WO2015113106A2 - Substrats pour séparation huile-eau - Google Patents

Substrats pour séparation huile-eau Download PDF

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Publication number
WO2015113106A2
WO2015113106A2 PCT/AU2015/000042 AU2015000042W WO2015113106A2 WO 2015113106 A2 WO2015113106 A2 WO 2015113106A2 AU 2015000042 W AU2015000042 W AU 2015000042W WO 2015113106 A2 WO2015113106 A2 WO 2015113106A2
Authority
WO
WIPO (PCT)
Prior art keywords
oil
substrate
polyelectrolyte
water separation
coating composition
Prior art date
Application number
PCT/AU2015/000042
Other languages
English (en)
Other versions
WO2015113106A3 (fr
Inventor
Dayang Wang
Xiaokong LIU
Original Assignee
University Of South Australia
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from AU2014900292A external-priority patent/AU2014900292A0/en
Application filed by University Of South Australia filed Critical University Of South Australia
Publication of WO2015113106A2 publication Critical patent/WO2015113106A2/fr
Publication of WO2015113106A3 publication Critical patent/WO2015113106A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F130/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F130/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus

Definitions

  • the present invention relates to substrates, such as membranes, that can be used to separate mixtures of oil and water, to methods for preparing these substrates, and to methods for separating oil and water mixtures using these substrates.
  • Oil and water mixtures can be separated using separation tanks in which the oil is allowed to separate from the water naturally and the oil is then removed from the water.
  • this method is time consuming, inefficient and not particularly suitable for separations using large volumes.
  • More commonly nowadays efficient oil-water separation relies on cross-flow filtration through hydrophobic (superhydrophobic) membranes which allow oil to pass through the membrane whilst retaining water above.
  • hydrophobic membranes which allow oil to pass through the membrane whilst retaining water above.
  • hydrophobic membranes of this type requires high energy input.
  • hydrophilic membranes which can completely repel oil underwater have been used for oil water separation driven only by gravity.
  • hydrophilic membranes can only be used in a water- wetted state because the hydrophilic membranes are easily contaminated by oil in when they are in a dry state. Once a membrane has been contaminated with oil in this way it cannot be used for oil water separation any more.
  • an oil-water separation substrate comprising a porous substrate and a coating formed from an epoxy functionalised polyelectrolyte on said substrate.
  • the oil-water separation substrate is a mesh, fabric, sponge, foam or other nanoporous material.
  • the substrate is a water purification membrane or filter.
  • the epoxy functionalised polyelectrolyte is a poly(ammonium phosphate). In certain specific embodiments, the epoxy functionalised polyelectrolyte has structural formula (I):
  • Rj , R 4 , and R 5 are each independently ( " -(% alkyl;
  • R 2 and R 3 are each independently selected from the group consisting of H and C i-C 2 alkyl; Re, R?, Rx are each independently Cj -C 2 alkyl; and R 9 is selected from the group consisting of CI and Br.
  • the coating formed from the epoxy functionalised polyelectrolyte is cross linked.
  • the coating formed from the epoxy functionalised may be cross linked using a cross linking agent.
  • the cross linking agent may be a polyamine.
  • the polyamine may be a polyamine comprising more than three primary amino groups.
  • the polyamine is selected from the group consisting of poly(allylamine), polyethylenimine (branched), and polyv inyl amine).
  • the polyamine is poly(allylamine).
  • the polyamine may be coated onto the porous substrate w r ith the epoxy functionalised polyelectrolyte or the epoxy functionalised polyelectrolyte may be treated with the polyamine after the former has been coated onto the porous substrate.
  • an epoxy functionalised polyelectrolyte having structural formula (I):
  • Rj , R 4 , and R 5 are each independently ( -( ⁇ alkyl;
  • R 2 and R 3 are each independently selected from the group consisting of H and Ci-C 2 alkyl; R 6 , R 7 , R are each independently Cj -C 2 alkyl; and R 9 is selected from the group consisting of CI and Br.
  • a coating composition for coating a porous substrate to form an oil-water separation substrate comprising an aqueous mixture of an epoxy functionalised polyelectrolyte.
  • the coating composition further comprises a cross linking agent.
  • the cross linking agent may be a polyamine.
  • the polyamine may be a polyamine comprising more than three primary amino groups.
  • the polyamine is selected from the group consisting of poly(allylamine), polyethylenimine (branched), and poly(vinyl amine).
  • the epoxy functionalised polyelectrolyte may be treated with the polyamine after the former has been coated onto the porous substrate.
  • a method for forming an oil-water separation substrate comprising providing a porous substrate and contacting the porous substrate with the coating composition according to the third aspect under conditions to form a coating formed from the epoxy functionalised polyelectrolyte on said substrate.
