CN112791606A - Modified halloysite nanotube/polyether copolyamide mixed matrix film and preparation method thereof - Google Patents
Modified halloysite nanotube/polyether copolyamide mixed matrix film and preparation method thereof Download PDFInfo
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- CN112791606A CN112791606A CN201911112928.8A CN201911112928A CN112791606A CN 112791606 A CN112791606 A CN 112791606A CN 201911112928 A CN201911112928 A CN 201911112928A CN 112791606 A CN112791606 A CN 112791606A
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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
- B01D71/56—Polyamides, e.g. polyester-amides
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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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/148—Organic/inorganic mixed matrix membranes
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Abstract
The invention discloses a modified halloysite nanotube/polyether copolyamide mixed matrix membrane and a preparation method thereof, and belongs to the technical field of membrane separation. The preparation method is characterized in that polyether copolyamide is used as a polymer substrate, and halloysite nanotubes are used as inorganic fillers; firstly, etching the surface of the halloysite nanotube, and then coating and modifying the surface of the etched halloysite nanotube. And blending the modified halloysite nanotube and polyether copolyamide to prepare a mixed matrix membrane. The preparation process is simple and easy to operate, and the prepared mixed matrix membrane is applied to CO2/N2Gas separation, has good separation performance.
Description
Technical Field
The invention relates to a modified halloysite nanotube/polyether copolyamide mixed matrix membrane and a preparation method thereof, belonging to the technical field of membrane separation.
Background
CO2Is widely recognized as the main greenhouse gas of the greenhouse effect. To realize CO2Reduction of emission, vigorous development and utilization of CO2Capture and Storage (CCS) technology is one of the promising solutions. CO 22The trapping method includes an absorption method, an adsorption method, a membrane separation method, and the like. Among them, the membrane separation method, as a new separation technology, has the significant advantages of simple process and low pollution, and has become one of the important carbon capture technologies.
The membrane material is the key to determine the separation effect of the mixed gas, and comprises organic materials and inorganic materials. The organic film prepared from organic material has low cost, easy preparation, and permeability and selectionThe selectivity can be mutually restricted; the inorganic film prepared by the inorganic material is corrosion resistant and high temperature resistant, but the mechanical property is poor, and the large-scale preparation is difficult. The mixed matrix membrane is an organic-inorganic composite membrane with inorganic components distributed on the matrix and the surface of the polymer membrane in a physical embedding way, and on one hand, the composite membrane can ensure that the polymer material has excellent stability and the inorganic material has excellent CO2The separation performance is combined, on the other hand, the defects of a pure organic membrane and a pure inorganic membrane can be avoided, and a possible technical breakthrough is provided for realizing high-efficiency gas separation.
Pebax1657 is a polyether block copolyamide polymer. The polyether segment is polyethylene oxide (PEO) which can provide high gas permeability; the polyamide segment is nylon 6(PA6) which provides mechanical strength. Pebax1657 is also a rubbery polymer, and Pebax1657 contains an ether oxygen group for CO, compared with glassy polymers (polysulfone, polyimide, etc.)2Has better affinity, thus having higher gas permeability and flexibility, and the preparation process of the membrane is simple, thus being widely used for preparing the gas separation membrane.
Currently, inorganic materials which are widely used include molecular sieves, Metal Organic Frameworks (MOFs), nanoparticles such as silicon dioxide or titanium dioxide, Carbon Nanotubes (CNTs), and the like. Halloysite Nanotubes (HNTs) are an aluminosilicate mineral, which have the following advantages over the inorganic materials mentioned above: the surface contains hydroxyl groups, and the compatibility with polar polymers is good; HNTs is of a tubular structure, and gas molecules can be diffused through a pipeline, so that the diffusion coefficient of the gas is increased; the composite material has good rigidity and obvious effects on enhancing and toughening the mechanical property of the high molecular organic matter; nanometer size and cavity make HNTs possess higher specific surface area. Compared with CNTs with the same tubular structure, HNTs have the advantages of abundant reserves, low cost and the like.
