WO2018091273A1 - Nouveaux procédés de traitement d'eau - Google Patents

Nouveaux procédés de traitement d'eau Download PDF

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Publication number
WO2018091273A1
WO2018091273A1 PCT/EP2017/078054 EP2017078054W WO2018091273A1 WO 2018091273 A1 WO2018091273 A1 WO 2018091273A1 EP 2017078054 W EP2017078054 W EP 2017078054W WO 2018091273 A1 WO2018091273 A1 WO 2018091273A1
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Prior art keywords
membrane
membranes
nanoparticles
process according
tfn
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PCT/EP2017/078054
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English (en)
Inventor
Vaibhav Ramchandra DALVI
Natalia Widjojo
Claudia Staudt
Marc Rudolf Jung
Tai-Shung Chung
Yupan TANG
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Basf Se
National University Of Singapore
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Publication of WO2018091273A1 publication Critical patent/WO2018091273A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/002—Forward osmosis or direct osmosis
    • B01D61/0023—Accessories; Auxiliary operations
    • 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
    • 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
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
    • 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
    • B01D69/1411—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix
    • B01D69/14111—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix with nanoscale dispersed material, e.g. nanoparticles
    • 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
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/16—Use of chemical agents
    • B01D2321/168—Use of other chemical agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/40—Details relating to membrane preparation in-situ membrane formation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/002—Forward osmosis or direct osmosis
    • 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
    • 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
    • B01D61/027—Nanofiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/445—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by forward osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/20—Prevention of biofouling
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/04—Surfactants, used as part of a formulation or alone
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/08—Nanoparticles or nanotubes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

Definitions

  • the present invention is directed to processes for treating water, wherein feed water is being treated with a membrane M, said membrane M being a reverse osmosis membrane, a forward osmosis membrane or a nanofiltration membrane, wherein membrane M is contacted with an anionic surfactant A, wherein said anionic surfactant preferably comprises a C6 to C10 aliphatic hydrocarbon chain.
  • membranes play an increasingly important role in many fields of technology.
  • methods for treating water rely more and more on membrane technology.
  • membranes are used for the desalination of water like sea water of brackish water.
  • RO reverse osmosis
  • FO forward osmosis
  • NF nanofiltration
  • US 8025159 B2 discloses an agent for increasing the rejection of inorganic electrolytes and organic substances soluble in water in the membrane separation using a selective permeable membrane such as a nano filtration membrane and a reverse osmosis membrane, process for increasing the rejection using the agent.
  • Said agents comprise a first agent for increasing rejection with a permeable membrane which comprises an aqueous solution of a cationic macromol- ecule having a weight average molecular weight of 100,000 or greater, wherein said cationic macromolecule is a polyvinylamidine or derivative thereof.
  • a second agent for increasing rejection with a permeable membrane which comprises an aqueous solution of an anionic macro- molecule having a weight average molecular weight of 100,000 or greater.
  • WO12121208A1 discloses enhancement of rejection of reverse osmosis membranes by use of certain organic compounds in a sequential manner without significantly reducing permeation flux.
  • the method involves passing a first organic compound having a molecular weight of less than 200, a second organic compound having a molecular weight of 200 to less than 500, and a third organic compound having a molecular weight of at least 500 through the reverse osmosis membrane.
  • the first organic compound is preferably an amino acid or an amino acid derivative.
  • US2010133172A discloses coatings being applied to and insolubilized upon an active surface of the selective membrane.
  • the surface-active agent comprises an amine-containing surfactant such as polyethoxylated aliphatic polyamine.
  • US2012168370AA describes a method of improving a rejection of a permeable membrane, more specifically, by allowing the low-molecular-weight amino compound to pass through the membrane, a degraded portion of the membrane can be restored without considerably lowering the permeation flux.
  • JP2008086945A discloses a method for recovering the performance of a permselective membrane by reducing a permeation flux to a proper range with regard to a nanofiltration membrane or reverse osmosis membrane.
  • the nanofiltration membrane or reverse osmosis membrane with anion charge is treated by bringing its surface into contact with a nonion surfactant to re- prise the permeation flux to the range from +20 to -20 percent of the value at the beginning of the use. The performance of the permselective membrane is thus recovered.
  • A. E. Childress et al, Desalination 1 18 (1998) 167-174 discloses anionic surfactant (SDS) influence performance of RO membrane by forming hemimicelle over RO surface which in turn acts as secondary layer; hence causing decrase in flux but improved rejection.
  • SDS anionic surfactant
  • the objective of the present invention was to provide processes for treating water that show excellent flux and rejection and that result in a long lifetime of the membranes used.
  • This objective was achieved by processes for treating water, wherein feed water is being treated with a membrane M, said membrane M being a reverse osmosis membrane, a forward osmosis membrane or a nanofiltration membrane, wherein said membrane M is contacted with an anionic surfactant A, wherein said anionic surfactant comprises preferably a C6 to Cio aliphatic hydrocarbon chain.
