LTA and 0.09% Ca(F6acac)2 as additive 16 in organic phase 18 produces - when fabricated at a 13.3 MPD/TMC ratio - a membrane 10 having a more than 50% flux improvement over its control membrane - and commercially useful membrane operational characteristics at a high 34.4 GFD with a 99.02% rejection rate. Further experimentation to adjust the concentrations, ratios and placement of the additive materials may be used to try to improve these characteristics. For example, using 0.05% LTA in aqueous phase 14 and 0.09% Ca(F6acac)2 together with 0.02% mhTMC in additive 16 in organic phase 18 produced a membrane with a 69% improvement over its control at 38.1 GFD and 99.31% rejection as illustrated in example 37.
E.3 Improved Rejection
[000259] Referring now to example 4, a nanocomposite TFC membrane with 0.05% LTA additive in the aqueous phase may yield a flux of 26.2 GFD, a 10% flux improvement over a control membrane without nanoparticle additives as well as a 99.17% salt rejection, below the 99.68% rejection of the control membrane. As a result, membrane 10 made in accordance with this example may not meet the requirements for some tasks, such as single pass seawater desalination.
[000260] Referring now to example 175, a TFC membrane with 0.02% mhTMC additive in the organic phase may yield a flux of 29.5 GFD having a 31% flux improvement over a control membrane without additives as well as a 99.24% salt rejection, also below the rejection of the control membrane.
[000261] Referring now to example 66, a hybrid TFC membrane with both the LTA and mhTMC additives in organic phase 18 may yield a flux of 25.8 GFD and perhaps more importantly, a substantially improved salt rejection of 99.63%, above the 99.5% salt rejection level which may be required for reverse osmosis membranes.
[000262] As an example membrane not shown in the tables, a hybrid TFC membrane with both the LTA in aqueous phase 14 and mhTMC additive in organic phase 18 may yield a further improved flux of 30.7 GFD and a salt rejection of 99.63%, above the 99.5% salt rejection level which may be required for reverse osmosis membranes.
E.4: Fouling Resistance
[000263] TFC membrane 10 may be used to desalinate waters containing materials which tend to accumulate on the membrane surface, decreasing the permeability of TFC membrane 10. This process is commonly called "fouling". The fouling materials which accumulate on the membrane surface can include, but are not limited to, natural organic matter, partially insoluble inorganic materials, organic surfactants, silt, colloidal material, microbial species including biofilms, and organic materials either excreted or released from microbial species such as proteins, polysaccharides, nucleic acids, metabolites, and the like. The drop in permeability is often smaller, that is, less fouling materials accumulate on the surface of TFC membrane 10 when nanoparticles are included in additive(s) 16.
[000264] This reduction in fouling, or improvement in fouling resistance, may - in part - be related to increased hydrophilicity of TFC membrane 10 when nanoparticles are included in additive(s) 16. The hydrophilicity of TFC membrane 10 can be measured by measuring the equilibrium contact angle of the surface of membrane 10 with a drop of distilled water at a controlled temperature. TFC membrane 10, when nanoparticles are included in additive(s) 16, can have a contact angle that is reduced by 5°, 10°, 15°, 25° or more, relative to a similarly prepared membrane without nanoparticles included in additive(s) 16. The equilibrium contact angle can be less than 45°, less than 40°, than 37°, or even less than 25°.
[000265] Improved resistance to accumulation for TFC membranes can in part be related to increased hydrophilicity of these membranes. The increased hydrophilicity can be measured by the equilibrium contact angle of the membrane surface with a drop of distilled water at a controlled temperature. Membranes prepared with additive 16 present during polymerization can have a contact angle that is reduced by 5, 15, or even 25 or more degrees relative to a similarly prepared membrane without the additive. The equilibrium contact angle can be less than 45°, less than 40°, or even less than 25°.
[000266} In some instances, hybrid TFC membranes 10 may be used to desalinate waters that contain materials which have a tendency to accumulate on the membrane surface in contact with the contaminated water, decreasing the effective membrane permeability, e.g. decreasing membrane flux over time. These materials can include but are not limited to natural organic matter, partially insoluble inorganic materials, organic surfactants, silt, colloidal material, microbial species including biofilms, and organic materials either excreted or released from microbial species such as proteins, polysaccharides, nucleic acids, metabolites, and the like. This drop in permeability or membrane flux is often smaller for membranes prepared as disclosed herein than for membranes prepared by conventional techniques due to a decreased amount, density, viability, thickness and/or nature of accumulated material. Membrane surface properties, such as hydrophilicity, charge, and roughness, often affect this accumulation and permeability change. Generally, membranes with highly hydrophilic, negatively charged, and smooth surfaces yield good permeability, rejection, and fouling behavior. The addition of nanoparticles, such as zeolite LTA nanoparticles, have been shown to reduce roughness, increase negative charge without addition of carboxylate groups, and reduce contact angles.
[000267] Referring now to Fig. 15, a simple graphical representation of the reduced loss of flux over time is shown in which the LTA alone shows low flux improvement with low flow loss due to fouling, the Ga(acac)3 additive alone shows high flux improvement with substantial flux loss due to fouling while the hybrid shows the best of both additives, high flux improvement with low flux loss due to fouling. It should also be noted that the TFC membrane with the additive alone has a lower flux than the nanocomposite TFC membrane while the nanocomposite hybrid TFC membrane shows a flux improvement over the nanoparticle hybrid TFC membrane of about 21% in only 2 days. The rate of flux drop tends to decrease in conventional membranes over time, but nanoparticle hybrid TFC membranes are expected to maintain an improvement of 20 to 100% above similar membranes with single additives or conventional membranes.
[000268] Referring now to Table 9, Fouling Test, example 184, TFC membrane 10 having 0.1% LTA included in additive 16 in organic phase 18 had 22.5 GFD flux rate - which is not an improvement over its control membrane - and a 98.5% salt rejection. The flux at 1 hour was 22.5 GFD and was maintained at 22.5 GFD by fouling after about two days which shows substantial resistance to fouling.
[000269] Referring now also to Table 9, membrane 10 with 0.08% Ga(acac)3 in organic phase 18 had a substantially improved flux of 30.9 GFD after 1 hour of operation under the same conditions, a substantial 37% flux improvement over its control membrane and the membrane of example 183. However, the flux was reduced to 20.9 GFD after 2 days as a result of fouling. This represents an almost 50% flux loss due to fouling in just 2 days and unfortunately not that uncommon.
[000270] However, referring again to Table 9, the LTA and Ga(acac)3 additives of example 185 were used together in this example. The resultant membrane had an even further increased flux of 31.9 GFD after operation in the same conditions but more importantly, retained a greater amount of flux even after 2 days of exposure to fouling. This membrane showed substantially improved fouling resistance, losing less than 17% of its flux due to fouling. The substantial improvement of resistance to fouling shown by the loss of only 17% - rather than 47% - indicates an improved resistance to fouling of almost 200%. We believe the increase of resistance to fouling is due to the combination of a nanostructured additive believed to reduce fouling with a complex additive, typically including a metal or other additive which substantially increases flux compared to its control membrane. The complexes to be combined with nanostructured additives to substantially reduce fouling while maintaining high flux and rejection may include compounds with alkaline earth metals, Al, Fe, Ga, Sn, Co, Cu and Pr or phosphorous. The combination of a nanostructured additive with mhTMC may also substantially reduce fouling.

Claims

Claims
1. A method of making a thin film composite membrane, comprising: combining one or more additives with either or both a polar liquid having a first monomer therein and a non-polar liquid having a second monomer therein; and contacting the polar and non-polar liquids to form a selective membrane by interfacial polymerization, wherein at least one of the additives includes an alkaline earth metal.
2. The method of claim 1 wherein the alkaline earth metal is present as a complex.
3. The method of claim 1 wherein the complex is a beta-diketonate complex.
4. The method of claim 2 wherein the complex is an acetylacetonate complex.
5. The method of claim 2 wherein the complex is a hexafluoroacetylacetonate complex,
6. The method of claim 2 wherein the complex is a trifluoroacetylacetonate complex.
7. The method of claims 2-6 wherein the complex is present in a concentration in one of the liquids of from about 0.005 wt.% to about 5 wt.%,
8. The method of claims 2-6 wherein the complex is present in a concentration in one of the liquids of from about 0.05 wt.% to about 1 wt.%.
9. The method of claims 1-8 wherein at least one of the additives includes magnesium.
10. The method of claims 1 -8 wherein at least one of the additives includes calcium.
11. The method of claims 1 -8 wherein at least one of the additives includes strontium.
12. The method of claims 1-8 wherein at least one of the additives includes beryllium.
13. The method of claims 1-12 wherein the polar liquid includes an amine.
14. The method of claims 1-13 wherein the polar liquid includes MPD.
15. The method of claims 1-14 wherein the non-polar liquid includes TMC.
16. The method of claims 1-14 wherein ratio of MPD in the polar liquid to TMC in the non-polar liquid is below 14.
17. The method of claims 1-14 wherein the ratio of MPD in the polar liquid to TMC in the non-polar liquid is low enough so that the resultant selective membrane has substantially higher flux than a control membrane.
