WO2016066633A1 - Nouveaux procédés de filtration - Google Patents

Nouveaux procédés de filtration Download PDF

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Publication number
WO2016066633A1
WO2016066633A1 PCT/EP2015/074847 EP2015074847W WO2016066633A1 WO 2016066633 A1 WO2016066633 A1 WO 2016066633A1 EP 2015074847 W EP2015074847 W EP 2015074847W WO 2016066633 A1 WO2016066633 A1 WO 2016066633A1
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WIPO (PCT)
Prior art keywords
water
polymer
process according
previous
membranes
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PCT/EP2015/074847
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English (en)
Inventor
Herbert Hommer
Arifin Davis Yohanes
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Basf Se
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Publication of WO2016066633A1 publication Critical patent/WO2016066633A1/fr

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    • 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
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • 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
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/16—Feed pretreatment
    • 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
    • B01D65/08—Prevention of membrane fouling or of concentration polarisation
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/04—Specific process operations in the feed stream; Feed pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/12—Addition of chemical agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/26—Further operations combined with membrane separation processes
    • B01D2311/2642—Aggregation, sedimentation, flocculation, precipitation or coagulation
    • 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
    • C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
    • 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
    • C02F2103/06—Contaminated groundwater or leachate
    • 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
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/12—Activated sludge processes
    • C02F3/1236—Particular type of activated sludge installations
    • C02F3/1268—Membrane bioreactor systems
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Definitions

  • the present invention pertains to processes for treating water comprising the following steps a) treating raw water with a polymer P,
  • step b) subjecting said water that has been treated according to step a) to ultrafiltration or microfiltration,
  • polymer P is a polyvinylamine
  • the present invention further relates to the use of polyvinylamines as a coagulant in filtration processes.
  • membrane filtration processes Many of such water treatment processes are today being carried out or supported by membrane filtration.
  • An important aspect of membrane filtration processes is to maintain the flux of water through the membrane at a high level for a long period of time and to facilitate the separation of solid material from the water.
  • coagulants are sometimes added to the raw water. Such coagulants help to agglomerate small solid particles to bigger agglomerates that are easier to separate.
  • Common coagulants used for such applications are inorganic salts of aluminum or iron like AlC or FeC .
  • inorganic coagulants are not suitable for all kinds of matter suspended in the water, require a relatively high dosage of the coagulant, are sensitive with respect to the flocculation conditions like the pH, yield coagulate with a relatively high volume.
  • inorganic coagulants, especially aluminium compounds are potentially toxic and result in high disposal costs. It was therefore the objective of the present invention to provide processes for the treatment of water that do not show the disadvantages associated with inorganic coagulants and that allow for efficient and versatile filtration of raw water.
  • Water that is be subjected to processes according to the invention can be any kind of water for which there is a need for filtration to remove suspended or dissolved mater like particles, viruses, bacteria, polymers or the like.
  • raw water includes sea water or brackish water; surface water like water from lakes, fluvial water or ground water; industrial or municipal waste water or sludge, or process water.
  • raw water is the effluent of a waste water treatment plant.
  • Sea water and brackish water may be subjected to filtration as a pretreatment step for desalination.
  • Waste water, sludge or process water may be filtrated for cleaning, removal of toxic substances with releasing it into nature.
  • Surface water may for example be subjected to filtration for making drinking water or for using it as process water.
  • processes according to the invention are applied in a membrane bioreactor (MBR).
  • MLR membrane bioreactor
  • step a) of processes according to the invention raw water is treated with at least one polymer P that is a polyvinylamine.
  • Polyvinylamines in the context of this application shall include all polymers that comprise amino groups bound to a polymeric backbone.
  • polyvinylamines are obtained by partial or complete hydrolysis of polymers of an N- vinyl acylamide, herein also referred to as vinylamides.
  • Suitable N-vinylamides are especially those of the general formula I
  • R 1 and R 2 are independently H, Ci, C2 or C3 alkyl
  • the vinylacylamine is N-vinylformamide (VFA).
  • the vinylacylamide is N-vinylacetamide.
