CN111151137B - High-flux high-salt-rejection reverse osmosis composite membrane and preparation method thereof - Google Patents
High-flux high-salt-rejection reverse osmosis composite membrane and preparation method thereof Download PDFInfo
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- CN111151137B CN111151137B CN202010006336.4A CN202010006336A CN111151137B CN 111151137 B CN111151137 B CN 111151137B CN 202010006336 A CN202010006336 A CN 202010006336A CN 111151137 B CN111151137 B CN 111151137B
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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
- B01D67/0002—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
- B01D69/12—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
- B01D71/66—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
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
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- 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
Abstract
The invention provides a method for modifying a reverse osmosis membrane by an amphiphilic core-shell hyperbranched polymer, which comprises the steps of soaking a polysulfone support layer in a m-phenylenediamine solution, drying in the shade, contacting with the hyperbranched polymer solution to enable an acyl chloride group at the tail end of the hyperbranched polymer to be in interfacial polymerization with an amino group, contacting with a trimesoyl chloride solution to perform secondary crosslinking reaction, and carrying out heat treatment to obtain a modified reverse osmosis composite membrane. The hyperbranched polymer used in the invention has a unique high-hydrophobic polyether core and a large number of highly hydrophilic PEO shell layers, and the size of the membrane pores can be regulated and controlled by introducing the hyperbranched polymer into a polyamide separation layer of the reverse osmosis composite membrane, so that the water transmission is accelerated. Meanwhile, the polyamide layer of the modified membrane is thin and compact, so that the retention rate of the membrane can be ensured. Under the condition of water inflow of 2000ppm NaCl, the modified membrane has increased water flux of 70 percent, and the NaCl retention rate is kept above 99 percent. The research provides an effective way for preparing the reverse osmosis composite membrane with excellent comprehensive performance.
Description
Technical Field
The invention relates to a novel membrane material and a preparation method thereof, in particular to a preparation method of a high-flux high-cut-off salt reverse osmosis composite membrane.
Background
At present, due to the rapid growth of population, the development of industry and agriculture and climate change, the worldwide demand for water resources is gradually increased, and the shortage of fresh water resources is becoming a global problem. The total amount of water resources on the seawater resource occupation ball is 97 percent, so that the method for obtaining clean water suitable for use by utilizing seawater desalination is the most effective method for solving the water resource crisis. Modern seawater desalination technologies mainly comprise a membrane technology and a heat treatment technology. Compared with the traditional hot method water treatment process, the membrane treatment process occupies more than 60 percent of the whole seawater desalination market due to low energy consumption, easy operation and convenient maintenance. Reverse osmosis is the most core seawater and brackish water desalination membrane treatment technology at present, but the requirement of high pressure by the reverse osmosis technology still has higher operation cost. Therefore, it is still a great challenge to further improve the performance of reverse osmosis membrane to reduce energy consumption and thus water production cost.
Hyperbranched polymer (abbreviated as HPs) is a highly branched three-dimensional macromolecule, generally has irregular topological structure and abundant terminal functional groups, and has the advantages of low viscosity, high solubility, high chemical reactivity and the like compared with linear polymer, so that the hyperbranched polymer is widely researched in a plurality of fields such as coating, photoelectric material, nano material, supramolecular material, biological material, mixed material, adhesive, modifier and the like. In recent years, researchers try to utilize the three-dimensional structure and the characteristics of multiple active sites of HPs to prepare or modify various separation membranes, and the research shows wide application prospects in the field of separation membranes. Abhijit et al (Sarkar A, Carver P I, Zhang T, et al, Dendrimer-based coatings for surface modification of polyamine reverse osmoses membranes [ J ]. Journal of mean Science,2010,349(1-2): 421) 428) first reported that dendrimers were used for modification of reverse osmosis membranes by cross-linking Polyamine (PAMAM) dendrimers with polyamine-polyethylene glycol (PAMAM-PEG) multi-arm star-shaped bifunctional molecules in situ coated on the Membrane, and the resulting highly hydrophilic coating provided the reverse osmosis Membrane with good anti-fouling properties, but the flux was not improved. Saren et al (S.Qi, W.Fang, W.Siti, W.Widjajannti, X.Hu, R.Wang, Polymer-based high-performance reversed emulsion membrane for depletion, Journal of membrane science,555(2018)177-184.) introduce the spherical block copolymer into the polyamide separation layer by Interfacial Polymerization (IP) to increase the modified membrane salt cut-off to 99.6%, but the water flux is unchanged from that of commercial membranes.