  • Such processes for treating water can in principle be all processes in which a feed water is subjected to a membrane based treatment.
  • a membrane shall be understood to be a thin, semipermeable structure capable of separating two fluids or separating molecular and/or ionic components or particles from a liquid.
  • a membrane acts as a selective barrier, allowing some particles, substances or chemicals to pass through, while retaining others.
  • Membranes M can for example be reverse osmosis (RO) membranes, forward osmosis (FO) membranes or nanofiltration (NF) membranes. These membrane types are generally known in the art.
  • FO membranes are normally suitable for treatment of seawater, brackish water, sewage or sludge streams. Thereby pure water is removed from those streams through a FO membrane into a so-called draw solution on the backside of the membrane having a high osmotic pressure.
  • FO type membranes similar as RO membranes separate liquid mixtures via a solu- tion diffusion mechanism, where only water can pass the membrane whereas monovalent ions and larger components are rejected.
  • FO membranes M are thin film composite (TFC) FO membranes.
  • TFC thin film composite
  • FO membranes M comprise a support layer, a separation layer and optionally a protective layer.
  • Said protective layer can be considered an additional coating to smoothen and/or hydrophilize the surface.
  • Said fabric layer can for example have a thickness of 10 to 500 ⁇ .
  • Said fabric layer can for example be a woven or nonwoven, for example a polyester nonwoven.
  • Said support layer of a TFC FO membrane M normally comprises pores with an average pore diameter of for example 0.5 to 100 nm, preferably 1 to 40 nm, more preferably 5 to 20 nm.
  • Said support layer can for example have a thickness of 5 to 1000 ⁇ , preferably 10 to 200 ⁇ .
  • Said support layer may for example comprise at least one polysulfone, polyethersulfone, polyphe- nylenesulfone (PPSU), PVDF, polyimide, polyimideurethane or cellulose acetate.
  • Nano particles such as zeolites, may be comprised in said support membrane. This can for example be achieved by including such nano particles in the dope solution for the preparation of said support layer.
  • Said separation layer can for example have a thickness of 0.05 to 1 ⁇ , preferably 0.1 to 0.5 ⁇ , more preferably 0. 15 to 0.3 ⁇ .
  • said separation layer can for example comprise polyamide or cellulose acetate as the main component.
  • TFC FO membranes M can comprise a protective layer with a thickness of 5 to 500 preferable 10 to 300 nm.
  • Said protective layer can for example comprise polyvinylalcohol (PVA) as the main component.
  • PVA polyvinylalcohol
  • the protective layer comprises a halamine like chloramine.
  • membranes M are TFC FO membranes comprising a support layer comprising polyethersulfone as main component and polymer P, a separation layer com- prising polyamide as main component and optionally a protective layer comprising polyvinylalcohol as the main component.
  • FO membranes M comprise a separation layer obtained from the condensation of a polyamine and a polyfunctional acyl halide. Said separation layer can for example be obtained in an interfacial polymerization process.
  • RO membranes are normally suitable for removing molecules and ions, in particular monovalent ions. Typically, RO membranes separate mixtures based on a solution/diffusion mechanism.
  • membranes M are thin film composite (TFC) RO membranes. Preparation methods and use of thin film composite membranes are principally known and, for example described by R. J. Petersen in Journal of Membrane Science 83 (1993) 81-150.
  • RO membranes M comprise a fabric layer, a support layer, a separation layer and optionally a protective layer. Said protective layer can be considered an additional coating to smoothen and/or hydrophilize the surface
  • Said fabric layer can for example have a thickness of 10 to 500 ⁇ .
  • Said fabric layer can for example be a woven or nonwoven, for example a polyester nonwoven.
  • Said support layer of a TFC RO membrane normally comprises pores with an average pore diameter of for example 0.5 to 100 nm, preferably 1 to 40 nm, more preferably 5 to 20 nm.
  • Said support layer can for example have a thickness of 5 to 1000 ⁇ , preferably 10 to 200 ⁇ .
  • Said support layer may for example comprise at least one polysulfone, polyethersulfone, polyphe- nylenesulfone (PPSU), PVDF, polyimide, polyimideurethane or cellulose acetate.
  • Nano particles such as zeolites, may be comprised in said support membrane. This can for example be achieved by including such nanoparticles in the dope solution for the preparation of said support layer.
  • Said separation layer can for example have a thickness of 0.02 to 1 ⁇ , preferably 0.03 to
  • TFC RO membranes M can comprise a protective layer with a thickness of 5 to 500 preferable 10 to 300 nm.
  • Said protective layer can for example comprise polyvinylalcohol (PVA) as the main component.
  • the protective layer comprises a halamine like chloramine.
  • membranes M are TFC RO membranes comprising a nonwoven polyester fabric, a support layer comprising polyethersulfone as main component and polymer P, a separation layer comprising polyamide as main component and optionally a protective layer comprising polyvinylalcohol as the main component.
