EP2621614A1 - Thin film composite membranes incorporating carbon nanotubes - Google Patents

Thin film composite membranes incorporating carbon nanotubes

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Publication number
EP2621614A1
EP2621614A1 EP11749977.2A EP11749977A EP2621614A1 EP 2621614 A1 EP2621614 A1 EP 2621614A1 EP 11749977 A EP11749977 A EP 11749977A EP 2621614 A1 EP2621614 A1 EP 2621614A1
Authority
EP
European Patent Office
Prior art keywords
carbon nanotubes
thin film
membrane
film composite
organic solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11749977.2A
Other languages
German (de)
English (en)
French (fr)
Inventor
Hua Wang
Gary William Yeager
Joseph Anthony Suriano
Steven Thomas Rice
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
General Electric Co
Original Assignee
General Electric Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US12/895,353 external-priority patent/US8591741B2/en
Priority claimed from US12/895,365 external-priority patent/US20120080381A1/en
Application filed by General Electric Co filed Critical General Electric Co
Publication of EP2621614A1 publication Critical patent/EP2621614A1/en
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B01D67/00793—Dispersing a component, e.g. as particles or powder, in another component
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0093—Chemical modification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B01D69/148—Organic/inorganic mixed matrix membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/021—Carbon
    • B01D71/0212—Carbon nanotubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/021—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/28—Solid content in solvents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/36—Diameter

Definitions

  • Reverse osmosis (RO) desalination uses membrane technology to transform seawater and brackish water into fresh water for drinking, irrigation and industrial applications. Reverse osmosis desalination processes require substantially less energy than thermal desalination processes. As a result, the majority of recent commercial projects use more cost-effective reverse osmosis membranes to produce fresh water from seawater or brackish water. Over the years, advances in membrane technology and energy recovery devices have made reverse osmosis more affordable and efficient. Despite its capacity to efficiently remove ionic species at as high as99.8% salt rejection, there remains a need for reverse osmosis membranes that possess improved flux characteristics while maintaining useful rejection characteristics.
  • Reverse osmosis is the process of forcing a solvent from a region of high solute concentration through a membrane to a region of low solute concentration by applying a pressure in excess of the osmotic pressure. This is the reverse of the normal osmosis process, which is the natural movement of solvent from an area of low solute concentration, through a membrane, to an area of high solute
  • the membrane here is semipermeable, meaning it allows the passage of solvent but not of solute.
  • the membranes used for reverse osmosis have a dense barrier layer where most separation occurs. In most cases the membrane is designed to allow only water to pass through this dense layer while preventing the passage of solutes (such as salt ions). Examples of reverse osmosis processes are the purification of brackish water and seawater, where often less than 1% of the impurity species in the seawater or brackish water are found in the permeate.
  • the reverse osmosis process requires that a high pressure be exerted on the high concentration side of the membrane, usually 2-17 bar (30-250 psi) for fresh and brackish water, and 40-70 bar (600-1000 psi) for seawater, which has around 24 bar (350 psi) natural osmotic pressure which must be overcome.
  • Nanofiltration in concept and operation, is much the same as reverse osmosis.
  • the key difference is the degree of removal of monovalent ions such as chlorides.
  • Reverse osmosis removes about 99% of the monovalent ions.
  • Nanofiltration membranes removal of monovalent ions varies between 50% to 90% depending on the material and manufacture of the membrane. Nanofiltration membranes and systems are used for water softening, food and pharmaceutical applications.
  • An example of a nanofiltration process is the desalting of a sugar solution, where 80% of the salt passes through the membrane with the water and 95% of the sugar is retained by the membrane.
  • Nanotubes such as carbon and boron nanotubes are fundamentally new nanoporous materials that have great potential for membrane applications.
  • the current methods of synthesis of CNT membranes involve multiple steps and are limited to making membrane samples of extremely small area. They are not scalable to large surface areas necessary for the fabrication of commercial membranes for practical applications.
  • Membranes containing carbon nanotubes have been disclosed for use in purifying water.
  • WO 2006/060721 assigned to National University of Singapore, describes thin film composite (TFC) membranes containing multi-walled carbon nanotubes (MWNT) in an active layer prepared by interfacial polymerization.
  • the WNTs are characterized as having an outside diameter of 30-50 nm.
  • further improvements in the performance of TFC membranes for reverse osmosis applications are desirable.
  • the present invention relates to processes for manufacturing a thin film composite membrane comprising multi-walled carbon nantubes.
  • the processes include contacting under interfacial polymerization conditions an organic solution comprising a polyacid halide with an aqueous solution comprising a polyamine to form a thin film composite membrane on a surface of a porous base membrane; at least one of the organic solution and the aqueous solution further including multi-walled carbon nanotubes having an outside diameter of less than about 30 nm.