The invention selects amphiphilic hyperbranched polyether molecules (HBPO-star-PEO) with a core-shell type hydrophilic/hydrophobic phase separation structure, and after the amphiphilic hyperbranched polyether molecules are subjected to acyl chlorination, the amphiphilic hyperbranched polyether molecules and m-phenylenediamine generate interfacial polymerization reaction, so that the amphiphilic hyperbranched polyether molecules are embedded into a polyamide separation layer, and the high-performance reverse osmosis composite membrane with high flux and high salt rejection rate is prepared.
Disclosure of Invention
The invention aims to provide a high-flux high-salt-rejection reverse osmosis composite membrane and a preparation method thereof aiming at the defects of the prior art.
In order to achieve the purpose, the invention implements the following technical scheme:
a preparation method of a high-flux high-salt-cut hyperbranched polymer modified reverse osmosis composite membrane is characterized in that amphiphilic core-shell hyperbranched polyether is introduced into a polyamide separation layer to prepare a novel reverse osmosis composite membrane, and the preparation method comprises the following specific steps:
(1) and (2) using thionyl chloride solution as an acyl chlorinating agent, acylating and chlorinating the amphiphilic core-shell hyperbranched polyether with carboxyl at the tail end to obtain the acyl chloride group-terminated amphiphilic core-shell hyperbranched polyether acyl chloride HBPO-star-PEO-COCl, and dissolving the acyl chloride group-terminated amphiphilic core-shell hyperbranched polyether acyl chloride HBPO-star-PEO-COCl in tetrahydrofuran solution to prepare the amphiphilic core-shell hyperbranched polyether acyl chloride HBPO-star-PEO-COCl/tetrahydrofuran solution with the mass concentration of 0.001% -0.2%.
(2) Pouring m-phenylenediamine aqueous solution with the mass concentration of 1-5% on the surface of the fixed polysulfone support membrane, soaking for 1-5 minutes, removing the redundant solution on the surface of the support membrane, and then placing the membrane in a ventilation place for drying in the shade.
(3) Pouring the amphiphilic core-shell hyperbranched polyether acyl chloride HBPO-star-PEO-COCl/tetrahydrofuran solution with the end containing the acyl chloride group prepared in the step (1) onto the polysulfone support membrane obtained in the step (2), wherein the contact time is 5-40 seconds, removing the redundant solution on the surface of the membrane, and drying the membrane in the shade in a ventilated place.
(4) And (4) continuously pouring 0.1-0.5 wt% of trimesoyl chloride/n-hexane solution on the support membrane obtained in the step (3), reacting for 10-100 seconds, removing the redundant solution, and drying the membrane in the shade in a ventilated place.
(5) And (3) drying the membrane obtained in the step (4) for 5-20 minutes at 50-100 ℃, and storing in deionized water at room temperature to obtain the high-flux high-salt-cut hyperbranched polymer modified reverse osmosis composite membrane.
Further, in the step (2), the m-phenylenediamine aqueous solution has a mass concentration of 2%, and the soaking time is 2 minutes.
Further, the m-phenylenediamine aqueous solution also comprises 0.15wt% of sodium dodecyl sulfate, 4wt% of camphorsulfonic acid and 2wt% of triethylamine.
Further, in the step (3), the contact time of the hyperbranched polymer/tetrahydrofuran solution is 10 seconds.
Further, in the step (4), the contact time of trimesoyl chloride is 40 seconds.
Further, in the step (5), the drying temperature is 60 ℃ and the drying time is 5 minutes.
Furthermore, the high-flux high-salt-rejection hyperbranched polymer modified reverse osmosis composite membrane prepared by the method is applied to brackish water desalination and seawater desalination.
