CN112742221A - Forward osmosis membrane based on hydrophilic modified polyolefin microporous substrate and preparation method - Google Patents
Forward osmosis membrane based on hydrophilic modified polyolefin microporous substrate and preparation method Download PDFInfo
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Abstract
The invention relates to a forward osmosis membrane based on a hydrophilic modified polyolefin microporous substrate and a preparation method thereof, wherein the forward osmosis membrane comprises a hydrophilic modified substrate and a selective skin layer on the substrate, and the substrate is subjected to hydrophilic modification through a corona method; wherein the corona voltage is 1-5 kw, and the corona time is 3-60 s. The polyolefin microporous substrate is subjected to hydrophilic modification by a corona method, low-temperature plasma is generated on the surface of polyolefin by corona discharge, the molecules of the treated surface are oxidized and polarized, the surface is eroded by ionic shock, and the hydrophilicity and the adhesive force of the surface of the microporous film are increased; interface polymerization is carried out on the polyolefin microporous substrate after hydrophilic modification, so that a selective cortex with uniform and defect-free surface can be obtained; because the corona treatment is only carried out on the surface of the substrate, the internal structure and the performance of the substrate are not substantially affected, and therefore, the substrate still maintains the original large aperture, high strength and good tolerance to organic substances.
Description
Technical Field
The invention relates to the technical field of forward osmosis membranes, in particular to a forward osmosis membrane based on a hydrophilic modified polyolefin microporous substrate and a preparation method thereof.
Background
With the rapid development of global industrialization, the problems of water pollution and water resource shortage are increasingly remarkable, and the problems of high-difficulty wastewater treatment, energy conservation, efficiency improvement and the like are increasingly outstanding and need to be solved urgently. The water treatment technology taking the membrane process as the core can effectively separate the required water molecules from useless impurities, thereby realizing the regeneration of water resources and having the characteristics of small occupied area, low energy consumption, wide applicability and the like.
Forward Osmosis (FO) is a process in which water molecules diffuse from the side of higher water chemical potential (feed solution side) through an ion selective membrane, i.e., a Forward Osmosis membrane, to the side of lower water chemical potential (draw solution side) while solute molecules and ions remain in the feed solution, using the osmotic pressure difference of the solutions on both sides of the membrane as a driving force. Due to the characteristics of low energy consumption in the forward osmosis process, no need of external pressure, less pollution to the membrane in the process, simple and easy process and the like, the forward osmosis membrane has good application prospect in many fields such as solution concentration treatment, seawater desalination, food concentration, power generation, drug release and the like.
The preparation of the forward osmosis membrane at present mainly comprises a cellulose triacetate forward osmosis membrane prepared by a phase inversion method, a composite polyamide forward osmosis membrane prepared by an interfacial polymerization method by taking porous polysulfone as a supporting layer, a composite forward osmosis membrane prepared by interfacial polymerization by taking porous polyethersulfone as a supporting layer and the like.
However, the traditional forward osmosis membrane cannot be widely applied in various fields, the defects of membrane pollution, easy membrane loss, poor organic solvent tolerance and the like cannot be overcome, and the development and application of the forward osmosis process are restricted by the forward osmosis membrane lacking high performance, high tolerance and pollution resistance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a forward osmosis membrane based on a hydrophilic modified polyolefin microporous substrate and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
a forward osmosis membrane based on a hydrophilic modified polyolefin microporous substrate comprises the hydrophilic modified substrate and a selective skin layer on the substrate, wherein the substrate is subjected to hydrophilic modification through a corona method; wherein the corona voltage is 1-5 kw, and the corona time is 3-60 s.
The selective skin layer is formed on the surface of the substrate through interfacial polymerization reaction of a water phase monomer and an oil phase monomer; the water phase monomer is at least one of m-phenylenediamine, o-phenylenediamine and p-phenylenediamine; the oil phase monomer is trimesoyl chloride.
The polyolefin microporous substrate is a microporous film prepared from polyolefin materials represented by polyethylene and polypropylene.