  • solvents for use in compositions containing nanotubes may have density greater than about 0.8 and solubility in water of less than about 100 g/L.
  • the solvent may be a single compound or a mixture having the specified density and water solubility.
  • Particularly suitable solvents having these properties are cis- and frans-decalin, and mixtures thereof.
  • Solvents for use in the processes of the present invention may additionally be insoluble in the polysulfone base membranes commonly used in preparing reverse osmosis membranes.
  • polysulfone insoluble and “insoluble in polysulfones” means that such materials swell or dissolve polysulfone.
  • Polysulfone insoluble materials may be included in compositions of the present invention in minor amounts, that is, less than about 50% by weight, based on total weight of the composition. In some embodiments, the polysulfone insoluble materials are present at less than or equal to about 10% by weight, in others at less than or equal to about 5% by weight, and in still others, less than or equal to about 3% by weight.
  • the solvent is a saturated cyclic C 5 -C 20 hydrocarbon solvent.
  • the saturated cyclic C 5 -C 2 o hydrocarbon solvent is a saturated polycyclic compound, or a mixture or one or more saturated polycyclic compounds, for example, cis-decalin, trans-decalin, cyclohexyl halides, and 1 ,5,9- cyclododecatrien and derivatives or a mixture thereof.
  • compositions of the present invention and organic solutions for use in the processes of the present invention may also include at least one saturated acyclic C4-C30 alkane compound, such as hexane or one or more isoparaffins.
  • Suitable isoparaffins include the ISOPARTM series from ExxonMobil (including, but not limited to, ISOPARTM E, ISOPARTM G, ISOPARTM H, ISOPARTM L, and ISOPARTM M).
  • the saturated cyclic C5-C20 hydrocarbon loading in the organic solution is greater than about 20% w w (weight of saturated cyclic C5-C20 hydrocarbon/total weight of solvent, not including monomer or nanotubes); in some embodiments, greater than about 50% w/w, and in other embodiments, greater than about 80% w/w.
  • the organic solution may additionally include a cyclic ketone such as cyclooctanone, cycloheptanone, 2 methylcyclohexanone, cyclohexanone, cyclohexene-3-one, cyclopentanone, cyclobutanone, 3-ketotetrahydrofuran, 3- ketotetrahydrothiophene, or 3-ketoxetane, particularly, cyclohexanone.
  • Aqueous dispersions may include dispersing aids such as polyvinylpyrrolidone, or surfactants, particularly non-ionic surfactants.
  • compositions of the present invention and organic solutions for use in the processes of the present invention may also include other additives.
  • the additive loading in the solvent mixture is in the range of 0.1 to 20 wt%, preferably in the range of 0.5% to 10%, and more preferably in the range of 1 to 10%.
  • These other additives include the following compounds with molar volumes in the range of 50 cm3/mol-1 or higher (preferably 80 or higher) and Hildebrand solubility parameters in the range of 8.5 to 10.5 cal n cm .
  • aromatic hydrocarbons such as tetralin, dodecylbenzene, octadecylbenzene, benzene, toluene, xylene, mesitylene, anisole, dimethylbenzenes, trimethylbenzenes, tetramethylbenzene, ethyl-benzene .fluorobenzene, chlorobenzene, bromobenzenes, dibromobenzenes, iodobenzene, nitrobenzene, ethyl-toluene, pentamethyl-benzene, octyl-benzene, cumene, pseudo- cumene, para-cymene, phenetole, and phenoxy-decane; naphthalenes such as methylnaphtha!enes, dimethylnaphthalenes, trimethylnaphthalenes, ethylnaphthalenes phen
  • Nanotubes for use with solvents having density greater than about 0.8 and solubility in water of less than about 100 g/L include single wall, double wall, and multiwall carbon nanotubes and boron nitride nanotubes with various internal and external diameters and length.
  • Nanotubes with carboxyl (COOH), hydroxyl (OH) carbonyl chloride (-COCI), functionalized with octadecylamine, functionalized with PEG (polyethylene glycol) may be used.
  • Nanotubes with carbonyl chloride (-COCI) may be covalently bonded to polyamide thin film to avoid the leach out of nanotubes during membrane service.
  • the nanotubes typically have a cylindrical nanostructure with an inside diameter (ID) and outside diameters (OD).
  • Concentration of the nanotubes in the organic solution or the aqueous solution is at least 0.025% w/w, and may range from about 0.025% w/w to about 10% w/w in some embodiments, and in others, ranges from about 0.025% w/w to about 5% w/w. In yet other embodiments, the concentration of the nanotubes ranges from about 0.05% w/w to about 1% w/w.
  • the thin film composite (TFC) membranes that may be prepared by a process according to the present invention are composed of a separating functional layer formed on a porous base support.
  • the separating functional layer is thin in order to maximize membrane flux performance, and is formed on a porous support or base membrane to provide mechanical strength.