18. The method of claims 1-17 wherein the concentration of TMC in the non- polar liquid is high enough so that the resultant selective membrane has substantially higher flux than a control membrane.
19. The method of claims 1-17 wherein the ratio of MPD in the polar liquid to TMC in the non-polar liquid is low enough so that the resultant selective membrane has substantially higher flux than a control membrane made without the complex including an alkaline earth metal.
20. The methods of any of the claims 1-19 including a further additive improving the flux of the selective membrane compared to a control membrane made without the other additive.
21. A TFC membrane made in accordance with any of claims 1- 20.
PCT/US2009/060927 2008-04-15 2009-10-15 Improved tfc membranes with alkaline earth metal and other additives WO2010120325A1 (en)

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Families Citing this family (148)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2007137124A (en) 2005-03-09 2009-04-20 Дзе Риджентс Оф Дзе Юниверсити Оф Калифорния (Us) NANOCOMPOSITE MEMBRANES AND METHODS FOR PRODUCING AND USING THEM
US8807350B2 (en) * 2005-07-14 2014-08-19 Ben-Gurion University Of The Negev Research & Development Authority Composite membranes and methods for their preparation
WO2008057842A2 (en) * 2006-10-27 2008-05-15 The Regents Of The University Of California Micro-and nanocomposite support structures for reverse osmosis thin film membranes
US20110168631A1 (en) * 2006-12-15 2011-07-14 General Electric Company Methods and apparatuses for water filtration using polyarylether membranes
CA2700333A1 (en) * 2007-09-21 2009-03-26 The Regents Of The University Of California Nanocomposite membranes and methods of making and using same
US8177978B2 (en) * 2008-04-15 2012-05-15 Nanoh20, Inc. Reverse osmosis membranes
US9039900B2 (en) * 2008-05-09 2015-05-26 New Jersey Institute Of Technology Membrane distillation apparatus and methods
JP5745512B2 (en) * 2009-06-29 2015-07-08 ナノエイチツーオー・インコーポレーテッド Improved hybrid TFCRO membrane containing nitrogen additive
US20110000861A1 (en) * 2009-07-06 2011-01-06 Bear Creek Services, LLC. Portable and Scalable Water Reclamation System and Method
US8545701B2 (en) * 2009-08-18 2013-10-01 Maher Isaac Kelada Induced symbiotic osmosis [ISO] for salinity power generation
US8661648B2 (en) * 2010-03-24 2014-03-04 Dow Global Technologies Llc Spiral wound filtration module
KR101258431B1 (en) * 2010-07-14 2013-04-26 웅진케미칼 주식회사 Forward osmosis membrane with high flux and manufacturing method thereof
JP5596784B2 (en) * 2010-04-30 2014-09-24 ウンジン ケミカル カンパニー,リミテッド Forward osmosis membrane for seawater fresh water and method for producing the same
KR100990168B1 (en) 2010-07-16 2010-10-29 한국과학기술연구원 Forward osmosis membranes and method for fabricating the same
CN101940883A (en) * 2010-08-03 2011-01-12 浙江大学 Preparation method of reverse osmosis composite membrane containing nano zeolite molecular sieves
US8545606B2 (en) * 2010-08-20 2013-10-01 Georgia Tech Research Corporation Treatment of molecular sieve particles for mixed matrix membranes
EP2615665B1 (en) * 2010-09-06 2018-10-31 LG Chem, Ltd. Separator, manufacturing method thereof, and electrochemical device comprising the same
US8591741B2 (en) * 2010-09-30 2013-11-26 General Electric Company Thin film composite membranes incorporating carbon nanotubes
AU2011312881B2 (en) * 2010-09-30 2015-07-16 Porifera, Inc. Thin film composite membranes for forward osmosis, and their preparation methods
JP5968328B2 (en) 2010-11-10 2016-08-10 ナノエイチツーオー・インコーポレーテッド Improved hybrid TFCRO membrane containing non-metallic additives
WO2012102678A1 (en) * 2011-01-24 2012-08-02 Nano-Mem Pte. Ltd. A forward osmosis membrane
EP2632576B1 (en) 2011-01-24 2014-10-08 Dow Global Technologies LLC Method for making a composite polyamide membrane
US20130287946A1 (en) 2011-01-24 2013-10-31 Dow Global Technologies Llc Composite polyamide membrane
ES2523453T3 (en) 2011-01-24 2014-11-26 Dow Global Technologies Llc Method for preparing a polyamide composite membrane
US20140008291A1 (en) * 2011-01-25 2014-01-09 Nanyang Technological University Forward osmosis membrane and method of forming a forward osmosis membrane
KR101267825B1 (en) 2011-03-04 2013-05-27 웅진케미칼 주식회사 Forward osmosis composite membrane and manufacturing method threrof
US9216391B2 (en) * 2011-03-25 2015-12-22 Porifera, Inc. Membranes having aligned 1-D nanoparticles in a matrix layer for improved fluid separation
JP2014501614A (en) 2011-06-20 2014-01-23 エルジー・ケム・リミテッド Reverse osmosis separation membrane excellent in salt removal rate and permeate flow rate characteristics and method for producing the same
CN103998932B (en) 2011-06-29 2017-06-06 中央研究院 Capture, purifying and release using face coat to biological substance
US8895104B2 (en) * 2011-07-01 2014-11-25 International Business Machines Corporation Thin film composite membranes embedded with molecular cage compounds
US20130015122A1 (en) * 2011-07-11 2013-01-17 King Fahd University Of Petroleum And Minerals Nanocomposite membranes
US9132389B2 (en) * 2011-08-08 2015-09-15 Colorado State University Research Foundation Magnetically responsive membranes
CN103764264B (en) 2011-08-31 2016-11-16 陶氏环球技术有限责任公司 It is derived from the composite polyamide membranes of the monomer comprising amine reactive functional groups and phosphorous functional group
US9090491B2 (en) 2011-09-02 2015-07-28 Saline Water Desalination Research Institute Removal of boron from saline water using alkalized NF membrane pretreatment
SG188687A1 (en) * 2011-09-22 2013-04-30 Univ Singapore Thin film composite osmosis membranes
US9029600B2 (en) 2011-09-29 2015-05-12 Dow Global Technologies Llc Method for preparing high purity mono-hydrolyzed acyl halide compound
KR101946792B1 (en) 2011-09-29 2019-02-13 다우 글로벌 테크놀로지스 엘엘씨 Composite polyamide membrane derived from carboxylic acid containing acyl halide monomer
WO2013059314A1 (en) 2011-10-17 2013-04-25 Porifera, Inc. Preparation of aligned nanotube membranes for water and gas separation applications
KR101407445B1 (en) 2011-12-08 2014-06-17 주식회사 엘지화학 Reverse osmotic membrane comprising silver nano wire layer and method of manufacturing the same
KR101907106B1 (en) 2011-12-16 2018-12-05 삼성전자주식회사 Semi-permeable film and membrane including nanoporous material, and method of manufacturing the same
US20130175218A1 (en) 2011-12-16 2013-07-11 The Research Foundation Of State University Of New York Polymeric nanofibrous composite membranes for energy efficient ethanol dehydration
JP5922403B2 (en) 2011-12-28 2016-05-24 東洋ゴム工業株式会社 Method for producing rubber composition and rubber composition
WO2013103666A1 (en) 2012-01-06 2013-07-11 Dow Global Technologies Llc Composite polyamide membrane
US20130284667A1 (en) * 2012-01-09 2013-10-31 Thomas J. Pinnavaia Polymer Filtration Membranes Containing Mesoporous Additives and Methods of Making the Same
JP5879161B2 (en) * 2012-03-09 2016-03-08 旭化成ケミカルズ株式会社 Water vapor separation membrane and method for producing the same
KR101919466B1 (en) 2012-05-24 2018-11-19 한양대학교 산학협력단 Separation membrane, and water treatment device including the same
JP2014521494A (en) 2012-06-08 2014-08-28 エルジー・ケム・リミテッド High permeation flow reverse osmosis membrane containing surface-treated zeolite and method for producing the same
CA2890360C (en) * 2012-07-02 2020-03-31 Dead Sea Works Ltd. Submerged plate forward osmosis systems
US9662615B2 (en) 2012-07-19 2017-05-30 Dow Global Technologies Llc Composite polyamide membrane
FR2996780B1 (en) * 2012-10-16 2014-12-19 Univ Claude Bernard Lyon METHOD AND DEVICE FOR GENERATING ENERGY
JP5947192B2 (en) 2012-11-08 2016-07-06 東洋ゴム工業株式会社 Rubber wet masterbatch production method, rubber wet masterbatch, and rubber composition containing rubber wet masterbatch