  • RO membranes M comprise a separation layer obtained from the condensation of a polyamine and a polyfunctional acyl halide. Said separation layer can for example be obtained in an interfacial polymerization process.
  • Suitable polyamine monomers can have primary or secondary amino groups and can be aro- matic (e. g. a diaminobenzene, a triaminobenzene, m-phenylenediamine, p-phenylenediamine,
  • Suitable polyfunctional acyl halides include trimesoyl chloride (TMC), trimellitic acid chloride, isophthaloyl chloride, terephthaloyl chloride and similar compounds or blends of suitable acyl halides.
  • the second monomer can be a phthaloyl halide.
  • a separation layer of polyamide is made from the reaction of an aqueous solution of meta-phenylene diamine (MPD) with a solution of trimesoyl chloride (TMC) in an apolar solvent.
  • NF membranes are normally especially suitable for removing separate multivalent ions and large monovalent ions.
  • NF membranes function through a solution/diffusion or/and filtration-based mechanism.
  • NF membranes are normally used in cross filtration processes.
  • NF membranes M can for example comprise as the main component polyarylene ether, polysul- fone, polyethersulfones (PES), polyphenylensulfone (PPSU) or mixtures thereof.
  • said main components of NF membranes are positively or negatively charged.
  • Nanofiltration membranes M often comprise charged polymers comprising sulfonic acid groups, carboxylic acid groups and/or ammonium groups.
  • membrane M comprises a separation layer of polyamide. In one embodiment membrane M does not comprise any nanoparticles.
  • membrane M comprises nanoparticles N. Nanoparticles N are preferably comprised in the separation layer of membrane M.
  • Nanoparticles N are normally comprised in amounts on 0.01 to 2 wt%, based on the membrane casting solution or based on the respective layer in which nanoparticles N are comprised.
  • nanoparticles can be comprised in amounts of 0.01 to 2 wt% in the casting solution for the preparation of membrane M.
  • Suitable nanoparticles N normally have median particle size (d50) as determined by Dynamic light scattering (DLS) method of 1 to 300 nm, preferably 2 to 100 nm
  • Nanoparticles N include particles of silica, titania, zirconia, alumina, zinc oxide or zeolites.
  • nanoparticles N are nanoparticles with a core-shell morphology, wherein the core and the shell are made of different materials.
  • the core of core-shell nanoparticles N can for example be made of silica, titania, zirconia, alumina, zinc oxide of combinations thereof.
  • the shell of core-shell nanoparticles N can for example be made of titania, silver, ceria, zirco- nia, alumina, zinc oxide or combinations thereof.
  • nanoparticles N are included in membranes M upon the manufacture of membrane M and are not subjected to a posttreatment with an organic solvent.
  • membranes M in which nanoparticles N have been included are subjected to a treatment with an organic solvent L after the manufacture of membrane M.
  • Organic solvent L can in principle be any organic solvent capable of at least partly removing nanoparticles from said membrane M.
  • Suitable solvents L are organic solvents and include Cs to C20 alkanes like pentane, hexane, heptane, aromatic solvents like benzene, toluene, xylene, alcohols like etha- nol, n/i-propanol, n/i/sec butanol.
  • Treatment of membranes M with organic solvent L is carried out at a temperature of 15 to 50°C preferably at room temperature by immersing the membrane M completely in solvent L for 1 to 60 min preferably from 5-15 minutes.
  • nanoparticles N which are not completely embedded or chemically linked in or with polyamide layer can dissociate from membrane M, thus forming defects or voids in the membrane.
  • membranes M are contacted with an anionic surfactant A.
  • membrane M is in some way treated with anionic surfactant A.
  • membrane M is treated with an aqueous solution S of anionic surfactant A.
  • anionic surfactant A is added to the feed water of a water treatment process. This way membrane M can be contacted with anionic surfactant A during operation of membrane M without having to interrupt the water treatment process.
  • Anionic surfactant A is a surfactant bearing at least one anionic group.
  • anionic surfactant A comprises a Ce to C10 hydrocarbon chain and no hydrocarbon chain longer than that.
  • anionic surfactant A is an alkyl sulfate, herein also preferred to alkylsulfate A.
  • alkyl sulfate shall be understood to mean the salt of a monoester of an alkanol with sulfuric acid.
  • alkylsulfate A is a Ce to C18 alkylsulfate-Preferably alkylsulfate A is an oc- tylsulfate, more preferably n-octylsulfate, also referred to as caprylsulfate or cprylylsulfate.
  • alkylsulfate A is a sodium salt or a potassium salt.
  • alkylsulfate a is sodium n-octylsulfate or potassium n-octylsulfate.
  • Solution S normally comprises alkylsulfate A in a concentration of 0.1 to 5000 ppm by weight, based on solution S, preferably 100 to 1500 ppm.
  • solution S has a pH of 4 to 12.
  • Normally membrane M is contacted with solution S for 5 minutes to 5 days per interval, preferably 10 min to 1 day.