  • TFC membranes that may be prepared include, but are not limited to, reverse osmosis membranes composed of a polyamide separating functional layer formed on a porous polysulfone support, nanofiltration membranes, and other thin film composite membrane.
  • Interfacial polymerization includes contacting an aqueous solution of one or more nucleophilic monomers onto a porous support membrane; followed by coating an organic solution, generally in an aliphatic solvent, containing one or more electrophilic monomers.
  • a thin film polymer is formed from condensation of the electrophilic and nucleophilic monomers and is adherent to the porous support. The rate of thin film formation may be accelerated by heating or addition of catalysts.
  • the polyacid halide monomer on contact with the polyamine monomer reacts on the surface of the porous base membrane to afford a polyamide disposed on the surface of the porous support membrane. Suitable monomers useful in the present invention are described below.
  • the membrane comprises a polymer having an amine group.
  • the polymer may be produced by interfacial polymerization.
  • Interfacial polymerization includes a process widely used for the synthesis of thin film membranes for reverse osmosis, hyperfiltration, and nanofiltration.
  • Interfacial polymerization includes coating a first solution, generally aqueous, of one or more nucleophilic monomers onto a porous base support; followed by coating a second solution, generally in an aliphatic solvent, containing one or more electrophilic monomers. The second solution is immiscible with the first solution.
  • a thin film polymer is formed from condensation of the electrophilic and nucleophilic monomers and is adherent to the porous base support.
  • the rate of thin film formation may be accelerated by heating or addition of catalysts.
  • nucleophilic monomers include, but are not limited to, amine containing monomers such as polyethylenimines; cyclohexanediamines; 1 ,2- diaminocyclohexane; 1 ,4-diaminocyclohexane; piperazine; methyl piperazine;
  • dimethylpiperazine e.g. 2,5-dimethyl piperazine
  • homopiperazine 1,3- bis(piperidyl)propane
  • 4-aminomethylpiperazine cyclohexanetriamines (e.g. 1,3,5- triaminocyclohexane)
  • xylylenediamines o-, m-, p-xylenediamine
  • phenylenediamines ⁇ e.g. m-phenylene diamine and p-phenylenediamine, 3,5- diaminobenzoic acid, 3,5-diamonsulfonic acid); chloropheny!enediamines (e.g. 4- or 5-chloro-m-phenylenediamine); benzenetriamines (e.g. 1 ,3,5-benzenetriamine, 1,2,4- triamino enzene); bis(aminobenzyl) aniline; tetraaminobenzenes; diaminobiphenyls (e.g. 4,4,'-diaminobiphenyl; tetrakis(aminomethyl)methane;
  • chloropheny!enediamines e.g. 4- or 5-chloro-m-phenylenediamine
  • benzenetriamines e.g. 1 ,3,5-benzenetriamine, 1,2,4- triamino
  • diaminodiphenylmethanes ⁇ , ⁇ '-diphenylethylenediamine
  • aminobenzamides e.g. 4- aminobenzamide, 3,3'-diaminobenzamide; 3,5-diaminobenzamide; 3,5- diaminobenzamide; 3,3'5,5'-tetraaminobenzamide); either individually or in any combinations thereof.
  • nucleophilic monomers for the present invention include m-phenylenediamine, p-phenylenediamine, 1 ,3,5-triaminobenzene, piperazine, 4- aminomethylpiperidine, and either individually or in any combinations thereof. More particularly, nucleophilic monomer useful in the present invention includes m- phenylene diamine.
  • electrophilic monomers include, but are not limited to, acid halide-terminated polyamide oligomers (e.g. copolymers of piperazine with an excess of isophthaloyl chloride); benzene dicarboxylic acid halides (e.g. isophthaloyl chloride or terephthaloyl chloride); benzene tricarboxylic acid halides (e.g. trimesoyl chloride or trimellitic acid trichloride); cyclohexane dicarboxylic acid halides (e.g.
  • cyclohexane tricarboxylic acid halides e.g.cis-1 ,3,5-cyclohexane tricarboxylic acid trichloride
  • pyridine dicarboxylic acid halides e.g. quinolinic acid dichloride or dipicolinic acid dichloride
  • trimellitic anhydride acid halides benzene tetra carboxylic acid halides (e.g. pyromellitic acid tetrachloride); pyromellitic acid dianhydride;
  • pyridine tricarboxylic acid halides sebacic acid halides; azelaic acid halides; adipic acid halides; dodecanedioic acid halides; toluene diisocyanate; methylenebis(phenyl isocyanates); naphthalene diisocyanates; bitolyl diisocyanates; hexamethylene diisocyanate; phenylene diisocyanates; isocyanato benzene dicarboxylic acid halides (e.g. 5-isocyanato isophthaloyl chloride); haloformyloxy benzene dicarboxylic acid halides (e.g.