US9211507B2 (en) * 2012-11-21 2015-12-15 Lg Chem, Ltd. Water-treatment separating membrane of high flux having good chlorine resistance and method of manufacturing the same
WO2014081230A1 (en) 2012-11-21 2014-05-30 주식회사 엘지화학 Outstandingly chlorine resistant high-flow-rate water-treatment separation membrane and production method for same
KR101972172B1 (en) * 2012-12-06 2019-04-24 도레이케미칼 주식회사 Polyamide composite membrane having high quality and manufacturing method thereof
KR101936924B1 (en) 2012-12-06 2019-01-09 삼성전자주식회사 Separation membrane, and water treatment device using said separation membrane
JP2016511288A (en) 2012-12-17 2016-04-14 ビーエーエスエフ ソシエタス・ヨーロピアBasf Se Membrane with improved flux and method for producing said membrane
CN104955552B (en) 2012-12-21 2017-03-08 波里费拉公司 For carrying out detached piece-rate system, element and method using stacking barrier film and distance piece
TWI519339B (en) 2012-12-28 2016-02-01 財團法人工業技術研究院 Filtering membrane
RU2516645C1 (en) * 2012-12-28 2014-05-20 Общество с ограниченной ответственностью Научно-производственное предприятие "Технофильтр" Method of treating semipermeable polymer membranes
CN104918688B (en) 2013-01-14 2016-12-14 陶氏环球技术有限责任公司 Comprise the composite polyamide membranes being substituted Benzoylamide monomer
US10137418B2 (en) 2013-01-14 2018-11-27 Dow Global Technologies Llc Composite polyamide membrane made via interfacial polymerization using a blend of non-polar solvents
EP2969145A4 (en) 2013-03-15 2017-01-25 Porifera Inc. Advancements in osmotically driven membrane systems including multi-stage purification
US9051227B2 (en) 2013-03-16 2015-06-09 Dow Global Technologies Llc In-situ method for preparing hydrolyzed acyl halide compound
US9289729B2 (en) 2013-03-16 2016-03-22 Dow Global Technologies Llc Composite polyamide membrane derived from carboxylic acid containing acyl halide monomer
US9051417B2 (en) 2013-03-16 2015-06-09 Dow Global Technologies Llc Method for solubilizing carboxylic acid-containing compound in hydrocarbon solvent
CN105163837B (en) 2013-05-03 2017-05-10 陶氏环球技术有限责任公司 Composite polyamide membrane derived from aliphatic acyclic tertiary amine compound
CN103240006A (en) * 2013-05-10 2013-08-14 天津大学 Bovine serum albumin-polycarbonate composite membrane and preparation method thereof
WO2015013358A1 (en) * 2013-07-24 2015-01-29 Hydration Systems, Llc Method to improve forward osmosis membrane performance
CN106170333B (en) 2013-12-02 2019-02-15 陶氏环球技术有限责任公司 The composite polyamide membranes handled with dihydroxy aryl compound and nitrous acid
WO2015084511A1 (en) 2013-12-02 2015-06-11 Dow Global Technologies Llc Composite polyamide membrane post treated with nitrious acid
KR102213238B1 (en) * 2013-12-06 2021-02-05 동의대학교 산학협력단 Semipermeable membranes and production methods thereof
EP3092056B1 (en) * 2014-01-07 2018-08-01 Dow Global Technologies LLC Desalination of aqueous mixture containing nano-sized particles using fouling resistant reverse osmosis membrane
WO2015105632A1 (en) * 2014-01-07 2015-07-16 Dow Global Technologies Llc Separation of hydrocarbons from aqueous mixture using fouling resistant reverse osmosis membrane
CA2935699C (en) 2014-01-09 2022-05-31 Dow Global Technologies Llc Composite polyamide membrane having azo content and high acid content
AU2014376253B2 (en) 2014-01-09 2018-07-26 Dow Global Technologies Llc Composite polyamide membrane having preferred azo content
WO2015105637A1 (en) 2014-01-09 2015-07-16 Dow Global Technologies Llc Composite polyamide membrane having high acid content and low azo content
US20160317977A1 (en) * 2014-01-13 2016-11-03 Dow Global Technologies Llc Highly swellable composite polyamide membrane
US9622483B2 (en) 2014-02-19 2017-04-18 Corning Incorporated Antimicrobial glass compositions, glasses and polymeric articles incorporating the same
US11039620B2 (en) 2014-02-19 2021-06-22 Corning Incorporated Antimicrobial glass compositions, glasses and polymeric articles incorporating the same
US11039621B2 (en) 2014-02-19 2021-06-22 Corning Incorporated Antimicrobial glass compositions, glasses and polymeric articles incorporating the same
US9902141B2 (en) 2014-03-14 2018-02-27 University Of Maryland Layer-by-layer assembly of graphene oxide membranes via electrostatic interaction and eludication of water and solute transport mechanisms
EP3126814B1 (en) 2014-04-01 2019-06-12 Academia Sinica Methods and systems for cancer diagnosis and prognosis
WO2015167759A1 (en) 2014-04-28 2015-11-05 Dow Global Technologies Llc Composite polyamide membrane post-treated with nitrous acid
AU2015259613B2 (en) 2014-05-14 2019-07-04 Dow Global Technologies Llc Composite polyamide membrane post treated with nitrous acid
JP6654576B2 (en) 2014-05-14 2020-02-26 ダウ グローバル テクノロジーズ エルエルシー Composite polyamide membrane post-treated with nitrous acid
JP6640739B2 (en) 2014-05-14 2020-02-05 ダウ グローバル テクノロジーズ エルエルシー Composite polyamide membrane post-treated with nitrous acid
CN104138716B (en) * 2014-08-06 2016-03-09 哈尔滨工业大学 A kind of nanometer MoS 2the preparation method of modification PVDF ultrafiltration membrane
CN105381824B (en) 2014-08-26 2019-04-23 中央研究院 Collector framework layout designs
WO2016070103A1 (en) 2014-10-31 2016-05-06 Porifera, Inc. Supported carbon nanotube membranes and their preparation methods
CN105709610B (en) * 2014-11-30 2017-12-22 中国科学院大连化学物理研究所 Support type ultra-thin two-dimension stratiform MOF films and preparation method thereof
CN105709614B (en) * 2014-11-30 2017-11-17 中国科学院大连化学物理研究所 Ultra-thin stratified material and preparation method thereof
CN104474910B (en) * 2014-12-11 2016-06-29 杭州水处理技术研究开发中心有限公司 A kind of preparation method of organo-mineral complexing separation film
US10005042B2 (en) * 2015-02-16 2018-06-26 International Business Machines Corporation Thin film composite forward osmosis membranes with performance enhancing layers
US10010833B2 (en) 2015-02-18 2018-07-03 Lg Nanoh2O, Inc. Spiral wound membrane module with reinforced fold line
DE112016001523T5 (en) * 2015-03-31 2018-03-15 Shinshu University Reverse Osmosis Composite Membrane and Method of Making a Reverse Osmosis Composite Membrane
SG11201708288SA (en) 2015-04-13 2017-11-29 Basf Se Processes for reducing the fouling of surfaces
US9731985B2 (en) * 2015-06-03 2017-08-15 Lg Nanoh2O, Inc. Chemical additives for enhancement of water flux of a membrane
US9695065B2 (en) 2015-06-03 2017-07-04 Lg Nanoh2O, Inc. Combination of chemical additives for enhancement of water flux of a membrane
ES2796605T3 (en) 2015-06-24 2020-11-27 Porifera Inc Methods of desiccation of alcoholic solutions by direct osmosis and related systems
US9724651B2 (en) 2015-07-14 2017-08-08 Lg Nanoh2O, Inc. Chemical additives for water flux enhancement
US9861940B2 (en) 2015-08-31 2018-01-09 Lg Baboh2O, Inc. Additives for salt rejection enhancement of a membrane
WO2017039112A2 (en) 2015-09-01 2017-03-09 주식회사 엘지화학 Water treatment membrane production method, water treatment membrane produced using same, and water treatment module comprising water treatment membrane
KR102010402B1 (en) * 2015-09-22 2019-08-13 주식회사 엘지화학 Molecular additive, manufacturing method for water-treatment membrane using by the same and water-treatment membrane comprising the same
EP3395434B1 (en) * 2015-12-25 2021-05-12 Toray Industries, Inc. Composite semipermeable membrane
US9737859B2 (en) 2016-01-11 2017-08-22 Lg Nanoh2O, Inc. Process for improved water flux through a TFC membrane
US10022676B2 (en) * 2016-01-19 2018-07-17 Uchicago Argonne, Llc Magnetic nanotube composite membranes
US10118124B2 (en) * 2016-01-25 2018-11-06 Ut-Battelle, Llc Integrated membrane-pyrolysis systems and methods
US10155203B2 (en) 2016-03-03 2018-12-18 Lg Nanoh2O, Inc. Methods of enhancing water flux of a TFC membrane using oxidizing and reducing agents