The invention has the beneficial effects that: the crosslinking degree of a polyamide separation layer of the reverse osmosis membrane is adjusted by utilizing the acyl chloride group of the amphiphilic core-shell hyperbranched polymer to participate in interfacial polymerization reaction, so that the size of a membrane pore is adjusted and controlled to improve the salt rejection rate of the membrane; on the other hand, the PEO shell of the polymer is highly hydrophilic, and the internal HBPO high hydrophobicity can be collapsed in water to form a three-dimensional quasi-spherical structure, and the formation of the core-shell two-phase interface is beneficial to water molecules to rapidly pass through the reverse osmosis membrane along the hydrophobic wall surface, so that the water flux of the membrane is improved; furthermore, PEO has good anti-pollution capability, and is expected to improve the anti-pollution performance of the membrane. Because HBPO-star-PEO-COCl is introduced into the reverse osmosis membrane at a molecular level through a covalent bond, the stability and the dispersibility of the HBPO-star-PEO-COCl can be ensured. Therefore, a reverse osmosis membrane incorporating HBPO-star-PEO-COCl would be expected to exhibit excellent overall performance.
Drawings
FIG. 1 is a flow chart of the preparation of the core-shell amphiphilic hyperbranched polymer modified membrane of the present invention
FIG. 2 is an electron microscope image of the surface of a modified reverse osmosis membrane according to an embodiment of the present invention, wherein a to e are electron microscope images of membranes prepared in examples 1 to 5, respectively.
FIG. 3 is a membrane performance graph of a modified reverse osmosis membrane provided in an example of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments.
The preparation process of the core-shell amphiphilic hyperbranched polymer modified membrane is shown in figure 1 and mainly comprises two steps:
step one, acyl chlorination of amphiphilic hyperbranched polyether molecules:
the selected hyperbranched polymer is amphiphilic hyperbranched polyether molecule with a carboxyl-terminated core-shell type hydrophilic/hydrophobic phase separation structure, and is prepared by the following method: a low-temperature thermometer and a constant-pressure funnel are arranged on a 500ml four-necked bottle, high-purity argon is respectively introduced into the other two ports of the bottle, the bottle is vacuumized, and water and oxygen are strictly removed before reaction. 3-Ethyl-3-hydroxymethylbutylene oxide (11.6ml, 0.1mol) was placed in a constant pressure funnel and 100ml of dried CH was added2Cl2Adding into a four-necked flask, cooling to 0 deg.C, and adding 6.4ml BF3·OEt2Adding into a four-necked bottle, opening the funnel, rapidly adding 3-ethyl-3-hydroxymethyl butylene oxide, and stirring for reacting for 24 h. The reaction temperature was then lowered to-20 ℃ and 1ml of ethylene oxide was added dropwise at a rate of 0.05ml/5 sec to a four-necked flask and the reaction was continued for 24h while maintaining vigorous stirring. (Experimental notes in Wen Yongfeng. amphiphilic hyperbranched multi-arm copolymer molecular self-assembly and its application in biomembrane bionic research [ D]Shanghai-Shanghai university of transportation 2005) the above reaction processObtaining HBPO-star-PEO-OH, and then carrying out carboxyl-terminated modification by acid anhydride to obtain HBPO-star-PEO-COOH; the structure is shown as (I):
the hyperbranched polymer functionalization flow is shown as (II):
and (3) taking thionyl chloride as an acyl chlorination solvent in the process, adding 20ml of thionyl chloride solution and 0.5g of HBPO-star-PEO-COOH into a 50ml round-bottom flask, and condensing and refluxing at 80 ℃ for 10 hours to obtain the hydrophilic hyperbranched polyether acyl chloride HBPO-star-PEO-COCl.
Step two, preparation of a reverse osmosis composite membrane:
(1) and (3) washing the polysulfone base membrane by using deionized water, placing the cleaned polysulfone base membrane into a polytetrafluoroethylene frame, and drying the polytetrafluoroethylene frame in the shade in a ventilated place for later use.
(2) Pouring an m-phenylenediamine aqueous solution with the mass concentration of 2% onto a polysulfone support membrane, soaking for 2 minutes, removing redundant solution, and drying in the shade at room temperature;
(3) dissolving the HBPO-star-PEO-COCl prepared in the first step by using a tetrahydrofuran solvent to prepare an amphiphilic core-shell hyperbranched polyether molecule/tetrahydrofuran solution with the mass concentration of 0.001-0.2% and the tail end containing an acyl chloride group, pouring the mixed solution on a membrane surface, reacting for 5-40 seconds, removing the redundant organic solution, and drying in the shade at room temperature; then pouring 0.1-0.5 wt% of trimesoyl chloride mixed solution on the membrane surface, reacting for 10-100 seconds, removing the redundant solution, and drying in the shade at room temperature;
(4) and (3) placing the dried film in a drying oven with the temperature of 50-80 ℃ for heat treatment for 5-10 minutes, and then placing the film in deionized water at room temperature for storage.