  • 5-chloroformyloxy isophthaloyl chloride dihalosulfonyl benzenes (e.g. 1 ,3-benzenedisulfonic acid chloride); halosulfonyl benzene dicarboxylic acid halides (e.g. 3-chlorosulfonyl isophthaloyl chloride); 1,3,6-tri(chlorosulfonyl)naphthalene; 1 ,3,7 tri(chlorosulfonyl)napthalene; trihalosulfonyl benzenes (e.g.
  • Particular electrophilic monomers include, but are not limited to, terephthaloyl chloride, isophthaloyl chloride, 5-isocyanato isophthaloyl chloride, 5-chloroformyloxy isophthaloyl chloride, 5-chlorosulfonyl isophthaloyl chloride, 1 ,3,6- (trichlorosutfonyl)naphthalene, 1 ,3,7-(trichlorosulfonyl)napthalene, 1 ,3,5- trichlorosulfonyl benzene, either individually or in any combinations thereof. More particular electrophilic monomers include trimesoyl chloride acid chloride
  • the interfacial polymerization reaction may be carried out at a temperature ranging from about 5°C to about 60°C, preferably from about 10°C to about 40°C to produce an interfacial polymer membrane.
  • interfacial polymers produced thereform include polyamide, polysulfonamide, polyurethane, polyurea, and polyesteramides, either individually or in any combinations thereof.
  • a porous base support includes a support material having a surface pore size in the approximate range from about 50 Angstroms to about 5000 Angstroms.
  • the pore sizes should be sufficiently large so that a permeate solvent can pass through the support without reducing the flux of the composite.
  • the pores should not be so large that the permselective polymer membrane will either be unable to bridge or form across the pores, or tend to fill up or penetrate too far into the pores, thus producing an effectively thicker membrane than 200 nanometers.
  • U.S. Pat. No. 4,814,082 W. J. Wrasidlo
  • U.S. Pat. No. 4,783,346 S. A. Sundet
  • Non-limiting examples of the material forming the porous base support include polysulfone, polyether sulfone, polyacrylonitrile, cellulose ester,
  • porous base membranes are either available commercially or may be prepared using techniques known to those of ordinary skill in the art.
  • a porous base membrane which is a polysulfone membrane or a porous polyethersulfone membrane are used because of their desirable mechanical and chemical properties. Those of ordinary skill in the art will be able to make the selection from among the suitable materials.
  • the thickness of the material forming the porous base support may be between about 75 and about 250 microns thick, although other thicknesses may be used. For example, a 25 microns thick porous base support permits production of higher flux films.
  • the porous base support may be relatively thick, for example, 2.5 cm or more, where aqueous solution is applied to only one side, which is subsequently contacted with the organic solution, forming the interface at which polymerization occurs.
  • the polymeric porous base support may be reinforced by backing with a fabric or a non-woven web material. Non-limiting examples include films, sheets, and nets such as a nonwoven polyester cloth.
  • the polymer of the porous base support may permeate through the pores, be attached on both sides of the support, or be attached substantially on one side of the support.
  • the thin film composite membrane may be post-treated with an oxidizing solution, such as a sodium hypochlorite solution.
  • an oxidizing solution such as a sodium hypochlorite solution.
  • concentration of sodium hypochlorite in the solution may range from about 50 ppm to about 4000 ppm, and, in some embodiments, from about 50 ppm to about 500 ppm.
  • the organic solution or the aqueous solution, or both the organic solution and the aqueous solution may include, in addition to the polyacid halide monomer or the polyamine monomer, multi- walled carbon nanotubes dispersed therein.
  • Suitable organic solvents include aliphatic hydrocarbons, alcohols, ketones, esters, ethers, amides, and mixtures thereof.
  • aliphatic hydrocarbons such as decalins, and isoparaffins, and mixtures thereof may be used.
  • the organic solution may additionally include a cyclic ketone such as cyclooctanone, cycloheptanone, 2 methylcyclohexanone, cyclohexanone, cyclohexene-3-one, cyclopentanone, cyclobutanone, 3-ketotetrahydrofuran, 3-ketotetrahydrothiophene, or 3-ketoxetane, particularly, cyclohexanone.
  • Aqueous dispersions may include dispersing aids such as polyvinylpyrrolidone, or surfactants, particularly non-ionic surfactants.
  • Carbon nanotubes have a cylindrical nanostructure with an inside diameter (ID) and outside diameters (OD). While single-walled carbon nanotubes (SWNT) are composed of a single layer of graphite in the shape of a tube or cylinder, multiwalled nanotubes (MWNT) are made up of a single rolled layer of graphite or multiple layers of graphite, arranged in concentric cylinders. The MWNTs for use in the processes and membranes of the present invention have an outside diameter of less than about 30 nm, particularly less than about 8 nm. The inner diameter of the multi-walled carbon nanotubes is less than about 8 nm, and particularly useful are nanotubes with inner diameters ranging from about 2 to about 5 nm.
