CN110548400A - Large-flux reverse osmosis membrane and preparation method thereof - Google Patents
Large-flux reverse osmosis membrane and preparation method thereof Download PDFInfo
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- CN110548400A CN110548400A CN201910833618.9A CN201910833618A CN110548400A CN 110548400 A CN110548400 A CN 110548400A CN 201910833618 A CN201910833618 A CN 201910833618A CN 110548400 A CN110548400 A CN 110548400A
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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
- B01D61/025—Reverse osmosis; Hyperfiltration
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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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
Abstract
The invention discloses a large-flux reverse osmosis membrane which comprises a non-woven fabric layer, a polysulfone microporous layer and a polyamide layer structure, wherein the polysulfone microporous layer is arranged on one side of the non-woven fabric layer, the polyamide layer structure is arranged on one side of the polysulfone microporous layer, the polysulfone microporous layer is positioned between the non-woven fabric layer and the polyamide layer structure, and the polyamide layer structure comprises a polyamide compact separation layer and a polyamide loose transition layer. Acid-soluble nano particles are introduced into an organic phase monomer solution to form a loose polyamide transition layer containing nano-scale holes, so that a foundation is provided for constructing an ultrathin compact separation layer; meanwhile, the diffusion depth of the water phase monomer m-phenylenediamine is controlled by utilizing a low-temperature preheating treatment mode during the second interface reaction to form an ultrathin compact polyamide separation layer, so that the permeation resistance is greatly reduced, and the permeation efficiency of the reverse osmosis membrane is improved on the premise of not sacrificing the original interception performance; in addition, the raw materials are mature industrial products, the operation is simple, and the application prospect is good.
Description
Technical Field
the invention belongs to the technical field of organic membrane preparation, and particularly relates to a high-flux reverse osmosis membrane and a preparation method thereof.
Background
Water is a source of life and plays a very important role in social development, and especially, the total amount of fresh water is less and less due to unreasonable utilization and the like in the past, and the shortage of water resources becomes a hot concern for human beings in the 21 st century. The reverse osmosis technology is considered to be an effective method for solving the shortage of fresh water resources, and is widely applied to the fields of daily life and industrial production, such as brackish water or seawater desalination, pure water preparation, sewage treatment and the like.
through more than 30 years of research, reverse osmosis membranes are highly developed, and most of the current commercial reverse osmosis membranes adopt polyamide composite membranes prepared by interfacial reaction, such as aromatic polyamide composite membranes and aliphatic polyamide composite membranes, and the desalting performance and the permeability of the polyamide composite membranes are greatly improved. However, under the large background of energy conservation, emission reduction and environmental protection, further improvement of the filtration efficiency of the reverse osmosis membrane and reduction of the operation pressure of the system become an important direction of current research.
The traditional approach for improving the flux of the reverse osmosis composite membrane mainly focuses on optimizing the interfacial polymerization process, for example, adding a phase transfer catalyst, a hydrophilic high molecular material and the like into a water phase to adjust the degree of polymerization reaction, or introducing a water molecule mass transfer channel such as a nano material and the like into a water phase organic phase, but the method has limited amplitude for finally improving the flux of osmosis, and the water flux is obviously improved, but at the cost of losing the desalination rate.
Disclosure of Invention
The invention provides a high-flux reverse osmosis membrane and a preparation method thereof, aiming at overcoming the defects of the prior art.
in order to achieve the purpose, the invention adopts the following technical scheme: a large flux reverse osmosis membrane characterized in that: the polyamide microporous membrane comprises a non-woven fabric layer, a polysulfone microporous layer and a polyamide layer structure, wherein the polysulfone microporous layer is arranged on one side of the non-woven fabric layer, the polyamide layer structure is arranged on one side of the polysulfone microporous layer, the polysulfone microporous layer is positioned between the non-woven fabric layer and the polyamide layer structure, and the polyamide layer structure comprises a polyamide compact separation layer and a polyamide loose transition layer.
