CN103846014B - A kind of preparation method of low-pressure high-throughput reverse osmosis membrane - Google Patents
A kind of preparation method of low-pressure high-throughput reverse osmosis membrane Download PDFInfo
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- CN103846014B CN103846014B CN201410035927.9A CN201410035927A CN103846014B CN 103846014 B CN103846014 B CN 103846014B CN 201410035927 A CN201410035927 A CN 201410035927A CN 103846014 B CN103846014 B CN 103846014B
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Abstract
The invention discloses a kind of preparation method of low-pressure high-throughput reverse osmosis membrane, comprise the following steps: 1) basement membrane is adhered on glass plate, glass plate is inserted and is immersed in amine aqueous phase monomers solution, after taking-up, remove surface liquid; 2) glass plate insertion is immersed in containing in multifunctional acyl chlorides oil-phase solution, dry after taking out, additive is added in aqueous phase monomers solution in step 1), the addition of additive is the additive that every 100 weight portion aqueous phase monomer solutions add 1-20 weight portion, additive is pyridone analog derivative or hydroxymorpholine analog derivative, the present invention can significantly improve the flux of film, obvious reduction can not be caused to salt rejection rate, additive raw material is cheap and easy to get, be industrialized product, be therefore convenient to industrial amplification production.
Description
Technical field
The present invention relates to a kind of preparation method of reverse osmosis membrane, specifically, the present invention relates to a kind of by adding additive to improve the preparation method of a kind of low-pressure high-throughput reverse osmosis membrane of reverse osmosis membrane flux in aqueous phase monomers solution.
Background technology
Existing commercialization RO film makes flux all lower due to the desalination layer of its surface compact, many researchers are had to add many hydrophilic small molecules additives etc. in aqueous phase and oil phase, the gas porosity of polyamide desalination layer is increased thus the flux of raising film by affecting the degree of reaction etc. in interface polymerization reaction, but the degree that general flux improves is lower, simultaneously owing to increasing the density reducing desalination layer, the salt rejection rate of film is declined more.Such as the more existing people preparing high flux RO film adopts in aqueous phase, adds small molecule alcohol or ethers, thus make the acyl chlorides monomer of itself and oil phase participate in reacting thus reduce the density of desalination layer, also have researcher to add in oil phase to have with polyamide solubility parameters non-protonic solvent relatively as N, dinethylformamide, N, dinethylformamide, dimethyl sulfoxide (DMSO) etc., control the hydrolysis degree of acyl chlorides thus the gas porosity of increase desalination layer.But it is not remarkable that the film properties that these methods are brought promotes effect, if because in these methods, addition is too little, then also very small on the impact of film properties, if addition is too large, one is cause to be deteriorated with the solubility property of aqueous phase oil phase to cause aqueous phase oil-phase solution uneven stable, and two is the sharp-decays causing film properties particularly salt rejection rate.
Summary of the invention
The object of the present invention is to provide a kind of flux significantly improving reverse osmosis membrane, simultaneously the basic preparation method keeping salt rejection rate not have the low-pressure high-throughput reverse osmosis membrane of significant change.
For achieving the above object, technical scheme provided by the invention is: a kind of preparation method of low-pressure high-throughput reverse osmosis membrane, comprise the following steps: 1) basement membrane is adhered on glass plate, glass plate is inserted and is immersed in amine aqueous phase monomers solution, after taking-up, remove surface liquid, 2) glass plate insertion is immersed in containing in multifunctional acyl chlorides oil-phase solution, dry after taking out, additive is added in aqueous phase monomers solution in step 1), the addition of additive is the additive that every 100 weight portion aqueous phase monomer solutions add 1-20 weight portion, additive is pyridone analog derivative or hydroxymorpholine analog derivative, pyridone analog derivative is following one: 4-chlorine-2-hydroxyl pyridine, 2-ethoxy pyridine, 4-pyridone, 2-methyl-3-pyridone, 2-amino-3-pyridone, 3-hydroxyl-2-nitropyridine, hydroxymorpholine analog derivative is following one: 4-hydroxyethyl morpholine, 4-benzyl-2-hydroxymorpholine, 2-hydroxyethyl morpholine, 3-hydroxymethyl morpholine.
