WO2005002712A1 - Membrane post treatment - Google Patents
Membrane post treatment Download PDFInfo
- Publication number
- WO2005002712A1 WO2005002712A1 PCT/AU2004/000922 AU2004000922W WO2005002712A1 WO 2005002712 A1 WO2005002712 A1 WO 2005002712A1 AU 2004000922 W AU2004000922 W AU 2004000922W WO 2005002712 A1 WO2005002712 A1 WO 2005002712A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pvme
- membrane
- polymeric
- solvent
- ultra
- Prior art date
Links
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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
-
- 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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- 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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
- B01D67/00111—Polymer pretreatment in the casting solutions
-
- 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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0018—Thermally induced processes [TIPS]
-
- 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
- B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
-
- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
- B01D71/26—Polyalkenes
-
- 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
- B01D71/26—Polyalkenes
- B01D71/262—Polypropylene
-
- 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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
-
- 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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/02—Hydrophilization
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/10—Specific pressure applied
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/28—Pore treatments
- B01D2323/283—Reducing the pores
-
- 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
- B01D2323/34—Use of radiation
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S55/00—Gas separation
- Y10S55/05—Methods of making filter
Definitions
- membranes particularly hollow fibre membranes for use in microfiltration and
- the invention also relates to membranes prepared in accordance with
- Synthetic membranes are used for a variety of applications including
- Microfiltration, ultrafiltration and reverse osmosis are examples of microfiltration, ultrafiltration and reverse osmosis.
- Microfiltration can remove very
- microfiltration can filter particles down to 0.1 ⁇ m, whereas ultrafiltration can retain
- Modules of such fibres can be made with an extremely large surface area per unit volume.
- Microporous synthetic membranes are particularly suitable for use in hollow
- At least one polymer is
- the polymer solution can be cast as a film or hollow fibre, and then immersed in a
- precipitation bath such as water. This causes separation of the homogeneous polymer solution into a solid polymer and liquid solvent phase. The precipitated polymer forms a
- Microporous phase inversion membranes are particularly well suited to the
- fibre contains the largest membrane area per unit volume.
- Flat sheet membranes are prepared by bringing a polymer solution consisting of
- Hydrophobic surfaces are defined as “water hating” and hydrophilic surfaces as
- Membranes may be damaged at
- hydrophobic membranes when used in water filtration applications, hydrophobic membranes need to be
- hydrophilised or “wet out” to allow water permeation Some hydrophilic materials are
- PVDF poly(vinylidene fluoride)
- PNDF Poly(vinylidene fluoride)
- the crystalline phase provides good thermal
- PVDF exhibits a number of desirable characteristics for membrane applications, including
- PVDF has to date proven to be one of the most desirable options from
- hydrophilic membranes are to synthesise membranes based around a hydrophobic polymer but with modification of the
- membrane property are (i) to modify the starting materials, reagents or conditions used to modify the starting materials, reagents or conditions used to modify the starting materials, reagents or conditions used to modify the starting materials, reagents or conditions used to modify the starting materials, reagents or conditions used to modify the starting materials, reagents or conditions used to modify the starting materials, reagents or conditions used to modify the starting materials, reagents or conditions used to modify the starting materials, reagents or conditions used to
- PVME can be used to modify, and in particular, reduce, the hydrophobicity of certain
- the PVME can be incorporated either by means of post-
- PVDF Poly(vinylidene fluoride)
- Halar chlorotrifluoroethylene
- PP Poly(propylene)
- PVME as a membrane additive was found to induce variations in the pore
- PVME also encompasses not onlythe polymeric form of the product, but also the monomeric form of the compound, namely vinylmethyl ether, as
- the invention provides a polymeric ultra or
- microfiltration membrane incorporating PVME.
- membrane may incorporate a coating of PVME or, alternatively include a homogeneous
- the polymeric membrane may include a heterogeneous dispersion of PVME throughout the polymer.
- the invention provides a hydrophilic polymeric membrane
- Halar including one or more of Halar, PVDF or PP.
- the invention provides a hydrophilic polymeric membrane
- the membrane has a reduced pore size as a result of the addition of
- the membrane is substantially free from macrovoids.
- the membrane according to the present invention contains cross linked PVME.