The polyolefin microporous substrate is a polyethylene microporous membrane.
The polyolefin microporous substrate is subjected to hydrophilic modification by a corona method, low-temperature plasma is generated on the surface of polyolefin by corona discharge, the molecules of the treated surface are oxidized and polarized, the surface is eroded by ionic shock, and the hydrophilicity and the adhesive force of the surface of the microporous film are increased. The selective cortex with uniform surface and no defect can be obtained by carrying out interfacial polymerization on the polyolefin microporous substrate after hydrophilic modification. Because the corona treatment is only carried out on the surface of the substrate, the internal structure and the performance of the substrate are not substantially affected, and therefore, the substrate still maintains the original large aperture, high strength and good tolerance to organic substances. Thus, the present application broadens the scope of use of forward osmosis membranes, particularly with solutions of polyolefin microporous base sheets having broader applicability and longer service life.
A preparation method of a composite forward osmosis membrane based on a hydrophilic modified polyolefin microporous substrate comprises the following specific steps:
(1) the polyolefin passes through a corona device to obtain a hydrophilic modified polyolefin microporous substrate, wherein the corona voltage is 1-5 kw, and the corona time is 3-60 s;
(2) soaking the surface and the inner pores of a hydrophilic modified polyolefin microporous substrate with an organic solvent, then placing the substrate in pure water for soaking, exchanging the organic solvent with water to soak the surface and the inner pores of the microporous substrate with water, then soaking the substrate soaked with water in a solution containing an aqueous phase monomer for 1-5 minutes, taking out, extruding to remove excess water on the surface of the substrate, then entering an oil phase solution containing an oil phase monomer, carrying out interfacial polymerization for 20 s-5 min, and taking out to obtain a primary product of the composite forward osmosis membrane. Soaking the prepared composite forward osmosis membrane in an acidic solution and an alkaline solution respectively to obtain the composite forward osmosis membrane;
the organic solvent is one of ethanol, isopropanol, N '-dimethylformamide and N, N' -dimethylacetamide.
In the aqueous phase solution, the concentration of an aqueous phase monomer is 1-50 g/L, the aqueous phase monomer is at least one of m-phenylenediamine, o-phenylenediamine and p-phenylenediamine, and the solvent is water.
In the oil phase solution, the concentration of an oil phase monomer is 0.5-3 g/L, the oil phase monomer is trimesoyl chloride, and a solvent is one or more than two mixed liquids of n-hexane, methylcyclohexane, ethylcyclohexane and Isopar.
The concentration of the acid solution of the post-treatment solution is 5-50 g/L, and the acid solution is at least one of a citric acid solution, a sulfuric acid solution and a hydrochloric acid solution; the concentration of the alkaline solution is 5-50 g/L, and the alkaline solution is at least one of a sodium carbonate solution, a sodium hydroxide solution and a sodium hypochlorite solution.
In the step (1):
the polyolefin microporous substrate is a microporous film prepared from polyolefin materials represented by polyethylene and polypropylene. The polyolefin microporous membrane can be obtained by dry-method or wet-method stretching, the pore diameter, pore size distribution, porosity and flatness of the polyolefin microporous membrane are controlled by the preparation process of the polyolefin microporous membrane, and the influence on the water flux of the composite forward osmosis membrane is obvious. However, the performance parameters of the polyolefin microporous membrane have no significant influence on the retention performance of the composite forward osmosis membrane, because the retention performance of the composite forward osmosis membrane is mainly determined by the selective skin layer of the composite forward osmosis membrane.
Further optimizing corona treatment conditions, wherein the corona power is preferably 2-3.5 KW, and the corona time is 5-30 s.
In the step (2):
further optimizing conditions, wherein the organic solvent is N, N' -dimethylacetamide; in the aqueous phase solution, an aqueous phase monomer is m-phenylenediamine, and the concentration is 10-30 g/L; soaking the hydrophilic modified polyolefin microporous substrate in a solution containing an aqueous phase monomer for 2-4 min to allow the aqueous phase monomer to be adsorbed on the surface and in surface pores of the substrate; in the oil phase solution, an oil phase monomer is trimesoyl chloride, the concentration is 1-2 g/L, and a solvent is one of n-hexane, Isopar E and ethylcyclohexane.