The present invention and existingly add Small molecular hydrophilic agent in aqueous phase and oil phase, and non-protonic solvent etc. is added in oil phase, mainly there is following advantage, one be add after effectiveness comparison obvious, the flux of film can be significantly improved, approximately can promote about 50%-70% on the basis of evc flux, two is can not cause obvious reduction to salt rejection rate, this method avoid aqueous phase to add the film salt rejection rate that Small molecular organic reagent causes and obviously reduce, the method is while significantly promoting membrane flux, the salt rejection rate of basic maintenance film reduces amplitude within 1-4 percentage point.Three is that additive raw material is cheap and easy to get, is industrialized product, is therefore convenient to industrial amplification production.For the shortcoming that existing reverse osmosis membrane relative motion pressure is lower compared with flux during Datong District, this technology mainly solves flux and obviously promotes.
Accompanying drawing explanation
When considered in conjunction with the accompanying drawings, by referring to detailed description below, more completely can understand the present invention better and easily learn wherein many adjoint advantages, but accompanying drawing described herein is used to provide a further understanding of the present invention, form a part of the present invention, schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention, wherein:
Fig. 1 reverse osmosis membrane prepared by embodiment 1 retains test result to NaCl solution;
Fig. 2 reverse osmosis membrane prepared by embodiment 2 retains test result to NaCl solution;
Fig. 3 reverse osmosis membrane prepared by embodiment 3 retains test result to NaCl solution;
Fig. 4 reverse osmosis membrane prepared by embodiment 4 retains test result to NaCl solution;
Fig. 5 reverse osmosis membrane prepared by embodiment 5 retains test result to NaCl solution.
Detailed description of the invention
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, and below in conjunction with the drawings and specific embodiments, the present invention is further detailed explanation.
Reverse osmosis membrane separation performance test
Be for feed liquid with the NaCl aqueous solution of 250mg/L, reverse osmosis membrane is adopted to evaluate the osmotic water flux of instrument mensuration Nano filtering composite membrane, related concentrations is released by the electrical conductivity of the electrical conductivity and diffusate that measure feeding liquid, then salt rejection rate is calculated according to formula 1, formula (2) calculates the osmotic water flux of film, film effective area is 23.75cm2, tests pressure used and is 0.3MPa.
(C
f-feeding liquid concentration, C
p-diffusate concentration) (1)
(volume of V-infiltration water, the effective area of A-film, t-time) (2)
Embodiment: 1:
The m-phenylene diamine (MPD) solution of preparation 3wt% mass fraction, add the 4-chlorine-2-hydroxyl pyridine (addition comprises 2wt%, 4wt%, 6wt%) of different quality mark wherein simultaneously, then after stirring, prepare the hexane solution of the polyfunctional group acyl chlorides of 0.08wt% again, then glass plate is inserted in aqueous phase solution on a glass, after placing 10s by fixing for polysulphone super-filter membrane sheet (molecular cut off about 68000), take out glass plate, after then being dried by the aqueous phase on film surface.Again glass plate is inserted in oil-phase solution, after placing 10s, take out glass plate, after the organic solvent on film surface volatilizees completely, namely obtained high-throughout reverse osmosis membrane, the film bubble of preparation is entered in pure water to be measured.The present embodiment retains test result as shown in Figure 1 to NaCl solution.
Embodiment 2:
The m-phenylene diamine (MPD) solution of preparation 3wt% mass fraction, add the 3-hydroxymethyl morpholine (addition comprises 2wt%, 4wt%, 6wt%) of different quality mark wherein simultaneously, then after stirring, prepare the hexane solution of the polyfunctional group acyl chlorides of 0.08wt% again, then glass plate is inserted in aqueous phase solution on a glass, after placing 10s by fixing for polysulphone super-filter membrane sheet (molecular cut off about 68000), take out glass plate, after then being dried by the aqueous phase on film surface.Again glass plate is inserted in oil-phase solution, after placing 10s, take out glass plate, after the organic solvent on film surface volatilizees completely, namely obtained high-throughout reverse osmosis membrane, the film bubble of preparation is entered in pure water to be measured.The present embodiment retains test result as shown in Figure 2 to NaCl solution.