- the membrane according to the present invention may incorporate adsorbed PVME and embedded PVME and wherein adsorbed PVME is cross-linked
- polymeric ultra or microfiltration membranes of the present invention are polymeric ultra or microfiltration membranes of the present invention.
- inventions contain PVDF and PVME in a ratio of 0.1 :24 to 0.5 to 24, more preferably in a
- the polymeric ultra or microfiltration membranes preferably contain 0.4 to 30
- polymeric ultra or microfiltration membranes of the present invention are present in one embodiment, polymeric ultra or microfiltration membranes of the present invention.
- hydrophobic polymeric ultra or microfiltration membranes are preferred.
- PVME with a concentration 0.05 to 5 wt%. More preferably, the polymeric ultra or
- microfiltration membranes are rendered hydrophilic by contacting the membrane with an
- aqueous or alcoholic solution of PVME with a concentration of 0.05 to 5 wt%, at a
- the invention provides a method of hydrophilising
- a membrane prepared from a polymeric material said method including the step of
- the at least partially water soluble polymeric hydrophilising agent is
- the at least partially water soluble polymeric hydrophilising agent contains
- the polymeric hydrophilising agent is
- the polymeric hydrophilising agent may be a copolymer containing vinylmethyl
- ether monomer is present in an amount of at least 50 mole% of the polymeric hydrophilising agent. If a co monomer is used, it is preferred if the co-monomer is selected from the
- the co-monomer is selected from the group consisting of: vinyl
- diallyl maleate maleic anhydride esters of adipic acid (divinyl adipate), ethylenically
- the invention provides a method of modifying the
- said method including the step of contacting said polymeric material with
- PVME polyvinylmethyl ether
- the polymeric material is a hydrophobic polymer and hydrophobic/hydrophilic balance of the polymer is modified to provide a hydrophilic
- the polymeric material is poly(vinylidene fluoride) (PVDF), poly(ethylene-chlorotrifluoroethylene) (Halar) and poly(propylene) (PP) or mixtures
- PVDF Poly(vinylidene fluoride)
- PVDF poly(ethylene-chlorotrifluoroethylene)
- the polymeric material may be a formed membrane treated with a solution of
- the polymeric material is treated with a solution of PVME at a
- the polymeric material is post treated by
- polymeric material is post treated by soaking in a solution of PVME in water
- the concentration of PVME is less than 10%, more preferably less
- concentration of PVME is greater then 0.1%.
- a range of 1 to 5% is particularly preferred. It is preferred that treatment with PVME takes place for between 5 minutes and
- the polymeric material is treated with PVME by
- the membrane dope may
- the membrane dope includes PVME in an amount up to lwt% when a
- TIPS process is employed, or higher if a DIPS process is used.
- the PVME is
- the solvent non-solvent mixture includes a PVME solvent and PVME non-solvent
- the PVME solvent possesses weak polarity, for example,
- the PVME non-solvent is strongly polar, for example,
- diethylene glycol triethylene glycol, 1,4-butanediol or mixtures thereof.
- the solvent mixture includes from 40-60% non-solvent.
- the solvent mixture includes PVME in an amount of 0.1-2wt%, and
- the method of casting is a TIPS process
- it further includes treatment with a coating solution which most preferably contains a solvent and a non-
- N-methylpyrrolidone is N-methylpyrrolidone
- the present invention also provides a method wherein PVME is incorporated in
- PVME adsorbed PVME.
- a preferred method of cross linking is e-beam irradiation. PVME readily cross-links upon irradiation with electron beams or ⁇ -radiation and
- ether monomer is readily hydrolysed at pH 7 or below and so can be readily removed
- PVME was surprisingly found to be effective at hydrophilising otherwise hydrophobic PP, PVDF and Halar membranes either by soaking the membrane as a post treatment or by including the PVME as a hydrophilising agent incorporated in the
- Hydrophilisation can be achieved either by soaking the membranes in a
- PVME polyvinyl ether
- a suitable solvent for example, ethanol or water, preferably at a level greater than 0.5wt%.
- PVDF and Halar membranes in particular demonstrate long
- non-solvent in the dope If the proportion of non-solvent used was lower than 60wt% a
- PVME could also be successfully incorporated into the dope via a DIPS process.
