CN114870645B - Method for improving flux of composite reverse osmosis membrane prepared by interfacial polymerization method - Google Patents

Method for improving flux of composite reverse osmosis membrane prepared by interfacial polymerization method Download PDF

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CN114870645B
CN114870645B CN202210266344.1A CN202210266344A CN114870645B CN 114870645 B CN114870645 B CN 114870645B CN 202210266344 A CN202210266344 A CN 202210266344A CN 114870645 B CN114870645 B CN 114870645B
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reverse osmosis
interfacial polymerization
porous support
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CN114870645A (en
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刘梅红
俞三传
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Zhejiang Sci Tech University ZSTU
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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
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • 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
    • 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
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

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Abstract

The invention relates to a method for improving flux of a composite reverse osmosis membrane prepared by an interfacial polymerization method. On the basis of preparing the polyamide composite membrane by conventional interfacial polymerization, the porous support membrane is heated and dried; quantitatively coating an aqueous phase solution containing polyamine on the dried porous support membrane; quantitatively coating an organic phase solution containing polyacyl chloride on the surface of a porous support membrane containing polyamine; carrying out single-side heat treatment on the separation layer side of the nascent state composite membrane; and carrying out water rinsing treatment on the composite membrane. The method has the advantages that more water molecule transmission channels are formed in the separation layer by utilizing the penetrating effect of the vaporized water phase monomer, the vaporized water phase solvent and the vaporized organic phase solvent on the separation layer in the single-side heat treatment process, the water permeation flux of the composite reverse osmosis membrane is improved, the process is simple, the application range is wide, and the scale is easy to realize.