The interfacial polymerization reaction time is 0.5-5 min, and the interfacial polymerization reaction temperature is 20-40 ℃.
The composite forward osmosis membrane prepared under the condition has better performance.
Because the prepared composite forward osmosis membrane primary product contains trace residual organic solvent, aqueous phase monomer and other substances, the long-term residue of the substances can cause negative influence or damage to the skin layer, thereby influencing the performance and the appearance of the forward osmosis membrane. Therefore, it is necessary to treat these residual substances in a post-treatment process to obtain a final product.
Preferably, the primary product of the forward osmosis membrane is subjected to an acid washing step, the selected acid solution is a citric acid solution, the concentration is 10-30 g/L, the acid washing temperature is 20-50 ℃, and the acid washing time is 1-3 min; and then, washing the forward osmosis membrane after the acid washing to remove redundant acid solution, wherein the washing time is 1-3 min, and the washing temperature is 20-30 ℃ of room temperature. Carrying out further alkali washing on the forward osmosis membrane subjected to acid washing and water washing, wherein the selected alkali solution is sodium carbonate, the concentration of the alkali solution is 10-30 g/L, the alkali washing temperature is 20-50 ℃, and the alkali washing time is 1-3 min; and then, washing the forward osmosis membrane subjected to alkali washing to remove redundant alkali solution, wherein the washing time is 1-3 min, and the washing temperature is 20-30 ℃ at room temperature.
The composite forward osmosis membrane final product obtained by treatment under the condition has better performance and appearance.
Compared with the prior art, the invention has the beneficial effects that:
(1) the composite forward osmosis membrane takes the hydrophilic modified polyolefin microporous membrane obtained by corona treatment as a substrate, the structure and the physical and chemical properties of the substrate are not substantially changed by the corona treatment, and the surface is only subjected to hydrophilic modification, so that the influence on the surface of the substrate is small; meanwhile, compared with means such as chemical oxidation modification and oxygen plasma treatment, the corona treatment can be continuously carried out on line, no waste water, waste gas and waste residue are generated, and the method is environment-friendly and low in cost. Therefore, under relatively friendly environment and conditions, the corona treatment greatly improves the hydrophilicity of the surface of the substrate, enables the substrate to adsorb water phase monomers, can be used for interfacial polymerization, reduces the membrane resistance of the base membrane, and further improves the water flux of the forward osmosis membrane.
(2) Compared with the traditional forward osmosis membrane substrate, the polyolefin microporous membrane has larger pore size and larger porosity, and the thickness of the substrate is only 1/10-1/2 of the traditional substrate, so that the membrane resistance of the base membrane is reduced, and the water flux of the forward osmosis membrane is further improved.
(3) The polyolefin microporous substrate has excellent tolerance to organic solvents and hardly swells or dissolves in any organic solvent, so that the forward osmosis membrane can be used in an environment containing organic solvents, and the application range of the forward osmosis membrane is widened.
(4) The polyolefin microporous substrate of the composite forward osmosis membrane prepared by the invention has the advantages of low price, convenient and simple corona treatment, firm structure of a cross-linked network formed by interfacial polymerization, simple preparation method, compact, uniform and complete selective cortex, suitability for large-scale continuous industrial production and very good development prospect.
Drawings
Fig. 1 is a schematic structural diagram of the present application.
1 an electronic balance, wherein the electronic balance is provided with a power supply,
2 the liquid is drawn up by the liquid-liquid extraction device,
3 a first peristaltic pump,
4 a first flow rate valve and a second flow rate valve,
5, a membrane pool is arranged in the device,
6 is a forward osmosis membrane which is provided with a positive osmosis membrane,
7, preparing a raw material liquid,
8 a first peristaltic pump, which is a peristaltic pump,
9 a first flow rate valve is arranged on the first flow rate valve,
Detailed Description
The following provides specific embodiments of a hydrophilic modified polyolefin microporous substrate-based forward osmosis membrane and a preparation method thereof.