  • suitable polyvinylamines are obtained by partial or complete hydrolysis of homopolymers of N-vinyl acylamides, especially homopolymers of VFA.
  • suitable polyvinylamines are obtained by partial or complete hydrolysis of copolymers of N-vinyl acylamides, especially copolymers of VFA.
  • N-vinylacylamide especially VFA
  • suitable polyvinylamines comprise at least one monomer b) or c).
  • the contents of monomers a), b) and c) in polymer P add up to 100 mol%.
  • suitable polyvinylamines are obtained by partial or complete hydrolysis of copolymers of VFA (monomer a) with at least one monomer b) that bears a positive charge.
  • Preferred monomers b) are those of the general formula II
  • R 3 is H or Ci , C2 or C3 alkyl
  • R 4 is an aliphatic, cycloaliphatic or aromatic rest bearing a positive charge
  • R 5 and R 6 are independently Ci to C 3 alkyl
  • X " is an anion
  • component b) Carr a positive charge.
  • compounds suitable as component b) carry a permanent positive charge.
  • component b) is zwitterionic or is cationic only at low pH.
  • component b) comprises an anion X- that can for example be selected from pseudo halides or halides like Ch, Br or I-; hydroxide, sulfates, carboxylates or alkylsulfonates like C1-C3 alkyl sulfonates.
  • anions X " are selected from Ch, OH- or alkylsulfonates like CH3SO4 " .
  • component b) bears a quarternary ammonium group or a pyridinium group.
  • R 3 is H or CH3. More preferably, R 3 is H.
  • component b) is a derivative of (meth)acrylic acid bearing cationic groups or a quaternized vinyl pyridine.
  • component b) is an ester or an amide of acrylic acid or methacrylic acid or a vinylpyridinium salt.
  • component b) is an ester of acrylic acid or methacrylic acid or a vinylpyridinium salt.
  • R 4 is selected from [(CH2) n NR 5 R 6 R 7 ] + X- .
  • n is a number from 1 to 8, preferably from 1 to 5, more preferably from 1 to 3.
  • component b) is selected from
  • R 5 , R 6 and R 7 are independently substituted or unsubstituted benzyl or Ci to C12 alkyl, and preferably methyl or ethyl. In a particularly preferred embodiment, R 5 , R 6 and R 7 are methyl.
  • Particularly preferred components b) are ⁇ , ⁇ -dimethylaminoethyl acrylate methyl chloride, Acry- loyloxyethyltrimethyl ammonium chloride, Acryloyloxyethyltrimethyl ammonium hydroxide, Acry- loyloxypropyltrimethyl ammonium chloride, Methacryloyloxyethyltri methyl ammonium chloride, ⁇ , ⁇ -dimethylaminopropylacrylamide methyl chloride.
  • Suitable polyvinylamines may also comprise mixtures of different cationic monomers b).
  • this Y group comprises an ethylenic unsaturation which can further take part in the copolymerization and thereby (i) form part of the same copolymer chain on a head-to-head configuration, (ii) form part of the same copolymer chain on a head-to-tail configuration, (iii) form part of a different copolymer chain, or (iv) remain unreacted.
  • suitable polyvinylamines are obtained by partial or complete hydrolysis of copolymers comprising VFA and diallyldimethylammoniumchlorid (DADMAC). In one embodiment, suitable polyvinylamines are obtained by partial or complete hydrolysis of copolymers comprising VFA and methacrylamidopropyl trimethyl-ammonium chloride (MAP- TAC).
  • DMDMAC diallyldimethylammoniumchlorid
  • suitable polyvinylamines are obtained by partial or complete hydrolysis of copolymers comprising VFA and methacrylamidopropyl trimethyl-ammonium chloride (MAP- TAC).
  • suitable polyvinylamines are obtained by partial or complete hydrolysis of copolymers comprising VFA (monomer a) and at least one vinylester or vinylether (monomer c).
  • monomer c) is vinylacetate.
  • Further monomers d) can be (meth)acrylic esters like methyl acrylate, ethyl acrylate, hydroxy- propyl(meth)acrylate and other water soluble (meth)acrylates like polyethylene glycol
  • Preferred polymers P contain 0 - 20 mass% of the (meth)acrylic esters d).