US10107726B2 (en) 2016-03-16 2018-10-23 Cellmax, Ltd. Collection of suspended cells using a transferable membrane
EP3436417A4 (en) 2016-03-22 2020-01-01 Dead Sea Works Ltd. Spherical fertilizers and process for the production thereof
JP2019529099A (en) * 2016-09-20 2019-10-17 アクア メンブレインズ エルエルシー Permeate flow pattern
CN109843834A (en) 2016-10-22 2019-06-04 死海工程有限公司 Binder for fertilizer granulation
UA125464C2 (en) 2016-12-17 2022-03-16 Дед Сі Воркс Лтд. Process for production of potassium sulphate and magnesium sulphate from carnallite and sodium sulphate
EP3558502A4 (en) * 2016-12-20 2020-07-29 Monash University Reverse osmosis membrane and method of use
US11541352B2 (en) 2016-12-23 2023-01-03 Porifera, Inc. Removing components of alcoholic solutions via forward osmosis and related systems
US20190388844A1 (en) 2017-01-31 2019-12-26 Toray Industries, Inc. Semipermeable composite membrane and method for manufacturing semipermeable composite membrane
CN110198779B (en) 2017-02-10 2022-06-28 艾斯尔欧洲合作社公司 Method for granulating polyhalite
CN106925119B (en) * 2017-03-10 2019-04-12 山东大学 Poly-epoxy succinic acid is as drawing application of the liquid in positive infiltration
EP3407613A1 (en) * 2017-05-23 2018-11-28 Thomson Licensing Control of display device content
US10646829B2 (en) 2017-06-22 2020-05-12 Teledyne Scientific & Imaging, Llc High flux, chlorine resistant coating for sulfate removal membranes
CN107473318B (en) * 2017-08-22 2021-03-09 承德人和矿业有限责任公司 Illite-containing mineral complex and preparation method and application thereof
CN108176246A (en) * 2017-12-14 2018-06-19 青岛科技大学 A kind of modified polyamide reverse osmosis membrane of chemical grafting treated graphene oxide and preparation method thereof
TWI661863B (en) 2018-06-21 2019-06-11 財團法人工業技術研究院 Multilayer composite membrane
JP2022515734A (en) 2018-12-20 2022-02-22 ソルベイ スペシャルティ ポリマーズ ユーエスエー, エルエルシー Porous membrane for high pressure filtration
JP2022514036A (en) 2018-12-20 2022-02-09 ソルベイ スペシャルティ ポリマーズ ユーエスエー, エルエルシー Porous membrane for high pressure filtration
KR20210141530A (en) * 2019-03-26 2021-11-23 닛토덴코 가부시키가이샤 separator
CN111821865B (en) * 2019-04-22 2022-09-23 苏州苏瑞膜纳米科技有限公司 Composite membrane with separation function and vapor deposition preparation method thereof
BR112021022979A2 (en) * 2019-05-15 2022-01-25 Via Separations Inc Durable graphene oxide membranes
EP3969158A1 (en) * 2019-05-15 2022-03-23 Via Separations, Inc. Filtration apparatus containing graphene oxide membrane
CN110449046A (en) * 2019-08-07 2019-11-15 恩泰环保科技(常州)有限公司 Modified antipollution complex reverse osmosis membrane of a kind of MOF and preparation method thereof
CN112755802B (en) * 2019-10-21 2023-02-28 中国石油化工股份有限公司 Method for preparing super-hydrophilic oil-water separation membrane
CN110876897B (en) * 2019-11-07 2022-05-03 恩泰环保科技(常州)有限公司 High-flux anti-pollution nano hybrid reverse osmosis membrane and preparation method and application thereof
CN111068519B (en) * 2019-12-17 2022-04-15 深圳大学 Forward osmosis membrane and preparation method thereof
WO2022050007A1 (en) * 2020-09-03 2022-03-10 株式会社クラレ Composite semipermeable membrane
CN112090297B (en) * 2020-09-14 2022-03-22 中国石油大学(华东) Composite membrane based on ultra-small MOF, preparation method and application of composite membrane in dye separation
CN114471183B (en) * 2020-11-11 2023-03-14 沃顿科技股份有限公司 Method for producing separation membrane and separation membrane produced thereby
JP7173407B1 (en) 2021-04-22 2022-11-16 東レ株式会社 composite semipermeable membrane
WO2022225063A1 (en) 2021-04-22 2022-10-27 東レ株式会社 Composite semipermeable membrane
JP7173408B1 (en) 2021-04-22 2022-11-16 東レ株式会社 composite semipermeable membrane
CN113501582B (en) * 2021-06-10 2022-03-29 华南理工大学 Ecological floating bed based on trimetal organic framework material and application thereof
WO2023097166A1 (en) 2021-11-29 2023-06-01 Via Separations, Inc. Heat exchanger integration with membrane system for evaporator pre-concentration
CN115105975A (en) * 2022-04-28 2022-09-27 西安建筑科技大学 Polyelectrolyte sandwich magnetic response type polypiperazine amide composite nanofiltration membrane and preparation method thereof
US11502322B1 (en) 2022-05-09 2022-11-15 Rahul S Nana Reverse electrodialysis cell with heat pump
US11502323B1 (en) 2022-05-09 2022-11-15 Rahul S Nana Reverse electrodialysis cell and methods of use thereof
CN114797472A (en) * 2022-05-20 2022-07-29 北京赛诺膜技术有限公司 Forward osmosis composite membrane prepared by magnetic field assisted thermally induced phase separation method and preparation method thereof
US11855324B1 (en) 2022-11-15 2023-12-26 Rahul S. Nana Reverse electrodialysis or pressure-retarded osmosis cell with heat pump
CN115738742B (en) * 2022-12-05 2023-06-13 蓝星(杭州)膜工业有限公司 Positive charged membrane for extracting lithium from salt lake and preparation method thereof
CN117138604B (en) * 2023-08-25 2024-03-12 苏州苏瑞膜纳米科技有限公司 Preparation method of high-flux nanofiltration composite membrane with customized retention rate

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4492721A (en) * 1983-05-10 1985-01-08 U.S. Philips Corporation Method of providing magnesium fluoride layers
US4931362A (en) * 1987-08-18 1990-06-05 F.Joh.Kwizda Gesellschaft M.B.H. Microcapsule and micromatrix bodies and method for their formation
US5017680A (en) * 1990-07-03 1991-05-21 Eastman Kodak Company Process and catalyst-inhibitor systems for preparing poly(ethylene terephthalate)
US20040234751A1 (en) * 1998-12-10 2004-11-25 Hideaki Sakurai Protective thin film for FPDs, method for producing said thin film and FPDs using said thin film
US20060204812A1 (en) * 2003-03-05 2006-09-14 Hideki Moriyama Aromatic polymer, film, electrolyte membrane and separator
US20080251447A1 (en) * 2006-10-10 2008-10-16 Atsuhito Koumoto Process for producing a dried composite semipermeable membrane

Family Cites Families (248)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3133137A (en) 1960-11-29 1964-05-12 Univ California High flow porous membranes for separating water from saline solutions
NL271831A (en) 1960-11-29
US3920612A (en) 1963-01-21 1975-11-18 Standard Oil Co Preparation of film forming polymer from carbocyclic aromatic diamine and acyl halide of trimellitic acid anhydride
US3260691A (en) 1963-05-20 1966-07-12 Monsanto Co Coating compositions prepared from condensation products of aromatic primary diamines and aromatic tricarboxylic compounds
US3480588A (en) 1963-08-20 1969-11-25 Monsanto Co Stable coating composition of a tricarboxylic acid or its partial or full ester and a diamine
US4092424A (en) 1964-04-17 1978-05-30 Biochemie Ges.M.B.H. Antibiotic derivatives
US3367504A (en) 1964-12-21 1968-02-06 Gulf General Atomic Inc Spirally wrapped reverse osmosis membrane cell
US3417870A (en) 1965-03-22 1968-12-24 Gulf General Atomic Inc Reverse osmosis purification apparatus
US3351244A (en) 1966-08-08 1967-11-07 Paul I Zandberg Dispenser for impression material
US4048144A (en) 1966-11-25 1977-09-13 Standard Oil Company (Indiana) Preparation of solid polymers from aromatic primary diamine and acyl halide of trimellitic anhydride
US3642707A (en) 1967-10-04 1972-02-15 Du Pont Fibers prepared from aromatic polyhydrazides
US3615024A (en) 1968-08-26 1971-10-26 Amicon Corp High flow membrane
US3567632A (en) 1968-09-04 1971-03-02 Du Pont Permselective,aromatic,nitrogen-containing polymeric membranes
FR1587422A (en) 1968-10-07 1970-03-20
US3597393A (en) 1969-01-21 1971-08-03 Monsanto Co Functionally substituted highly ordered azo-aromatic polyamides
US3663510A (en) 1969-05-08 1972-05-16 Gen Electric Process for producing polyamide coating materials
US3692740A (en) 1969-06-24 1972-09-19 Showa Electric Wire & Cable Co Phnolic-solvent-soluble aromatic polyamide-imide and process for producing same
NL171019C (en) 1969-07-08 1983-02-01 Consiglio Nazionale Ricerche MEMBRANES FOR REVERSE OSMOSIS.