The specific method for membrane performance testing in the examples is as follows:
and (3) measuring the water flux: the forward osmosis membrane test device is shown in figure 1.
And (3) measuring the retention rate: the measurement is carried out by a conductivity meter, namely a Shanghai thunder magnetic DDS-307A conductivity meter.
Specifically, the raw material solution was 0.1M sodium chloride solution, the draw solution was 4M glucose solution, and the test temperature was 25 ± 2 ℃. In the testing process, the draw solution 2 is driven by the first peristaltic pump 3 to flow in the testing membrane pool 5 on two sides of the forward osmosis membrane in a cross flow mode through the peristaltic pump pipe and the first flow valve 4. The raw material liquid 7 is driven by a second peristaltic pump 8 to respectively flow in the test membrane pools 5 on the two sides of the forward osmosis membrane in a cross flow mode through a peristaltic pump pipe and a second flow valve 9. The draw solution is placed on an electronic balance to test the mass change of the draw solution so as to calculate the water flux of the membrane, and the electric conductivity of solutes in the draw solution is tested to calculate the rejection rate of the membrane.
Water flux (Jw) membranes the volume of water per unit area of membrane per unit time, usually expressed in LMH (L.m)-2·h-1)
Where Δ m is the draw solution mass change (kg), ρ is the density of the water, and A is the effective membrane area for the forward osmosis filtration test(m2) And Δ t is the forward osmosis filtration test time.
The rejection rate (R) is a measure of the solute rejection capability of the membrane, i.e. the ratio of the concentration of the solute retained by the membrane to the concentration of the solute in the original solution, and during the test, the ratio of the concentration of the solute in the permeated water to the concentration of the solute in the original solution is usually measured, and in actual operation, the direct relationship between the conductivity and the concentration of the solute at a certain temperature is usually used, and the calculation formula is as follows:
CPand CFConcentration (mg/L), σ, of the permeate and the original solution, respectivelyPAnd σFConductivity of permeate and original solution, respectively.
Example 1
A polyethylene microporous membrane (thickness 20 μm, average pore diameter 0.04 μm, porosity 38%) was cut into a sheet shape, placed in a corona device, set at a corona voltage of 3kw and a corona time of 10s, and subjected to corona treatment. And obtaining the polyethylene microporous substrate with the surface subjected to hydrophilic modification after corona.
Fully infiltrating the surface and the internal pores of the hydrophilic modified polyolefin microporous substrate with N, N '-dimethylacetamide, then placing the substrate in pure water for rinsing and soaking, and fully exchanging the N, N' -dimethylacetamide with water to ensure that the surface and the internal of the substrate are infiltrated by the water. And then contacting and soaking the surface of the substrate soaked by water with a solution containing a water phase monomer (m-phenylenediamine, the concentration of which is 10g/L) for 2min, taking out the substrate, removing the redundant water phase solution on the surface of the substrate by using a squeezing roller, fixing the substrate loaded with a small amount of water phase monomer on the surface in a self-made frame to facilitate experimental operation, contacting an oil phase solution containing an oil phase monomer (trimesoyl chloride, the concentration of which is 1.5g/L, and the solvent of which is Isopar E) with the surface of the substrate to perform interfacial polymerization reaction, removing the oil phase solution after 30s, immediately placing the membrane after the reaction in a forced air oven at 70 ℃ to bake for 2min, and obtaining the primary product of the composite forward osmosis membrane.
And carrying out post-treatment on the prepared composite forward osmosis membrane primary product. (a) Rinsing and soaking the membrane in a citric acid solution with the temperature of 50 ℃ and the concentration of 20g/L for 2min, and then rinsing the membrane in pure water at room temperature for 2 min; (b) the film pieces were then rinsed and soaked for 2min in a 10g/L sodium carbonate solution at a temperature of 30 ℃ and then rinsed for 2min with pure water at room temperature. Obtaining the composite forward osmosis membrane product.