  • Normally polymers P are obtained by polymerizing suitable N-vinylamides like VFA, optionally together with further monomers, and subsequent hydrolysis of the polymer obtained.
  • Said hydrolysis can be carried out by an inorganic or organic acid or base.
  • the hydrolysis is carried out using an inorganic base.
  • the amount of acid or base used to hydrolyze the copolymers in solution can vary widely and is generally added in a molar ratio of from 0.05: 1 to 3: 1 , preferably from 0.1 : 1 to 1 :1 based on the N-vinylamide monomer content of the initially formed polymer.
  • a suitable acid such as inorganic acids as, for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid, sulfuric acid, nitric acid, phosphoric acid and the like
  • suitable bases such as inorganic bases as, for example, sodium hydroxide, ammonia, ammonium hydroxide, potassium hydroxide, and the like may also be used.
  • the degree of hydrolysis can be controlled by controlling the amount of acid or base, the reaction temperature and/or the reaction time. In general, greater amounts of acid or base, higher reaction tempera- tures and longer reaction times result in higher degrees of hydrolysis.
  • ester or amide groups originating from component b) or c) can also be partially hydrolyzed.
  • vinyl acetate will also be at least partly hydrolyzed in such a hydrolysis step.
  • the degree of hydrolysis of the vinylamide groups is 10 to 100 mol% based on the vi- nylamide groups initially present in the polymer.
  • the degree of hydrolysis is 30 to 95 mol %, more preferably 40 to 80 mol %.
  • polymer P is branched.
  • a branched polymer in this context is a polymer which contains some crosslinking but is still sufficiently water soluble to be used as a coagulant in filtration applications. This is achieved by presence of crosslinkers like triallylamin, tetraallylammonium chloride or methylene bisacryla- mide during the polymerization in a dosage that is low enough to ensure complete water solubil- ity without any gel formation.
  • the dosage depends on the chain length of the polymer. If polymers with a molecular weight of several thousands to 10.000 g/mol are branched, the maximum dosage can be in a range of up to 1000 ppms. If the molecular is higher the maximum dosage of the crosslinker is significantly lower (below 100 ppm).
  • Copolymers P normally have an average molecular weight Mw (determined by light scattering) of 50,000 to 1 ,000,000, preferably 100,000 to 500,000, more preferably 150,000 to 400,000.
  • average molecular weight in the context of this application means the weight average molecular weight Mw.
  • the average molecular weight Mw can be determined by light scattering using a field flow frac- tionation apparatus coupled with a multi-angle light scattering detector and a refractive index detector.
  • step a) of processes according to the invention raw water is treated with at least one polymer P.
  • This treatment involves adding and optionally homogenization of said at least one polymer P with the raw water.
  • polymer P is added to the raw water continuously in line.
  • polymer P is added to the raw water batchwise.
  • said polymer P is preferably mixed and homogenized with the raw water to achieve essentially homogenous concentration of polymer P in the raw water.
  • Said mixing can for example be done by mechanical stirring and/or ultrasound.
  • substance particles comprised in the raw water are coagulated to form larger coagulates that can be separated more easily.
  • the raw water is subjected to coagulation for a period of 10 seconds to 10 hours, preferably 2 minutes to 1 hour and even more preferably 5 minutes to 30 minutes.
  • the coagulation time is preferably 10 seconds to 10 minutes. If the treatment of the raw water is carried out continuously, these treatment periods are to be understood as number averages.
  • raw water is treated with polymer P in an amount of 0.01 to ppm bis 10 ppm, preferably 0.05 to 5. While processes according to the invention are relatively tolerant with respect to the pH of the raw water, the addition of polymer P to the raw water is preferably carried out at a pH of 6 to 8.
  • raw water is treated with polymer P in combination with at least one inorganic coagulant like iron chloride, aluminium chloride, KAI(S0 4 )2, Alum, polyaluminiumchloride PAC or calcium carbonate, for example by first adding 0.1 to 1 ppm of at least one inorganic coagulant like polyaluminiumchloride and subsequently adding 0.05 to 1 ppm, preferably 0.1 to 0.3 ppm of polymer P.
