CN105983348A - Preparation method for polyesteramide composite nanofiltration membrane - Google Patents
Preparation method for polyesteramide composite nanofiltration membrane Download PDFInfo
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- CN105983348A CN105983348A CN201510100056.9A CN201510100056A CN105983348A CN 105983348 A CN105983348 A CN 105983348A CN 201510100056 A CN201510100056 A CN 201510100056A CN 105983348 A CN105983348 A CN 105983348A
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Abstract
The invention discloses a preparation method for a polyesteramide composite nanofiltration membrane. A polysulfone or polyvinylidene fluoride slab or a hollow fiber ultrafiltration membrane is adopted as a base membrane, the surface of the membrane is subjected to dip coating of an ethanol solution with the concentration being 0.05-2.0%, drying is performed under the room temperature for 1-60 min, the surface is subjected to drip-coating of a trimesoyl chloride solution with the concentration being 0.01-0.30%, drying is performed under the room temperature for 1-60 min, the membrane is placed into an oven under the temperature of 30-120 DEG C for thermal treatment for 1-30 min, and the polyesteramide composite nanofiltration membrane can be prepared. The base membrane of the composite nanofiltration membrane is one of the polysulfone or polyvinylidene fluoride slab and hollow fiber ultrafiltration membrane; the surface of the prepared composite nanofiltration membrane is of electronegativity in a neutral solution, the flux is high, the service life is long, and the good retention effect on a conventional divalent ion salt solution and micromolecule organic dye is achieved. The preparation method is simple in technology, low in cost and capable of obtaining the composite nanofiltration membrane through industrial scaling-up.
Description
Technical field
The present invention relates to technical field of membrane separation, the preparation method of specially a kind of polyesteramide composite nanometer filtering film.
Background technology
Nanofiltration (Nanofiltration, NF) be 20th century the mid-80 grow up between ultrafiltration and counter-infiltration, belong to pressure-actuated new membrane isolation technics.It is suitable for separating relative molecular mass at 200 Da
Above, molecular size is about the dissolved constituent of 1 nm, it is considered that it retains relative molecular mass between 200-1000, is generally 40%～90% to the rejection of NaCl, is up to 99% to the rejection of divalence or high valence ion.It is generally less than 1.5 MPa, also referred to as low-pressure reverse osmosis membrane or loose reverse osmosis membrane owing to operating pressure.The aperture of NF membrane is usually 1-10 nm, and it is charged simultaneously, charged nanofiltration membrane can by electrostatic repulsion repel in solution with the electrically charged identical ion of institute on film, by electrostatic attraction adsorb with electrically charged contrary ion.Therefore, the separating property to material for the charged membrane is mainly based upon the nanometer level microporous sieve effect of electric charging effect and film.Its filter area, between counter-infiltration and ultrafiltration, has promoted membrane technology and the development in related application field, and has been used widely in the fields such as petrochemical industry, biochemistry and medicine, food, papermaking, textile printing and dyeing and water treatment procedure.
Document (J. Membr.
Sci, 2008,320,198-205) report the synthetic method of a kind of polyester NF membrane.Owing to the ester group generated in interface polymerization reaction process is more flexible, thus form fine and close network structure, cause less (the J=11.5 L/m of flux in water treatment procedure for this film2H).Simultaneously as the impact of dense skin thickness, further nucleophilic displacement of fluorine polycondensation reaction generates with high-crosslinking-degree HMW and the longitudinal degree of depth increasing film, thus affects the combination property of final membrane material.Document (J. Membr.
Sci, 2014,465,41-48) also report a kind of synthetic method preparing polyester NF membrane with dopamine for aqueous phase monomers.But membrane flux drastically declines with the increase of dopamine concentration, thus causing the function of film to deteriorate, quality declines.On the whole, this few class NF membrane all employ in preparation technology that some are relatively costly also or have monomer or the polymer of nerve/skin toxins, will inevitably bring fringe cost and environmental hazard in industrial applications.
Content of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of with polysulfones Flat Membrane, polyvinylidene fluoride flat film, one in ps hollow fiber uf membrane or Pvdf Microporous Hollow Fiber Membrane is basement membrane, and is prepared the preparation method of the composite nanometer filtering film of polyesteramide functional layer by interfacial polymerization on this surface.This preparation method selects the monomer AEEA of commercialization, with low cost and environmentally friendly；This composite nanometer filter membrane product manufacturing process is simple, and combination property is good.