a preparation method of a large-flux reverse osmosis membrane comprises the following steps:
S1, uniformly dispersing a certain amount of acid-soluble nano particles into an organic solvent Isopar G, adding trimesoyl chloride with the mass concentration of 0.1-1.0%, and reacting to obtain an organic phase monomer solution;
s2, soaking the polysulfone microporous base membrane into a m-phenylenediamine solution A with the mass concentration of 0.5% -2.0% for 1-5 minutes, and then removing the excessive aqueous solution on the surface for later use;
S3, contacting the polysulfone microporous membrane obtained in the S2 step with the organic phase monomer solution obtained in the S1 step for 1-5 minutes, carrying out preheating treatment for 1-5 minutes, contacting with m-phenylenediamine solution B for 1-7 minutes, and carrying out secondary heat treatment in an oven at 80-100 ℃ for 3-5 minutes to obtain a reverse osmosis composite membrane containing nanoparticles;
s4, immersing the reverse osmosis membrane composite membrane obtained in the S3 step into an acidic aqueous solution for 5-40 minutes, and then washing the membrane composite membrane to be neutral, thereby obtaining the high-flux reverse osmosis membrane.
Preferably, the acidic nanoparticles in step S1 are one or more of aluminum oxide and zinc oxide.
preferably, the diameter of the acidic nanoparticles in step S1 is 20-80 nm.
Preferably, the mass concentration of the acidic nanoparticles in step S1 is 0.1% -2.0%.
Preferably, the pretreatment temperature in step S3 is 20 to 60 ℃.
Preferably, the concentration of the m-phenylenediamine solution B in the step S3 is 0.1 to 1.5% by mass.
preferably, the acidic solution in step S4 is one or more of hydrochloric acid, sulfuric acid, phosphoric acid, and citric acid.
preferably, the acidic solution described in step S4 has a pH of 2 to 4.
Preferably, the reverse osmosis membrane composite membrane in the step S4 is immersed in the acidic aqueous solution for 10 to 30 minutes.
in conclusion, acid-soluble nano particles are introduced into the organic phase monomer solution to form a loose polyamide transition layer containing nano-scale holes, so that a foundation is provided for constructing an ultrathin compact separation layer; the diffusion depth of the water phase monomer m-phenylenediamine is controlled by utilizing a low-temperature preheating treatment mode during the second interface reaction to form an ultrathin and compact polyamide separation layer, so that the permeation resistance is greatly reduced, and the permeation efficiency of the reverse osmosis membrane is improved on the premise of not sacrificing the original interception performance; in addition, the raw materials are mature industrial products, the operation is simple, and the application prospect is good.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
a large-flux reverse osmosis membrane comprises a non-woven fabric layer, a polysulfone microporous layer and a polyamide layer structure, wherein the non-woven fabric layer is a conventional non-woven fabric on the market; the polysulfone microporous layer is coated on the non-woven fabric layer, which is the prior art and therefore is not described in detail herein; the polyamide layer structure comprises a polyamide compact separation layer and a polyamide loose transition layer, wherein the loose polyamide transition layer is formed by introducing acid-soluble nano particles into an interfacial polymerization organic phase, forming a film through preheating treatment, and dissolving and removing the nano particles, and the compact polyamide layer is obtained by adopting a secondary interfacial reaction.
Hereinafter, the present invention will be described in detail with reference to examples of the present invention and comparative examples.
Example 1:
s1, uniformly dispersing 0.1% by mass of aluminum trioxide nanoparticles (with the average particle size of about 20 nm) into an organic solvent Isopar G, adding 0.5% by mass of trimesoyl chloride, and reacting to obtain an organic phase monomer solution;
s2, soaking the polysulfone microporous base membrane into a m-phenylenediamine solution A with the mass concentration of 1.5%, taking out after 2 minutes, and removing excessive water solution on the surface for later use;
S3, contacting the polysulfone microporous membrane obtained in the S2 step with the organic phase monomer solution obtained in the S1 step for 1 minute, preheating at 40 ℃ for 2 minutes, contacting with a m-phenylenediamine solution B with the mass concentration of 1.5 percent for 3 minutes, and performing secondary heat treatment in a baking oven with the temperature of 100 ℃ for 5 minutes to obtain a reverse osmosis composite membrane containing nano particles;
S4, immersing the reverse osmosis membrane composite membrane obtained in the S3 step in an aqueous hydrochloric acid solution at pH 2 for 20 minutes, and then washing to neutrality (the neutrality is pH 7), thereby obtaining a large-flux reverse osmosis membrane;
The separation performance of the reverse osmosis membrane was evaluated by cross-flow permeation, specifically using 2000mg/l aqueous sodium chloride as the feed solution, and controlling the operating pressure at 1.5MPa and the temperature at 25 ℃ as shown in Table 1.