Description

Method for improving flux of composite reverse osmosis membrane prepared by interfacial polymerization method
Technical Field
The invention relates to a method for improving the flux of a high-molecular separation membrane, in particular to a method for improving the water flux of a composite reverse osmosis membrane prepared by an interfacial polymerization process, and belongs to the technical field of separation membrane preparation. The method has the advantages of wide application range, simple operation, easy scale production and the like, and can effectively realize flux promotion of the composite reverse osmosis membrane, thereby further reducing the energy consumption in the reverse osmosis process.
Background
The membrane separation technology has the advantages of high efficiency, low energy consumption, easy operation and the like, is widely applied to the fields of drinking water purification, wastewater treatment, bio-pharmaceuticals, petrochemical industry and the like, and is an important support technology for solving the problem of water resource shortage and realizing the resource utilization of wastewater at present. Reverse osmosis is widely used in the fields of desalination and purification of water, separation and concentration of materials, reclamation of wastewater and the like as a membrane separation process of molecular level separation. The core of the membrane separation technology is a high-performance separation membrane, and the separation membrane materials currently applied to the field of reverse osmosis mainly comprise two types, namely an asymmetric membrane and a composite membrane. Among them, the composite reverse osmosis membrane prepared by the interfacial polymerization process is a mainstream membrane variety in the reverse osmosis field at present due to excellent water permeability and selective separability.
The composite reverse osmosis membrane is prepared by interfacial polymerization, usually a wet polysulfone porous membrane is used as a supporting layer, and an active separation layer is formed on the porous supporting layer through interfacial polymerization between a polyfunctional monomer dissolved in a water phase and a polyfunctional monomer dissolved in an organic phase immiscible with water through two-side heat treatment and post treatment to obtain the composite reverse osmosis membrane. For example, U.S. Pat. No. 4,277,344 discloses a method for preparing a composite reverse osmosis membrane, which comprises immersing a polysulfone porous support membrane in an aqueous solution containing m-phenylenediamine for a certain period of time, taking out and squeezing, covering the surface of the support membrane with a trimesoyl chloride solution, reacting for a certain period of time, performing two-sided heat treatment on the composite membrane at a certain temperature, and finally rinsing and post-treating to obtain the final composite reverse osmosis membrane. Compared with asymmetric membranes, the composite reverse osmosis membrane has the advantages of thin layering, low permeation resistance and the like, but still has the problems of high use pressure, high operation cost and the like, and restricts the large-scale application of the composite reverse osmosis membrane, particularly the application in the fields of seawater desalination, drinking water purification, water recycling and the like. Therefore, how to improve the permeation flux of the composite reverse osmosis membrane prepared by interfacial polymerization and reduce the operating pressure of the composite reverse osmosis membrane is the key for improving the operating efficiency of the composite reverse osmosis membrane and reducing the operating cost at present.
In the aspect of improving the permeation flux of the composite reverse osmosis membrane, the main way comprises changing the microstructure and the chemical and physical properties of a high-molecular desalting layer of the composite reverse osmosis membrane. For example, the permeation flux of the reverse osmosis membrane can be improved by introducing a phenolic monomer, a hydrophilic macromolecule, or a water-soluble monomer such as isopropanol into an aqueous phase solution of interfacial polymerization, but the introduction of isopropanol, the phenolic monomer or the hydrophilic macromolecule during the interfacial polymerization process easily causes the structure of a separation layer to become loose and the salt interception performance to be reduced; the adjustment of the crosslinking degree and the surface hydrophilicity of the composite membrane can be realized by changing the temperature of the organic phase solution of interfacial polymerization and the content of the crosslinking agent, so that the permeation flux of the composite membrane is improved, but the change of the crosslinking structure improves the water flux while inevitably causing the reduction of the density of a separation layer, and further reducing the retention performance of the membrane on inorganic salt; by carrying out sodium hypochlorite soaking post-treatment on the membrane, the permeation flux of the membrane can also be improved to a certain extent by utilizing the degradation effect of free chlorine on the separation layer, but the service life of the membrane is often shortened.
Therefore, although great progress has been made in improving the permeation flux of the composite reverse osmosis membrane prepared by the interfacial polymerization process, how to improve the permeation flux of the composite reverse osmosis membrane by a simple method without losing the inorganic salt rejection performance and the service life of the composite membrane is still one of the goals pursued by the membrane academia and the membrane industry.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for improving the flux of a composite reverse osmosis membrane prepared by interfacial polymerization, which improves the water permeation flux of the composite reverse osmosis membrane, reduces the operation pressure and improves the operation efficiency.
The technical problem to be solved by the invention is how to fully vaporize residual aqueous phase monomers, aqueous phase solvents and organic phase solvents in the interfacial polymerization process and enable the residual aqueous phase monomers, aqueous phase solvents and organic phase solvents to penetrate through a separation layer in the form of gas molecules in the heat treatment process of a nascent state separation layer obtained by interfacial polymerization, so that more water molecule transmission channels are formed in the finally formed separation layer of a composite membrane, and the water permeation flux of the composite reverse osmosis membrane is improved.
The invention is realized by the following technical scheme:
a method for improving flux of a composite reverse osmosis membrane prepared by an interfacial polymerization method is characterized by comprising the following steps:
(1) Heating and drying the porous support membrane;
(2) Quantitatively coating an aqueous phase solution containing polyamine on the dried porous support membrane;
(2) Quantitatively coating an organic phase solution containing polybasic acyl chloride on the surface of a porous support membrane containing polybasic amine;
(3) Carrying out single-side heat treatment on the separation layer side of the nascent state composite membrane;
(4) And rinsing the composite membrane with water.
Preferably, in the method for improving the flux of the composite reverse osmosis membrane prepared by the interfacial polymerization method, the temperature for heating and drying the porous support membrane is 100-150 ℃ and the time is 30-180 seconds.
Preferably, in the method for improving the flux of the composite reverse osmosis membrane prepared by the interfacial polymerization method, the polyamine is metaphenylene diamine, or methyl metaphenylene diamine, or benzenetriamine, or a mixture of the metaphenylene diamine and the methyl metaphenylene diamine.
Preferably, in the method for improving the flux of the composite reverse osmosis membrane prepared by the interfacial polymerization method, the poly-acyl chloride is trimesoyl chloride, isophthaloyl dichloride, terephthaloyl dichloride or a mixture thereof.
