CN111203104A - Preparation method of reverse osmosis membrane with ultrathin asymmetric polyamide rejection layer - Google Patents
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- 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
- B01D61/025—Reverse osmosis; Hyperfiltration
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- C02F1/00—Treatment of water, waste water, or sewage
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Abstract
The invention discloses a preparation method of a reverse osmosis membrane with an ultrathin asymmetric polyamide interception layer, wherein the reverse osmosis membrane consists of a porous base membrane and the ultrathin asymmetric polyamide interception layer, the ultrathin asymmetric polyamide interception layer is of a double-layer structure, the bottom layer structure is a PIP-TMC polyamide layer, the top layer structure is an MPD-TMC polyamide layer, and the total thickness of the ultrathin asymmetric polyamide interception layer is less than 100 nm; the preparation method comprises the following steps: (1) preparing a PIP-TMC polyamide layer on a porous base membrane by using an interfacial polymerization reaction; (2) and (2) preparing the MPD-TMC polyamide layer on the PIP-TMC polyamide layer obtained in the step (1) by utilizing an interfacial polymerization reaction. The method has the advantages of simple and safe preparation process, easily controlled conditions and low cost, and the prepared reverse osmosis membrane with the ultrathin asymmetric polyamide interception layer greatly improves the water flux of the ultrathin reverse osmosis membrane and improves the interception performance of the ultrathin reverse osmosis membrane to a certain extent.
Description
Technical Field
The invention relates to a preparation method of a reverse osmosis membrane with an ultrathin and asymmetric polyamide rejection layer.
Background
Water resources are indispensable natural resources for human survival development, but the occupancy rate of fresh water resources available for human on the earth is less than 1%, so how to solve the problem that the shortage of water resources is a critical solution for human survival development is solved. The membrane separation technology is widely applied to the fields of brackish water desalination, sewage treatment, seawater desalination and the like due to the advantages of high efficiency, environmental protection, low cost and the like.
The core of the membrane separation technology is a separation membrane, and the design of the membrane material directly determines the quality of the membrane separation performance. Polyamide is a membrane separation material with excellent performance and has been widely used in the field of seawater desalination. Researchers have also attempted to develop higher rejection, high throughput polyamide composite membranes using various methods. Among them, by reducing the thickness of the polyamide separation layer, it is considered as an effective method for directly improving the membrane performance, particularly the throughput.
Science (stage 348, page 1347-1351, 2015) reports that a chromium hydroxide nano-sacrificial layer is formed on an ultrafiltration support membrane as a substrate, the nano-sacrificial layer is previously dipped with an MPD aqueous solution, and a n-hexane layer containing TMC is synthesized into a polyamide ultrathin film through interfacial polymerization. And then removing the nano sacrificial layer through acid dissolution to form an independent nano film attached to the substrate. The thickness of the prepared polyamide selective layer is only 8nm, and the flux is greatly improved.
Environmentscience & Technology (Vol.52, No. 16, p.9341-9349, 2018) reported that a nano-layer of tannin/iron was first supported on a porous membrane of polysulfone, and then an aqueous solution of PIP was dip-coated thereon, and a layer of n-hexane containing TMC was used to synthesize a polyamide ultrathin film by interfacial polymerization. The water flux is greatly improved.
The inventors designed a multi-layer molecular deposition polymerization strategy starting from a 10-20nm initial layer using a bottom-up approach in Journal of Membrane Science (volume 540, 10-18, 2017). The ultra-thin multilayer polyamide membrane composite membrane for desalination is prepared by alternately coating the ultra-low concentration MPD aqueous solution and TMC n-hexane solution, and the flux of the membrane is improved by about 60 percent compared with the flux of a domestic commercial membrane.
From this, it is found that the water flux can be effectively increased by reducing the thickness of the polyamide separation layer. However, Science (356, 6343, 10-18, 2017) proposed that when the polyamide separation layer was reduced to a certain thickness (about less than 100 nm), the effect of increasing the water flux by reducing the thickness of the polyamide separation layer was significantly reduced.
The invention provides a novel ultrathin polyamide separation layer structure and a preparation method thereof based on a high-molecular polymerization technology, and the novel ultrathin polyamide separation layer structure is used for desalting.