- PVME modified membranes can be further modified, for example, by irradiation
- PVME is cross-linkable and under irradiation will cross-link on
- Irradiation can be applied either to membranes that have been
- PVME post-treated in PVME or to membranes that have had PVME included in the dope.
- PVME may, under appropriate conditions, also cross-link with PVDF when this is
- PVDF and fluoropolymers with a similar structure are known to undergo some cross-linking upon irradiation with electrons or ⁇ -radiation and similar crosslinking with PVME is also possible.
- Membranes with a cross-linkable hydrophilising agent in the dope may also be
- crosslinkable agent to cross-link with the embedded PVME agent, reducing the
- hydrophilising agent was investigated. PVDF, Halar and PP membranes were all tested.
- Halar membranes The membrane was soaked in ethanol for 12hrs,
- Wicking is said to have occurred occurs if a solution of dye is spontaneously absorbed into a fibre that is partially submerged vertically in such a solution and travels
- the surface may not be completely hydrophilic which may in turn affect complexing and linking.
- Halar MF fibre ranges between 1500- 2000LMH/bar, with Halar UF membranes varying between 200-600LMH/bar.
- the results from the Halar membranes are difficult to quantify with precision because it is believed that glycerol in the pores results in lower initial clean water
- Halar has a mildly polar structure not dissimilar to PVDF and the affinity
- PVME may bind more firmly to the Halar surface rather than the PVDF surface, from an
- TIPS Membranes PVME was added to standard TIPS PVDF or TIPS Halar dope in proportions varying from 0 to lwt%. The TIPS extrusion was operated in a continuous process
- PVME was dissolved into the solvent/non-solvent mixture of GTA and diethylene
- PVDF dope that contained poly(vinylpyrrolidone-vinylacetate) (S630) as an alternative
- the fibres show an increase in break extension, break force and bubble point by
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Thermal Sciences (AREA)
- Plasma & Fusion (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006517906A JP4908208B2 (en) | 2003-07-08 | 2004-07-08 | Membrane post-treatment |
EP04737543.1A EP1654053B8 (en) | 2003-07-08 | 2004-07-08 | Hollow fibre membrane comprising pvme and method of production |
CN2004800192881A CN1819867B (en) | 2003-07-08 | 2004-07-08 | Membrane post treatment |
CA2530805A CA2530805C (en) | 2003-07-08 | 2004-07-08 | Membranes containing poly(vinyl methyl ether) and hydrophilisation of membranes using poly(vinyl methyl ether) |
US10/564,024 US7662212B2 (en) | 2003-07-08 | 2004-07-08 | Membrane post treatment |
AU2004253197A AU2004253197B2 (en) | 2003-07-08 | 2004-07-08 | Membrane post treatment |
US12/647,734 US8057574B2 (en) | 2003-07-08 | 2009-12-28 | Membrane post treatment |
US13/206,845 US8262778B2 (en) | 2003-07-08 | 2011-08-10 | Membrane post treatment |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2003903507A AU2003903507A0 (en) | 2003-07-08 | 2003-07-08 | Membrane post-treatment |
AU2003903507 | 2003-07-08 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/564,024 A-371-Of-International US7662212B2 (en) | 2003-07-08 | 2004-07-08 | Membrane post treatment |
US12/647,734 Continuation US8057574B2 (en) | 2003-07-08 | 2009-12-28 | Membrane post treatment |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2005002712A1 true WO2005002712A1 (en) | 2005-01-13 |
Family
ID=31983139
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/AU2004/000922 WO2005002712A1 (en) | 2003-07-08 | 2004-07-08 | Membrane post treatment |
Country Status (8)
Country | Link |
---|---|
US (3) | US7662212B2 (en) |
EP (1) | EP1654053B8 (en) |
JP (2) | JP4908208B2 (en) |
CN (1) | CN1819867B (en) |