  • a WNT designated as having an outside diameter of less than about 30 nm this means that greater than about 50% of the MWNT particles have an outer diameter of less than about 30 nm, in some embodiments, more than about 75% of the MWNT particles have an outer diameter of less than about 30 nm.
  • MWNTs are designated as having an outer diameter of less than about 8 nm, it means that more than about 50% of the MWNT particles have an outer diameter of less than about 8 nm, in some embodiments, more than about 75% of the MWNT particles have an outer diameter of less than about 8 nm.
  • Concentration of the multi-walled carbon nanotubes in the organic solution or the aqueous solution is at least 0.025% w/w, and may range from about 0.025% w/w to about 10% w/w in some embodiments, and in others, ranges from about 0.025% w/w to about 5% w/w. In yet other embodiments, the concentration of the multi- walled carbon nanotubes ranges from about 0.05% w/w to about 1 % w/w. In yet other embodiments, the concentration of the multi-walled carbon nanotubes ranges from about 0.1 % w/w to about 1 % w/w.
  • the concentration of the multi-walled carbon nanotubes ranges from about 0.1 % w/w to about 0.5% w/w.
  • the amount of carbon nanotubes contained in the final product ranges from about 0.1%-30% by weight in some embodiments; in other embodiments, from about 1 %-10% by weight, and in still other embodiments, from about 0.5%-5% by weight.
  • dispersions of carbon nanotubes in non-polar hydrocarbons such as hexane, cydohexane, and isoparaffins are stable only for short periods, even after prolonged sonication. Dispersion instability may be minimized by incorporating an in-line, continuous mixer/ homogenizer. A dispersion of nanotubes may be mixed with the monomer-containing solutions prior to use in the coating operation using an in-line, continuous mixer/homogenizer in the processes of the present invention in order to maximize stability of the nanotube dispersions.
  • a higher-volume stream of a solution of one of the monomers is mixed with a lower volume stream of a carbon nanotube dispersion to form a new dispersion containing both nanotubes and one of the monomers just before the combined coating solution mixture is dispensed on the porous support membrane.
  • Suitable mixing/homogenizing devices include static mixers, ultrasonic mixers, dynamic mixers, and other mechanical devices such as industrial mixers and blenders with various types of blades, shafts, and impellers. Static mixers and ultrasonic mixers are examples of preferred devices due to their simplicity and effectiveness.
  • the nanotubes dispersion may be under constant or intermittent mixing during the coating operation to ensure the homogeneous dispersion of nanotubes in the coating solution(s).
  • the mixing device includes (but not limited to) ultrasonic mixing device, dynamic mixer, and other mechanical devices such as industrial mixers and blenders with various types of blades, shafts, and impellers to make a good quality homogeneous mixture. Ultrasonic mixing is one of the preferred methods.
  • the advantage of separating the nanotube dispersion from the monomer solution is that it decouples the various (and often conflicting) requirements of nanotube dispersion stability and solvent compatibility with the porous support.
  • conventional coating formulation including conventional solvents such as hexane and ISOPARTM G
  • more aggressive solvents that are better at dispersing nanotubes may be used in making the nanotube dispersion prior to combining the two. Since the residence time between the in-line mixing and the coating is minimized, the nanotubes in the dispersion do not have time to agglomerate and segregate. Also, since the solvent used in dispersing nanotubes is typically a minor fraction in the final coating formulation after the in-line mixing, the problem of solvent attacking the porous support is resolved.
  • Coating methods typically include dip coating, slot die coating, and spray coating.
  • the coating tanks may be used as catch pans to recycle the unused coating solutions.
  • the nanotube dispersions may be in-line homogenized outside the coating tanks and recirculated andreplenished during the coating operation.
  • the treated surface of the porous base membrane was then contacted with 100 grams of an organic solution containing trimesoyl chloride (0.16% by weight) and carbon nanotubes (type and amount shown in examples) in ISOPARTM G solvent.
  • an organic solution containing trimesoyl chloride 0.16% by weight
  • carbon nanotubes type and amount shown in examples
  • Membrane Performance Testing Membrane tests were carried out on composite membranes configured as a flat sheet in a cross-flow test cell apparatus (Sterlitech Corp., Kent WA) (model CF042) with an effective membrane area of 35.68 cm 2 .
  • the test cells were plumbed two in series in each of 6 parallel test lines. Each line of cells was equipped with a valve to turn feed flow on/off and regulate concentrate flow rate, which was set to 1 gallon per minute (gpm) in all tests.
  • the test apparatus was equipped with a temperature control system that included a temperature measurement probe, a heat exchanger configured to remove excess heat caused by pumping, and an air-cooled chiller configured to reduce the temperature of the coolant circulated through the heat exchanger.