  • membrane M is treated with solution S in intervals that differ between one day to five years. This means that from one treatment (contacting) of membrane M with solution S to the next treatment of membrane M with solution S a time from 1 day to five years passes without such treatment.
  • the intervals between two treatments of membrane M with solution S is 2 days to 365 days, more preferably 7 days to 30 days.
  • the intervals between treatments of membrane M with solution S may vary from time to time, depending on the performance and the condition of membrane M.
  • the temperature of the treatment of membrane M with solution S is not critical and is normally the operation temperature of the water treatment process conducted with membrane M, usually between 1 °C and 99 °C, preferably 15 °C to 50 °C.
  • Processes according to the invention are useful for treating water.
  • Processes according to the invention can for example be used for treating industrial waste water, municipal waste water, sea water, brackish water, fluvial water, surface water, drinking wa- ter, mining water, waste water from oil wells or power plants.
  • Processes according to the invention are used for the desalination of sea water or brackish water.
  • Processes according to the invention can be used for the desalination of water with a particularly high salt content of for example 3 to 8 % by weight.
  • processes according to the invention are suitable for the desalination of water from mining and oil/gas production and frack- ing processes, to obtain a higher yield in these applications.
  • Processes according to the invention can be used in food processing, for example for concentrating, desalting or dewatering food liquids (such as fruit juices), for the production of whey protein powders and for the concentration of milk, wine processing, providing water for car washing, making maple syrup, during electrochemical production of hydrogen to prevent formation of minerals on electrode surface, for supplying water to reef aquaria.
  • food liquids such as fruit juices
  • wine processing providing water for car washing, making maple syrup
  • electrochemical production of hydrogen to prevent formation of minerals on electrode surface, for supplying water to reef aquaria.
  • Processes according to the invention can be used for rehabilitation of mines, homogeneous catalyst recovery, desalting reaction processes.
  • Processes according to the invention can be used for separating divalent ions or heavy and/or radioactive metal ions, for example in mining applications, homogeneous catalyst recovery, desalting reaction processes.
  • Processes according to the invention are easy and economical to carry out. They do not require suspension of the operation of the membrane, rather defects in the membrane can be repaired during operation. Processes according to the invention require the addition of only a small amount of anionic surfactant A. Through processes according to the invention, defects in membranes M can be repaired of reduced. Processes according to the invention extend the life time of membranes M Processes according to the invention allow for the treatment of water with high flux and high rejection.
  • Another aspect of the present invention is the use of C6 to Cio alkyl sulfates for healing defects of a membrane M, membrane M being a reverse osmosis membrane, a forward osmosis membrane or a nanofiltration membrane.
  • membranes can be stored in contact with a solution S.
  • Another aspect of the present invention are membranes obtained in a process comprising the following steps:
  • step b) Subjecting the membrane obtained in step a) to a treatment with an organic solvent L, c) Treating the membranes obtained in step b) with a solution S comprising anionic surfactant A.
  • Nanoparticles N and organic solvent L are those named above Step c) herein is carried out as a one-time treatment after steps a) and b).
  • anionic surfactant A used in step c) in processes for making membranes according to the invention is an alkyl sulfate.
  • anionic surfactant A used in step c) in processes for making membranes according to the invention is a C6 to Cis alkylsulfate.
  • anionic surfactant A used in step c) in processes for making membranes according to the invention is sodium dodecylsulfate (SDS) or potassium dodcecylsulfate. In one embodiment, anionic surfactant A used in step c) in processes for making membranes according to the invention is a C6 to C10 alkylsulfate.
  • anionic surfactant A used in step c) in processes for making membranes according to the invention is sodium or potassium octylsulfate.
  • solution S comprises 0.1 to 5000 ppm of anionic surfactants A.
  • Solution S is applied in step c) for a period of 1 minute to 5 days preferably 10 min to 1 day by directly adding anionic surfactant A into the feed water. Normally this is done at a temperature of between 1 °C and 99 °C preferably at room temperature.
  • Membranes so prepared have are easy and economical to make, have a long lifetime, have excellent flux and rejections.
  • Another aspect of the present invention are thin film composite membranes (TFC) with an ultra- thin polyamide layer formed through an interfacial polymerization process remain to be of paramount importance due to their commercial success in desalination applications.
  • Incorporation of nanoparticles in the polyamide layer to produce thin film nanocomposite (TFN) membranes is one of the most promising approaches to improve water flux.
  • the puzzle of permeabil- ity/selectivity trade-off remains unresolved. Additional challenges of defect formation with the introduction of nanoparticles need careful adjustments of the membrane properties.
  • the tailored TFN membranes with combining the effects of nanoparticles, post treatment by a suitable solvent and followed by surfactant treatment was found to outperform most of the commercial TFN membranes under our test conditions.
  • This work may provide useful insights about development of innovative approaches to improve membrane properties to overcome the usual trade-off between permeability and selectivity of the RO membrane by a targeted approach with a suitable surface active material.
