CN106914156B - A kind of preparation method of polyvinyl alcohol nanofiltration membrane - Google Patents

A kind of preparation method of polyvinyl alcohol nanofiltration membrane Download PDF

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Publication number
CN106914156B
CN106914156B CN201710228754.6A CN201710228754A CN106914156B CN 106914156 B CN106914156 B CN 106914156B CN 201710228754 A CN201710228754 A CN 201710228754A CN 106914156 B CN106914156 B CN 106914156B
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polyvinyl alcohol
solution
solvent
water
mentioned
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CN106914156A (en
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周勇
郭淼
高从堦
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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    • 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
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • 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
    • 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
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/24—Mechanical properties, e.g. strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/30—Chemical resistance

Abstract

The invention discloses a kind of preparation methods of polyvinyl alcohol nanofiltration membrane, the following steps are included: 1) by ethylene glycol monomethyl ether and the miscible solvent that is made into of deionized water 1:1 in mass ratio, it is separately added into terephthalaldehyde in above-mentioned solvent and mixed solution is made in dodecyl sodium sulfate, above-mentioned mixed solution is heated to 60-65 DEG C of stirring and dissolving, cross-linking agent solution is made；2) polyvinyl alcohol is dissolved in deionized water and the aqueous solution that mass fraction is 0.05-0.1% is made, above-mentioned aqueous solution is heated to 1.5 hours obtained polyvinyl alcohol water solutions of 90-100 DEG C of stirring；3) 1) cross-linking agent solution made from is poured on polysulfones counterdie, stands five minutes and outwell excess of solvent, is put into 28 DEG C of baking oven and dries；Again film surface pour into 2) made from polyvinyl alcohol water solution, be transferred to baking oven and dry film forming at 60-90 DEG C.Prepared polyvinyl alcohol nanofiltration membrane permselective property with higher and stain resistance, method is simple and easy, and modifying agent used is simple and easy to get.

Description

A kind of preparation method of polyvinyl alcohol nanofiltration membrane
Technical field
The invention belongs to filter field of membrane preparation more particularly to a kind of preparation method of polyvinyl alcohol nanofiltration membrane.
Background technique
Polyvinyl alcohol (PVA) is the product of polyvinyl acetate ester hydrolysis, nontoxic for white powder, cotton-shaped or chip solid It is non-corrosive；Stringent linear structure, the cross-linking formation macromolecular network of a large amount of hydroxyl in strand.PVA has good Water-soluble, film forming and caking property, can spontaneously form gel layer.But pure PVA film easily even dissolve in water by swelling, to water and molten Matter has high-permeability simultaneously, or even to salt without rejection.So needing to be modified to improve its water resistance.
Therefore people have carried out the research of the compound membrane modifying of a large amount of PVA, such as use chemical crosslink technique, with band aldehyde radical or carboxyl Substance crosslink and react with PVA, form stable macromolecular network structure, keep separating layer more stable.Cross-linking modified increasing PVA water resistance and mechanical strength are added, but the water penetration of film can simultaneously reduced.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of preparation method of polyvinyl alcohol nanofiltration membrane, film can be made to have Higher permselective property and stain resistance, while preparation method is simple.
Adopt the following technical scheme that thus: a kind of preparation method of polyvinyl alcohol nanofiltration membrane, feature include following step It is rapid:
Step (1) by ethylene glycol monomethyl ether with deionized water 1:1 in mass ratio is miscible is made into solvent, in above-mentioned solvent respectively Terephthalaldehyde is added and mixed solution is made in dodecyl sodium sulfate, it is 0.05- that the mixed solution ingredient, which is mass fraction, 0.5% terephthalaldehyde and mass fraction is the dodecyl sodium sulfate of 0.1-0.3%, and above-mentioned mixed solution is heated to Cross-linking agent solution is made in 60-65 DEG C of stirring and dissolving；
Polyvinyl alcohol is dissolved in deionized water and the aqueous solution that mass fraction is 0.05-0.1% is made by step (2), will be above-mentioned Aqueous solution is heated to 1.5 hours obtained polyvinyl alcohol water solutions of 90-100 DEG C of stirring；
Cross-linking agent solution made from step (1) is poured on polysulfones counterdie by step (3), and standing is outwelled extra molten for five minutes Agent is put into 28 DEG C of baking oven and dries；Polyvinyl alcohol water solution made from step (2) is poured into film surface again, baking oven is transferred to and exists Film forming is dried at 60-90 DEG C.
Preparation method provided by the invention selects terephthalaldehyde to make crosslinking agent, while adding anionic surfactant Dodecyl sodium sulfate pre-processes counterdie, then pours into PVA solution film forming.Anionic surfactant dodecyl sulphur Sour sodium is white powder substance, dissolves in pure water, and after ionizing in water, fatty acid radical anion plays surface-active action, can The wellability for significantly improving counterdie facilitates PVA and is uniformly securely attached on basement membrane, greatly improves the flux of nanofiltration membrane；Together When terephthalaldehyde can with PVA occur aldolisation cyclization, improve its water resistance and separating property；The phenyl ring of its band can also mention High compound film strength.Therefore prepared polyvinyl alcohol nanofiltration membrane permselective property with higher and stain resistance, film Method is simple and easy, and modifying agent used is simple and easy to get, has good industrial applications prospect.
Specific embodiment
Embodiment 1
By ethylene glycol monomethyl ether with pure water 1:1 in mass ratio is miscible is made into solvent, using its for solvent be added terephthalaldehyde with Dodecyl sodium sulfate mass fraction is respectively 0.1% and 0.15%, and cross-linking agent solution is made in heating stirring dissolution；By polyethylene Alcohol is dissolved in deionized water, and mass fraction 0.05%, 60 DEG C are made aqueous solution in heating stirring 1.5 hours.Cross-linking agent solution is fallen It on polysulfones counterdie, stands five minutes and outwells excess of solvent, be put into 28 DEG C of baking oven until dry out solvent；It is poured into again in film surface Polyvinyl alcohol water solution is dried 10 minutes at 70 DEG C and is formed a film.
It is tested under 0.8MPa pressure, diaphragm permeation flux is 142.5L/m2.h, to Na2SO4With cutting for semixylenol orange Staying rate is respectively 74.7% and 94%.
Embodiment 2
The mass fraction of terephthalaldehyde in change cross-linking agent solution, other steps operating method same as Example 1, Prepare composite membrane and test, obtain the result is as follows:
Embodiment 3
Change cross-linking agent solution in dodecyl sodium sulfate mass fraction, PVA mass fraction 0.1%, other steps with The identical operating method of embodiment 1, prepares composite membrane and tests, obtain the result is as follows:
Embodiment 4
Change the mass fraction of polyvinyl alcohol water solution, terephthalaldehyde mass fraction is 0.2% other steps and implements The identical operating method of example 1, prepares composite membrane and tests, obtain the result is as follows:
Embodiment 5
Change drying temperature when film forming, other steps are same as Example 1.