Realize the technical scheme is that the preparation method of a kind of polyesteramide composite nanometer filtering film, with polysulfones or polyvinylidene fluoride flat or hollow fiber ultrafiltration membrane as basement membrane, surface dip-coating concentration is the AEEA aqueous solution of 0.05-2.0 wt%, natural drying or dry after 1-60 min under room temperature, then at the pyromellitic trimethylsilyl chloride solution that its surface dip-coating concentration is 0.01-0.30 wt%, it after drying in the shade under room temperature or drying 1-60 min, is placed in 30-120 in baking ovenoC heat treatment time 1-30 min can be prepared by polyesteramide composite nanometer filtering film.
In the present invention, indication basement membrane is the polysulfones of molecular cut off 10000-50000 or the one of the flat board of Kynoar or hollow fiber ultrafiltration membrane.
Compared with prior art, its remarkable advantage is the present invention:
(1) aqueous phase monomers used in the present invention is AEEA, which is a kind of colourless, light yellow clear thick liquid, it is industrially widely used in producing the aspects such as dyestuff, resin, rubber, flotation agent, insecticide, surfactant, there is the advantages such as with low cost, Stability Analysis of Structures, low toxicity low-corrosiveness；
(2) described technique is simple, it is not necessary to catalyst；Reaction condition is gentle, is that prepared by laboratory or large-scale industrial production provides possibility；
(3) polyesteramide functional layer structure contains hydroxy-acid group, make the surface of film with substantial amounts of negative electrical charge with this divalence retaining in solution and above more expensive state ion, reach to remove the purpose of salinity in solution；
(4) this composite nanometer filtering film is during water treatment applications, and structure and performance are highly stable, it is easy to industrialized production.Using the technology of the present invention, the rejection to sodium sulphate for the obtained composite nanometer filtering film is more than 85%, is more than 93% to organic molecule organic dyestuff (Congo red) clearance, processes at water and has preferable prospect in water softening application.
Brief description
Fig. 1 is HEDA concentration and polyesteramide composite nanometer filter membrane separating property relation schematic diagram of the present invention.
Fig. 2 is TMC concentration and polyesteramide composite nanometer filter membrane separating property relation schematic diagram of the present invention.
Fig. 3 polyesteramide of the present invention composite nanometer filtering film surface Zeta potential and the relation schematic diagram of pH.
Fig. 4 polyesteramide of the present invention composite nanometer filtering film continuous runnability effect schematic diagram.
Detailed description of the invention
The specific embodiment of the present invention is given below, and these embodiments are only used for specifically describing the present invention, do not constitute the restriction to the present patent application claim.
Embodiment 1
(1) polysulfones (PSF) Flat Membrane is immersed in AEEA (HEDA) aqueous phase solution that mass fraction is 0.3% 3 minutes, after under normal temperature, air is dried, it is immersed in the pyromellitic trimethylsilyl chloride oil-phase solution that mass fraction is 0.1% 2 minutes, make organic solvent fully volatilize in atmosphere.
(2) above-mentioned film is placed in puts in baking oven 60oHeat treatment under C obtains polyesteramide composite nanometer filtering film in 5 minutes.
(3) above-mentioned composite nanometer filtering film is put in deionized water and clean, and deposit to be measured in deionized water.
Water treatmenting performance mensuration has been carried out to the composite nanometer filtering film of above-mentioned preparation.Test shows, under 0.5 MPa pressure, the pure water flux of this composite nanometer filtering film is 24.7 L/m2H, to 1.0 g/L sodium sulphate, 1.0 g/L magnesium sulfate and 0.1 g/L Congo red retain respectively the 64.7%th, 42% and 93.3%.
Embodiment 2
(1) polysulfones (PSF) hollow-fibre membrane is immersed in the HEDA aqueous phase solution that mass fraction is 0.5% 3 minutes, after under normal temperature, air is dried, it is immersed in the pyromellitic trimethylsilyl chloride oil-phase solution that mass fraction is 0.1% 2 minutes, make organic solvent fully volatilize in atmosphere.
(2) above-mentioned film is placed in puts in baking oven 60oHeat treatment under C obtains polyesteramide composite nanometer filtering film in 10 minutes.
(3) above-mentioned composite nanometer filtering film is put in deionized water and clean, and deposit to be measured in deionized water.