  • rhodamine WT from Cole-Parmer
  • a dye solution comprising 1% rhodamine red dye was sprayed on the polyamide surface of the composite membrane and allowed to stand for 1 minute, after which time the red dye was rinsed off. Since rhodamine red dye does not stain polyamide, but stains polysulfone strongly, a defect-free membrane should show no dye stain after thorough rinse.
  • dye stain patterns e.g. red spots or other irregular dye staining patterns
  • the membranes were cut into 2 inch x 6 inch rectangular coupons, and loaded into cross flow test cells.
  • test coupons were exposed to a 70 ppm aqueous solution of sodium hypochlorite at 25°C for 30 minutes. The test coupons were then rinsed with deionized water for 1 hour. [0039] Following the "chlorination" procedure, the test coupons were again tested for reverse osmosis membrane performance with the synthetic feed solution containing 500 ppm sodium chloride used before as described herein. Solution conductivities and temperatures were measured with a CON 11 conductivity meter (Oakton Instruments). Conductivites were compensated to measurement at 25°C. The pH was measured with a Russell RL060P portable pH meter (Thermo Electron Corp). Permeate was collected in a graduated cylinder.
  • Permeability or "A value" of each membrane was determined at standard temperatures (77°F or 25°C). Permeability is defined as the rate of flow through the membrane per unit area per unit pressure. Avalues were calculated from permeate weight, collection time, membrane area, and transmembrane pressure. A values reported herein have units of 10 -5 cm 3 /s-cm 2 -atm. Salt concentrations determined from the conductivities of permeate and feed solutions were used to calculate salt rejection values. Conductivitiesof the permeate and feed solutions were measured, and salt concentrations calculated from the conductivity values, to yield salt rejection values.
  • the product composite membrane was rinsed with hot deionized water and stored in a refrigerator before until testing or element fabrication.
  • the product composite membrane was treated with a solution containing polyvinyl alcohol solution and then dried before storage, testing, or element fabrication.
  • a polyamide coated thin film com osite RO membrane was fabricated using a handframe coating apparatus
  • An aqueous coating solution (Solution A) was prepared and contained 2.6 wt% m-phenylene diamine (mPD) and 6.6 wt% triethylammonium camphorsulfonate (TEACSA).
  • An organic coating solution (Solution B) was prepared and contained 0.16 wt% trimesoyl chloride (TMC) in ISOPARTM G.
  • a wet polysulfone porous support film was first coated with the aqueous solution containing the m-phenylenediamine (Solution A) and then coated with the organic solution comprising the trimesoyl chloride (Solution B) to effect an interfacial polymerization reaction between the diamine and the triacid chloride at one surface of the polysulfone porous support film, thereby producing a thin film composite reverse osmosis membrane.
  • the product membrane was tested in triplicate using a solution of magnesium sulfate (500 ppm in NaCl) at an applied operating pressure of 115 pounds per square inch (psi) and operating crossflow rate of 1.0 gram per minute (grams per mole), at pH 7.0.
  • the permeability and salt passage results are shown in Table 1.
  • Comparative Example 1-1 with the exception that the organic coating solution (Solution A) also contained 0.1 wt% fullerene C60 (BU-602-BuckyUSA, Houston TX).
  • the product composite membranes were tested and membrane A-values and salt passage properties were measured. Data are shown in Table 1. The data show that coating solution contains fullerene C60 nano-particles showed no significant increase in performance relative to a control (Comparative Example 1-1 ).
  • Comparative Example 1 -1 Comparative Example 1 -1 with the exception that the organic coating solution (Solution A) also included 0.1 % w/w single-walled carbon nanotubes (SWNT, P-3, Carbon Solutions, Inc. Riverside, CA, I.D. -1.4 nm, O.D. ⁇ 2 nm.
  • the product composite membranes were tested and membrane A-values and salt passage properties were measured. Data are presented in Table 1 -1.
  • Comparative Example 1-1 Comparative Example 1-1 with the exception that the organic coating solution (Solution A) further comprised 0.1 wt% multi-walled carbon nanotubes (1238YJS, Nanostructured & Amorphous Materials, Inc., Houston, TX) with inner diameters of 5- 15 nm, outside diameters of 30-50 nm, and 0.5-2 ⁇ in length.
  • the product composite membranes were tested and membrane A-values and salt passage properties were measured. Data is shown in Table 1.
  • Polyamide thin film composite RO membranes were fabricated as in Comparative Example 1-1 with the exception that the organic coating solution (Solution A) further comprised 0.05% or 0.1 wt% w/w multi-walled carbon nanotubes (1225YJS, Nanostructured & Amorphous Materials, Inc., Houston, TX) I.D.2-5 nm, O.D. ⁇ 8 nm, and 0.5-2 ⁇ in length.