In order to increase the surface area and the porous structure of the HNTs and promote gas diffusion, the invention carries out etching modification on the HNTs; in order to improve the dispersibility and compatibility of inorganic materials in a polymer substrate, the method further modifies the etched HNTs by a surface coating method, fills the modified HNTs into a polyether copolyamide film,prepare and is suitable for CO2/N2Separated gas separation membrane having CO2High permeation flux, good separation effect, good strength, stable structure and the like.
Disclosure of Invention
The invention aims to provide a modified halloysite nanotube/polyether copolyamide mixed matrix film to overcome the defects of the prior art.
The invention provides a modified halloysite nanotube/polyether copolyamide mixed matrix film, which is characterized by comprising the following steps:
A. and (3) putting the halloysite nanotube and an acidic reagent into a high-temperature resistant container, uniformly mixing, heating at the maximum temperature of 350 ℃, cooling, washing, removing soluble salts and impurities, and drying to obtain the etched halloysite nanotube.
B. And putting the etched halloysite nanotube into a container, vacuumizing, adding ultrapure water, and ultrasonically vacuumizing the solution. Adding Tris-HCL buffer solution, dopamine and polyethyleneimine, fully stirring, testing the pH value of the mixture, adjusting the pH value to about 8.5 by using an alkaline reagent, stirring for 6-24h, centrifuging the mixture, removing supernatant, washing a precipitate, and freeze-drying to obtain the halloysite nanotube with the surface modified.
C. And putting the solvent and the modified halloysite nanotube into a beaker for ultrasonic treatment. The mixture and polyether copolyamide were placed in a flask. And refluxing and stirring for 2-24h at 70-85 ℃ to obtain the casting mold liquid.
D. And vacuumizing and defoaming the obtained casting mold liquid, pouring the casting mold liquid into a mold, drying the casting mold liquid in a drying oven at 40-60 ℃ for 24-72 hours, and then putting the casting mold liquid into a vacuum drying oven at 40-60 ℃ to further volatilize the solvent to obtain the modified halloysite nanotube/polyether copolyamide mixed matrix membrane.
Preferably, the acidic reagent in step a is sodium carbonate, sodium nitrate, sulfuric acid or hydrochloric acid; the high-temperature resistant container is a ceramic crucible; the precipitate is washed with dilute nitric acid, dilute sulfuric acid, dilute hydrochloric acid, or deionized water.
Preferably, the precipitate in step B is washed with deionized water; the alkaline reagent is sodium hydroxide.
Preferably, the ratio of the halloysite nanotubes to ultrapure water, Tris-HCL buffer, dopamine and polyethyleneimine in the step B is as follows: 4:0.1:0.3152:0.3792:1.
Preferably, the solvent in step C is ethanol and water; the polyether copolyamide is Pebax 1657; the polymer accounts for 2-5% of the solvent by mass.
The invention has the advantages that:
1. the modified halloysite nanotube/polyether copolyamide mixed matrix membrane provided by the invention is simple and easy to operate in the preparation process and good in production repeatability.
2. The etched halloysite nanotube has increased surface area and increased contact area with the polymer substrate, and the compatibility of the inorganic filler and the polymer substrate is improved.
3. The dopamine modified halloysite nanotube can increase the dispersibility of the dopamine modified halloysite nanotube in a polymer substrate and reduce agglomeration, thereby improving the comprehensive performance of the mixed matrix membrane.
4. Modification of halloysite nanotube to CO by dopamine and polyethyleneimine2The adsorption capacity is enhanced, and the obtained mixed matrix membrane has good separation performance.
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Detailed Description
The following are examples of modified halloysite nanotube and polyether copolyamide mixed matrix membranes, but are not limited to the following examples.
The polyether copolyamide used as the matrix in the embodiment of the invention is Pebax1657, which is hereinafter referred to as Pebax.
