CN113786742A - Nano compact composite reverse osmosis membrane and preparation method thereof - Google Patents
Nano compact composite reverse osmosis membrane and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 68
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 29
- 239000002159 nanocrystal Substances 0.000 claims abstract description 26
- 235000015696 Portulacaria afra Nutrition 0.000 claims abstract description 10
- 235000018747 Typha elephantina Nutrition 0.000 claims abstract description 10
- 244000177175 Typha elephantina Species 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 57
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- RVWUHFFPEOKYLB-UHFFFAOYSA-N 2,2,6,6-tetramethyl-1-oxidopiperidin-1-ium Chemical compound CC1(C)CCCC(C)(C)[NH+]1[O-] RVWUHFFPEOKYLB-UHFFFAOYSA-N 0.000 claims description 12
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 12
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 108010022355 Fibroins Proteins 0.000 claims description 11
- 239000012071 phase Substances 0.000 claims description 10
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000007853 buffer solution Substances 0.000 claims description 9
- 239000008346 aqueous phase Substances 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 8
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 7
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 7
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 7
- 239000001263 FEMA 3042 Substances 0.000 claims description 7
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 229920002492 poly(sulfone) Polymers 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 7
- 229940033123 tannic acid Drugs 0.000 claims description 7
- 235000015523 tannic acid Nutrition 0.000 claims description 7
- 229920002258 tannic acid Polymers 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 5
- MCHZKGNHFPNZDP-UHFFFAOYSA-N 2-aminoethane-1,1,1-triol;hydrochloride Chemical compound Cl.NCC(O)(O)O MCHZKGNHFPNZDP-UHFFFAOYSA-N 0.000 claims description 2
- -1 uniformly stirring Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000284 extract Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009920 chelation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a preparation method of a nano compact composite reverse osmosis membrane, which extracts nanocrystals from elephant grass leaves, synthesizes gel nanocrystals and introduces the gel nanocrystals into an ultrafiltration membrane, and simultaneously carries out hydrophilic modification on an interface polymerization layer, and forms a strong chelating nano compact layer with the interface polymerization layer by utilizing the high strength of the nanocrystals and the channel effect of nano water. Test results show that the nano compact composite reverse osmosis membrane prepared by the invention has high compactness and hydrophilic performance.
Description
Technical Field
The invention relates to the technical field of reverse osmosis membranes, in particular to a preparation method and application of a nano compact composite reverse osmosis membrane.
Background
The reverse osmosis membrane technology is the most widely applied membrane separation technology with the highest technical difficulty in the field of membrane separation, and has the advantages of normal-temperature operation, no chemical addition, high efficiency and low energy consumption in the use process. However, the problem of peeling off and pollution resistance of the reverse osmosis membrane in the using process is still a great problem to be solved at present.
At present, modification aiming at the problems of cortex shedding and pollution resistance is mainly focused on post-treatment and hydrophilic material addition improvement, and CN200810162610.6 applies a method for surface grafting on a polyamide layer to form a stable layer to improve the performance of a membrane, but the problem of cortex shedding caused by insufficient strength in the using process of surface grafting still exists.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a nano compact composite reverse osmosis membrane by extracting nanocrystals from elephant grass, modifying the nanocrystals and introducing the nanocrystals into the reverse osmosis membrane through strong chelation. According to the invention, the nanocrystals are extracted from the elephant grass, and are subjected to hydrophilic modification by utilizing the high strength and nano water channel effect of the nanocrystals, so that a strong chelating nano compact layer is formed with an interface polymerization layer, and the stability and the hydrophilicity of the reverse osmosis membrane are greatly improved.