  • the present invention provides a method for separating oil and water from an oil- water mixture, the method comprising contacting the oil-water mixture with the substrate of the first aspect of the invention under conditions to separate at least some of the oil from the oil-water mixture.
  • Figure 1 shows X-ray photoelectron spectroscopy (XPS) wide scans for a stainless steel mesh without (a) and with (b) an epoxy functionalised PMPC coating.
  • XPS X-ray photoelectron spectroscopy
  • Figure 2 shows a time series of optical photos recorded during the stainless steel meshes (aperture of 100 ⁇ ) were contaminated by Nile red labelled canola oil in air, and then were immersed into water.
  • the left sample is a piece of raw stainless steel mesh and the right one is a piece of stainless steel mesh coated with epoxy functionalised PMPC.
  • Figure 3 shows photographs showing: a. the epoxy functionalised PMPC coated stainless steel mesh is wetted by water; b. oil-water mixture was poured above the epoxy functionalised PMPC coated mesh; c. the oil-water mixture is separated.
  • Figure 4 shows a time series of optical photos recorded during which stainless steel mesh covered plastic tubes were immersed in an oil-water mixture to skim the oil out. It can be observed that the epoxy functionalised PMPC coated mesh can successfully skim the oil out from the oil-water mixture, but the same result cannot be achieved with the raw mesh.
  • the present invention provides an oil-water separation substrate, said substrate comprising a porous substrate and a coating fonned from an epoxy functionalised polyelectrolyte on said substrate.
  • hydrophilic membranes are known for use in separating oil from oil- water mixtures.
  • these membranes tend to be contaminated with oil in a dry state which then renders them not fit for purpose.
  • the substrates of the present invention are hydrophilic, oil-repellent underwater and self-cleaning which means that oil contaminations on the substrate can simply be washed away with water.
  • the substrates of the present invention are particularly suitable for use in oil-water separations and for oil skimming from oil-water mixtures.
  • the fonner property is highly desirable for remediating oil contaminated waters whilst the latter property is highly desired for oil spill remediation.
  • the functional groups of the polyelectrolyte such as the phosphate and ammonium groups of the epoxy functionalised polyelectrolyte of formula (1), have a strong hydration ability and this enables the surface of the substrate to strongly trap water molecules. Even if the surface is contaminated by oil the oil can be replaced by water.
  • the coating can be used for oil-water separation because it can be highly hydrated in water, thus forming a dense water layer which can retain oil above the water layer.
  • the porous substrate may be any flexible, rigid or semi-rigid metal, plastic or ceramic material having pores of a size sufficient to allow water to pass through.
  • the coating comprising the epoxy functionalised polyelectrolyte can be formed on a range of substrate materials and, indeed, its effectiveness as a coating is largely independent of the material used in the substrate.
  • suitable metal substrates that can be used include iron, titanium, aluminium, nickel, copper, and alloys of any of these metals such as steel.
  • the metal substrate may be in the form of a mesh, fabric, sponge, foam or other porous material.
  • Suitable plastic substrates that can be used include polytetrafluoroethylenene (Teflon), polyethylene, polypropylene (PP), polydimethylsiloxane (PDMS), polystyrene (PS), poly(ether sulfone), polyacrylonitrile, cellulose acetate, polyvinylidene fluoride, polysulfone, polyamide, polyurethane, poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP), poly(ethylene terephthalate) (PET), and poly(4-methyl- l -pentene) (PMP).
  • the plastic substrate may be in the form of a mesh, fabric, sponge or foam.
  • the substrate may be any suitable form, such as a membrane, filter, film, boom, and the like. It can be any shape.
  • the porous substrate is in the form of a water purification membrane or filter.
  • the porous substrate is in the form of an elongate, flexible boom that can be used to contain oil spills and/or skim oil from the surface of a body of water.
  • the average pore diameter of the substrate may be in the range of about 50 nm to about 5 mm.
  • the substrate may be a stainless steel mesh with apertures of about 25 ⁇ , about 50 ⁇ or about 100 ⁇ .
  • the epoxy functionalised polyelectrolyte may be any polyelectrolyte having one or more epoxy groups covalently bonded thereto.
  • the polyelectrolyte is a poly(ammonium phosphate).
  • the polyelectrolyte is a poly(tetraalkyl ammonium phosphate).
  • the epoxy functionalised polyelectrolyte has structural formula (I):
  • R R 4 , and R 5 are each independently C1-C3 alkyl
  • R 2 and R 3 are each independently selected from the group consisting of H and C i-C 2 alkyl; [0035] R 6 , R 7 , R 8 are each independently Cj-C 2 alkyl; and [0036] R 9 is selected from the group consisting of CI and Br.