US3687842A (en) 1969-07-08 1972-08-29 Consiglio Nazionale Ricerche Osmosis process
US3648845A (en) 1969-09-02 1972-03-14 Us Interior Thin film separation membranes and processes for making same
US3710945A (en) 1969-11-26 1973-01-16 Du Pont Preservation of polyamidic membranes
US3690811A (en) 1970-06-01 1972-09-12 Thiokol Chemical Corp Acid dyeing for tertiary aminated polyamide,polyolefin and polyamide blends and disperse dyeing of said polyolefin and polyester blends
US3744642A (en) 1970-12-30 1973-07-10 Westinghouse Electric Corp Interface condensation desalination membranes
US3791526A (en) 1971-08-10 1974-02-12 Westinghouse Electric Corp Solvent weld adhesive for reverse osmosis membranes
US3904519A (en) 1971-10-19 1975-09-09 Us Interior Reverse osmosis process using crosslinked aromatic polyamide membranes
US4188418A (en) 1972-08-09 1980-02-12 Lever Brothers Company Separation process
JPS5223346B2 (en) 1972-08-30 1977-06-23
US4039440A (en) 1972-09-19 1977-08-02 The United States Of America As Represented By The Secretary Of The Interior Reverse osmosis membrane
GB1462171A (en) 1972-12-21 1977-01-19 Nederlandse Appl Scient Res Process for making thin polymer foils and their use in a dynamic membrane
US3993625A (en) 1973-05-28 1976-11-23 Toray Industries, Inc. Permselective polymeric membranes of organic polyamide or polyhydrazide
US3906250A (en) 1973-07-03 1975-09-16 Univ Ben Gurion Method and apparatus for generating power utilizing pressure-retarded-osmosis
US4051300A (en) 1973-09-03 1977-09-27 Gulf South Research Institute Hollow synthetic fibers
US3951815A (en) 1974-09-05 1976-04-20 Universal Oil Products Company Composite semipermeable membranes made from polyethylenimine
US3926798A (en) 1974-10-17 1975-12-16 Us Interior Reverse osmosis membrane
DE2602493A1 (en) 1975-01-27 1976-07-29 Ramot Plastics PROCESS FOR THE REMOVAL OF UREA FROM AQUATIC SOLUTIONS
US4020142A (en) 1975-08-21 1977-04-26 Celanese Corporation Chemical modification of polybenzimidazole semipermeable
US4005012A (en) 1975-09-22 1977-01-25 The United States Of America As Represented By The Secretary Of The Interior Semipermeable membranes and the method for the preparation thereof
US4060488A (en) 1975-11-20 1977-11-29 E. I. Du Pont De Nemours And Company Particulate membrane ultrafiltration device
US4214994A (en) 1976-12-20 1980-07-29 Matsushita Electric Industrial Co., Ltd. Reverse osmosis membrane
DE2808293C2 (en) 1978-02-27 1982-04-01 Akzo Gmbh, 5600 Wuppertal Process for the production of a shaped body with inclusions and use of the shaped body
US5130025A (en) 1978-04-20 1992-07-14 Unisearch Limited Membrane separation and purification of compounds
US4259183A (en) * 1978-11-07 1981-03-31 Midwest Research Institute Reverse osmosis membrane
US4277344A (en) * 1979-02-22 1981-07-07 Filmtec Corporation Interfacially synthesized reverse osmosis membrane
US4559139A (en) 1979-12-13 1985-12-17 Toray Industries, Inc. High performance semipermeable composite membrane and process for producing the same
US4387024A (en) 1979-12-13 1983-06-07 Toray Industries, Inc. High performance semipermeable composite membrane and process for producing the same
JPS5695304A (en) 1979-12-28 1981-08-01 Teijin Ltd Perm selective composite membrane and its production
IL63638A0 (en) 1980-09-16 1981-11-30 Aligena Ag Semipermeable composite membranes,their manufacture and their use
JPS5840694U (en) 1981-09-11 1983-03-17 株式会社ハツコ− Tube for pipe lining
CH656626A5 (en) 1982-02-05 1986-07-15 Pall Corp POLYAMIDE MEMBRANE HAVING CONTROLLED SURFACE PROPERTIES, ITS USE AND ITS PREPARATION METHOD.
US4707266A (en) 1982-02-05 1987-11-17 Pall Corporation Polyamide membrane with controlled surface properties
DE3220376A1 (en) 1982-05-29 1983-12-01 Seitz-Filter-Werke Theo & Geo Seitz GmbH und Co, 6550 Bad Kreuznach MEMBRANE FILTER FOR MICROFILTRATION AND METHOD FOR THE PRODUCTION THEREOF
IL70415A (en) 1982-12-27 1987-07-31 Aligena Ag Semipermeable encapsulated membranes,their manufacture and their use
US4606943A (en) * 1983-03-18 1986-08-19 Culligan International Company Method for preparation of semipermeable composite membrane
US4693985A (en) 1984-08-21 1987-09-15 Pall Corporation Methods of concentrating ligands and active membranes used therefor
JPS61127731A (en) 1984-11-26 1986-06-16 Asahi Chem Ind Co Ltd Novel production method of polyamide
JPS61156165A (en) 1984-12-28 1986-07-15 Toshiba Corp Image forming device
US4740219A (en) 1985-02-04 1988-04-26 Allied-Signal Inc. Separation of fluids by means of mixed matrix membranes
US4795559A (en) 1985-03-29 1989-01-03 Firma Carl Freudenberg Semipermeable membrane support
US4765915A (en) 1985-05-23 1988-08-23 The Dow Chemical Company Porous filter media and membrane support means
US4762619A (en) 1985-07-17 1988-08-09 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Method of forming dynamic membrane on stainless steel support
US4713438A (en) 1985-07-23 1987-12-15 Amoco Corporation Amide and/or imide containing polymers and monomers for the preparation thereof
GB2189168B (en) 1986-04-21 1989-11-29 Aligena Ag Composite membranes useful in the separation of low molecular weight organic compounds from aqueous solutions containing inorganic salts
US4765897A (en) * 1986-04-28 1988-08-23 The Dow Chemical Company Polyamide membranes useful for water softening
JPS6312310A (en) 1986-07-04 1988-01-19 Toray Ind Inc Production of semipermeable composite membrane
US4948506A (en) * 1986-07-07 1990-08-14 Bend Research, Inc. Physicochemically functional ultrathin films by interfacial polymerization
US5024594A (en) 1986-07-23 1991-06-18 Membrane Technology & Research, Inc. Protective clothing material
DK169616B1 (en) 1986-08-27 1994-12-27 Dow Danmark Permeable, porous, polymer-treated plastic membrane with hydrophilic character, processes for their preparation and use thereof
US4814082A (en) 1986-10-20 1989-03-21 Memtec North America Corporation Ultrafiltration thin film membranes
US5069945A (en) 1986-10-20 1991-12-03 Memtec America Corporation Ultrapous thin-film membranes
US5108607A (en) 1987-05-20 1992-04-28 Gelman Sciences, Inc. Filtration membranes and method of making the same
US4830885A (en) 1987-06-08 1989-05-16 Allied-Signal Inc. Chlorine-resistant semipermeable membranes
US4840977A (en) 1987-10-01 1989-06-20 General Electric Company Polymeric iodonium salts, method for making, and heat curable compositions
US4859384A (en) 1987-11-18 1989-08-22 Filmtec Corp. Novel polyamide reverse osmosis membranes
US4769148A (en) 1987-11-18 1988-09-06 The Dow Chemical Company Novel polyamide reverse osmosis membranes
DK249689A (en) 1988-05-24 1989-11-25 Alcan Int Ltd COMPOSITE MEMBRANE AND PROCEDURE IN ITS MANUFACTURING
US4842736A (en) 1988-09-06 1989-06-27 Desalination Systems, Inc. Spiral wound membrane
US4872984A (en) 1988-09-28 1989-10-10 Hydranautics Corporation Interfacially synthesized reverse osmosis membrane containing an amine salt and processes for preparing the same
US4948507A (en) 1988-09-28 1990-08-14 Hydranautics Corporation Interfacially synthesized reverse osmosis membrane containing an amine salt and processes for preparing the same
DE3839966A1 (en) 1988-11-26 1990-05-31 Akzo Gmbh HOLLOW THREAD MODULE
US4971697A (en) 1989-02-23 1990-11-20 Minnesota Mining And Manufacturing Company Thin silica flakes and method of making
US5104632A (en) 1989-02-23 1992-04-14 Minnesota Mining And Manufacturing Company Method of making thin silica flakes
IL89970A (en) 1989-04-14 1994-10-21 Weizmann Kiryat Membrane Prod Composite membranes containing a coated layer of crosslinked polyaromatic polymers and/or sulfonated poly (haloalkylenes)
US5089460A (en) * 1989-07-26 1992-02-18 Academy Of Applied Science, Inc. Vanadium catalyst systems for olefin polymerization
US5032268A (en) 1989-08-17 1991-07-16 Wallace von Medlin Self-contained canister unit for filtering tap water
US4950404A (en) 1989-08-30 1990-08-21 Allied-Signal Inc. High flux semipermeable membranes
US5002590A (en) 1989-09-19 1991-03-26 Bend Research, Inc. Countercurrent dehydration by hollow fibers
US5342431A (en) 1989-10-23 1994-08-30 Wisconsin Alumni Research Foundation Metal oxide membranes for gas separation
US5269926A (en) 1991-09-09 1993-12-14 Wisconsin Alumni Research Foundation Supported microporous ceramic membranes
US5183566A (en) 1989-11-01 1993-02-02 Exxon Research And Engineering Company Hollow fiber module built up from concentric cylinders of hollow fibers
US4983291A (en) 1989-12-14 1991-01-08 Allied-Signal Inc. Dry high flux semipermeable membranes
US5096584A (en) 1990-01-29 1992-03-17 The Dow Chemical Company Spiral-wound membrane separation device with feed and permeate/sweep fluid flow control
FR2660874B1 (en) 1990-04-12 1992-06-12 Aluminum Co Of America SEMI-PERMEABLE POROUS INORGANIC COMPOSITE MEMBRANE AND PREPARATION METHOD.