  • inorganic coagulant like iron chloride, aluminium chloride, KAI(S0 4 )2, Alum, polyaluminiumchloride PAC or calcium carbonate
  • raw water is pretreated with inorganic coagulants like iron chloride, aluminium chloride or calcium carbonate and is then treated with polymers P.
  • inorganic coagulants like iron chloride, aluminium chloride or calcium carbonate
  • the raw water After completion of the coagulation, the raw water is subjected to a filtration step.
  • Said filtration can in principle be any kind of filtration in which solid particles are separated from the raw water.
  • said filtration step is carried out by at least one membrane.
  • 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 can be reverse osmosis (RO) membranes, forward osmosis (FO) membranes, nanofiltration (NF) membranes, ultrafiltration (UF) membranes or microfiltration (MF) membranes.
  • RO reverse osmosis
  • FO forward osmosis
  • NF nanofiltration
  • UF ultrafiltration
  • MF microfiltration
  • said membrane step is an ultrafiltration or a microfiltration.
  • UF membranes are normally suitable for removing suspended solid particles and solutes of high molecular weight, for example above 100 kDa.
  • UF membranes are normally suitable for removing bacteria and viruses.
  • UF membranes normally have an average pore diameter of 2 nm to 50 nm, preferably 5 to 40 nm, more preferably 5 to 20 nm.
  • UF membranes comprise as the main component at least one polyamide (PA), polyvinylalcohol (PVA), Cellulose Acetate (CA), Cellulose Triacetate (CTA), CA-triacetate blend, Cellulose ester, Cellulose Nitrate, regenerated Cellulose, aromatic , aromatic/aliphatic or aliphatic Polyamide, aromatic, aromatic/aliphatic or aliphatic Polyimide, Polybenzimidazole (PBI), Polybenzimidazolone (PBIL), Polyacrylonitrile (PAN), PAN-poly(vinyl chloride) copolymer (PAN-PVC), PAN-methallyl sulfonate copolymer, Poly(dimethylphenylene oxide) (PPO), Poly- carbonate, Polyester, Polytetrafluroethylene PTFE, Poly(vinylidene fluoride) (PVDF), Polypropylene (PP), Polyelectrolyte complexes, Poly(methyl methacrylate)
  • PA
  • UF membranes comprise further additives like polyvinyl pyrrolidones or pol- yalkylene oxides like polyethylene oxides.
  • UF membranes comprise as major components polysulfones, polyphenylenesulfone or polyethersulfone with further additives like polyvinylpyrrolidone.
  • UF membranes comprise 99.9 to 50% by weight of a polyether- sulfone and 0.1 to 50 % by weight of polyvinylpyrrolidone.
  • UF membranes comprise 95 to 80% by weight of polyethersulfone and 5 to 15 % by weight of polyvinylpyrrolidone.
  • UF membranes are present as spiral wound membranes, as pillows or flat sheet membranes.
  • UF membranes are present as tubular membranes. In another embodiment of the invention, UF membranes are present as hollow fiber membranes or capillaries.
  • UF membranes are present as single bore hollow fiber membranes.
  • UF membranes are present as multibore hollow fiber membranes.
  • Multiple channel membranes also referred to as multibore membranes, comprise more than one longitudinal channels also referred to simply as "channels”.
  • the number of channels is typically 2 to 19.
  • multiple channel membranes comprise two or three channels.
  • multiple channel membranes comprise 5 to 9 channels.
  • multiple channel membranes comprise seven channels.
  • the number of channels is 20 to 100.
  • Such channels also referred to as "bores" may vary.
  • such channels have an essentially circular diameter.
  • such channels have an essentially ellipsoid diameter.
  • channels have an essentially rectangular diameter. In some cases, the actual form of such channels may deviate from the idealized circular, ellipsoid or rectangular form.