Preferably, the concentration of the m-phenylenediamine aqueous solution is 2wt%, and the m-phenylenediamine aqueous solution further contains 0.15wt% of sodium dodecyl sulfate, 4wt% of camphorsulfonic acid and 2wt% of triethylamine.
Preferably, the polymer has the best effect at a mixed solution concentration of 0.005 wt%.
Preferably, the concentration of the trimesoyl chloride solution in (3) is 0.15wt%, and the reaction time is 40 seconds.
Preferably, the heat treatment temperature in (4) is 60 ℃ and the heat treatment time is 5 minutes.
Example 1:
soaking the polysulfone support membrane for 2 minutes by using a metaphenylene diamine aqueous phase solution with the mass concentration of 1 percent, removing the redundant solution, and then placing the membrane in the air for drying for 5 to 10 minutes in the shade. After the film surface is dried in the shade, pouring a proper amount of trimesoyl chloride/n-hexane solution with the mass concentration of 0.1 percent into the film, carrying out interfacial polymerization on the surface of the supporting layer for 40 seconds, removing the redundant solution, drying in the shade at room temperature, and then placing into a 60 ℃ oven for heat treatment for 5 minutes. Film No. 1, M1, was obtained.
Example 2:
soaking the polysulfone support membrane in an aqueous solution of m-phenylenediamine with the mass concentration of 2% for 2 minutes, removing the redundant solution, and drying in the air for 5-10 minutes. After the film surface is dried in the air, pouring the mixed solution containing 0.001 wt% of HBPO-star-PEO-COCl/tetrahydrofuran, the contact time is 10 seconds, removing the redundant solution, and drying in the shade at room temperature. After the film surface is dried, 0.15% of trimesoyl chloride/n-hexane solution is poured into the film surface for 60 seconds, then the redundant solution is removed, and the film surface is placed into an oven at 80 ℃ for heat treatment for 5 minutes after being dried in the shade at room temperature. Film No. 2, M2, was obtained.
Example 3:
soaking the polysulfone support membrane in a 3% m-phenylenediamine aqueous phase solution for 2 minutes, removing the redundant solution, and drying in the air for 5-10 minutes. After the film surface is dried in the air, pouring the mixed solution containing 0.01 wt% of HBPO-star-PEO-COCl/tetrahydrofuran, the contact time is 10 seconds, removing the redundant solution, and drying in the shade at room temperature. After the film surface is dried, 0.2% of trimesoyl chloride/n-hexane solution is poured into the film surface for contact time of 80 seconds, then the redundant solution is removed, and the film surface is placed into a 90 ℃ oven for heat treatment for 5 minutes after being dried in the shade at room temperature. Film No. 3, M3, was obtained.
Example 4:
soaking the polysulfone support membrane for 2 minutes by using a metaphenylene diamine aqueous phase solution with the mass concentration of 4 percent, removing the redundant solution, and then placing the membrane in the air for drying for 5 to 10 minutes in the shade. After the film surface is dried in the air, pouring the mixed solution containing 0.1 wt% of HBPO-star-PEO-COCl/tetrahydrofuran, the contact time is 10 seconds, removing the redundant solution, and drying in the shade at room temperature. After the film surface is dried, 0.15% of trimesoyl chloride/n-hexane solution is poured into the film surface, the contact time is 100 seconds, then the redundant solution is removed, and the film surface is placed into a 90 ℃ oven for heat treatment for 3 minutes after being dried in the shade at room temperature. Film No. 4, M4, was obtained.
Example 5:
soaking the polysulfone support membrane for 2 minutes by using a metaphenylene diamine aqueous phase solution with the mass concentration of 5 percent, removing the redundant solution, and then placing the membrane in the air for drying for 5 to 10 minutes in the shade. After the film surface is dried in the air, pouring the mixed solution containing 0.2 wt% of HBPO-star-PEO-COCl/tetrahydrofuran, the contact time is 10 seconds, removing the redundant solution, and drying in the shade at room temperature. After the film surface is dried in the air, 0.5% of trimesoyl chloride/n-hexane solution is poured into the film surface, the contact time is 100 seconds, then the redundant solution is removed, and after the film surface is dried in the shade at room temperature, the film surface is placed into an oven at 100 ℃ for heat treatment for 2 minutes. Film No. 5, M5, was obtained.