Embodiment 3:
The m-phenylene diamine (MPD) solution of preparation 3wt% mass fraction, add 4-chlorine-2-hydroxyl pyridine, 2-ethoxy pyridine, 4-hydroxyethyl morpholine, the 4-benzyl-2-hydroxymorpholine of 4wt% mass fraction wherein respectively simultaneously, then after stirring, prepare the hexane solution of the polyfunctional group acyl chlorides of 0.08wt% again, polysulphone super-filter membrane sheet (molecular cut off about 68000) is fixed on a glass, then glass plate is inserted in aqueous phase solution, after placing 10s, take out glass plate, after then being dried by the aqueous phase on film surface.Again glass plate is inserted in oil-phase solution, after placing 10s, take out glass plate, after the organic solvent on film surface volatilizees completely, namely obtained high-throughout reverse osmosis membrane, the film bubble of preparation is entered in pure water to be measured.The present embodiment retains test result as shown in Figure 3 to NaCl solution.
Embodiment 4:
The m-phenylene diamine (MPD) solution of preparation 3wt% mass fraction, add 4-pyridone, 2-methyl-3-pyridone, 2-amino-3-pyridone, the 3-hydroxyl-2-nitropyridine of 4wt% mass fraction wherein simultaneously, 2-hydroxyethyl morpholine, then after stirring, prepare the hexane solution of the polyfunctional group acyl chlorides of 0.08wt% again, polysulphone super-filter membrane sheet (molecular cut off about 68000) is fixed on a glass, then glass plate is inserted in aqueous phase solution, after placing 10s, take out glass plate, after then being dried by the aqueous phase on film surface.Again glass plate is inserted in oil-phase solution, after placing 10s, take out glass plate, after the organic solvent on film surface volatilizees completely, namely obtained high-throughout reverse osmosis membrane, the film bubble of preparation is entered in pure water to be measured.The present embodiment retains test result as shown in Figure 4 to NaCl solution.
Embodiment 5:
The m-phenylene diamine (MPD) solution of preparation 3wt% mass fraction, add the 2-hydroxyethyl morpholine of 1wt%-20wt% mass fraction wherein simultaneously, then after stirring, prepare the hexane solution of the polyfunctional group acyl chlorides of 0.08wt% again, then glass plate is inserted in aqueous phase solution on a glass, after placing 10s by fixing for polysulphone super-filter membrane sheet (molecular cut off about 68000), take out glass plate, after then being dried by the aqueous phase on film surface.Again glass plate is inserted in oil-phase solution, after placing 10s, take out glass plate, after the organic solvent on film surface volatilizees completely, namely obtained high-throughout reverse osmosis membrane, the film bubble of preparation is entered in pure water to be measured.The present embodiment retains test result as shown in Figure 5 to NaCl solution.
Obviously, the many modifications and variations that those skilled in the art do based on aim of the present invention belong to protection scope of the present invention.
The explanation of above example just understands core concept of the present invention for helping; Meanwhile, for one of ordinary skill in the art, according to thought of the present invention, all will change in specific embodiments and applications, in sum, this description should not be construed as limitation of the present invention.
Claims (1)
1. a preparation method for low-pressure high-throughput reverse osmosis membrane, comprises the following steps: 1) adhere on glass plate by basement membrane, is inserted by glass plate and is immersed in amine aqueous phase monomers solution, remove surface liquid after taking-up, 2) glass plate insertion is immersed in containing in multifunctional acyl chlorides oil-phase solution, dry after taking out, it is characterized in that, additive is added in aqueous phase monomers solution in step 1), the addition of additive is the additive that every 100 weight portion aqueous phase monomer solutions add 1-20 weight portion, additive is pyridone analog derivative or hydroxymorpholine analog derivative, pyridone analog derivative is following one: 4-chlorine-2-hydroxyl pyridine, 2-ethoxy pyridine, 4-pyridone, 2-methyl-3-pyridone, 2-amino-3-pyridone, 3-hydroxyl-2-nitropyridine, hydroxymorpholine analog derivative is following one: 4-hydroxyethyl morpholine, 4-benzyl-2-hydroxymorpholine, 2-hydroxyethyl morpholine, 3-hydroxymethyl morpholine.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049799A (en) * | 1989-08-30 | 1991-03-13 | 联合信号股份有限公司 | High flux semipermeable membranes |
| CN103143270A (en) * | 2013-03-19 | 2013-06-12 | 中国科学院长春应用化学研究所 | Hydrophilic antiosmosis composite membrane and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049799A (en) * | 1989-08-30 | 1991-03-13 | 联合信号股份有限公司 | High flux semipermeable membranes |
| CN103143270A (en) * | 2013-03-19 | 2013-06-12 | 中国科学院长春应用化学研究所 | Hydrophilic antiosmosis composite membrane and preparation method thereof |
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