CN114471162A - Preparation method of composite nanofiltration membrane with adjustable and controllable aperture - Google Patents
Preparation method of composite nanofiltration membrane with adjustable and controllable aperture Download PDFInfo
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- CN114471162A CN114471162A CN202210186781.2A CN202210186781A CN114471162A CN 114471162 A CN114471162 A CN 114471162A CN 202210186781 A CN202210186781 A CN 202210186781A CN 114471162 A CN114471162 A CN 114471162A
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- 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
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- 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
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- 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
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- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
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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
- B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
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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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a preparation method of a composite nanofiltration membrane with adjustable and controllable aperture. Polyvinyl alcohol, glutaraldehyde, boric acid, sodium dodecyl sulfate and concentrated sulfuric acid are used as raw materials, and the nanofiltration composite membrane is obtained by means of acetal reaction between the glutaraldehyde and hydroxyl and condensation reaction between the boric acid and adjacent hydroxyl under a gradient crosslinking process. The aperture of the nanofiltration membrane prepared by the method can be adjusted to 0.34-0.58nm, and the pure water flux of the corresponding membrane is 1.19-19.61 L.m under the working pressure of 0.75MPa‑2·h‑1。
Description
Technical Field
The invention relates to a nanofiltration membrane, in particular to a preparation method of a composite nanofiltration membrane with adjustable and controllable aperture.
Background
Nanofiltration is one of the membrane separation techniques, the separation of which is mainly achieved by means of pore size sieving and charge effects. The nanofiltration membrane has the characteristics of low operating pressure, high removal rate on bivalent or multivalent ions and organic matters with relative molecular mass more than 200, and the like. Currently, the pore size regulation is mainly realized by a phase inversion method and an interface polymerization method, and the pore size regulation is relatively less researched by other methods.
Polyvinyl alcohol is a polymer obtained by alcoholysis of polyvinyl acetate, and has wide application in various fields due to low price, easy availability, good chemical stability and no toxicity. Because the molecular chain of the polyvinyl alcohol contains a large number of hydroxyl groups, the surface of the polyvinyl alcohol film has good hydrophilicity and stain resistance. However, a film made of only polyvinyl alcohol is likely to swell in water and fall off, and thus, many studies have been made on modification of a polyvinyl alcohol film. For example, a chemical crosslinking method is adopted, and a part of hydroxyl groups in polyvinyl alcohol molecules are reacted by a compound which has aldehyde groups, carboxyl groups and the like and can react with the hydroxyl groups on the polyvinyl alcohol molecular chains, so that a compact chemical crosslinking network is formed.
The gradient crosslinking method has the advantages of simple operation, controllable reaction solution amount and the like, and can also adjust the crosslinking degree of a separation layer and the thickness of the film in the reaction process, thereby providing possibility for further modifying the film later.
Disclosure of Invention
The invention aims to provide a preparation method of a composite nanofiltration membrane with adjustable and controllable aperture, which is characterized in that the composite nanofiltration membrane with adjustable and controllable aperture is prepared on an ultrafiltration membrane through acetal crosslinking and esterification crosslinking reaction of ortho-position hydroxyl, aldehyde group and boric acid molecules.
The invention is realized by the following technical scheme:
(a) fixing the ultrafiltration membrane on an epoxy polyester frame by using a clamp, and airing the surface of the ultrafiltration membrane at room temperature;
(b) 0.15% by weight sodium dodecylsulfonate solution is prepared (mixture of ethanol and water as solvent, V)Ethanol：VWater (W)1: 1) then adding a certain amount of boric acid, after the boric acid is dissolved, adding a certain amount of glutaraldehyde and concentrated sulfuric acid, uniformly mixing them to obtain the cross-linking agent solution. Coating the surface of the base film obtained in the step (a) with the solution, removing the excess solution, and drying in an oven at 30 ℃.
(c) Stirring polyvinyl alcohol at 95 ℃ for 2h to obtain a polyvinyl alcohol aqueous solution. And (3) cooling to room temperature, fully soaking the ultrafiltration membrane treated by the cross-linking agent in the step (b) by using a polyvinyl alcohol solution, removing excessive solution, and drying in an oven at 80 ℃ to form the composite nanofiltration membrane with adjustable aperture.
The ultrafiltration membrane in the step (a) is one of polysulfone and polyethersulfone.
The mass fraction of the boric acid in the step (b) is 0.5-2.5%.
The mass fraction of the glutaraldehyde in the step (b) is 0.5-1%.
The mass fraction of the concentrated sulfuric acid in the step (b) is 0.5-1%.
The mass fraction of the polyvinyl alcohol in the step (c) is 0.002% -1%.
The aperture of the aperture-adjustable composite nanofiltration membrane is 0.34-0.58nm, and the pure water flux is 1.19-19.61 L.m under the pressure of 0.75MPa-2·h-1. The invention adopts a gradient cross-linking method, realizes the membrane aperture regulation and control by changing the concentration of the solvent, and can regulate the membrane aperture according to the actual condition.
Has the advantages that: the invention utilizes the gradient cross-linking method with simple preparation process, and the prepared nanofiltration membrane not only can regulate and control the aperture of the membrane, has high stability and good pollution resistance effect, but also has the characteristic of separating mono-salt and divalent salt. The method can prepare the composite nanofiltration membrane with adjustable aperture according to actual conditions, and is suitable for purifying micro-polluted water and tap water.