  • Desalination provides a promising solution to secure water supply by producing fresh and clean water from seawater. Desalination processes are typically divided into thermal and membrane processes [2].
  • the thermal process usually comprises energy intensive multi-stage flash distillation (MSF) to treat water with high salinity [3].
  • MSF energy intensive multi-stage flash distillation
  • RO reverse osmosis
  • the RO process has shown continuous improvements in terms of membrane materials, process modifications, module design and pre-treatment processes in order to improve its economics [6, 7].
  • Most of today's RO membranes, which are thin film composite (TFC) membranes, are based on Cadott's work in which the membrane performance is achieved by a thin selective polyamide layer [8-10].
  • TFC thin film composite
  • Many novel approaches have been reported to improve the performance of polyamide-TFC membranes and to enhance the productivity and efficiency of the desalination process [2-7].
  • One of them is based on nanotechnology that offers completely new possibilities for the new generations of RO membranes.
  • TFN thin film nanocomposite
  • Hoek and his co-workers [1 1-13].
  • NaA zeolite nanoparticles as inorganic fillers into the polyamide layer, they produced high performance TFN membranes with improved flux and comparable rejection to commercial RO membranes.
  • the NaA zeolite nanoparticles not only improved the hydrophilicity, surface charge, porosity and antimicrobial properties, but also improved water permeability because of preferential water flow through zeolite pores. Meanwhile, a high solute rejection was maintained due to the combination of steric and Donnan exclusion [12, 13]. Similar hypotheses were assumed by Huang et.al. [14].
  • T1O2 nanoparticles received much attention because of their unique physico- chemical properties to impart TFN membranes with superior hydrophilicity, antifouling properties and overall membrane performance [17-20].
  • the other one was the introduction of polyhedral oligomeric silsesquioxane (POSS) into the selective polyamide layer. Dalwani et. al. [21] observed that POSS particles did not react readily with the acyl chloride solution but required special conditions in order to form a highly crosslinked hybrid structure.
  • POSS polyhedral oligomeric silsesquioxane
  • TFN membranes with desired performance by the use of na- noparticles, solvent post-treatment and surfactant addition.
  • Two inorganic nanomaterials T1O2- S1O2 core-shell nanoparticles, (2) commercially available water-soluble octammonium POSS (AM0285), would be used to fabricate TFN membranes. These nanoparticles could disperse easily in casting solutions and form highly cross-linked membrane structures.
  • the selfsynthe- sized TiC"2-Si02 nanoparticles were employed because of their core-shell morphology with multi- functional characteristics of aforementioned individual metal oxides.
  • Nexsil silica suspensions and POSS particles namely, AM0285 were procured from Nyacol Inc and Hybrid Plastics, respectively. Ethanol (analytical grade) was supplied by Fischer Scientific.
  • Deionized (Dl) water was generated by a Millipore water purification system.
  • m-Phenylenediamine >98%, MPD, Tokyo Chemical Industry Co. Ltd, Japan
  • trimesoyi chloride >98%, TMC, Tokyo Chemical Industry Co. Ltd, Japan
  • n-Hexane (Fisher Scientific) were utilized to synthesize the selective polyamide layer of TFC and TFN membranes. All reagents were used as received without further purification.
  • Commercially available polysulfone ultrafiltra- tion flat sheet membranes (under the trade name of UP20) with an average pore radius of 5 nm was procured from Microdyn Nadir. Prior to use, the UP20 membrane was soaked in Dl water overnight.
  • Figure 1 shows the schematic procedures of an in-house proprietary method to synthesize Ti0 2 -
  • Titanium /sotri- propoxide of 0.005 mole was first dissolved in ethanol of 0.1 mole. Then acetyl acetone of 0.0025 mole was added into the mixture to form a deep red solution.
  • the prepared titania precursor was added into an aqueous solution containing colloidal silica (Nexsil 85) of 0.05 mole in Dl water of 2 moles, followed by stirring and forming a uniform solution. Subsequently, triethylamine of 0.02 mole was added dropwise under stirring overnight at room temperature.
  • the resultant suspension was precipitated by the addition of 10 moles of acetone, centrifuged and washed three times with fresh acetone.
  • the sediments were dried in a vacuum oven for 4 h at 60 °C.
  • the solids were crushed by using a mortar and pestle to fine powders and then calcined at 600 °C for 4 h.
  • the calcined core-shell type nanoparticles were consecutively nano-milled in Dl water at a concentration of -25 wt% in Dl water using zirconia beads of 2 mm in size for 48 h, sonicated prior to use in membrane casting solutions.