Preferably, in the method for improving the flux of the composite reverse osmosis membrane prepared by the interfacial polymerization method, the temperature of the single-side heat treatment on the separation layer side of the nascent state composite membrane is 110-150 ℃ for 1-10 minutes.
The composite reverse osmosis membrane is a flat membrane, or a hollow fiber membrane, or a tubular membrane.
Has the advantages that:
compared with the existing technology of adopting a wet porous support membrane and carrying out double-sided heat treatment on the nascent state composite membrane, the invention carries out heating and drying treatment on the porous support membrane and carries out single-sided heat treatment on the separation layer side of the nascent state composite membrane, utilizes the penetrating action of a water phase monomer, a water phase solvent and an organic phase solvent on the separation layer after vaporization, and forms more water molecule transmission channels in the separation layer on the premise of not changing the cross-linking structure of the separation layer, thereby realizing the improvement of the water permeation flux of the composite reverse osmosis membrane on the premise of not reducing the interception performance of the membrane, and having simpler process.
Detailed Description
The practice of the present invention is described in detail below.
The following examples provide methods and effects for improving flux of a composite reverse osmosis membrane prepared by an interfacial polymerization method. However, these examples are provided only for illustration and not for limiting the invention.
Preparing a composite reverse osmosis membrane by:
heating and drying the porous support membrane: and (3) carrying out hot air circulation heating and drying treatment on the wet polysulfone support membrane with the aperture of about 30nm at the temperature of 100-150 ℃ for 30-180 seconds.
Preparing a nascent state separation layer by interfacial polymerization: coating an aqueous solution containing 3.0wt% of triethylamine, polyamine, 0.2wt% of sodium dodecyl sulfate and 5.0wt% of camphorsulfonic acid on the surface of the porous support membrane, wherein the coating amount is 300ml/m 2 Drying the surface of the support membrane by using an air knife after staying for 10 seconds; coating n-heptane solution containing polyacyl chloride on the surface of the support membrane in the amount of 300ml/m 2 Residence time ofAnd 60 seconds, and removing excessive organic solution. Wherein the polyamine is metaphenylene diamine, methyl metaphenylene diamine, pyromellitic triamine or their mixture, and the content is 3.0wt%; wherein the polyacyl chloride is trimesoyl chloride, isophthaloyl chloride, terephthaloyl chloride or a mixture thereof, and the content is 0.15wt%.
Heat treatment of the nascent state composite membrane: the separation layer side containing the nascent state composite membrane prepared in the previous step is subjected to heat treatment for 1-10 minutes at the temperature of 110-150 ℃.
Rinsing treatment of composite membrane water: rinsing the prepared composite membrane for 30 minutes by using deionized water at 35-40 ℃.
And (3) evaluating the separation performance of the composite reverse osmosis membrane: the salt rejection rate and the water flux are two important parameters for evaluating the separation performance of the composite reverse osmosis membrane. And evaluating the sodium chloride rejection rate and the water flux of the composite membrane through a cross-flow permeation test.
The salt rejection (R) is defined as: feed solution solute concentration (C) at certain operating conditions f ) With the concentration of solute (C) in the permeate p ) The difference is divided by the feed solution solute concentration. The specific calculation formula is as follows:
Figure BDA0003551939110000041
water flux (F) is defined as: under certain operating conditions, the volume (V) of water per unit membrane area (A) permeated per unit time (t) is expressed in l/m 2 H. The specific calculation formula is as follows:
Figure BDA0003551939110000042
the operation conditions adopted for measuring the separation performance of the composite reverse osmosis membrane are as follows: the feed liquid is 1000mg/l sodium chloride aqueous solution, the operating pressure is 1.0MPa, the operating temperature is 25 ℃, and the pH of the solution is 6.8.
As a result:
comparative examples 1 to 6:
the polyamide composite membrane is prepared by adopting a conventional interfacial polymerization process, the porous support membrane is not dried, and the synchronous double-sided heat treatment is carried out on the two sides of the support layer and the separation layer of the nascent state composite membrane. The separation performance of the prepared composite reverse osmosis membrane is shown in table 1.
Table 1: comparative examples 1 to 6
Figure BDA0003551939110000043
/>
Figure BDA0003551939110000051
Figure BDA0003551939110000061
/>
The above examples show that: the polyamide composite membrane is prepared by adopting a conventional interfacial polymerization process, a porous support membrane is not subjected to drying treatment, and double-sided heat treatment is synchronously performed on the two sides of a support layer and a separation layer of a nascent state composite membrane, so that the composite reverse osmosis membrane with stable performance can be prepared, but the water permeation flux of the composite membrane is low.
Examples 7 to 12:
the polyamide composite membrane is prepared by adopting the prior art, the porous support membrane is dried for 60 seconds at 120 ℃, and the separating layer side of the nascent state composite membrane is subjected to single-side heat treatment for 5 minutes at 110 ℃. The separation performance of the obtained composite reverse osmosis membrane is shown in table 2.
Table 2: examples 7 to 12
Figure BDA0003551939110000062
/>
Figure BDA0003551939110000071
The above examples show that: the porous support membrane is dried and the separation layer side of the nascent state composite membrane is subjected to single-side heat treatment, so that the permeation flux of the composite membrane can be remarkably improved.
Examples 13 to 18:
a composite reverse osmosis membrane was prepared by the same preparation method as in example 7, except that the temperature and time for the drying treatment of the porous support membrane were varied. The separation performance of the prepared composite reverse osmosis membrane is shown in table 3.
Table 3: examples 13 to 18
Figure BDA0003551939110000072
/>
Figure BDA0003551939110000081
The above examples show that: the technological conditions of the heat treatment of the single surface of the separation layer side of the fixed nascent state composite membrane are adopted, different heat treatment technologies are adopted to dry the porous support membrane, the permeation flux of the composite membrane can be obviously improved, and the good correlation is formed between the permeation flux of the composite membrane and the drying temperature of the porous support membrane.
Examples 19 to 23:
a composite reverse osmosis membrane was prepared by the same preparation method as in example 15, except that the temperature and time of the heat treatment of the single side of the separation layer of the nascent state composite membrane were different. The separation performance of the prepared composite reverse osmosis membrane is shown in table 4.
Table 4: examples 19 to 23
Figure BDA0003551939110000091
/>
Figure BDA0003551939110000101
The above examples show that: fixing the temperature and time for drying the porous support membrane, and performing single-side heat treatment on the separation layer side of the nascent state composite membrane by adopting different heat treatment processes, so that the permeation flux of the composite membrane can be remarkably improved, and the better correlation is realized between the permeation flux of the composite membrane and the heat treatment temperature.