JP3195377B2 (en) 1990-06-14 2001-08-06 リンテック株式会社 Organic solvent selective permeable membrane
US5084179A (en) 1990-06-28 1992-01-28 Cuno, Incorporated Narrow pore-size distribution polytetramethylene adipamide or nylon 46 membranes and process for making them
IL95075A0 (en) 1990-07-13 1991-06-10 Joseph Yaeli Method and apparatus for processing liquid solutions or suspensions particularly useful in the desalination of saline water
FR2665087B1 (en) 1990-07-24 1992-10-09 Lorraine Carbone PROCESS FOR THE MANUFACTURE OF AN ULTRA-THIN AND ASYMMETRIC MINERAL MEMBRANE.
JPH04126529A (en) 1990-09-14 1992-04-27 Nitto Denko Corp Antifungal liquid separation membrane
EP0478842A1 (en) 1990-10-05 1992-04-08 PALL BIOMEDIZIN GmbH Filter for the filtration of human cerebrospinal fluid
US5147541A (en) 1990-11-14 1992-09-15 Koch Membrane Systems, Inc. Spiral filtration module with strengthened membrane leaves and method of constructing same
US5258203A (en) 1991-02-04 1993-11-02 E. I. Du Pont De Nemours And Company Process for the manufacture of thin film composite membranes
US5114582A (en) 1991-04-12 1992-05-19 W. R. Grace & Co.-Conn. Filter element and spiral-wound membrane cartridge containing same
JP2562137Y2 (en) 1991-05-01 1998-02-10 株式会社マルタカ Massage machine
US5254261A (en) 1991-08-12 1993-10-19 Hydranautics Interfacially synthesized reverse osmosis membranes and processes for preparing the same
JPH05245349A (en) 1991-11-06 1993-09-24 Nitto Denko Corp Antibacterial liquid separation membrane and its production
WO1993022038A1 (en) 1992-05-01 1993-11-11 Filmtec Corporation Spiral wound membrane element
US5234598A (en) 1992-05-13 1993-08-10 Allied-Signal Inc. Thin-film composite membrane
NL9200902A (en) 1992-05-21 1993-12-16 Cornelis Johannes Maria Van Ri CERAMIC MICROFILTRATION MEMBRANE AND METHOD FOR MANUFACTURING SUCH MEMBRANE.
US5281430A (en) 1992-12-08 1994-01-25 Osmotek, Inc. Osmotic concentration apparatus and method for direct osmotic concentration of fruit juices
US5262054A (en) 1992-12-30 1993-11-16 E. I. Du Pont De Nemours And Company Process for opening reverse osmosis membranes
JP3006976B2 (en) 1993-06-24 2000-02-07 日東電工株式会社 Method for producing highly permeable composite reverse osmosis membrane
US5435957A (en) 1993-09-03 1995-07-25 Pall Corporation Method of preparing a support material for use with a filtration medium
JP3342928B2 (en) 1993-09-13 2002-11-11 オルガノ株式会社 Hanging equipment for filtration equipment using hollow fiber modules
EP0764461B1 (en) 1994-06-07 2002-08-28 Mitsubishi Rayon Co., Ltd. Porous polysulfone membrane and process for producing the same
US6241893B1 (en) 1994-06-17 2001-06-05 Ehud Levy Water filtration media, apparatus and processes
US5783079A (en) * 1994-08-29 1998-07-21 Toyo Boseki Kabushiki Kaisha Composite hollow fiber membrane and process for its production
GB9505038D0 (en) 1994-10-01 1995-05-03 Imas Uk Ltd A filter, apparatus including the filter and a method of use of the apparatus
US5693227A (en) 1994-11-17 1997-12-02 Ionics, Incorporated Catalyst mediated method of interfacial polymerization on a microporous support, and polymers, fibers, films and membranes made by such method
JP3489922B2 (en) 1994-12-22 2004-01-26 日東電工株式会社 Method for producing highly permeable composite reverse osmosis membrane
US5614099A (en) 1994-12-22 1997-03-25 Nitto Denko Corporation Highly permeable composite reverse osmosis membrane, method of producing the same, and method of using the same
JPH08182921A (en) 1994-12-28 1996-07-16 Mitsubishi Rayon Co Ltd Polyolefin composite fine porous film
KR970703805A (en) 1995-05-01 1997-08-09 유니온 카바이드 케미칼즈 앤드 플라스틱스 테크놀러지 코포레이션 Membrane Separation
US5650479A (en) 1995-06-06 1997-07-22 The Cynara Co. Interfacially polymerized polyester films
US5989426A (en) 1995-07-05 1999-11-23 Nitto Denko Corp. Osmosis membrane
US6171497B1 (en) 1996-01-24 2001-01-09 Nitto Denko Corporation Highly permeable composite reverse osmosis membrane
US5755964A (en) 1996-02-02 1998-05-26 The Dow Chemical Company Method of treating polyamide membranes to increase flux
US5800706A (en) 1996-03-06 1998-09-01 Hyperion Catalysis International, Inc. Nanofiber packed beds having enhanced fluid flow characteristics
CN1213985A (en) 1996-03-18 1999-04-14 日东电工株式会社 Composite reverse osmosis membrane and method of reverse osmotic treatment of water using same
JP3681214B2 (en) * 1996-03-21 2005-08-10 日東電工株式会社 High permeability composite reverse osmosis membrane
JP3430783B2 (en) 1996-04-11 2003-07-28 東レ株式会社 Liquid separation element, apparatus and processing method
US5658460A (en) 1996-05-07 1997-08-19 The Dow Chemical Company Use of inorganic ammonium cation salts to maintain the flux and salt rejection characteristics of reverse osmosis and nanofiltration membranes during drying
US5681467A (en) 1996-09-19 1997-10-28 The Dow Chemical Company Method for forming a membrane into a predetermined shape
EP1015099A4 (en) 1997-01-10 2003-01-22 Ellipsis Corp Micro and ultrafilters with controlled pore sizes and pore size distribution and method for making
ID20551A (en) 1997-03-25 1999-01-14 Toray Industries POLYMERIZATION CATALYST, METHOD OF MAKING IT, AND METHOD OF MAKING POLYESTER USING SUCH CATALYST
US6413425B1 (en) 1997-04-10 2002-07-02 Nitto Denko Corporation Reverse osmosis composite membrane and reverse osmosis treatment method for water using the same
US5919026A (en) 1997-06-02 1999-07-06 Kann Manufacturing Corporation Carry can discharge floor
US5914039A (en) 1997-07-01 1999-06-22 Zenon Environmental Inc. Filtration membrane with calcined α-alumina particles therein
US6354444B1 (en) 1997-07-01 2002-03-12 Zenon Environmental Inc. Hollow fiber membrane and braided tubular support therefor
DE19741498B4 (en) 1997-09-20 2008-07-03 Evonik Degussa Gmbh Production of a ceramic stainless steel mesh composite
US5876602A (en) 1997-11-04 1999-03-02 The Dow Chemical Company Treatment of composite polyamide membranes to improve performance
US5938934A (en) 1998-01-13 1999-08-17 Dow Corning Corporation Dendrimer-based nanoscopic sponges and metal composites
AU2584299A (en) * 1998-02-09 1999-08-23 Robert L. Mcginnis Osmotic desalinization process
US6015495A (en) 1998-02-18 2000-01-18 Saehan Industries Incorporation Composite polyamide reverse osmosis membrane and method of producing the same
US6162358A (en) 1998-06-05 2000-12-19 Nl Chemicals Technologies, Inc. High flux reverse osmosis membrane
WO2000000268A1 (en) 1998-06-29 2000-01-06 Microban Products Company Antimicrobial semi-permeable membranes
US6368507B1 (en) 1998-10-14 2002-04-09 Saekan Industries Incorporation Composite polyamide reverse osmosis membrane and method of producing the same
FR2786710B1 (en) 1998-12-04 2001-11-16 Ceramiques Tech Soc D MEMBRANE COMPRISING A POROUS SUPPORT AND A LAYER OF A MODULAR SIEVE AND ITS PREPARATION METHOD
US6156680A (en) 1998-12-23 2000-12-05 Bba Nonwovens Simpsonville, Inc. Reverse osmosis support substrate and method for its manufacture
CN1173770C (en) 1999-01-14 2004-11-03 东丽株式会社 Composite semipermeable membrane, procedss for producing the same, and method of purifying water with the same
US6185940B1 (en) 1999-02-11 2001-02-13 Melvin L. Prueitt Evaporation driven system for power generation and water desalinization
WO2000064579A1 (en) 1999-04-23 2000-11-02 Nexttec Gmbh Use of a composite polymer-coated sorbent for separation, purification, desalting and concentration of biopolymers
US6652751B1 (en) 1999-04-27 2003-11-25 National Research Council Of Canada Intrinsically bacteriostatic membranes and systems for water purification
US6245234B1 (en) 1999-06-03 2001-06-12 Saehan Industries Incorporation Composite polyamide reverse osmosis membrane and method of producing the same
US6280853B1 (en) 1999-06-10 2001-08-28 The Dow Chemical Company Composite membrane with polyalkylene oxide modified polyamide surface
MX250079B (en) 1999-06-11 2007-10-08 Gas Separation Technology Inc Porous gas permeable material for gas separation.