Water treatmenting performance mensuration has been carried out to the composite nanometer filtering film of above-mentioned preparation.Test shows, under 0.6 MPa pressure, the pure water flux of this composite nanometer filtering film is 14.8 L/m2H, to 1.0 g/L sodium sulphate, 1.0 g/L magnesium sulfate and 0.1 g/L Congo red retain respectively 85.5%, 73.8% and 99.4%.
Embodiment 3
(1) Kynoar (PVDF) Flat Membrane is immersed in the HEDA aqueous phase solution that mass fraction is 1.0% 3 minutes, after under normal temperature, air is dried, it is immersed in the pyromellitic trimethylsilyl chloride oil-phase solution that mass fraction is 0.1% 2 minutes, make organic solvent fully volatilize in atmosphere.
(2) above-mentioned film is placed in puts in baking oven 80oHeat treatment under C obtains polyesteramide composite nanometer filtering film in 10 minutes.
(3) above-mentioned composite nanometer filtering film is put in deionized water and clean, and deposit to be measured in deionized water.
Water treatmenting performance mensuration has been carried out to the composite nanometer filtering film of above-mentioned preparation.Test shows, under 0.5 MPa pressure, the pure water flux of this composite nanometer filtering film is 14.8 L/m2H, to 1.0 g/L sodium sulphate, 1.0 g/L magnesium sulfate and 0.1 g/L Congo red retain respectively 85.5%, 73.8% and 99.35%.
Embodiment 4
(1) Kynoar (PVDF) hollow-fibre membrane is immersed in the HEDA aqueous phase solution that mass fraction is 2.0% 3 minutes, after under normal temperature, air is dried, it is immersed in the pyromellitic trimethylsilyl chloride oil-phase solution that mass fraction is 0.15% 2 minutes, make organic solvent fully volatilize in atmosphere.
(2) above-mentioned film is placed in puts in baking oven 100oHeat treatment under C obtains polyesteramide composite nanometer filtering film in 10 minutes.
(3) above-mentioned composite nanometer filtering film is put in deionized water and clean, and deposit to be measured in deionized water.
Water treatmenting performance mensuration has been carried out to the composite nanometer filtering film of above-mentioned preparation.Test shows, under 0.6 MPa pressure, the pure water flux of this composite nanometer filtering film is 14.8 L/m2H, to 1.0 g/L sodium sulphate, 1.0 g/L magnesium sulfate and 0.1 g/L Congo red retain respectively 83.5%, 74.5% and 99.05%.
Flux and rejection tests (as shown in Figure 1) are carried out to the present invention uses the composite nanometer filtering film prepared by different HEDA concentration.Result shows, with the increase of HEDA concentration, and the pure water flux of film and sodium sulphate, magnesium sulfate, Congo red retaining all are tended towards stability.Wherein the pure water flux of composite nanometer filtering film is about 15.0 L/m2Above-mentioned three kinds of materials are retained respectively greater than the 85%th, 70% and 99% by h.
Flux and rejection tests (as shown in Figure 2) are carried out to the present invention uses the composite nanometer filtering film prepared by different TMC concentration.Result shows, with the increase of HEDA concentration, and the pure water flux of film and sodium sulphate, magnesium sulfate, Congo red retaining all are tended towards stability.Wherein the pure water flux of composite nanometer filtering film is about 15.0 L/m2Above-mentioned three kinds of materials are retained respectively greater than the 85%th, 70% and 99% by h.
Selecting the composite nanometer filtering film in embodiment 2 to carry out the mensuration of surface Zeta potential, result shows, film surface potential is gradually reduced (as shown in Figure 3) with the increase of pH, and the isoelectric point of film is about 6.0.Under neutrallty condition (pH=7.0), film surface is electronegative.
Selecting the composite nanometer filtering film in embodiment 2 to carry out long-time continuous service test (as shown in Figure 4), result shows, runs one week continuously under 0.6 MPa pressure, and it is 15.0 L/m that the pure water flux of this composite nanometer filtering film is maintained at2H is upper and lower, retains 1.0 g/L sodium sulphate also constant about 85.0%, embodies splendid stability.
Claims (6)
1. the preparation method of a polyesteramide composite nanometer filtering film, it is characterized in that, described method is with the one in polysulfones Flat Membrane, polyvinylidene fluoride flat film, ps hollow fiber uf membrane or Pvdf Microporous Hollow Fiber Membrane as basement membrane, the surface dip-coating AEEA aqueous solution, after being dried under room temperature, then at its surface dip-coating pyromellitic trimethylsilyl chloride solution, after being dried under room temperature, it is heat-treated, can be prepared by polyesteramide composite nanometer filtering film again.