Disclosure of Invention
The invention provides a preparation method of a reverse osmosis membrane with an ultrathin asymmetric polyamide rejection layer, which constructs the ultrathin asymmetric polyamide rejection layer consisting of a relatively compact MPD-TMC polyamide top layer with high rejection and a relatively loose PIP-TMC polyamide bottom layer with extremely high water permeability, and improves the water flux and separation performance of the ultrathin polyamide membrane.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a reverse osmosis membrane with an ultrathin asymmetric polyamide rejection layer comprises a porous base membrane and the ultrathin asymmetric polyamide rejection layer, wherein the ultrathin asymmetric polyamide rejection layer is of a double-layer structure, the bottom layer structure is a PIP-TMC polyamide layer, the top layer structure is an MPD-TMC polyamide layer, and the total thickness of the ultrathin asymmetric polyamide rejection layer is less than 100 nm; the preparation method comprises the following steps:
(1) preparing a PIP-TMC polyamide layer on a porous base membrane by using an interfacial polymerization reaction;
(2) and (2) preparing the MPD-TMC polyamide layer on the PIP-TMC polyamide layer obtained in the step (1) by utilizing an interfacial polymerization reaction.
The porous basement membrane can be a commercial ultrafiltration membrane, and preferably is one of a polysulfone ultrafiltration membrane, a polyether sulfone ultrafiltration membrane and a polytetrafluoroethylene ultrafiltration membrane.
Preferably, step (1) is carried out as follows: firstly, soaking the surface of a porous base membrane in 0.001-2 wt% piperazine aqueous solution for 10-300 s, and purging the surface of the porous base membrane with nitrogen to remove redundant piperazine aqueous solution; and then soaking the substrate in 0.001-2 wt% trimesoyl chloride n-hexane solution for 10-300 s, quickly taking out, and preparing the PIP-TMC polyamide layer on the porous base membrane.
As a further preference, the concentration of the aqueous piperazine solution in step (1) is 0.01 wt% to 0.1 wt%, more preferably 0.05 wt%; the concentration of the n-hexane solution of trimesoyl chloride is 0.005 wt% to 0.015 wt%, more preferably 0.01 wt%.
More preferably, in the step (1), the soaking time in the piperazine water solution is 1 to 3 minutes, and more preferably 2 minutes; the soaking time in the n-hexane solution of trimesoyl chloride is 30-90 s, and more preferably 60 s.
Preferably, step (2) is carried out as follows: firstly, soaking the PIP-TMC polyamide layer prepared in the step (1) with a m-phenylenediamine aqueous solution with the concentration of 0.001-2 wt% for 10-300 s, and purging the surface of a polysulfone base membrane with nitrogen to remove redundant m-phenylenediamine aqueous solution; and then soaking the substrate for 10-300 s by using 0.001-2 wt% of trimesoyl chloride n-hexane solution, and then quickly taking out the substrate to obtain the MPD-TMC polyamide layer.
Further preferably, in the step (2), the concentration of the m-phenylenediamine aqueous solution is 0.01 to 0.1 wt%, more preferably 0.05 wt%; the concentration of the trimesoyl chloride n-hexane solution is 0.005 wt% to 0.015 wt%, more preferably 0.01 wt%.
More preferably, in the step (2), the soaking time in the m-phenylenediamine aqueous solution is 1 to 3 minutes, and more preferably 2 minutes; the soaking time in the trimesoyl chloride n-hexane solution is 30-90 s, and more preferably 60 s.
The reverse osmosis membrane with the ultrathin asymmetric polyamide interception layer has good salt interception rate and can be used for brackish water desalination and seawater desalination.
Compared with the prior art, the invention has the advantages that:
1) the method has the advantages of simple preparation process, safety, easily-controlled conditions and low cost. Specifically, the method only takes a commercial grade porous base membrane as a raw material, uses a common chemical reagent, and carries out interface polymerization again only on the basis of a PIP-TMC ultrathin and relatively loose polyamide layer prepared by conventional interface polymerization to obtain a relatively compact polyamide layer of MPD-TMC, namely, the structure of a novel structure of an ultrathin asymmetric polyamide interception layer is completed. Compared with the traditional preparation of polyamide membranes, the method uses lower monomer concentration, so the raw material consumption is smaller.
2) The ultrathin asymmetric interception layer structure constructed by the prepared reverse osmosis membrane with the ultrathin asymmetric polyamide interception layer can further reduce the membrane passing resistance of the ultrathin polyamide composite membrane, greatly improve the water flux of the ultrathin reverse osmosis membrane and improve the interception performance of the ultrathin reverse osmosis membrane to a certain extent.
Drawings
FIG. 1 is a process diagram for preparing a polyamide composite membrane.