  • such channels have a diameter (for essentially circular diameters), smaller diameter (for essentially ellipsoid diameters) or smaller feed size (for essentially rectangular diameters) of 0.05 mm to 3 mm, preferably 0.5 to 2 mm, more preferably 0.9 to 1 .5 mm.
  • such channels have a diameter (for essentially circular diameters), smaller diameter (for essentially ellipsoid diameters) or smaller feed size (for essentially rectangular diameters) in the range from 0.2 to 0.9 mm.
  • these channels can be arranged in a row.
  • channels with an essentially circular shape these channels are in a preferred embodiment arranged such that a central channel is surrounded by the other channels.
  • a membrane comprises one central channel and for example four, six or 18 further channels arranged cyclically around the central channel.
  • the wall thickness in such multiple channel membranes is normally from 0.02 to 1 mm at the thinnest position, preferably 30 to 500 ⁇ , more preferably 100 to 300 ⁇ .
  • the membranes and carrier membranes have an essentially circular, ellipsoid or rectangular diameter.
  • membranes according to the invention are essentially circular.
  • membranes according to the invention have a diameter (for essentially circular diameters), smaller diameter (for essentially ellipsoid diameters) or smaller feed size (for essentially rectangular diameters) of 2 to 10 mm, preferably 3 to 8 mm, more preferably 4 to 6 mm.
  • multibore membranes have a diameter (for essentially circular diameters), smaller diameter (for essentially ellipsoid diameters) or smaller feed size (for essentially rectangular diameters) of 2 to 4 mm.
  • the channels of a multibore membrane may incorporate an active layer with a pore size different to that of the carrier membrane or a coated layer forming the active layer.
  • Suitable materials for the coated layer are polyoxazoline, polyethylene glycol, polystyrene, hydro- gels, polyamide, zwitterionic block copolymers, such as sulfobetaine or carboxybetaine.
  • the active layer can have a thickness in the range from 10 to 500 nm, preferably from 50 to 300 nm, more preferably from 70 to 200 nm.
  • multi bore membranes are designed with pore sizes between 0.2 and 0.01 ⁇ .
  • the inner diameter of the capillaries can lie between 0.1 and 8 mm, preferably between 0.5 and 4 mm and particularly preferably between 0.9 and 1.5 mm.
  • the outer diameter of the multi bore membrane can for example lie between 1 and 26 mm, preferred 2.3 and 14 mm and particularly preferred between 3.6 and 6 mm.
  • the multi bore membrane can contain 2 to 94, preferably 3 to 19 and particularly preferred between 3 and 14 channels.
  • multi bore membranes contain seven channels.
  • the permeability range can for example lie between 100 and 10000 L/m 2 hbar, preferably between 300 and 2000 L/m 2 hbar.
  • multi bore membranes of the type described above are manufactured by extruding a polymer, which forms a semi-permeable membrane after coagulation through an extrusion noz- zle with several hollow needles.
  • a coagulating liquid is injected through the hollow needles into the extruded polymer during extrusion, so that parallel continuous channels extending in extrusion direction are formed in the extruded polymer.
  • the pore size on an outer surface of the extruded membrane is controlled by bringing the outer surface after leaving the extrusion nozzle in contact with a mild coagulation agent such that the shape is fixed without active layer on the outer surface and subsequently the membrane is brought into contact with a strong coagulation agent.
  • suitable coagulation agents include solvents and/or non-solvents.
  • the strength of the coagulations may be adjusted by the combination and ratio of non-solvent/solvent.
  • Coagulation solvents are known to the person skilled in the art and can be adjusted by routine experiments.
  • An example for a solvent based coagulation agent is N-methylpyrrolidone.
  • Non-solvent based coagulation agents are for instance water, iso-propanol and propylene glycol.
  • MF membranes are normally suitable for removing particles with a particle size of 0.1 ⁇ and above.
  • MF membranes normally have an average pore diameter of 0.05 ⁇ to 10 ⁇ , preferably 1 .0 ⁇ to 5 ⁇ .
  • Microfiltration can use a pressurized system but it does not need to include pressure.