The finally obtained membrane was tested for water flux and rejection by the above-mentioned measurement methods. The performance test result shows that the water flux is 11.2LMH, and the retention rate is 98.2%.
Example 2
A polyethylene microporous membrane (thickness 14 μm, mean pore diameter 0.06 μm, porosity 42%) having different parameters from those of example 1 was selected, and the corona treatment voltage was set at 2.2kw for 7 s. Other parameters and operating steps were the same as in example 1.
The finally obtained membrane sheet was tested for water flux and rejection by the same measurement methods as in example 1. The performance test results show that the water flux is 15.9LMH, and the retention rate is 97.5%.
Example 3
Preparing m-phenylenediamine aqueous solution with 15g/L of water-phase monomer solution, and Isopar E solution with 1g/L of oil-phase monomer solution. Other parameters and operating steps were the same as in example 1.
The finally obtained membrane sheet was tested for water flux and rejection by the same measurement methods as in example 1. The performance test result shows that the water flux is 12.6LMH, and the retention rate is 98.5%.
Example 4
The operation procedure was the same as in example 1 except that the interfacial polymerization reaction time was changed to 20 seconds, and the baking temperature in the oven was changed to 80 ℃ for 4 minutes in a forced air oven.
The finally obtained membrane sheet was tested for water flux and rejection by the same measurement methods as in example 1. The performance test results show that the water flux is 18.3LMH, and the retention rate is 95.1%.
Example 5
After the interfacial polymerization reaction, the concentration of the acid washing solution in the post-treatment of the membrane primary product is changed to 30g/L citric acid solution, the acid washing is carried out for 3min, the concentration of the alkali washing solution is changed to 20g/L, the alkali washing time is 3min, and other parameters and operation steps are the same as those of example 1.
The finally obtained membrane sheet was tested for water flux and rejection by the same measurement methods as in example 1. The performance test results show that the water flux is 11.7LMH, and the retention rate is 98.4%.
Comparative example 1
A commercial polysulfone ultrafiltration membrane (with the molecular weight cut-off of 10kDa) is used as a substrate of the composite forward osmosis membrane, and an N, N' -dimethylacetamide infiltration process is avoided. Other polymerization parameters and procedure were the same as in example 1.
The finally obtained membrane sheet was used for the measurement method of example 1 to test the water flux and the rejection rate. The performance test result shows that the water flux is 6.9LMH, and the retention rate is 98.9%.
Comparative example 2
The home-made polysulfone ultrafiltration membrane (pure water flux of 120LMH/bar) is used as the substrate of the composite forward osmosis membrane, and the N, N' -dimethylacetamide infiltration process is not adopted. Other polymerization parameters and procedure were the same as in example 1.
The finally obtained membrane sheet was used for the measurement method of example 1 to test the water flux and the rejection rate. The performance test result shows that the water flux is 9.5LMH, and the retention rate is 98.7%.
Table 1 results of water flux and rejection tests for examples 1-5 forward osmosis membranes
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | |
| Water flux LMH | 11.2 | 15.9 | 12.6 | 18.3 | 11.7 | 6.9 | 9.5 |
| Retention rate% | 98.2 | 97.5 | 98.5 | 95.1 | 98.4 | 98.9 | 98.7 |
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and decorations can be made without departing from the concept of the present invention, and these modifications and decorations should also be regarded as being within the protection scope of the present invention.
Claims (10)
1. A forward osmosis membrane based on a hydrophilic modified polyolefin microporous substrate is characterized by comprising the hydrophilic modified substrate and a selective skin layer on the substrate, wherein the substrate is subjected to hydrophilic modification through a corona method; wherein the corona voltage is 1-5 kw, and the corona time is 3-60 s.
2. The forward osmosis membrane based on a hydrophilic modified polyolefin microporous substrate according to claim 1, wherein the selective skin layer is formed by interfacial polymerization of an aqueous phase monomer and an oil phase monomer on the surface of the substrate; the water phase monomer is at least one of m-phenylenediamine, o-phenylenediamine and p-phenylenediamine; the oil phase monomer is trimesoyl chloride.