Example 1: modified halloysite nanotube/Pebax-0.5 mixed matrix membrane (modified halloysite nanotube loading of 0.5 wt%)
Preparing the surface modified halloysite nanotube: weighing 4g of halloysite nanotube, 1.2g of sodium carbonate and 20g of sodium nitrate, putting the halloysite nanotube, the sodium carbonate and the sodium nitrate into a ceramic crucible, uniformly mixing, putting the ceramic crucible into a muffle furnace, heating at the speed of 5 ℃/min and the highest temperature of 350 ℃ for 1h, cooling, washing with dilute nitric acid and deionized water, removing soluble salts and impurities, and drying to obtain the etched halloysite nanotube. Modifying the etched halloysite nanotube by using dopamine and polyethyleneimine, weighing 4g of the etched halloysite nanotube in a beaker, vacuumizing for 0.5h, adding 100ml of ultrapure water, performing ultrasonic treatment for 0.5h, and vacuumizing for 0.5 h. Adding 0.3152g of Tris-HCl buffer solution, 0.3792g of dopamine and 1g of polyethyleneimine, fully stirring, testing the pH value of the mixture, adjusting the pH value to about 8.5 by using NaOH, stirring for 6 hours, then centrifuging the mixture, and drying the obtained precipitate for 12 hours by using a freeze dryer to obtain the halloysite nanotubes subjected to surface modification treatment.
Preparation of mixed matrix membrane: ethanol/water (7/3) was measured into a beaker, 0.01g of modified halloysite was added and sonicated for 2 h. The mixed solution and 2g of Pebax were put into a single-neck flask, and the mass fraction of the polymer was 3%. The content of the halloysite nanotubes is 0.5 percent of the mass of the polyether copolyamide. The mixture was stirred at reflux in a single-neck flask for 4 hours. And (3) vacuumizing and defoaming the obtained solution, pouring the solution into a film-forming glass mold, drying the glass mold in a 40 ℃ oven for 48 hours, and then drying the glass mold in a 40 ℃ vacuum oven for 24 hours to obtain the modified halloysite nanotube/polyether copolyamide mixed matrix film.
The permeability coefficient of the membrane to pure gas is measured at 25 ℃ and 0.2MPa as follows: PCO2＝93.9Barrer，CO2/N2The selectivity was 45.14.
Example 2: modified halloysite nanotube/Pebax-1 mixed matrix membrane (modified halloysite nanotube loading of 1 wt%)
Preparing the surface modified halloysite nanotube: weighing 4g of halloysite nanotube, 1.2g of sodium carbonate and 20g of sodium nitrate, putting the halloysite nanotube, the sodium carbonate and the sodium nitrate into a ceramic crucible, uniformly mixing, putting the ceramic crucible into a muffle furnace, heating at the speed of 5 ℃/min and the highest temperature of 350 ℃ for 1h, cooling, washing with dilute nitric acid and deionized water, removing soluble salts and impurities, and drying to obtain the etched halloysite nanotube. Modifying the etched halloysite nanotube by using dopamine and polyethyleneimine, weighing 4g of the etched halloysite nanotube in a beaker, vacuumizing for 0.5h, adding 100ml of ultrapure water, performing ultrasonic treatment for 0.5h, and vacuumizing for 0.5 h. Adding 0.3152g of Tris-HCl buffer solution, 0.3792g of dopamine and 1g of polyethyleneimine, fully stirring, testing the pH value of the mixture, adjusting the pH value to about 8.5 by using NaOH, stirring for 6 hours, then centrifuging the mixture, and drying the obtained precipitate for 12 hours by using a freeze dryer to obtain the halloysite nanotubes subjected to surface modification treatment.
Preparation of mixed matrix membrane: ethanol/water (7/3) was measured into a beaker, 0.02g of modified halloysite was added and sonicated for 2 h. The mixed solution and 2g of Pebax were put into a single-neck flask, and the mass fraction of the polymer was 3%. The content of the halloysite nanotubes is 1 percent of the mass of the polyether copolyamide. The mixture was stirred at reflux in a single-neck flask for 4 hours. And (3) vacuumizing and defoaming the obtained solution, pouring the solution into a film-forming glass mold, drying the glass mold in a 40 ℃ oven for 48 hours, and then drying the glass mold in a 40 ℃ vacuum oven for 24 hours to obtain the modified halloysite nanotube/polyether copolyamide mixed matrix film.