  • MF membranes can be capillaries, hollow fibers, flat sheet, tubular, spiral wound, pillows, hollow fine fiber or track etched. They are porous and allow water, monovalent species (Na+, CI-), dis- solved organic matter, small colloids and viruses through but retain particles, sediment, algae or large bacteria.
  • Microfiltration systems are designed to remove suspended solids down to 0.1 micrometres in size, in a feed solution with up to 2-3% in concentration.
  • MF membranes comprise as the main component at least polyamide (PA), polyvinylalcohol (PVA), Cellulose Acetate (CA), Cellulose Triacetate (CTA), CA-triacetate blend, Cellulose ester, Cellulose Nitrate, regenerated Cellulose, aromatic , aromatic/aliphatic or aliphatic Polyamide, aromatic, aromatic/aliphatic or aliphatic Polyimide, Polybenzimidazole (PBI), Polybenzimidazolone (PBIL), Polyacrylonitrile (PAN), PAN-poly(vinyl chloride) copolymer (PAN- PVC), PAN-methallyl sulfonate copolymer, Poly(dimethylphenylene oxide) (PPO), Polycar- bonate, Polyester, Polytetrafluroethylene PTFE, Poly(vinylidene fluoride) (PVDF), Polypropylene (PP), Polyelectrolyte complexes, Poly(methyl methacrylate)
  • PA
  • MF membranes comprise as the main component at least one polysulfone, polyphenylenesulfone and/or polyethersulfone.
  • Processes according to the invention allow for the efficient coagulation and separation of suspended solids in raw water, especially humic acids or fulvic acids, solid particles, dissolved or suspended organic matter, organic or inorganic particulate material, biopolymers, carbohydrates, proteins, soluble microbial products.
  • Processes according to the invention reduce the formation of toxic disinfection by-products (DBP) such as trihalomethanes or haloacetic acids in the water.
  • DBP toxic disinfection by-products
  • Processes according to the invention reduce the fouling of the membranes used in filtration steps and increase the flux of water through such membranes. Processes according to the invention also allow for long filtration cycles without cleaning or backwashing of the membrane. Processes according to the invention require only a small dosage of polymers P.
  • Processes according to the invention are very tolerant to a wide range of process conditions with respect, for example, to the pH, the temperature, the load of the raw water with organic material. Examples
  • humic acid Sigma-Aldrich
  • 50 ml of NaOH 0.1 M
  • the concentrated solution was diluted to 1 L with deionized water and pH re-adjusted to 7. Insoluble material formed during storage over night was removed by decanting. Prior to use, the concentrated stock solution was filtered over a 25 ⁇ paper filter and diluted with tap water at a ratio of 1 :20.
  • a solution of organic coagulants has been prepared at a concentration of 0.01 % by weight and 0.02 % by weight for the inorganic coagulants, respectively.
  • Varying amounts of said polymer solution were added into 250 ml of humic acid solution that was obtained as described above and stirred with a mechanical stirrer. After stirring for 1.5 minutes at 400 rpm, the stirring speed was reduced to 150 rpm for 8.5 minutes for flock maturation. Finally, the coagulated material was allowed to settle for 10 minutes before filtering over a 12 - 25 ⁇ paper filter.
  • a sample from the filtrate was taken and the turbidity measured in nephelometric turbidity units (NTU) with a Turbiquant 1500 T (Merck) equipment. The lower the NTU value the better the coagulation.
  • the UV254 absorption was measured with a Spekol 1500 instrument from Analytic Jena after filtration over a 0.45 ⁇ syringe filter.
  • Organic coagulant 1 Polyvinylamine with a degree of hydrolysis of 50 % ("50 % d.h.”), obtained analogously to example 1 .3 of US 4,421 ,602.
  • Organic coagulant 2 Polyvinylamine, 95 % d.h. *)* ' obtained analogously to example 1.1 of US 4,421 ,602.
  • Organic coagulant 3 Poly-(vinylamine-co-vinylalcohol), molar ratio vinylamine : vinylalcohol 50:50 , obtained analogously to example 2 of EP 216 387.