example 2:
S1, uniformly dispersing 0.5 mass percent of aluminum trioxide nanoparticles (the average particle size is about 20 nm) into an organic solvent Isopar G, adding 0.5 mass percent of trimesoyl chloride, and reacting to obtain an organic phase monomer solution;
S2, soaking the polysulfone microporous base membrane into a m-phenylenediamine solution A with the mass concentration of 1.5%, taking out after 2 minutes, and removing excessive water solution on the surface for later use;
S3, contacting the polysulfone microporous membrane obtained in the S2 step with the organic phase monomer solution obtained in the S1 step for 1 minute, preheating at 40 ℃ for 2 minutes, contacting with a m-phenylenediamine solution B with the mass concentration of 1.5 percent for 3 minutes, and performing secondary heat treatment in a baking oven with the temperature of 100 ℃ for 5 minutes to obtain a reverse osmosis composite membrane containing nano particles;
S4, immersing the reverse osmosis membrane composite membrane obtained in the S3 step in an aqueous hydrochloric acid solution at pH 2 for 20 minutes, and then washing to neutrality (the neutrality is pH 7), thereby obtaining a large-flux reverse osmosis membrane;
The separation performance of the reverse osmosis membrane was evaluated by cross-flow permeation, specifically using 2000mg/l aqueous sodium chloride as the feed solution, and controlling the operating pressure at 1.5MPa and the temperature at 25 ℃ as shown in Table 1.
example 3:
s1, uniformly dispersing 0.5% by mass of aluminum trioxide nanoparticles (with an average particle size of about 50 nm) into an organic solvent Isopar G, adding 0.5% by mass of trimesoyl chloride, and reacting to obtain an organic phase monomer solution;
s2, soaking the polysulfone microporous base membrane into a m-phenylenediamine solution A with the mass concentration of 1.5%, taking out after 2 minutes, and removing excessive water solution on the surface for later use;
S3, contacting the polysulfone microporous membrane obtained in the S2 step with the organic phase monomer solution obtained in the S1 step for 1 minute, preheating at 40 ℃ for 2 minutes, contacting with a m-phenylenediamine solution B with the mass concentration of 1.5 percent for 3 minutes, and performing secondary heat treatment in a baking oven with the temperature of 100 ℃ for 5 minutes to obtain a reverse osmosis composite membrane containing nano particles;
s4, immersing the reverse osmosis membrane composite membrane obtained in the S3 step in an aqueous hydrochloric acid solution at pH 2 for 20 minutes, and then washing to neutrality (the neutrality is pH 7), thereby obtaining a large-flux reverse osmosis membrane;
The separation performance of the reverse osmosis membrane was evaluated by cross-flow permeation, specifically using 2000mg/l aqueous sodium chloride as the feed solution, and controlling the operating pressure at 1.5MPa and the temperature at 25 ℃ as shown in Table 1.
Example 4:
S1, uniformly dispersing zinc oxide nano particles (with the average particle size of about 30 nm) with the mass fraction of 0.5% into an organic solvent Isopar G, adding trimesoyl chloride with the mass concentration of 0.5%, and reacting to obtain an organic phase monomer solution;
s2, soaking the polysulfone microporous base membrane into a m-phenylenediamine solution A with the mass concentration of 1.5%, taking out after 2 minutes, and removing excessive water solution on the surface for later use;
S3, contacting the polysulfone microporous membrane obtained in the S2 step with the organic phase monomer solution obtained in the S1 step for 1 minute, preheating at 40 ℃ for 2 minutes, contacting with a m-phenylenediamine solution B with the mass concentration of 1.5 percent for 3 minutes, and performing secondary heat treatment in a baking oven with the temperature of 100 ℃ for 5 minutes to obtain a reverse osmosis composite membrane containing nano particles;
s4, immersing the reverse osmosis membrane composite membrane obtained in the S3 step in an aqueous hydrochloric acid solution at pH 2 for 20 minutes, and then washing to neutrality (the neutrality is pH 7), thereby obtaining a large-flux reverse osmosis membrane;
The separation performance of the reverse osmosis membrane was evaluated by cross-flow permeation, specifically using 2000mg/l aqueous sodium chloride as the feed solution, and controlling the operating pressure at 1.5MPa and the temperature at 25 ℃ as shown in Table 1.
comparative example:
Immersing a polysulfone microporous base membrane into a m-phenylenediamine aqueous phase solution with the mass concentration of 1.5%, removing redundant aqueous solution after 2 minutes, contacting with a solution containing 0.5% of trimesoyl chloride Isopar G for 1 minute, and performing heat treatment in a 100 ℃ oven for 5 minutes to obtain a reverse osmosis composite membrane;
The separation performance of the reverse osmosis membrane was evaluated by cross-flow permeation, specifically using 2000mg/l aqueous sodium chloride as the feed solution, and controlling the operating pressure at 1.5MPa and the temperature at 25 ℃ as shown in Table 1.