FIG. 2 is a scanning electron microscope image of the ultrathin non-aligned polyamide rejection layer composite membrane prepared in example 1, example 2 and example 3.
FIG. 3 is a scanning electron microscope image of conventional ultrathin polyamide composite films prepared in comparative example 1, comparative example 2 and comparative example 3.
Fig. 4 is an atomic force microscope image of example 2 and comparative example 2 supported on a silicon wafer.
FIG. 5 is an SEM image of a porous polysulfone ultrafiltration membrane used in the examples.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples, but the scope of the present invention is not limited thereto:
the porous polysulfone ultrafiltration basement membrane (60-80 micrometers of polyester non-woven fabric layer and 10-50 micrometers of polysulfone layer thickness) used in the embodiment of the invention is from Huzhou research institute of Membrane science and technology center of Zhejiang industry university, and TMC, PIP, MPD and n-hexane (AR) are purchased from Shanghai Arlatin Biotechnology Co., Ltd.
The embodiment of the invention is as follows:
example 1
An aqueous phase containing PIP at a concentration of 0.05% by weight was covered on the membrane surface of a porous polysulfone base porous membrane. And horizontally standing for 2min to enable the PIP aqueous solution to fully infiltrate the surface of the polysulfone membrane. The polysulfone-based membrane surface was then purged with nitrogen to remove excess PIP water phase. Thereafter, on the base film which was left standing horizontally, n-hexane containing TMC at a concentration of 0.01% by weight was slowly poured until it naturally spread on the base film and completely covered the base film. The time was started and the interfacial polymerization time was 1 min. The base film was tilted so that the n-hexane liquid containing TMC flowed away from the film surface. At this point, the time of termination of the interfacial polymerization reaction is regarded as the time of termination. The bottom release layer of polyamide was constructed. And then, placing the membrane at room temperature for about 3-5min to naturally evaporate the n-hexane solution on the surface of the membrane. On the basis of the prepared polyamide membrane, the membrane preparation steps are repeated, the second interfacial polymerization is carried out, only the water-phase monomer is changed from PIP to MPD with the concentration of 0.05 wt%, and the oil solution is still the n-hexane solution with the concentration of 0.01 wt% TMC. The top layer structure of the polyamide separation layer was prepared in the same procedure and method. And finally, obtaining the composite membrane with the ultrathin asymmetric polyamide structure.
Example 2:
the process steps of example 1 were followed, wherein only the concentrations of both MPD and TMC reactive monomers in the second interfacial polymerization were varied. Wherein the concentration of MPD is 0.1% wt and the concentration of TMC is 0.02% wt.
Example 3:
the process steps of example 1 were followed, wherein only the concentrations of both MPD and TMC reactive monomers in the second interfacial polymerization were varied. Wherein the concentration of MPD is 0.2% wt and the concentration of TMC is 0.04% wt
Comparative example 1:
an aqueous phase containing wtMPD at a concentration of 0.05% was coated on the membrane surface of the porous polysulfone base porous membrane. And horizontally standing for 2min to enable the MPD aqueous solution to fully infiltrate the surface of the polysulfone membrane. The polysulfone-based membrane surface was then purged with nitrogen to remove excess PIP water phase. Thereafter, on the base film which was left standing horizontally, n-hexane containing TMC at a concentration of 0.01% by weight was slowly poured until it naturally spread on the base film and completely covered the base film. The time was started and the interfacial polymerization time was 1 min. The base film was tilted so that the n-hexane liquid containing TMC flowed away from the film surface. At this point, the interfacial polymerization reaction is considered to be stopped. Obtaining the traditional ultrathin polyamide composite membrane.
Comparative example 2:
the process steps of comparative example 1 were followed, wherein only the concentrations of both MPD and TMC reactive monomers were varied. Wherein the concentration of MPD is 0.1% wt and the concentration of TMC is 0.02% wt.
Comparative example 3:
the process steps of comparative example 1 were followed, wherein only the concentrations of both MPD and TMC reactive monomers were varied. Wherein the concentration of MPD is 0.2% wt and the concentration of TMC is 0.04% wt.
The physical morphology of the prepared ultrathin polyamide composite film is observed by a field emission scanning electron microscope (Hitachi SU8010), and the result is shown in fig. 2 and 3.
The thickness of the prepared film was measured by an atomic force microscope (AFM, ICON, Bruker, Billerica, MA) and its analysis software, and the results are shown in FIG. 4, in which the thickness of the polyamide layer prepared in example 2 and comparative example 2 was less than 20nm and the Ra value was less than 20 nm.