  • the C 1 -C3 alkyl group may be selected from the group consisting of: -CH 2 -, -CH 2 CH 2 -, - CH 2 CH 2 CH 2 -, and -CH 2 (CH 3 )CH 2 -.
  • the Cj-C? alkyl group may be selected from the group consisting of: -CH 2 -, and -CH 2 CH 2 -.
  • a coating formed from an epoxy functionalised polyelectrolyte is used herein because the porous substrate is coated with a coating composition comprising the epoxy functionalised polyelectrolyte which may, in turn, react with functional groups on the substrate.
  • the epoxy group of the epoxy functionalised polyelectrolyte may react with hydroxy or amino groups on the substrate and, therefore, after coating not all of the molecules in the coating may be in the form of the epoxy functionalised polyelectrolyte.
  • the epoxy functionalised polyelectrolyte in the coating may be cross linked using a cross linking agent.
  • the cross linking agent may be a multifunctional molecule having two or more functional groups that are capable of reacting with functional groups of the epoxy functionalised polyelectrolyte.
  • the cross linking agent is a polyamine and the coating is formed from the epoxy fiinctionalised polyelectrolyte and the polyamine.
  • the polyamine may be a polyamine comprising more than three primary amino groups.
  • the polyamine is selected from the group consisting of poly(allylamine), polyethylenimine (branched), and poly(vinyl amine).
  • the polyamine is poly(allylamine).
  • the epoxy functionalised polyelectrolyte may be cross linked during coating of the porous substrate with the epoxy functionalised polyelectrolyte or the epoxy functionalised polyelectrolyte may be treated with the cross linking agent after the former has been coated onto the porous substrate.
  • the polyamine may be coated onto the porous substrate with the epoxy functionalised polyelectrolyte or the epoxy functionalised polyelectrolyte may be treated with the polyamine after the former has been coated onto the porous substrate.
  • the primary amine groups of the polyamine react with the epoxy groups of the epoxy functionalised polyelectrolyte to form a cross-linked composite.
  • Polyamines comprising more than three primary amino groups are particularly suitable for this purpose.
  • Polyamines that can be used include poly(allylamine), polyethylenimine (branched), and polyvinyl amine). Without intending to be bound by any specific theory, we suggest that the polyamine facilitates the adhesion of the epoxy functionalised polyelectrolyte onto the substrate and improve the coating stability because the primary amine groups react with the epoxy groups to cross link the epoxy functionalised polyelectrolyte.
  • an aqueous coating composition comprising the epoxy functionalised polyelectrolyte and polyamine (if present) is formed.
  • the concentration of the epoxy functionalised polyelectrolyte in the aqueous coating composition may be from about 0.05 mg/mL to about 500 mg/mL.
  • the concentration of the polyamine in the coating composition may be from about 0.01 mg/mL to about 100 mg/mL.
  • the concentration of the epoxy functionalised polyelectrolyte in the aqueous coating composition is about 5 mg/mL and the concentration of the polyamine in the coating composition (if present) is about 1 mg/mL.
  • the mass ratio of epoxy functionalised polyelectrolyte to polyamine in the coating composition may be in the range of 5000: 1 to 5: 1.
  • the coating composition can contain solvents, excipients and/or additives as required.
  • the coating composition may contain conventional coating adjuvants, such as, for example, tackifiers, pigments, extenders, emulsifiers, crosslinkers, coalescing agents, buffers, neutralisers, thickeners or rheology modifiers, humectants, wetting agents, biocides, plasticisers, antifoaming agents, colorants, waxes, anti-oxidants, and the like.
  • the present invention provides an epoxy functionalised polyelectrolyte having structural formula (I):
  • R 1 ; R 4 , and R 5 are each independently C 1-C3 alkyl;
  • R 2 and R 3 are each independently selected from the group consisting of H and C i-C 2 alkyl;
  • R 6 , R 7 , R 8 are each independently C
  • the present invention also provides a method for forming an oil-water separation substrate, the method comprising providing a porous substrate and contacting the porous substrate with a coating composition comprising an epoxy functionaliscd polyelectrolyte to form a coating fonned from the epoxy functionalised polyelectrolyte on said substrate.
  • the surface of the substrate may be contacted with the coating composition by conventional application methods such as dip coating, spin coating, spray coating, curtain coating, roller coating, and the like.
  • the surface of the substrate is contacted with the aqueous coating composition by dipping the substrate into the coating composition for a time and at a temperature that results in adsorption of at least some of the coating materials to the surface of the substrate.
  • the substrate is immersed in the coating composition for a period of from about 1 hour to about 36 hours. In specific embodiments, the immersion time is 24 hours.