  • the product composite membranes were tested and membrane A-values and salt passage properties were measured. Data are gathered in Table 1-1.
  • coating solution contains SWNT showed had a significant increase in performance relative to the control without CNTs (Comparative Example 1-1 ), controls with SWNTs (Comparative Example 1-3), and controls with large OD (30-50 nm) MWNT (Comparative Example 1-4).
  • Comparative Example 2-1 Instability of CNT dispersions in ISOPARTM G, hexane, and cyclohexane
  • 0.01 % single wall carbon nanotubes (P-3 from Carbon Solutions) were dispersed in ISOPARTM G by first sonicating for 60 minutes using a bath sonicator (Branson 5510 model) in a glass vial with screw cap.
  • 0.01 wt% multiwall carbon nanotubes with inside diameters of 2-5 nm and outside diameters of less than 8 nm, and a length of 0.5 to 2 mm (1225YJS from Nanostructured and Amorphous Materials, Inc) were dispersed in ISOPARTM G, hexane, and cyclohexane.
  • Example 2-3 Stability of CNTs dispersions in decalin , cyclohexanone, and their mixtures.
  • 0.1 wt% multiwall carbon nanotubes (1225YJS) were dispersed in a variety of decalins ISOPARTM G mixtures by first sonicating for 60 minutes using a bath sonicator (Branson 5510 model) in a glass vial. After the sonication stopped, the dispersion stability was observed. The dispersions in these decalin mixtures showed fair stability.
  • Multiwall carbon nanotubes (1225YJS) at 0.01 wt% loading were dispersed in a variety of cyclohexanone/ ISOPARTM G, mixtures by first sonicating for 60 minutes using a bath sonicator (Branson 5510 model) inside a glass vial with screw cap. After the sonication stopped, the dispersion instability was observed. These carbon nanotube dispersions showed no visible segregation within 30 minutes. Thus the carbon nanotube dispersions in these decalin mixtures showed excellent stability ⁇ Table 5).
  • a polyamide coated thin film composite RO membrane was fabricated using a handframe apparatus.
  • An aqueous coating solution (Solution A, nominally 90.8 wt% water) was prepared and contained 2.6 wt% meta-phenylene diamine (mPD), and 6.6 wt% triethylammonium camphorsulfonate (TEACSA).
  • An organic coating solution (Solution B) was prepared and contained 0.16 wt% trimesoyl chloride (TMC) in ISOPARTM G.
  • a wet polysulfone porous support film was first coated with the aqueous solution containing the m-phenylenediamine (Solution A) and then coated with the organic solution comprising the trimesoyl chloride (Solution B) to effect an interfacial polymerization reaction between the diamine and the triacid chloride at one surface of the polysulfone porous support film, thereby producing a thin film composite reverse osmosis membrane.
  • the product membrane was tested in triplicate as described in this section using a solution of magnesium sulfate (2000 ppm in NaCl) at an applied operating pressure of 225 pounds per square inch (psi) and operating crossflow rate of 1.0 gallons per minute (gpm), at pH 7.0.
  • the test results are shown in Table 6.
  • the membrane was contacted with an aqueous solution containing to 70 parts per million (ppm) of sodium hypochlorite at 25 °C for 30 minutes.
  • the membrane was then rinsed with water for 1 hour, and then tested again with the magnesium sulfate solution under the same conditions used previously (2000 ppm NaCl, operating pressure 225 psi and operating crossflow rate of 1.0 gpm, pH 7.0, ambient temperature to provide the data in Table 6 labeled "Membrane A Value (after chlorination)" and "% Salt Passage (after chlorination)".
  • Polyamide thin film composite RO membranes were fabricated as in Comparative Example 2-1 with the exception that the organic coating solvent (Solution B) were made of decalins, 50:50 decalin/ ISOPARTM G mixture, and 97:3 decalins/cyclohexanone mixture, respectively.
  • the product composite membranes were tested and membrane A-values and salt passage properties were measured. Data are gathered in Table 7. The data show that when the organic coating solution contains carbon nanotubes performance is enhanced relative to a control (Comparative Example 2-6)
  • Polyamide thin film composite RO membranes were fabricated as in Comparative Example 2-1 with the exception that the organic coating solution (Solution B) further comprised 0.025, 0.05, and 0.1 wt% multiwall carbon nanotubes (1225YJS).