  • TFC thin film composite
  • TFN thin film nanocomposite
  • TFC trimesoyl chloride
  • TFN membranes The procedure to fabricate TFN membranes was similar except a predefined amount of nanoparticles was prepared in MPD solution. In the case of using titania-silica core-shell nanoparti- cles, they were uniformly dispersed by sonication before adding into the MPD solution. In the case of POSS, AM0285 particles were dissolved completely into MPD solution. The TFN membranes incorporated with AM0285 and titania-silica core-shell nanoparticle were referred to as TFN-P, and TFN-T. Sodium dodecyl sulphate (SDS) was used to enhance the RO performance in two different approaches. Method A: the TFC and TFN membranes were soaked in a 0.1wt% aqueous solution of SDS for 15 min. Method B: SDS was added directly into the feed tank at a concentration of 0.1 wt% after the first reading of salt rejection without interrupting the test run. The RO results were compared before and after the SDS addition.
  • SDS Sodium do
  • Salt and surfactant SDS of 0.1 wt% was added directly into the feed tank immediately after the first salt reading, followed by readings at an interval of 1 h each.
  • Second salt reading After the above two sets of readings, the RO testing machine was de- pressurized, thoroughly washed with Dl water (5 washing cycles if not stated otherwise). The second salt reading was started with a freshly prepared NaCI solution under conditions identical to the first salt reading.
  • Figure 4 (a) to 4 (c) shows the morphology and size of the synthesized Ti0 2 -Si0 2 nanoparticles and their elemental compositions determined by transmission electron microscopy (TEM, 200KV JEOL 201 OF microscope) and its EDX.
  • the samples were prepared by placing a drop of well dispersed nanoparticle dispersion onto a copper grid with a carbon film, and then dried in a desiccator.
  • the nanoparticle size was also confirmed by dynamic light scattering (DLS)
  • FESEM JEOL JSM-6700F Prior to SEM observation by a field emission scanning electron microscope (FESEM JEOL JSM-6700F), the membrane samples were freeze dried and fractured in liquid nitrogen before platinum coating using a JEOL JFC- 1300 Platinum coater.
  • X-ray Photoelectron Spectroscopy XPS, Kratos AXIS UltraDLD, Kratos Analytical Ltd., England was employed to investigate the nanoparticles in the polyamide layer using the procedures described elsewhere [33, 34]. Wide scans in the binding energy range of 0-1 100 eV and narrow scans of core-level Ti2p and Si2p were performed on the selective surface of the membranes.
  • the TFC and TFN membranes were measured by Doppler Broadening Energy Spectroscopy (DBES) using a positron annihilation system coupled with a slow positron beam at the National University of Singapore. Details of the system and measurements have been described in the literature [35, 36].
  • DBES Doppler Broadening Energy Spectroscopy
  • a radioisotope 22 Na with an energy of 50 mCi was used as the positron source.
  • the DBES spectra were recorded using an HP Ge detector at a counting rate of approximately 2000 cps and the total number of counts for each spectrum was 1 .0 million.
  • a SurPASS electrokinetic analyzer (Anton Paar GmbH, Austria) was utilized to measure the surface charge of the TFC and TFN membranes. The experiments were based on streaming potential measurements [37, 38]. The samples were die cast to fit into the measuring cell followed by circulation of a 0.01 M NaCI solution through the measuring cell to attain the zeta- potential of the membrane surfaces. Afterwards, 0.1 M HCI and 0.1 M NaOH solutions were used to auto-adjust pH values at the pre-specified range of 2-10 at 25 °C. Results and discussion
  • the TEM images of the calcined nanoparticles exhibit a core- shell ("raspberry") morphology with silica as the core and titania as the shell material.
  • the titania nanoparticles have a size of ⁇ 5 nm, they are uniformly deposited on a spherical silica core.
  • the EDX analysis in Figure 4 (c) indicates the ratio of Si to Ti to be nearly the same as the ratio of the starting materials used in the synthesis (i.e., 0.005 mole of titanium isopropoxide and 0.05 mole of silica).
  • FIG. 5 shows the surface and cross-sectional FESEM images of the membrane substrate (i.e., UP20), TFC and TFN membranes.
  • the substrate layer has an asymmetrical structure that consists of a tighter skin, a sponge-like porous sublayer, and finger-like macrovoids underneath.
  • the top surfaces of TFC and TFN membranes have a ridge- and-valley morphology with a thickness of around 150 nm resulting from interfacial polymerization of the polyamide layer [12, 31 , 32].
  • the polyamide layer of the TFN-T membrane has spherical globules in the ridge-and-valley morphology, which can be observed easily in the cross-section image ( Figure 5 (d) bottom). This is due to the fact that the Ti02-Si02 nanoparticles are wrapped by the polyamide during the interfacial polymerization.
  • FIG. 6 summarizes the XPS spectra of the TFC and TFN membranes.
  • the inset (b) clearly shows the Si 2p peaks in the spectra of the two TFN membranes, as an indication for the suc- cessful incorporation of nanoparticles.
  • the absence of the Ti signal in the TFN-T membrane may be attributed to its low concentration in the membrane. Nevertheless, a very low amount of Ti is detected by EDX, as shown in Figure 4 (c).
  • the microstructure of the TFC, TFN-P and TFN-T membranes was investigated by PAS.
  • Figure 7 presents their S and R parameters as a function of the incident positron energy.