Claims (1)

1. a kind of preparation method of polyvinyl alcohol nanofiltration membrane, feature the following steps are included:
Step (1) by ethylene glycol monomethyl ether with deionized water 1:1 in mass ratio is miscible is made into solvent, be separately added into above-mentioned solvent Mixed solution is made in terephthalaldehyde and dodecyl sodium sulfate, and it is 0.05-0.5% that the mixed solution ingredient, which is mass fraction, Terephthalaldehyde and mass fraction be 0.1-0.3% dodecyl sodium sulfate, above-mentioned mixed solution is heated to 60-65 DEG C Cross-linking agent solution is made in stirring and dissolving；
Polyvinyl alcohol is dissolved in deionized water and the aqueous solution that mass fraction is 0.05-0.1% is made by step (2), will be above-mentioned water-soluble Liquid is heated to 1.5 hours obtained polyvinyl alcohol water solutions of 90-100 DEG C of stirring；
Cross-linking agent solution made from step (1) is poured on polysulfones counterdie by step (3), is stood five minutes and is outwelled excess of solvent, puts Enter and is dried in 28 DEG C of baking oven；Polyvinyl alcohol water solution made from step (2) is poured into film surface again, is transferred to baking oven in 60-90 Film forming is dried at DEG C.
CN201710228754.6A 2017-04-10 2017-04-10 A kind of preparation method of polyvinyl alcohol nanofiltration membrane Active CN106914156B (en)

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Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108159894A (en) * 2018-01-17 2018-06-15 浙江工业大学 A kind of preparation method of polyvinyl alcohol composite nanometer filtering film
CN109135141A (en) * 2018-08-29 2019-01-04 佛山市森昂生物科技有限公司 A kind of preparation method of Halogen-free flame-retardant polyvinyl alcohol film
CN109126489B (en) * 2018-09-30 2020-10-02 浙江工业大学 Preparation method of small-interception-molecular-weight polysulfone ultrafiltration membrane

Citations (3)

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CN101524626A (en) * 2008-03-07 2009-09-09 浙江欧美环境工程有限公司 External pressure type hollow fiber nano filtering film and preparation method thereof
CN102091538A (en) * 2011-01-10 2011-06-15 杭州水处理技术研究开发中心有限公司 Method for preparing polyvinyl alcohol nanofiltration membrane with high rejection coefficient
CN102814126A (en) * 2011-06-09 2012-12-12 中国科学院城市环境研究所 Preparation method of high-flux antioxidant nanofiltration membrane

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Publication number Priority date Publication date Assignee Title
CN101524626A (en) * 2008-03-07 2009-09-09 浙江欧美环境工程有限公司 External pressure type hollow fiber nano filtering film and preparation method thereof
CN102091538A (en) * 2011-01-10 2011-06-15 杭州水处理技术研究开发中心有限公司 Method for preparing polyvinyl alcohol nanofiltration membrane with high rejection coefficient
CN102814126A (en) * 2011-06-09 2012-12-12 中国科学院城市环境研究所 Preparation method of high-flux antioxidant nanofiltration membrane

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