Film Performance testing
FIGS. 2a-e are electron micrographs of the films prepared in examples 1-5, respectively, from which it can be seen that the surface properties of the modified film are not significantly different from those of the control film.
The flux rejection performance of the membranes was evaluated by a cross-flow filtration test system. Installing a membrane to be tested in a membrane pool of a flat plate membrane device, and pre-pressing the membrane for 1h by using 2000ppm NaCl solution at 1.5MPa and 25 ℃; the permeability of the membrane was tested when the flux stabilized. The results obtained are shown in FIG. 3 and in the following table:
according to the test results, compared with the conventional reverse osmosis membrane, the modified reverse osmosis membrane prepared by the invention has the advantages that on the premise of ensuring the salt rejection rate,greatly improves the water flux, and the flux reaches 70L/m under the optimal condition2The desalination rate reaches over 99.2 percent after h, and the method can be widely applied to the treatment of brackish water and seawater.
Claims (7)
1. A preparation method of a high-flux high-salt-cut reverse osmosis composite membrane is characterized in that amphiphilic core-shell hyperbranched polyether is introduced into a polyamide separation layer to prepare a novel reverse osmosis composite membrane, and the preparation method comprises the following specific steps:
(1) performing acyl chlorination on amphiphilic core-shell hyperbranched polyether HBPO-star-PEO-COOH of which the tail end contains carboxyl by using a thionyl chloride solution as an acyl chlorinating agent to obtain acyl chloride group-terminated amphiphilic core-shell hyperbranched polyether acyl chloride HBPO-star-PEO-COCl, and dissolving the acyl chloride group-terminated amphiphilic core-shell hyperbranched polyether acyl chloride HBPO-star-PEO-COCl by using a tetrahydrofuran solution to prepare the tetrahydrofuran solution of the amphiphilic core-shell hyperbranched polyether acyl chloride HBPO-star-PEO-COCl with the mass concentration of 0.001% -0.2%;
(2) pouring a m-phenylenediamine aqueous solution with the mass concentration of 1-5% on the surface of a fixed polysulfone support membrane, soaking for 1-5 minutes, removing redundant solution on the surface of the support membrane, and then placing the membrane in a ventilation place for drying in the shade;
(3) pouring the tetrahydrofuran solution of the amphiphilic core-shell hyperbranched polyether acyl chloride HBPO-star-PEO-COCl with the end containing the acyl chloride group prepared in the step (1) onto the polysulfone support membrane obtained in the step (2), wherein the contact time is 5-40 seconds, removing the redundant solution on the surface of the membrane, and placing the membrane in a ventilated place for drying in the shade;
(4) continuously pouring 0.1-0.5 wt% of trimesoyl chloride normal hexane solution on the support membrane obtained in the step (3), reacting for 10-100 seconds, removing redundant solution, and placing the membrane in a ventilated place for drying in the shade;
(5) and (3) drying the membrane obtained in the step (4) for 5-20 minutes at 50-100 ℃, and storing in deionized water at room temperature to obtain the high-flux high-salt-rejection reverse osmosis composite membrane.
2. The production method according to claim 1, wherein in the step (2), the m-phenylenediamine aqueous solution has a mass concentration of 2% and the soaking time is 2 minutes.
3. The method according to claim 2, wherein said m-phenylenediamine aqueous solution further comprises 0.15wt% sodium dodecylsulfonate, 4wt% camphorsulfonic acid, 2wt% triethylamine.
4. The preparation method according to claim 1, wherein in the step (3), the contact time of the tetrahydrofuran solution of the amphiphilic core-shell hyperbranched poly (ether-acid chloride) containing the acid chloride group at the terminal is 10 seconds.
5. The method according to claim 1, wherein in the step (4), the contact time of trimesoyl chloride is 40 seconds.
6. The method according to claim 1, wherein in the step (5), the drying temperature is 60 ℃ and the drying time is 5 minutes.
7. The application of the high-flux high-salt-cut reverse osmosis composite membrane is characterized in that the high-flux high-salt-cut reverse osmosis composite membrane prepared by the preparation method of any one of claims 1 to 6 is applied to brackish water desalination and seawater desalination.
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