Table 1: permeation flux and sodium chloride removal rate of reverse osmosis membrane
The above examples show that the permeation flux of the reverse osmosis membrane prepared by the traditional interfacial polymerization is 55.3l/m 2 h, the rejection rate of sodium chloride is 99.1%, the permeation flux is improved to 63.1l/m 2 h after the aluminum trioxide nano particles with the mass concentration of 0.1% and the particle size of about 20nm are added, and the permeation flux can be further improved to 65.9l/m 2 h after the mass concentration is increased to 0.5%, thus the preparation method of the reverse osmosis composite membrane has a better application prospect.
it is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. a large flux reverse osmosis membrane characterized in that: the polyamide microporous membrane comprises a non-woven fabric layer, a polysulfone microporous layer and a polyamide layer structure, wherein the polysulfone microporous layer is arranged on one side of the non-woven fabric layer, the polyamide layer structure is arranged on one side of the polysulfone microporous layer, the polysulfone microporous layer is positioned between the non-woven fabric layer and the polyamide layer structure, and the polyamide layer structure comprises a polyamide compact separation layer and a polyamide loose transition layer.
2. A preparation method of a large-flux reverse osmosis membrane is characterized by comprising the following steps: the method comprises the following steps:
S1, uniformly dispersing a certain amount of acid-soluble nano particles into an organic solvent Isopar G, adding trimesoyl chloride with the mass concentration of 0.1-1.0%, and reacting to obtain an organic phase monomer solution;
s2, soaking the polysulfone microporous base membrane into a m-phenylenediamine solution A with the mass concentration of 0.5% -2.0% for 1-5 minutes, and then removing the excessive aqueous solution on the surface for later use;
S3, contacting the polysulfone microporous membrane obtained in the S2 step with the organic phase monomer solution obtained in the S1 step for 1-5 minutes, carrying out preheating treatment for 1-5 minutes, contacting with m-phenylenediamine solution B for 1-7 minutes, and carrying out secondary heat treatment in an oven at 80-100 ℃ for 3-5 minutes to obtain a reverse osmosis composite membrane containing nanoparticles;
S4, immersing the reverse osmosis membrane composite membrane obtained in the S3 step into an acidic aqueous solution for 5-40 minutes, and then washing the membrane composite membrane to be neutral, thereby obtaining the high-flux reverse osmosis membrane.
3. The method of claim 2 for preparing a high flux reverse osmosis membrane, wherein: the acidic nanoparticles in step S1 are one or more of aluminum oxide and zinc oxide.
4. The method of claim 2 for preparing a high flux reverse osmosis membrane, wherein: the diameter of the acidic nano-particles in the step S1 is 20-80 nm.
5. The method of claim 2 for preparing a high flux reverse osmosis membrane, wherein: the mass concentration of the acidic nanoparticles in the step S1 is 0.1-2.0%.
6. The method of claim 2 for preparing a high flux reverse osmosis membrane, wherein: the pretreatment temperature in step S3 is 20-60 ℃.
7. The method of claim 2 for preparing a high flux reverse osmosis membrane, wherein: the mass concentration of the m-phenylenediamine solution B in the step S3 is 0.1-1.5%.
8. The method of claim 2 for preparing a high flux reverse osmosis membrane, wherein: the acidic solution in step S4 is one or more of hydrochloric acid, sulfuric acid, phosphoric acid, and citric acid.
9. the method of claim 2 for preparing a high flux reverse osmosis membrane, wherein: the acidic solution described in step S4 has a pH of 2 to 4.
10. a method of preparing a reverse osmosis membrane according to claim 2, wherein: in the step S4, the time of immersing the reverse osmosis membrane composite membrane into the acidic aqueous solution is 10-30 minutes.
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Application publication date: 20191210 |