  • Organic coagulant 4 Poly-(vinylamine-co-vinylether) molar ratio vinylamine : vinylalcohol 90:10), obtained analogously to example 2 of EP 216 387 by replacing vinylacetate by Vi- nyloxybutylenpolyethylenglykol with the following formula
  • n having a molar average value of 12.
  • Table 1 a Residual turbidity (in NTU) of humic acid solution after treatment with organic coagulants and filtration over 12-25 ⁇ filter. dose / ppm 10 15 20 25 30 35 40 45 50 55 polyaluminium- chloride > 10 4 2 3 2 2 3 1 2 1
  • Table 1 b Residual turbidity (in NTU) of humic acid solution after treatment with inorganic coagulants and filtration over 12-25 ⁇ filter. dose / ppm 4 5 6 7 8 9 10 1 1 12 13
  • Table 2a UV254 absorption of humic acid solution after treatment with organic polymers and filtration over 0.45 ⁇ filter.
  • Table 2b UV254 absorption of humic acid solution after treatment with inorganic coagulants and filtration over 0.45 ⁇ filter.
  • Organic coagulant 20 14 ml 12 ml 12 ml 12 ml acc. invention
  • Humic acid solution was charged at a rate of 2.5 L/h, yielding in a flux rate of 50 Lnr 2 r 1 .
  • the coagulant was online dosed into the feed at a rate of 18g/h (optimum dose). After each filtration cycle of 20 minutes a backwash at a flux rate of 100 Lnr 2 hr 1 was performed for 1 minute.
  • TMP trans-membrane pressure
  • organic coagulant 1 Poly-vinylamine, 50 % degree of hydrolyses
  • x-axis time (h:min);
  • y axis transmembrane pressure [mbar];
  • vertical line indicate a backwash operation of the membrane hat are exemplarily marked with an asterisk * for some cases).
  • ⁇ TMP 70 mbar

Abstract

L'invention concerne un procédé de traitement de l'eau comprenant les étapes suivantes a) traitement de l'eau brute avec au moins un polymère P, b) soumission de ladite eau qui a été traité conformément à l'étape a) à une filtration, ledit ou lesdits polymère P étant une polyvinylamine.
PCT/EP2015/074847 2014-10-29 2015-10-27 Nouveaux procédés de filtration WO2016066633A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108017128A (zh) * 2017-11-29 2018-05-11 无锡锐众环保科技有限公司 一种高分子多元絮凝改性剂、其制备方法及应用
US20230050962A1 (en) * 2021-08-06 2023-02-16 Dupont Safety & Construction, Inc. Method for dosing coagulant and adsorbent in a membrane filtration system

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4421602A (en) * 1981-07-18 1983-12-20 Basf Aktiengesellschaft Linear basic polymers, their preparation and their use
EP0216387A2 (fr) * 1985-09-26 1987-04-01 BASF Aktiengesellschaft Procédé de préparation de copolymères contenant des unités vinylamine et leur usage comme agent améliorant la résistance à l'état humide et sec du papier
WO2013153004A1 (fr) * 2012-04-13 2013-10-17 Basf Se Nouveaux polymères cationiques
US20130270189A1 (en) * 2012-04-17 2013-10-17 Water Solutions, Inc. Treatment of contaminated impound water

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4421602A (en) * 1981-07-18 1983-12-20 Basf Aktiengesellschaft Linear basic polymers, their preparation and their use
EP0216387A2 (fr) * 1985-09-26 1987-04-01 BASF Aktiengesellschaft Procédé de préparation de copolymères contenant des unités vinylamine et leur usage comme agent améliorant la résistance à l'état humide et sec du papier
WO2013153004A1 (fr) * 2012-04-13 2013-10-17 Basf Se Nouveaux polymères cationiques
US20130270189A1 (en) * 2012-04-17 2013-10-17 Water Solutions, Inc. Treatment of contaminated impound water

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108017128A (zh) * 2017-11-29 2018-05-11 无锡锐众环保科技有限公司 一种高分子多元絮凝改性剂、其制备方法及应用
US20230050962A1 (en) * 2021-08-06 2023-02-16 Dupont Safety & Construction, Inc. Method for dosing coagulant and adsorbent in a membrane filtration system

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