3. The forward osmosis membrane based on a hydrophilically modified polyolefin microporous substrate according to claim 1, wherein the polyolefin microporous substrate is a polyethylene microporous membrane.
4. A preparation method of a composite forward osmosis membrane based on a hydrophilic modified polyolefin microporous substrate is characterized by comprising the following specific steps:
(1) the polyolefin passes through a corona device to obtain a hydrophilic modified polyolefin microporous substrate, wherein the corona voltage is 1-5 kw, and the corona time is 3-60 s;
(2) soaking the surface and the inner pores of a hydrophilic modified polyolefin microporous substrate with an organic solvent, then placing the substrate in pure water for soaking, exchanging the organic solvent with water to soak the surface and the inner pores of the microporous substrate with water, then soaking the substrate soaked with water in a solution containing an aqueous phase monomer for 1-5 minutes, taking out, extruding to remove excess water on the surface of the substrate, then entering an oil phase solution containing an oil phase monomer, carrying out interfacial polymerization for 20 s-5 min, and taking out to obtain a primary product of the composite forward osmosis membrane. And respectively soaking the prepared composite forward osmosis membrane in an acidic solution and an alkaline solution to obtain the composite forward osmosis membrane.
5. The method for preparing a composite forward osmosis membrane based on a hydrophilically modified polyolefin microporous substrate according to claim 4, wherein the organic solvent is one of ethanol, isopropanol, N '-dimethylformamide and N, N' -dimethylacetamide.
6. The method for preparing the composite forward osmosis membrane based on the hydrophilic modified polyolefin microporous substrate according to claim 4, wherein the concentration of an aqueous phase monomer in the aqueous phase solution is 1-50 g/L, the aqueous phase monomer is at least one of m-phenylenediamine, o-phenylenediamine and p-phenylenediamine, and the solvent is water.
7. The method for preparing the composite forward osmosis membrane based on the hydrophilic modified polyolefin microporous substrate according to claim 4, wherein the oil phase monomer concentration in the oil phase solution is 0.5-3 g/L, the oil phase monomer is trimesoyl chloride, and the solvent is one or more than two mixed liquids of n-hexane, methylcyclohexane, ethylcyclohexane and Isopar.
8. The method for preparing the composite forward osmosis membrane based on the hydrophilic modified polyolefin microporous substrate according to claim 4, wherein the concentration of the acid solution of the post-treatment solution is 5-50 g/L, and the acid solution is at least one of a citric acid solution, a sulfuric acid solution and a hydrochloric acid solution; the concentration of the alkaline solution is 5-50 g/L, and the alkaline solution is at least one of a sodium carbonate solution, a sodium hydroxide solution and a sodium hypochlorite solution.
9. The preparation method of the composite forward osmosis membrane based on the hydrophilic modified polyolefin microporous substrate, according to claim 4, is characterized in that the corona treatment condition is further optimized, the corona power is preferably 2-3.5 KW, and the corona time is 5-30 s.
10. The method for preparing a composite forward osmosis membrane based on a hydrophilically modified polyolefin microporous substrate according to claim 4, wherein the organic solvent is N, N' -dimethylacetamide; in the aqueous phase solution, an aqueous phase monomer is m-phenylenediamine, and the concentration is 10-30 g/L; soaking the hydrophilic modified polyolefin microporous substrate in a solution containing an aqueous phase monomer for 2-4 min to allow the aqueous phase monomer to be adsorbed on the surface and in surface pores of the substrate; in the oil phase solution, an oil phase monomer is trimesoyl chloride, the concentration is 1-2 g/L, and a solvent is one of n-hexane, Isopar E and ethylcyclohexane.
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|---|---|---|---|---|
| CN113522058A (en) * | 2021-08-16 | 2021-10-22 | 中国科学院上海高等研究院 | High-performance composite forward osmosis membrane based on polyolefin microporous substrate and preparation method thereof |
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