The permeability coefficient of the membrane to pure gas is measured at 25 ℃ and 0.2MPa as follows: PCO2＝98.2Barrer，CO2/N2The selectivity was 46.43.
Example 3: modified halloysite nanotube/Pebax-1.5 mixed matrix membrane (modified halloysite nanotube loading of 1.5 wt%)
Preparing the surface modified halloysite nanotube: weighing 4g of halloysite nanotube, 1.2g of sodium carbonate and 20g of sodium nitrate, putting the halloysite nanotube, the sodium carbonate and the sodium nitrate into a ceramic crucible, uniformly mixing, putting the ceramic crucible into a muffle furnace, heating at the speed of 5 ℃/min and the highest temperature of 350 ℃ for 1h, cooling, washing with dilute nitric acid and deionized water, removing soluble salts and impurities, and drying to obtain the etched halloysite nanotube. Modifying the etched halloysite nanotube by using dopamine and polyethyleneimine, weighing 4g of the etched halloysite nanotube in a beaker, vacuumizing for 0.5h, adding 100ml of ultrapure water, performing ultrasonic treatment for 0.5h, and vacuumizing for 0.5 h. Adding 0.3152g of Tris-HCl buffer solution, 0.3792g of dopamine and 1g of polyethyleneimine, fully stirring, testing the pH value of the mixture, adjusting the pH value to about 8.5 by using NaOH, stirring for 6 hours, then centrifuging the mixture, and drying the obtained precipitate for 12 hours by using a freeze dryer to obtain the halloysite nanotubes subjected to surface modification treatment.
Preparation of mixed matrix membrane: ethanol/water (7/3) was measured into a beaker, and 0.03g of modified halloysite was added and sonicated for 2 h. The mixed solution and 2g of Pebax were put into a single-neck flask, and the mass fraction of the polymer was 3%. The content of the halloysite nanotubes is 1.5 percent of the mass of the polyether copolyamide. The mixture was stirred at reflux in a single-neck flask for 4 hours. And (3) vacuumizing and defoaming the obtained solution, pouring the solution into a film-forming glass mold, drying the glass mold in a 40 ℃ oven for 48 hours, and then drying the glass mold in a 40 ℃ vacuum oven for 24 hours to obtain the modified halloysite nanotube/polyether copolyamide mixed matrix film.
The permeability coefficient of the membrane to pure gas is measured at 25 ℃ and 0.2MPa as follows: PCO2＝101Barrer，CO2/N2The selectivity was 46.98.
Example 4: modified halloysite nanotube/Pebax-2 mixed matrix membrane (the filling amount of the modified halloysite nanotube is 2 wt%)
Preparing the surface modified halloysite nanotube: weighing 4g of halloysite nanotube, 1.2g of sodium carbonate and 20g of sodium nitrate, putting the halloysite nanotube, the sodium carbonate and the sodium nitrate into a ceramic crucible, uniformly mixing, putting the ceramic crucible into a muffle furnace, heating at the speed of 5 ℃/min and the highest temperature of 350 ℃ for 1h, cooling, washing with dilute nitric acid and deionized water, removing soluble salts and impurities, and drying to obtain the etched halloysite nanotube. Modifying the etched halloysite nanotube by using dopamine and polyethyleneimine, weighing 4g of the etched halloysite nanotube in a beaker, vacuumizing for 0.5h, adding 100ml of ultrapure water, performing ultrasonic treatment for 0.5h, and vacuumizing for 0.5 h. Adding 0.3152g of Tris-HCl buffer solution, 0.3792g of dopamine and 1g of polyethyleneimine, fully stirring, testing the pH value of the mixture, adjusting the pH value to about 8.5 by using NaOH, stirring for 6 hours, then centrifuging the mixture, and drying the obtained precipitate for 12 hours by using a freeze dryer to obtain the halloysite nanotubes subjected to surface modification treatment.