The ultrathin polyamide composite membrane prepared by the invention is used for a salinity separation experiment and measuring the membrane separation performance. The experimental conditions were a test pressure of 1.6MPa, a test temperature of 25 ℃ and a feed of 2000ppm sodium chloride solution. Generally, the separation performance is expressed in terms of pure water flux J (LMH).
The separation performance of the reverse osmosis membrane was tested as follows: putting the reverse osmosis membrane into a membrane pool, prepressing for 0.5h under 1.6MPa, measuring the water permeability of the reverse osmosis membrane within 1h under the conditions of pressure of 1.6MPa and temperature of 25 ℃, and calculating the pure water flux by the following formula: q is J/(A.t), wherein J is water permeability (L), and QIs the water flux (L/m)-2h-1) A is the effective membrane area (m2) of the reverse osmosis membrane, and t is the time (h). Then, adding a certain amount of sodium chloride into pure water to prepare 2000ppm sodium chloride circulating liquid, continuously circulating for 0.5h, and measuring the conductivity f of the circulating liquid1And the electrical conductivity f of the filtrate2,The rejection rate R of sodium chloride of the membrane was calculated by the following formula as 1-f1/f2The pure water flux Q and the sodium chloride retention rate R are used as the evaluation indexes of the membrane performance. The results of the experimental columns and the comparative examples mentioned herein are shown in table 1, and the pure water flux and the retention performance of the experimental examples are improved, particularly, the pure water flux is improved by 2 to 3 times compared with the comparative examples.
TABLE 1
Claims (10)
1. A preparation method of a reverse osmosis membrane with an ultrathin asymmetric polyamide rejection layer is characterized by comprising the following steps: the reverse osmosis membrane consists of a porous base membrane and an ultrathin asymmetric polyamide interception layer, wherein the ultrathin asymmetric polyamide interception layer is of a double-layer structure, the bottom layer structure is a PIP-TMC polyamide layer, the top layer structure is an MPD-TMC polyamide layer, and the total thickness of the ultrathin asymmetric polyamide interception layer is less than 100 nm; the preparation method comprises the following steps:
(1) preparing a PIP-TMC polyamide layer on a porous base membrane by using an interfacial polymerization reaction;
(2) and (2) preparing the MPD-TMC polyamide layer on the PIP-TMC polyamide layer obtained in the step (1) by utilizing an interfacial polymerization reaction.
2. The method of claim 1, wherein: the porous basement membrane is one of a polysulfone ultrafiltration membrane, a polyether sulfone ultrafiltration membrane and a polytetrafluoroethylene ultrafiltration membrane.
3. The method of claim 1 or 2, wherein: the step (1) is implemented as follows: firstly, soaking the surface of a porous base membrane in 0.001-2 wt% piperazine aqueous solution for 10-300 s, and purging the surface of the porous base membrane with nitrogen to remove redundant piperazine aqueous solution; and then soaking the substrate in 0.001-2 wt% trimesoyl chloride n-hexane solution for 10-300 s, quickly taking out, and preparing the PIP-TMC polyamide layer on the porous base membrane.
4. The method of claim 3, wherein: in the step (1), the concentration of the piperazine water solution is 0.01-0.1 wt%, and the concentration of the n-hexane solution of trimesoyl chloride is 0.005-0.015 wt%.
5. The method of claim 3, wherein: in the step (1), the soaking time in the piperazine water solution is 1-3 minutes, and the soaking time in the n-hexane solution of trimesoyl chloride is 30-90 s.
6. The method of claim 3, wherein: the concentration of the piperazine water solution in the step (1) is 0.05 wt%; the concentration of the trimesoyl chloride n-hexane solution is 0.01 wt%; the soaking time in the piperazine water solution is 2 minutes; the soaking time in the trimesoyl chloride n-hexane solution was 60 seconds.
7. The method of claim 1 or 2, wherein: the step (2) is implemented as follows: firstly, soaking the PIP-TMC polyamide layer prepared in the step (1) with a m-phenylenediamine aqueous solution with the concentration of 0.001-2 wt% for 10-300 s, and purging the surface of a polysulfone base membrane with nitrogen to remove redundant m-phenylenediamine aqueous solution; and then soaking the substrate for 10-300 s by using 0.001-2 wt% of trimesoyl chloride n-hexane solution, and then quickly taking out the substrate to obtain the MPD-TMC polyamide layer.