US6187192B1 (en) 1999-08-25 2001-02-13 Watervisions International, Inc. Microbiological water filter
US6355072B1 (en) 1999-10-15 2002-03-12 R.R. Street & Co. Inc. Cleaning system utilizing an organic cleaning solvent and a pressurized fluid solvent
DE19959264A1 (en) 1999-12-03 2001-07-12 Elipsa Gmbh Template-embossed composite materials with high binding specificity and selectivity, processes for their production and their use
KR20010100304A (en) 2000-04-14 2001-11-14 한형수 Producing method of the reverse osmosis membrane of drying type
US6337018B1 (en) 2000-04-17 2002-01-08 The Dow Chemical Company Composite membrane and method for making the same
IL152998A0 (en) 2000-05-23 2003-06-24 Osmonics Inc Polysulfonamide matrices
US6837996B2 (en) 2000-05-23 2005-01-04 Ge Osmonics, Inc. Polysulfonamide matrices
KR100575113B1 (en) 2000-06-21 2006-05-03 가부시키가이샤 구라레 Porous hollow fiber membranes and method of making the same
IL137226A0 (en) 2000-07-09 2001-07-24 Nirosoft Ind Ltd Method for modifying membrane rejection characteristics
US6605140B2 (en) 2000-08-09 2003-08-12 National Research Council Of Canada Composite gas separation membranes
CN1258234C (en) 2000-08-12 2006-05-31 Lg化学株式会社 Multi-component composite film method for preparing the same
US6503295B1 (en) 2000-09-20 2003-01-07 Chevron U.S.A. Inc. Gas separations using mixed matrix membranes
US7048855B2 (en) 2000-12-22 2006-05-23 Ge Osmonics, Inc. Cross flow filtration materials and cartridges
AU2002247049A1 (en) * 2001-02-01 2002-08-12 Yale University Osmotic desalination process
FR2820342B1 (en) 2001-02-07 2003-12-05 Inst Francais Du Petrole PROCESS FOR THE PREPARATION OF ZEOLITHIC MEMBRANES SUPPORTED BY TEMPERATURE CONTROLLED CRYSTALLIZATION
GB0104700D0 (en) * 2001-02-26 2001-04-11 Isis Innovation Luminescent polymers
US6841601B2 (en) * 2001-03-13 2005-01-11 Dais-Analytic Corporation Crosslinked polymer electrolyte membranes for heat and moisture exchange devices
EP1283068A1 (en) 2001-07-30 2003-02-12 Saehan Industries, Inc. Reverse osmosis membrane having excellent anti-fouling property and method for manufacturing the same
JP2003088730A (en) 2001-09-20 2003-03-25 Nitto Denko Corp Treatment method for reverse osmosis membrane element and reverse osmosis membrane module
US6913694B2 (en) 2001-11-06 2005-07-05 Saehan Industries Incorporation Selective membrane having a high fouling resistance
KR100493113B1 (en) 2001-12-07 2005-05-31 주식회사 코오롱 A braid-reinforced hollow fiber membrane
JP4917234B2 (en) 2001-12-07 2012-04-18 日本碍子株式会社 Ceramic filter and water purification method
US20030131731A1 (en) 2001-12-20 2003-07-17 Koros William J. Crosslinked and crosslinkable hollow fiber mixed matrix membrane and method of making same
US6713519B2 (en) 2001-12-21 2004-03-30 Battelle Memorial Institute Carbon nanotube-containing catalysts, methods of making, and reactions catalyzed over nanotube catalysts
US7109140B2 (en) 2002-04-10 2006-09-19 Virginia Tech Intellectual Properties, Inc. Mixed matrix membranes
US6881336B2 (en) 2002-05-02 2005-04-19 Filmtec Corporation Spiral wound element with improved feed space
AU2003239332A1 (en) 2002-05-03 2003-11-17 Pall Corporation Blended polymer membrane media for treating aqueous fluids
WO2003097218A1 (en) 2002-05-16 2003-11-27 Mcmaster University Novel composite tecto-membranes formed by interfacial reaction of crosslinked polymer microspheres with coupling agents
AU2003230426A1 (en) 2002-05-17 2003-12-02 Para Limited Hollow fiber membrane having supporting material for reinforcement, preparation thereof and spinneret for preparing the same
KR20050083674A (en) 2002-09-04 2005-08-26 바이오랩, 인크. Disinfection of reverse osmosis membrane
ES2291859T3 (en) * 2003-03-07 2008-03-01 Seldon Technologies, Llc PURIFICATION OF FLUIDS WITH NANOMATERIALS.