Preparation of mixed matrix membrane: ethanol/water (7/3) was measured into a beaker, and 0.04g of modified halloysite was added and sonicated for 2 h. The mixed solution and 2g of Pebax were put into a single-neck flask, and the mass fraction of the polymer was 3%. The content of the halloysite nanotubes is 2 percent of the mass of the polyether copolyamide. The mixture was stirred at reflux in a single-neck flask for 4 hours. And (3) vacuumizing and defoaming the obtained solution, pouring the solution into a film-forming glass mold, drying the glass mold in a 40 ℃ oven for 48 hours, and then drying the glass mold in a 40 ℃ vacuum oven for 24 hours to obtain the modified halloysite nanotube/polyether copolyamide mixed matrix film.
At 25 ℃ and 0.2MPaUnder the conditions, the permeability coefficient of the membrane to pure gas is measured as follows: PCO2＝101.5Barrer，CO2/N2The selectivity was 44.91.
Claims (6)
1. A modified halloysite nanotube/polyether copolyamide mixed matrix film and a preparation method thereof are characterized by being prepared by the following method:
A. and (3) putting the halloysite nanotube and an acidic reagent into a high-temperature resistant container, uniformly mixing, heating at the maximum temperature of 350 ℃, cooling, washing, removing soluble salts and impurities, and drying to obtain the etched halloysite nanotube.
B. And putting the etched halloysite nanotube into a container, vacuumizing, adding ultrapure water, and ultrasonically vacuumizing the solution. Adding Tris-HCL buffer solution, dopamine and polyethyleneimine, fully stirring, testing the pH value of the mixture, adjusting the pH value to about 8.5 by using an alkaline reagent, stirring for 6-24h, centrifuging the mixture, removing supernatant, washing a precipitate, and freeze-drying to obtain the halloysite nanotube with the surface modified.
C. And putting the solvent and the modified halloysite nanotube into a beaker for ultrasonic treatment. The mixture and polyether copolyamide were placed in a flask. And refluxing and stirring for 2-24h at 70-85 ℃ to obtain the casting mold liquid.
D. And vacuumizing and defoaming the obtained casting mold liquid, pouring the casting mold liquid into a mold, drying the casting mold liquid in a drying oven at 40-60 ℃ for 24-72 hours, and then putting the casting mold liquid into a vacuum drying oven at 40-60 ℃ to further volatilize the solvent to obtain the modified halloysite nanotube/polyether copolyamide mixed matrix membrane.
2. The modified halloysite nanotube/polyether copolyamide mixed matrix membrane according to claim 1, wherein the acidic reagent in step a is sodium carbonate, sodium nitrate, sulfuric acid or hydrochloric acid; the high-temperature resistant container is a ceramic crucible; the precipitate is washed with dilute nitric acid, dilute sulfuric acid, dilute hydrochloric acid, or deionized water.
3. The modified halloysite nanotube/polyether copolyamide mixed matrix membrane according to claim 1, wherein the precipitate in step B is washed with deionized water; the alkaline reagent is sodium hydroxide.
4. The modified halloysite nanotube/polyether copolyamide mixed matrix membrane according to claim 1, wherein the ratio of halloysite nanotubes to ultrapure water, Tris-HCL buffer, dopamine and polyethyleneimine in step B is: 4:0.1:0.3152:0.3792:1.
5. The modified halloysite nanotube/polyether copolyamide mixed matrix membrane according to claim 1, wherein the solvent in step C is ethanol and water; the polyether copolyamide is Pebax 1657; the polymer accounts for 2-5% of the solvent by mass.
6. Use of the mixed matrix membrane according to any one of claims 1 to 5 for membrane separation.
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| CN113385055A (en) * | 2021-06-18 | 2021-09-14 | 大连理工大学 | Preparation method of composite material UiO-66@ HNT-based mixed matrix film |
| CN114725617A (en) * | 2022-04-06 | 2022-07-08 | 华南理工大学 | Coating slurry for lithium battery diaphragm, preparation method of coating slurry and lithium battery diaphragm |
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