AU (1) | AU2003903507A0 (en) |
CA (1) | CA2530805C (en) |
MY (1) | MY144159A (en) |
WO (1) | WO2005002712A1 (en) |
Cited By (20)
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WO2006002469A1 (en) * | 2004-07-02 | 2006-01-12 | U.S. Filter Wastewater Group, Inc | Gas transfer membrane |
WO2006058384A1 (en) * | 2004-12-03 | 2006-06-08 | Siemens Water Technologies Corp. | Membrane post treatment |
WO2006135966A1 (en) * | 2005-06-20 | 2006-12-28 | Siemens Water Technologies Corp. | Cross linking treatment of polymer membranes |
WO2009070381A1 (en) * | 2007-11-30 | 2009-06-04 | Baxter International Inc. | Multizone polymer membrane and dialyzer |
AU2005312347B2 (en) * | 2004-12-03 | 2010-03-25 | Evoqua Water Technologies Llc | Membrane post treatment |
WO2010081511A1 (en) * | 2009-01-16 | 2010-07-22 | Sartorius Stedim Biotech Gmbh | Electron beam induced modification of membranes by polymers |
AU2005259830B2 (en) * | 2004-07-02 | 2010-12-23 | Evoqua Water Technologies Llc | Gas transfer membrane |
WO2011015517A1 (en) | 2009-08-03 | 2011-02-10 | Solvay Solexis S.P.A. | Process for the preparation of ethylene/chlorotrifluoroethylene polymer membranes |
US8057574B2 (en) | 2003-07-08 | 2011-11-15 | Siemens Industry, Inc. | Membrane post treatment |
AU2006314838B2 (en) * | 2005-05-09 | 2012-03-29 | Mabtech Ab | PVDF membranes |
US8999454B2 (en) | 2012-03-22 | 2015-04-07 | General Electric Company | Device and process for producing a reinforced hollow fibre membrane |
US9022229B2 (en) | 2012-03-09 | 2015-05-05 | General Electric Company | Composite membrane with compatible support filaments |
US9061250B2 (en) | 2009-06-26 | 2015-06-23 | Bl Technologies, Inc. | Non-braided, textile-reinforced hollow fiber membrane |
US9132390B2 (en) | 2009-03-26 | 2015-09-15 | Bl Technologies Inc. | Non-braided reinforced holow fibre membrane |
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US9227362B2 (en) | 2012-08-23 | 2016-01-05 | General Electric Company | Braid welding |
US9321014B2 (en) | 2011-12-16 | 2016-04-26 | Bl Technologies, Inc. | Hollow fiber membrane with compatible reinforcements |
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AUPR692401A0 (en) * | 2001-08-09 | 2001-08-30 | U.S. Filter Wastewater Group, Inc. | Method of cleaning membrane modules |
AUPS300602A0 (en) | 2002-06-18 | 2002-07-11 | U.S. Filter Wastewater Group, Inc. | Methods of minimising the effect of integrity loss in hollow fibre membrane modules |
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- 2004-07-08 CN CN2004800192881A patent/CN1819867B/en not_active Expired - Fee Related
- 2004-07-08 JP JP2006517906A patent/JP4908208B2/en not_active Expired - Fee Related
-
2009
- 2009-12-28 US US12/647,734 patent/US8057574B2/en not_active Expired - Fee Related
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2011
- 2011-08-10 US US13/206,845 patent/US8262778B2/en active Active
- 2011-10-14 JP JP2011227009A patent/JP2012040559A/en active Pending
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Also Published As
Publication number | Publication date |
---|---|
US8057574B2 (en) | 2011-11-15 |
US20060157404A1 (en) | 2006-07-20 |
CA2530805C (en) | 2016-01-05 |
US7662212B2 (en) | 2010-02-16 |
EP1654053B1 (en) | 2013-10-02 |
CN1819867A (en) | 2006-08-16 |
MY144159A (en) | 2011-08-15 |
JP2007504934A (en) | 2007-03-08 |
EP1654053A1 (en) | 2006-05-10 |
JP2012040559A (en) | 2012-03-01 |
JP4908208B2 (en) | 2012-04-04 |
EP1654053B8 (en) | 2014-02-26 |
EP1654053A4 (en) | 2008-08-13 |
US20100213117A1 (en) | 2010-08-26 |
US20110290717A1 (en) | 2011-12-01 |
AU2003903507A0 (en) | 2003-07-24 |
US8262778B2 (en) | 2012-09-11 |
CA2530805A1 (en) | 2005-01-13 |
CN1819867B (en) | 2013-03-13 |
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