Claims (3)

1. A method for improving flux of a composite reverse osmosis membrane prepared by an interfacial polymerization method is characterized by comprising the following steps:
(1) Heating and drying the porous support membrane;
(2) Quantitatively coating an aqueous phase solution containing polyamine on the dried porous support membrane; the polyamine is one or a mixture of m-phenylenediamine, methyl m-phenylenediamine and pyromellitic triamine;
(3) Quantitatively coating an organic phase solution containing polyacyl chloride on the surface of a porous support membrane containing polyamine; the poly-acyl chloride is one or a mixture of more of trimesoyl chloride, isophthaloyl chloride and terephthaloyl chloride;
(4) Carrying out single-side heat treatment on the separation layer side of the nascent state composite membrane; the temperature for carrying out the single-sided heat treatment on the separation layer side of the nascent state composite membrane is 110-150 ℃, and the time is 1-10 minutes;
(5) And carrying out water rinsing treatment on the composite membrane.
2. The method for improving flux of a composite reverse osmosis membrane prepared by an interfacial polymerization method according to claim 1, wherein the temperature for heating and drying the porous support membrane is 100-150 ℃ and the time is 30-180 seconds.
3. The method for improving flux of a composite reverse osmosis membrane prepared by an interfacial polymerization method according to claim 1, wherein the polyamide composite membrane is a flat membrane, a hollow fiber membrane or a tubular membrane.
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JP2012066181A (en) * 2010-09-22 2012-04-05 Asahi Kasei Corp Composite reverse osmosis membrane and manufacturing method therefor
CN105879701B (en) * 2016-05-06 2018-09-25 北京林业大学 A kind of NEW TYPE OF COMPOSITE forward osmosis membrane of two-dimension nano materials inlay and preparation method thereof
CN108786500A (en) * 2018-06-26 2018-11-13 国家***天津海水淡化与综合利用研究所 A kind of one-step method realizes the polyamide reverse osmose membrane and preparation method thereof in the active initiation site in surface
CN109499384A (en) * 2018-11-21 2019-03-22 华东理工大学 A kind of method that hot water post-processing prepares high-flux nanofiltration membrane with pH regulation
CN111841346B (en) * 2020-07-21 2023-04-14 浙江奥氏环境科技有限公司 Preparation method of reverse osmosis membrane
CN111905577A (en) * 2020-08-12 2020-11-10 浙江奥氏环境科技有限公司 Method for reducing content of residual amine of reverse osmosis membrane
CN113351026A (en) * 2021-05-17 2021-09-07 浙江理工大学 Preparation method of polyamide composite membrane with high controllability

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