8. The method of claim 7, wherein: in the step (2), the concentration of the m-phenylenediamine aqueous solution is 0.01-0.1 wt%, and the concentration of the trimesoyl chloride n-hexane solution is 0.005-0.015 wt%.
9. The method of claim 7, wherein: in the step (2), the soaking time in the m-phenylenediamine aqueous solution is 1-3 minutes, and the soaking time in the trimesoyl chloride n-hexane solution is 30-90 s.
10. The method of claim 6, wherein: in the step (2), the concentration of the m-phenylenediamine aqueous solution is 0.05 wt%; the concentration of the trimesoyl chloride n-hexane solution is 0.01 wt%, and the soaking time in the m-phenylenediamine aqueous solution is 2 minutes; the soaking time in the trimesoyl chloride n-hexane solution was 60 seconds.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111841343A (en) * | 2020-07-30 | 2020-10-30 | 河南师范大学 | Asymmetric polyamide nano-film and preparation method thereof |
| CN112246110A (en) * | 2020-10-28 | 2021-01-22 | 湖南澳维环保科技有限公司 | Double-functional-layer composite reverse osmosis membrane and preparation method thereof |
| CN113491955A (en) * | 2021-06-04 | 2021-10-12 | 中国石油大学(华东) | Composite membrane with heterostructure separation layer and preparation method thereof |
| CN113717379A (en) * | 2021-07-27 | 2021-11-30 | 暨南大学 | Method for preparing polyamide membrane through gas-phase polymerization, polyamide membrane and application |
| CN114558465A (en) * | 2020-11-27 | 2022-05-31 | 中国科学院大连化学物理研究所 | Preparation and application of porous nickel hydroxide ion screening membrane |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103071403A (en) * | 2013-01-31 | 2013-05-01 | 北京碧水源膜科技有限公司 | Double desalting layer composite reverse osmosis membrane and preparation method thereof |
| CN108187506A (en) * | 2018-03-20 | 2018-06-22 | 延怀军 | A kind of waste water desalination forward osmosis membrane |
| CN108339403A (en) * | 2018-04-16 | 2018-07-31 | 延怀军 | A kind of water process polyamide forward osmosis membrane |
| CN108905624A (en) * | 2018-06-28 | 2018-11-30 | 杭州电子科技大学 | A kind of polyester-polyamide both sexes charge recombination nanofiltration membrane and preparation method thereof |
-
2020
- 2020-01-17 CN CN202010053956.3A patent/CN111203104A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103071403A (en) * | 2013-01-31 | 2013-05-01 | 北京碧水源膜科技有限公司 | Double desalting layer composite reverse osmosis membrane and preparation method thereof |
| CN108187506A (en) * | 2018-03-20 | 2018-06-22 | 延怀军 | A kind of waste water desalination forward osmosis membrane |
| CN108339403A (en) * | 2018-04-16 | 2018-07-31 | 延怀军 | A kind of water process polyamide forward osmosis membrane |
| CN108905624A (en) * | 2018-06-28 | 2018-11-30 | 杭州电子科技大学 | A kind of polyester-polyamide both sexes charge recombination nanofiltration membrane and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111841343A (en) * | 2020-07-30 | 2020-10-30 | 河南师范大学 | Asymmetric polyamide nano-film and preparation method thereof |
| CN111841343B (en) * | 2020-07-30 | 2022-04-15 | 河南师范大学 | Asymmetric polyamide nano-film and preparation method thereof |
| CN112246110A (en) * | 2020-10-28 | 2021-01-22 | 湖南澳维环保科技有限公司 | Double-functional-layer composite reverse osmosis membrane and preparation method thereof |
| CN114558465A (en) * | 2020-11-27 | 2022-05-31 | 中国科学院大连化学物理研究所 | Preparation and application of porous nickel hydroxide ion screening membrane |
| CN114558465B (en) * | 2020-11-27 | 2022-11-15 | 中国科学院大连化学物理研究所 | Preparation and application of porous nickel hydroxide ion screening membrane |
| CN113491955A (en) * | 2021-06-04 | 2021-10-12 | 中国石油大学(华东) | Composite membrane with heterostructure separation layer and preparation method thereof |
| CN113717379A (en) * | 2021-07-27 | 2021-11-30 | 暨南大学 | Method for preparing polyamide membrane through gas-phase polymerization, polyamide membrane and application |
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Application publication date: 20200529 |