Detailed Description
The following examples show the pore size of the controllable-pore composite nanofiltration membrane under certain conditions. However, these examples are for illustration only and are not intended to limit the invention.
Example 1:
with a mixture of ethanol and water as solvent (V)Ethanol：VWater (W)1: 1) a crosslinking agent solution was prepared which contained 0.15 wt% of a sodium dodecylsulfate solution, 2.0 wt% of boric acid, 0.5 wt% of glutaraldehyde and 0.5 wt% of concentrated sulfuric acid. And (3) coating the cross-linking agent solution on the surface of the polyether sulfone ultrafiltration membrane, standing for 5 minutes, removing the excessive solution, and drying in an oven at 30 ℃ for 10 minutes. And coating 0.2 wt% of polyvinyl alcohol solution on the surface of the film, and drying in an oven at 80 ℃ after 5 minutes. The membrane obtained after drying is the nanofiltration membrane which has adjustable aperture and is compounded by taking polyether sulfone as a bottom membrane and polyvinyl alcohol as a main separation layer.
Adopting a cross flow testing device, and operating the pressure at 0.75MPaThe pure water flux of the membrane was 70.88 L.m-2·h-1For NaCl and Na2SO4The retention rates of (a) and (b) were 38.19% and 96.62%, respectively.
Examples 2 to 6
In the same way as in example 1, the polysulfone ultrafiltration membrane is used as the bottom membrane, and the mass fraction of polyvinyl alcohol is changed to obtain the composite nanofiltration membrane, and the test results are as follows:
examples 7 to 9
As in example 1, varying the mass fraction of boric acid yielded composite nanofiltration membranes with the following test results:
| examples | Boric acid mass fraction/% | Pure water flux/L.m-2·h-1 | Pore size/nm |
| 7 | 0.5 | 18.60 | 0.38 |
| 8 | 1.0 | 27.45 | 0.41 |
| 9 | 1.5 | 52.13 | 0.48 |
Examples 10 to 13
Like example 1, the polysulfone ultrafiltration membrane was used as the base membrane, the mass fraction of polyvinyl alcohol was 0.5%, and the mass fraction of boric acid was changed to obtain a composite nanofiltration membrane, and the test results were as follows:
Claims (6)
1. a preparation method of a composite nanofiltration membrane with adjustable aperture is characterized by comprising the following steps:
(a) fixing the ultrafiltration membrane on an epoxy polyester frame by using a clamp, and airing the surface of the ultrafiltration membrane at room temperature;
(b) using a mixture of ethanol and water as solvent, VEthanol：VWater (W)1: 1, preparing 0.15 wt% of sodium dodecyl sulfate solution, adding a certain amount of boric acid into the solution, adding a certain amount of glutaraldehyde and concentrated sulfuric acid into the solution after the boric acid is dissolved, and uniformly mixing the solution and the glutaraldehyde to prepare a cross-linking agent solution; coating the solution on the surface of the base film obtained in the step a, removing the excessive solution, and drying in a drying oven at 30 ℃;
(c) stirring polyvinyl alcohol at 95 ℃ for 2h to obtain a polyvinyl alcohol aqueous solution; and (c) cooling to room temperature, fully soaking the ultrafiltration membrane obtained in the step (b) by using a polyvinyl alcohol solution, removing excessive solution, and drying in an oven at 80 ℃ to form the composite nanofiltration membrane with adjustable aperture.
2. The method for preparing the composite nanofiltration membrane with the adjustable pore size according to claim 1, wherein the ultrafiltration membrane in the step a is one of polysulfone and polyethersulfone.
3. The method for preparing the composite nanofiltration membrane with the adjustable pore size according to claim 1, wherein the mass fraction of boric acid in the step b is 0.5-2.5%.
4. The method for preparing the composite nanofiltration membrane with the controllable pore diameter according to claim 1, wherein the mass fraction of glutaraldehyde in the step b is 0.5-1%.
5. The method for preparing the composite nanofiltration membrane with the adjustable pore diameter according to claim 1, wherein the mass fraction of the concentrated sulfuric acid in the step b is 0.5-1%.
6. The method for preparing the composite nanofiltration membrane with the adjustable pore size according to claim 1, wherein the mass fraction of polyvinyl alcohol in the step c is 0.002% -1%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202210186781.2A CN114471162A (en) | 2022-02-28 | 2022-02-28 | Preparation method of composite nanofiltration membrane with adjustable and controllable aperture |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210186781.2A CN114471162A (en) | 2022-02-28 | 2022-02-28 | Preparation method of composite nanofiltration membrane with adjustable and controllable aperture |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050011826A1 (en) * | 2001-07-20 | 2005-01-20 | Childs Ronald F. | Asymmetric gel-filled microporous membranes |
| 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 |
| CN112295418A (en) * | 2019-07-30 | 2021-02-02 | 上海恩捷新材料科技有限公司 | Polyethylene-based composite graphene oxide nanofiltration membrane and preparation method thereof |
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2022
- 2022-02-28 CN CN202210186781.2A patent/CN114471162A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050011826A1 (en) * | 2001-07-20 | 2005-01-20 | Childs Ronald F. | Asymmetric gel-filled microporous membranes |
| 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 |
| CN112295418A (en) * | 2019-07-30 | 2021-02-02 | 上海恩捷新材料科技有限公司 | Polyethylene-based composite graphene oxide nanofiltration membrane and preparation method thereof |
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Application publication date: 20220513 |