US20040178135A1 (en) 2003-03-13 2004-09-16 Beplate Douglas K. Filtering device incorporating nanoparticles
US7172075B1 (en) 2003-08-08 2007-02-06 Accord Partner Limited Defect free composite membranes, method for producing said membranes and use of the same
US8022013B2 (en) 2003-08-29 2011-09-20 Illumina, Inc. Method of forming and using solid-phase support
US7490725B2 (en) 2003-10-09 2009-02-17 Membrane Technology & Research Reverse osmosis membrane and process
KR20050056892A (en) 2003-12-10 2005-06-16 학교법인 성균관대학 Electrical cell including porous continuous fiber membrane
US7166146B2 (en) 2003-12-24 2007-01-23 Chevron U.S.A. Inc. Mixed matrix membranes with small pore molecular sieves and methods for making and using the membranes
KR100527898B1 (en) 2004-01-27 2005-11-15 한국해양연구원 Reverse osmosis composite membrane with nano particle tourmaline and manufacturing method
US7306823B2 (en) * 2004-09-18 2007-12-11 Nanosolar, Inc. Coated nanoparticles and quantum dots for solution-based fabrication of photovoltaic cells
ES2400910T3 (en) 2004-02-25 2013-04-15 Dow Global Technologies Llc Apparatus for treating high osmotic resistance solutions
US7182894B2 (en) 2004-03-12 2007-02-27 Council Of Scientific & Industrial Research Process for the preparation of free standing membranes
US20050230305A1 (en) 2004-03-26 2005-10-20 Kulkarni Sudhir S Novel method for forming a mixed matrix composite membrane using washed molecular sieve particles
US7604746B2 (en) 2004-04-27 2009-10-20 Mcmaster University Pervaporation composite membranes
CA2564774A1 (en) 2004-05-27 2005-12-15 Nanophase Technologies Corporation Enhanced scratch resistance of articles containing a combination of nano-crystalline metal oxide particles, polymeric dispersing agents, and surface active materials
US7459121B2 (en) * 2004-07-21 2008-12-02 Florida State University Research Foundation Method for continuous fabrication of carbon nanotube networks or membrane materials
US20060083694A1 (en) 2004-08-07 2006-04-20 Cabot Corporation Multi-component particles comprising inorganic nanoparticles distributed in an organic matrix and processes for making and using same
JP4484635B2 (en) 2004-09-02 2010-06-16 日東電工株式会社 Spiral type reverse osmosis membrane element and manufacturing method thereof
IL164122A (en) 2004-09-19 2009-09-22 Charles Linder Process for improving membranes
EP1796822A4 (en) 2004-10-06 2008-09-17 Res Foundation Suny High flux and low fouling filtration media
US7578939B2 (en) 2004-12-09 2009-08-25 Board Of Trustees Of Michigan State University Ceramic membrane water filtration
JP2006187731A (en) 2005-01-06 2006-07-20 Kurita Water Ind Ltd Separation membrane and water treatment apparatus
RU2007137124A (en) 2005-03-09 2009-04-20 Дзе Риджентс Оф Дзе Юниверсити Оф Калифорния (Us) NANOCOMPOSITE MEMBRANES AND METHODS FOR PRODUCING AND USING THEM
WO2006099078A2 (en) 2005-03-11 2006-09-21 Uop Llc High flux, microporous, sieving membranes and separators containing such membranes and processes using such membranes
WO2007084169A2 (en) 2005-04-20 2007-07-26 Board Of Regents, The University Of Texas System Metal oxide nanoparticle filled polymers
US20060249446A1 (en) 2005-05-04 2006-11-09 Gary Yeager Solvent-resistant composite membrane composition
US7569254B2 (en) 2005-08-22 2009-08-04 Eastman Kodak Company Nanocomposite materials comprising high loadings of filler materials and an in-situ method of making such materials
KR100716210B1 (en) 2005-09-20 2007-05-10 웅진코웨이주식회사 Preparation method of polyamide reverse osmosis composite membrane and polyamide reverse osmosis composite membrane prepared therefrom
WO2007050408A2 (en) 2005-10-26 2007-05-03 Nanoresearch, Development And Consulting Llc Metal complexes for enhanced dispersion of nanomaterials, compositions and methods therefor
WO2007065867A1 (en) 2005-12-05 2007-06-14 Solvay (Societe Anonyme) Aromatic sulfone polymer composition comprising tetrafluoroethylene polymer particles
US20110031180A1 (en) 2006-01-12 2011-02-10 Yasuhiro Tada Hollow-Fiber Module and Process for Producing The Same
CA2642186A1 (en) 2006-02-13 2007-08-23 Donaldson Company, Inc. Filter web comprising fine fiber and reactive, adsorptive or absorptive particulate
US7846496B2 (en) 2006-03-10 2010-12-07 Uop Llc Mixed matrix membranes incorporating surface-functionalized molecular sieve nanoparticles and methods for making the same
MY145048A (en) 2006-05-09 2011-12-15 Porex Corp Porous composite membrane materials and applications thereof
EP2021586B1 (en) * 2006-05-12 2015-02-25 Energy Recovery, Inc. Hybrid ro/pro system
KR101360751B1 (en) 2006-05-12 2014-02-07 다우 글로벌 테크놀로지스 엘엘씨 Modified membrane
JP2008093544A (en) 2006-10-10 2008-04-24 Nitto Denko Corp Composite semipermeable membrane and manufacturing method thereof
WO2008057842A2 (en) * 2006-10-27 2008-05-15 The Regents Of The University Of California Micro-and nanocomposite support structures for reverse osmosis thin film membranes
WO2008118228A2 (en) * 2006-12-05 2008-10-02 Stonybrook Water Purification Articles comprising a fibrous support
AU2008209499A1 (en) 2007-01-24 2008-07-31 Whatman Inc. Modified porous membranes, methods of membrane pore modification, and methods of use thereof
JP5201930B2 (en) * 2007-02-16 2013-06-05 富士フイルム株式会社 Hydrophilic member and method for producing the same
US8424687B2 (en) 2007-07-31 2013-04-23 Toray Industries, Inc. Support for separation membrane, and method for production thereof
EP2554570A1 (en) 2007-08-20 2013-02-06 Technion Research and Development Foundation, Ltd. Polysulfone polymers and membranes for reverse osmosis, nanofiltration and ultrafiltration
JP5568835B2 (en) 2007-10-01 2014-08-13 栗田工業株式会社 Reverse osmosis membrane, reverse osmosis membrane device, and method of hydrophilizing reverse osmosis membrane
JP5245349B2 (en) 2007-10-17 2013-07-24 日本電気株式会社 Registration destination way fixing method, processor, and information processing apparatus
AU2009236162B2 (en) 2008-04-15 2013-10-31 Nanoh2O, Inc. Hybrid nanoparticle TFC membranes
US8177978B2 (en) 2008-04-15 2012-05-15 Nanoh20, Inc. Reverse osmosis membranes
US7993524B2 (en) 2008-06-30 2011-08-09 Nanoasis Technologies, Inc. Membranes with embedded nanotubes for selective permeability
US8147735B2 (en) * 2008-07-09 2012-04-03 Eltron Research & Development, Inc. Semipermeable polymers and method for producing same
JP5463355B2 (en) 2008-07-10 2014-04-09 ボード・オブ・リージエンツ,ザ・ユニバーシテイ・オブ・テキサス・システム Water purification membrane with improved contamination resistance
GB0816258D0 (en) 2008-09-05 2008-10-15 Ulive Entpr Ltd Process
WO2010039255A2 (en) * 2008-10-03 2010-04-08 Hlz Innovation, Llc Adjustable pneumatic supporting surface
CN102405267A (en) * 2009-03-09 2012-04-04 3M创新有限公司 Aziridine crosslinking agents for acrylic adhesives
JP5745512B2 (en) * 2009-06-29 2015-07-08 ナノエイチツーオー・インコーポレーテッド Improved hybrid TFCRO membrane containing nitrogen additive
CN101695636B (en) 2009-11-04 2012-06-20 天津大学 Grafted modified aromatic polyamide composite reverse osmosis membrane and preparation method thereof
US8011517B2 (en) 2009-11-24 2011-09-06 International Business Machines Corporation Composite membranes with performance enhancing layers
CN101816900B (en) 2010-04-21 2011-12-21 天津大学 Aromaticpolyamide composite reverse osmosis membrane modified by graft polymerization and preparation method thereof
US8727135B2 (en) * 2010-09-01 2014-05-20 International Business Machines Corporation Composite filtration membranes and methods of preparation thereof
US20120111791A1 (en) 2010-11-04 2012-05-10 Board Of Regents, The University Of Texas System Surface Deposition of Small Molecules to Increase Water Purification Membrane Fouling Resistance
JP5968328B2 (en) * 2010-11-10 2016-08-10 ナノエイチツーオー・インコーポレーテッド Improved hybrid TFCRO membrane containing non-metallic additives
US20130287946A1 (en) * 2011-01-24 2013-10-31 Dow Global Technologies Llc Composite polyamide membrane
WO2012105397A1 (en) * 2011-01-31 2012-08-09 東レ株式会社 Separation membrane for water treatment and production method for same
US9022227B2 (en) 2011-03-21 2015-05-05 International Business Machines Corporation Composite membranes and methods of preparation thereof
WO2013176524A1 (en) 2012-05-24 2013-11-28 주식회사 엘지화학 Reverse osmosis membrane
JP2016511288A (en) * 2012-12-17 2016-04-14 ビーエーエスエフ ソシエタス・ヨーロピアBasf Se Membrane with improved flux and method for producing said membrane

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4492721A (en) * 1983-05-10 1985-01-08 U.S. Philips Corporation Method of providing magnesium fluoride layers
US4931362A (en) * 1987-08-18 1990-06-05 F.Joh.Kwizda Gesellschaft M.B.H. Microcapsule and micromatrix bodies and method for their formation
US5017680A (en) * 1990-07-03 1991-05-21 Eastman Kodak Company Process and catalyst-inhibitor systems for preparing poly(ethylene terephthalate)
US20040234751A1 (en) * 1998-12-10 2004-11-25 Hideaki Sakurai Protective thin film for FPDs, method for producing said thin film and FPDs using said thin film
US20060204812A1 (en) * 2003-03-05 2006-09-14 Hideki Moriyama Aromatic polymer, film, electrolyte membrane and separator
US20080251447A1 (en) * 2006-10-10 2008-10-16 Atsuhito Koumoto Process for producing a dried composite semipermeable membrane

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