  • the initial sharp increase in S parameter is due to the back diffusion and scattering of positroniums near the membrane surface [35, 36].
  • a smaller S parameter in the selective layer indicates ei- ther a smaller free volume size or a lower free volume content of the membrane.
  • the smaller S parameter of the TFN-T membrane suggests its denser selective layer compared with the other two membranes.
  • the R parameter indicates that TFN-T has a thicker polyamide layer than the other two membranes, which is consistent with the observation from FESEM.
  • Figure 8 compares the flux and rejection between TFC and TFN-P membranes as a function of POSS content and testing procedures at 15.5 bar and 55 bar for feed concentrations of
  • the TFC membrane shows a rejection of 96% and a permeate flux of 20 kg/h.m 2 at 55 bar.
  • the TFN-P membranes are also stable at both pressures.
  • Figure 8 (b) indicates that the flux shows a maximum at 0.25 wt% POSS, while the rejection displays an opposite trend. Since the polyamide film is growing on the organic side of the interface between the two monomer solvents [9, 10, 31 , 32, 42], the water soluble nanoparticles may be either chemically or physically trapped in the polyamide layer.
  • FIG. 9 shows the performance of TFN-T membranes with different concentrations of T1O2- S1O2 particles; followed by the surfactant addition in the feed tank.
  • the TFN-T membrane con- taining 0.125 wt% Ti02-Si02 has a rejection of 93% and a permeate flux of 23 kg/h.m 2 at 55 bar. However, the rejection decreases while the permeate flux increases as a function of nanoparti- cle content. Larger error bars were seen for TFN-T membranes with a higher nanoparticle concentration possibly because of greater non-uniform particle distribution and agglomeration in the polyamide layer as well as interference of inorganic nanoparticles during the interfacial polymerization [17, 21 , 23].
  • the hydrophobic segments of SDS can be easily adsorbed on the membrane surface via hydrophobic-hydrophobic interaction, which limits the contact between the surfactant head and the membrane surface. Therefore, the anionic SDS surfactant may be aligned in a hydrophilic "head out” position and overlaps the defects by forming a secondary filter layer. Furthermore, the electrostatic repulsion between the SDS and negatively charged membrane surface also facilitates the alignment of the surfactant in "head out” position.
  • the self-assembly characteristics of surfactants on membrane surface have been observed by Chil- dress et.al. [46]. As a result, the aforementioned surfactant assisted healing effect will improve rejection but reduce flux.
  • the TFN membranes showed significant recovery in the selectivity in the presence of SDS.
  • the anionic SDS surfactant may be aligned in a hydro- philic "head out” position and exhibits "healing effect" by overlapping the defects. As a result, overall improvements of both rejection (through the surfactant self-assembly) and permeate flux takes place.
  • Transport mechanism through RO membranes are commonly explained by a solu- tion diffusion model (dense polyamide layer without pores) and a pore flow model (dense polyamide layer with existence of nanometer size pores) [48, 49].
  • the current findings are suggesting that pore flow may be what is responsible for increased flux. It does not exclude the solution diffusion model as a transport mechanism that is happening in parallel, but the observed effects are easier explained by the pore flow model.
  • the preferential flow path could be established through the selective layer of the membrane and accounted for increase in the permeate flow. This probably could be due to presence of extensive defects/imperfections inside the polyamide layer.
  • the proposed mecha- nism differs from the Maxwell's mixing model in terms of improving flux through the defect formation without sacrificing the rejection.
  • TFN-T membrane by incorporating 0.125 wt% of Ti02-Si02 nanoparticles and with combinational effect of solvent post treatment and surfactant healing shows competitive performance compared to all commercial membranes.
  • This example in accordance with the hypothesis explained in Figure 13 illustrates an effective way of tailoring RO membrane properties by overcoming trade-off effect between permeability and selectivity.
  • Nanoparticles irrespective of size and shape are prone to form defects in polyamide layer.
  • the defect formation appeared explicitly with larger size and higher concentrations of nanoparticles; as in most of these cases lower salt rejections were observed.
  • the transport mechanism was influenced by existence of preferential flow channel through imperfections of polyam- ide layer and the presence of a surfactant acting as secondary filter layer.
  • This concept could open the door to a new paradigm of hybrid RO membrane fabrication in which desired performance properties can be achieved by a clever design of a surfactant-induced surface active polymer in combination with an imperfect polyamide layer.
  • By increasing the selectivity of the deposition sites of the surface active compounds highly productive and selective membranes could be produced. Defective membranes could be repaired in situ.
  • the concept may also help to extend the useful lifetime of RO membranes by continuous low dosage treatment.
  • FIG. 1 Schematic procedures for the synthesis of Ti02-Si02 nanoparticles
  • FIG. 1 Flow diagram of reverse osmosis testing unit
  • Figure 4 (a, b) TEM images, (c) EDX and (d) particle size distribution of Ti02-Si02 nanoparticles
  • Figure 5 FESEM images of top surfaces and cross-sections of (a) PES support, (b) TFC, (c)
  • TFN-P and (d) TFN-T membranes are TFN-P and (d) TFN-T membranes.