  • the product composite membranes were tested and membrane A-values and salt passage properties were measured. Data are gathered in Table 8. The data show that when the organic coating solution contains carbon nanotubes performance was enhanced relative to a control (Comparative Example 2-6)

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Families Citing this family (20)

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FR2996780B1 (fr) 2012-10-16 2014-12-19 Univ Claude Bernard Lyon Procede et dispositif de production d'energie
EP2886187B1 (en) * 2012-11-21 2017-04-05 LG Chem, Ltd. Outstandingly chlorine resistant high-flow-rate water-treatment separation membrane and production method for same
US10898865B2 (en) * 2013-01-31 2021-01-26 American University In Cairo (AUC) Polymer-carbon nanotube nanocomposite porous membranes
WO2014168629A1 (en) * 2013-04-12 2014-10-16 General Electric Company Membranes comprising graphene
CN105080366B (zh) * 2014-04-22 2017-05-31 中国石油化工股份有限公司 一种反渗透膜及其制备方法
WO2016158992A1 (ja) * 2015-03-31 2016-10-06 国立大学法人信州大学 逆浸透複合膜及び逆浸透複合膜の製造方法
CN105498547B (zh) * 2015-11-26 2018-05-22 中国科学院生态环境研究中心 一种低压正电荷中空纤维纳滤膜的制备方法
JP6750017B2 (ja) 2015-12-17 2020-09-02 日東電工株式会社 選択透過性酸化グラフェン膜
US11724234B2 (en) 2016-08-31 2023-08-15 South Dakota Board Of Regents Multilayer thin film nanocomposite membranes prepared by molecular layer-by-layer assembly
JP6733959B2 (ja) * 2016-09-29 2020-08-05 国立大学法人信州大学 逆浸透複合膜
CN107398188A (zh) * 2017-07-19 2017-11-28 浙江工业大学 接枝有机硅烷多壁碳纳米管嵌入聚酰胺分离层的纳米复合正渗透的制备方法
KR102046818B1 (ko) * 2017-10-16 2019-12-02 한국과학기술연구원 질화 붕소 나노 물질을 이용한 가열 재생 가능한 한외여과막과 그 제조 및 재생 방법
CN108114614A (zh) * 2017-12-21 2018-06-05 天津工业大学 一种含zsm-5沸石的高通量复合反渗透膜及其制备方法
JP6969727B2 (ja) * 2018-07-09 2021-11-24 エルジー・ケム・リミテッド 水処理分離膜、これを含む水処理モジュールおよびその製造方法
WO2020056414A1 (en) * 2018-09-14 2020-03-19 Ohio State Innovation Foundation Membranes for gas separation
CN110252155A (zh) * 2019-06-20 2019-09-20 西华大学 一种抗污染功能化多壁碳纳米管复合膜及其制备方法
JP6999958B2 (ja) * 2019-12-03 2022-02-10 国立大学法人信州大学 半透複合膜の製造方法及び半透複合膜
WO2021225958A1 (en) * 2020-05-04 2021-11-11 Atom H20, Llc Carbon nanotube based membrane and methods of manufacturing
KR102623644B1 (ko) * 2021-11-18 2024-01-10 이화여자대학교 산학협력단 고안정성의 보론나이트라이드 세라믹 멤브레인 및 그 제조방법
CN116061510B (zh) * 2022-12-07 2023-12-05 南通大学 一种基于多层自我调节复合非织造材料及制备方法与应用

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4814082A (en) 1986-10-20 1989-03-21 Memtec North America Corporation Ultrafiltration thin film membranes
US4783346A (en) 1987-12-10 1988-11-08 E. I. Du Pont De Nemours And Company Process for preparing composite membranes
US5234598A (en) * 1992-05-13 1993-08-10 Allied-Signal Inc. Thin-film composite membrane
US7001556B1 (en) * 2001-08-16 2006-02-21 The Board Of Regents University Of Oklahoma Nanotube/matrix composites and methods of production and use
JP3861747B2 (ja) * 2002-05-17 2006-12-20 株式会社豊田自動織機 カーボンナノチューブの精製方法
US20060257638A1 (en) * 2003-01-30 2006-11-16 Glatkowski Paul J Articles with dispersed conductive coatings
US7481952B2 (en) * 2004-04-29 2009-01-27 Compagnie Plastic Omnium Electrically conductive PTFE tape
US20060122284A1 (en) 2004-12-03 2006-06-08 William Marsh Rice University Well dispersed polymer nanocomposites via interfacial polymerization
US9169579B2 (en) * 2005-03-11 2015-10-27 New Jersey Institute Of Technology Carbon nanotube mediated membrane extraction
TWI386420B (zh) * 2005-12-06 2013-02-21 Mitsubishi Rayon Co 含碳奈米管組成物、複合體以及其製造方法
US20090321355A1 (en) * 2008-06-30 2009-12-31 NANOASIS TECHNOLOGIES, INC., a corporation of the state of Delaware Membranes with embedded nanotubes for selective permeability
CN101797522A (zh) * 2009-02-09 2010-08-11 乌鲁木齐现代石油化工有限公司 蜡油非临氢降凝催化剂再生烧焦的装置及方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2012047359A1 *

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