2. the preparation method of polyesteramide composite nanometer filtering film according to claim 1, it is characterised in that the mass concentration of the described AEEA aqueous solution is 0.05-2.0%, and time of immersion is 1-60
min。
3. the preparation method of polyesteramide composite nanometer filtering film according to claim 1, it is characterised in that the solvent of described pyromellitic trimethylsilyl chloride solution is n-hexane or Isopar
One in G or its mixing, its mass concentration is 0.01-0.30%, and time of immersion is 1-60 min.
4. the preparation method of polyesteramide composite nanometer filtering film according to claim 1, it is characterised in that be dried under described room temperature and use natural drying or drying.
5. the preparation method of polyesteramide composite nanometer filtering film according to claim 1, it is characterised in that described heat treatment uses oven drying, and heat treatment temperature is 30-120
oC, heat treatment time is 1-30 min.
6. the preparation method of polyesteramide composite nanometer filtering film according to claim 1, it is characterised in that the molecular cut off of described basement membrane is 10000-50000.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106345308A (en) * | 2016-10-13 | 2017-01-25 | 哈尔滨工业大学 | Preparation method for polyesteramide compound nanofiltration membrane with strong chlorine resistance and pollution resistance |
| CN107469644A (en) * | 2017-09-08 | 2017-12-15 | 中国科学技术大学 | A kind of nanofiltration membrane and preparation method thereof |
| CN110327794A (en) * | 2019-06-28 | 2019-10-15 | 杭州天创环境科技股份有限公司 | A kind of preparation method of nanofiltration membrane |
| CN114210213A (en) * | 2021-12-17 | 2022-03-22 | 中化(宁波)润沃膜科技有限公司 | Preparation method of hollow nanofiltration membrane |
| CN115382403A (en) * | 2022-09-06 | 2022-11-25 | 南京理工大学 | Composite membrane with volatile substance interception characteristic for membrane distillation and preparation method thereof |
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| CN1785488A (en) * | 2005-11-09 | 2006-06-14 | 华东理工大学 | Preparation method of polymer hollow fiber composite nano filtering membrane |
| CN101934201A (en) * | 2009-06-29 | 2011-01-05 | 北京时代沃顿科技有限公司 | High-selectivity composite nanofiltration membrane and preparation method thereof |
| CN103768963A (en) * | 2014-01-23 | 2014-05-07 | 南通苏通分离工程科技有限公司 | Preparation method for polyamide composite nanofiltration membrane |
| CN104324619A (en) * | 2014-03-12 | 2015-02-04 | 唐山曹妃甸海清源科技有限公司 | Compound nanofiltration membrane with high selectivity, and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106345308A (en) * | 2016-10-13 | 2017-01-25 | 哈尔滨工业大学 | Preparation method for polyesteramide compound nanofiltration membrane with strong chlorine resistance and pollution resistance |
| CN106345308B (en) * | 2016-10-13 | 2019-06-14 | 哈尔滨工业大学 | A kind of chlorine resistance is strong and the preparation method of resistant to pollution polyesteramide composite nanometer filtering film |
| CN107469644A (en) * | 2017-09-08 | 2017-12-15 | 中国科学技术大学 | A kind of nanofiltration membrane and preparation method thereof |
| CN110327794A (en) * | 2019-06-28 | 2019-10-15 | 杭州天创环境科技股份有限公司 | A kind of preparation method of nanofiltration membrane |
| CN110327794B (en) * | 2019-06-28 | 2021-10-26 | 杭州天创环境科技股份有限公司 | Preparation method of nanofiltration membrane |
| CN114210213A (en) * | 2021-12-17 | 2022-03-22 | 中化(宁波)润沃膜科技有限公司 | Preparation method of hollow nanofiltration membrane |
| CN114210213B (en) * | 2021-12-17 | 2024-04-05 | 中化(宁波)润沃膜科技有限公司 | Preparation method of hollow nanofiltration membrane |
| CN115382403A (en) * | 2022-09-06 | 2022-11-25 | 南京理工大学 | Composite membrane with volatile substance interception characteristic for membrane distillation and preparation method thereof |
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