  • the thickness of the coating that is deposited on the surface of the substrate will depend, at least in part, on the l ength of time the substrate is immersed in the coating composition. The thickness may be between about 2 nm and about 1000 nm.
  • the substrate After removal from the coating composition the substrate is typically dried, or allowed to dry, to form a film on the surface.
  • the solvent can be removed by diying the coating composition at room temperature or at elevated temperature (e.g. from about 5°C to about 95°C).
  • the substrate can also be dried using a stream of air or nitrogen or at reduced pressure, if necessary.
  • the coating composition will normally be applied so as to provide a substantially uniform application of the coating composition onto the surface of the substrate and the formation of a continuous layer on the substrate.
  • the coating composition can be applied so as to form a discontinuous layer on the substrate.
  • the coating may cover the whole of the surface to which it is appl ied or it may cover only part of the surface to which it is applied.
  • the substrate is a water purification membrane or filter.
  • Membranes of this type are typically made from poly(ether sulfone), polyacrylonitrile or polyvinylidene fluoride and are commonly used in water or wastewater filtration.
  • the coating described herein separates oil from oil contaminated water that is passed through the membrane or filter.
  • the methods of the present invention provide a relatively simple, and therefore inexpensive, way to separate oil from water and can be used for a range of applications such as remediation of oil
  • the substrates of the present invention could also be used to separate two immiscible oils.
  • the present invention also provides a method for separating oil and water from an oil-water mixture, the method comprising contacting the oil-water mixture with the substrate of the first aspect of the invention under conditions to separate at least some of the oil from the oil-water mixture.
  • a coating composition comprising an aqueous solution of the epoxy functionalised PMCP was prepared by dissolving the epoxy functionalised PMCP from Example 1 in water at a concentration of 5mg/mL.
  • a coating composition comprising an aqueous solution of the epoxy functionalised PMCP and poly(allylamine) was prepared by dissolving the epoxy functionalised PMCP from Example 1 in water at a concentration of 5mg/mL and poly(allylkamine) (A/ w ⁇ 58000) at a concentration of 1 mg/mL.
  • Example 4 Preparation of coated stainless steel meshes for oil-water separation
  • Stainless steel mesh with aperture of 100 ⁇ was successively cleaned by sonication in acetone, iso-propanol and ethanol for 10 min for each step.
  • the cleaned stainless steel mesh was dried using N 2 and then immersed in the coating composition of Example 2 for 24 h.
  • the stainless steel mesh was then rinsed by water and dried by N 2 .
  • the epoxy functionalised PMPC coated stainless steel meshes exhibit excellent self-cleaning properties. Specifically, the oil contamination on the meshes can be easily and completely washed away by water without aid of any surfactant.
  • the epoxy functionalised PMPC coated stainless steel meshes exhibit perfect oil repellence in water. Therefore, the epoxy functionalised PMPC coated stainless steel meshes can be used for oil-water separation.
  • the epoxy functionalised PMPC coated stainless steel mesh can be used for oil skimming.
  • Example 5 Preparation of coated stainless steel meshes for oil-water separation
  • a coated stainless steel mesh with aperture of 100 ⁇ can be prepared using the coating composition of Example 3 and the coating method described in Example 4.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention concerne un substrat de séparation huile-eau comprenant un substrat poreux et un revêtement formé à partir d'un polyélectrolyte à fonctionnalité époxy sur ledit substrat.
PCT/AU2015/000042 2014-01-31 2015-01-30 Substrats pour séparation huile-eau WO2015113106A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU2014900292 2014-01-31
AU2014900292A AU2014900292A0 (en) 2014-01-31 Substrates for oil and water separation

Publications (2)

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WO2015113106A2 true WO2015113106A2 (fr) 2015-08-06
WO2015113106A3 WO2015113106A3 (fr) 2016-06-23

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112960788A (zh) * 2021-02-25 2021-06-15 南京市生态环境保护科学研究院 船舶含油洗舱废水回用处理工艺

Family Cites Families (3)

* Cited by examiner, † Cited by third party
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DE69939469D1 (de) * 1998-07-07 2008-10-16 Nof Corp Zusammensetzung zur wundheilung, wundverband und verfahren zur behandlung vonwunden
KR100808116B1 (ko) * 2006-08-22 2008-03-03 전남대학교산학협력단 미생물 점착 방지용 공중합체 수지 코팅재
WO2013017825A1 (fr) * 2011-07-29 2013-02-07 The University Of Sheffield Synthese de copolymeres a blocs

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112960788A (zh) * 2021-02-25 2021-06-15 南京市生态环境保护科学研究院 船舶含油洗舱废水回用处理工艺
CN112960788B (zh) * 2021-02-25 2022-02-15 南京市生态环境保护科学研究院 船舶含油洗舱废水回用处理工艺

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