  • Figure 6 (a) XPS wide-scanned spectra, (b) Si 2p core-level spectra and (c) Ti 2p core-level spectra of TFC, TFN-P and TFN-T membranes
  • Figure 7 S and R parameters of TFC, TFN-P and TFN-T membranes as a function of incident positron energy (or mean depth).
  • FIG. 10 Performance comparison for two surfactant treatment approaches (Method A: SDS post treatment vs Method B: SDS in feed tank addition) for TFC, TFN-P, TFN-T membranes as per testing procedures of 1 ) First salt reading (no SDS) 2) Salt + SDS in feed tank 3) Second salt reading (after removal of SDS). For each TFN membrane nanoparticle concentration was 0.125 wt%
  • FIG. 1 Surface zeta potential of TFC, TFN-P and TFN-T membranes
  • Figure 12 Illustrative example of tailoring the membrane properties by combining influential effects of nanoparticles, ethanol post-treatment solvent and SDS in feed tank addition and comparing with standard TFC membrane
  • FIG 13 Schematics for healing membrane hypothesis showing surfactant assisted healing effect to overcome defect/imperfections in polyamide layer of (a) TFC and (b) TFN membranes
  • Figure 14 Performance benchmarking of commercial and hand casted TFC, TFN-T membranes tested at 55 bar, -35000 ppm.
  • Commercial Membranes (1 ) NanoH20 ES (without PVA), (2) Dow Filmtec (SW30XLE), (3) Toray UTC-80E, TFN-T: TFN membrane with 0.125wt% Ti02-Si02 nanoparticles, with ethanol post treatment and SDS in feed tank.
  • TFN membranes were dried at room temperature for 15 min. Before performance testing, as standard procedure the membrane was soaked with Dl water for 15 min.
  • the procedure to fabricate TFN membranes was similar, with an exception that predefined amount of BASF nanoparticles were uniformly dispersed by sonication before adding into the MPD solution and in the case of POSS materials namely, AM0285 and AM0265 particles were dissolved completely into MPD and TMC solution respectively prior to the casting process. Solvent post treatment methods were explored by soaking membrane into (1 ) ethanol only or (2) n-hexane only or (3) n-hexane followed by ethanol. The soaking time was either 15 min or 1 h.
  • the TFN membranes incorporated with the AM0285, AM0265 and BASF nanoparticle were referred to as TFN-P1 , TFN-P2 and TFN-T.
  • Anionic Surfactant A was added directly into feed tank at a concentration of 0.1 wt% after the first reading of salt rejection without interrupting the test run and comparing the results before / after anionic surfactant addition.
  • RO tests of TFN and TFC RO membranes were carried out at 55bar (-800 psi), 35000 ppm salt concentration (NaCI in Dl water) and 25 °C in a continuous cross flow process using proprietary testing systems.
  • the schematics of the RO testing unit is shown in Figure 2. Prior to tests, all membrane samples were run and allowed to equilibrate for 1 h until a stable reading could be obtained. Water flux (J) was calculated by measuring the permeate flow at a specific interval of time
  • Salt and surfactant Surfactant (0.1 wt%) was added directly into feed tank immediately after first salt readings, followed by readings at intervals of 1 h each.
  • Second salt reading After the above two sets of readings, the RO testing machine was depres- surized, thoroughly washed with Dl water (5 washing cycles if not stated otherwise). The second salt reading was started with freshly prepared NaCI solution under conditions identical to the first salt reading.
  • TFN membranes (with nanoparticles induced defects) are compared with standard TFC membranes.
  • the nanoparticle addition with/without combination of solvent post treatment methods can induce defects or imperfections into the PA layer of the membrane. These carefully induced imperfections can offer preferential flow for water; as consequence multifold increase in the flux but at loss of selectivity. With aid of surfactant additions these imperfections can be healed to recover rejections.
  • the anionic SDS surfactant may be aligned in a hydrophilic "head out” position and exhibits "healing effect" by overlapping the defects.
  • suit- able surfactant e.g. o
  • gives opportunity (as seen from one of the example from figure 4a and b) to overcome compromise in flux hence effectively can break permeability/selectivity trade-off the RO membrane with overall improvement flux as well as rejection.
  • NF nanofiltration

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Abstract

L'invention concerne un procédé de traitement d'eau, dans lequel de l'eau d'alimentation est traitée avec une membrane M, ladite membrane M étant une membrane d'osmose inverse, une membrane d'osmose directe ou une membrane de nanofiltration, ladite membrane M étant mise en contact avec un tensioactif anionique A, ledit tensioactif anionique comprenant une chaîne hydrocarbonée aliphatique C6 à C10.
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CN110860218A (zh) * 2019-12-15 2020-03-06 天津工业大学 一种具有光催化功能的pan基油水分离微孔膜的制备方法
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