A nanometer compact composite reverse osmosis membrane and a preparation method thereof comprise the following steps:
(1) sequentially soaking the ground elephant grass blades in 1mol/L sulfuric acid solution and 2mol/L sodium hydroxide solution for 40min respectively, washing with deionized water, and sieving with a 30-mesh sieve to obtain nano crystals;
(2) sequentially adding 2,2,6, 6-tetramethylpiperidine oxide, sodium bromide, sodium hypochlorite and the nanocrystalline prepared in the step (1) into deionized water, stirring and reacting at 25 ℃ for 3 hours, and centrifuging to obtain oxidized nanocrystalline;
the solution comprises the following raw materials: 1-5 wt% of nanocrystalline, 0.5-2 wt% of 2,2,6, 6-tetramethylpiperidine oxide, 1-3 wt% of sodium bromide, 0.5-4 wt% of sodium hypochlorite and the balance of deionized water solution;
(3) adding the oxidized nanocrystalline and glutaraldehyde prepared in the step (2) into silk fibroin solution, uniformly stirring, coating on a polysulfone ultrafiltration membrane, and carrying out heat treatment at 60 ℃ for 10min to obtain a gel nanocrystalline ultrafiltration membrane;
the silk fibroin solution comprises the following raw materials: 1-5 wt% of oxidized nanocrystalline, 0.5-3 wt% of glutaraldehyde, 15wt% of silk fibroin and the balance of water;
(4) immersing the ultrafiltration membrane prepared in the step (3) in an aqueous phase solution with the pH =7 for 40s, removing redundant solution through a rubber roller, immersing in an oil phase solution for 60s, and performing heat treatment at 80 ℃ for 10min to obtain a primary reverse osmosis membrane;
the water phase solution comprises the following raw materials: 2.5wt% of o-phenylenediamine, 0.3wt% of triethylamine, 0.3wt% of camphorsulfonic acid and the balance of water;
the oil phase solution comprises the following raw materials: 0.05wt% of p-trimesoyl chloride and the balance of solvent ethylcyclohexane;
(5) immersing the nascent reverse osmosis membrane prepared in the step (4) in a trihydroxymethyl aminomethane hydrochloride buffer solution with pH =5 and containing sodium periodate and tannic acid, and washing with deionized water to obtain a nano compact composite reverse osmosis membrane;
the buffer solution comprises the following raw materials: 0.5-2 wt% of sodium periodate, 0.5-1 wt% of tannic acid and the balance of tris hydrochloride buffer solution;
the dipping time is 5min-10 min;
compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, the gel nanocrystal is synthesized by modifying the nanocrystal and is introduced into the ultrafiltration membrane, the high dispersibility and the hydrophilicity of the gel nanocrystal avoid the problem of falling of a subsequent interface polymerization layer, and the compatibility between the ultrafiltration layer and the interface polymerization layer is improved.
(2) According to the nano compact composite reverse osmosis membrane prepared by the invention, the gel nanocrystals are distributed in the ultrafiltration membrane layer and form strong chelating nano compact crosslinking with the hydrophilic modification layer in the interface polymerization layer, and the water channel effect of the nanocrystals also greatly improves the stability and the hydrophilicity of the reverse osmosis membrane.
Detailed Description
The following provides a specific embodiment of the nano-compact composite reverse osmosis membrane of the present invention.
Example 1
And sequentially soaking the ground elephant grass blades in 1mol/L sulfuric acid solution and 2mol/L sodium hydroxide solution for 40min respectively, washing with deionized water, and sieving with a 30-mesh sieve to obtain the nanocrystalline.
Stirring 2,2,6, 6-tetramethyl piperidine oxide, sodium bromide, sodium hypochlorite and the nanocrystal at 25 ℃ for 1h for reaction, and centrifuging to obtain the oxidized nanocrystal. Wherein, the raw material components are respectively 0.5wt% of 2,2,6, 6-tetramethyl piperidine oxide, 1wt% of sodium bromide, 1wt% of sodium hypochlorite, 1wt% of nanocrystalline and the balance of deionized water.
Uniformly stirring a solution consisting of 1wt% of oxidized nanocrystalline, 0.5wt% of glutaraldehyde, 15wt% of silk fibroin and the balance of water, coating the solution on a polysulfone ultrafiltration membrane, and carrying out heat treatment at 60 ℃ for 10min to obtain the gel nanocrystalline ultrafiltration membrane.
Dipping the gel nanocrystalline ultrafiltration membrane in an aqueous phase solution which is composed of 2.5wt% of o-phenylenediamine, 0.3wt% of triethylamine, 0.3wt% of camphorsulfonic acid and the balance of water and has the pH =7 for 40s, removing redundant solution through a rubber roller, dipping the gel nanocrystalline ultrafiltration membrane in an oil phase solution which is composed of 0.05wt% of terephthaloyl chloride and the balance of solvent ethylcyclohexane for 60s, and carrying out heat treatment at 80 ℃ for 10min to obtain the nascent reverse osmosis membrane.
And (2) immersing the nascent reverse osmosis membrane in a buffer solution which is composed of 0.5wt% of sodium periodate with the pH =5, 0.5wt% of tannic acid and the balance of tris hydrochloride for 5min, and washing with deionized water to obtain the nano compact composite reverse osmosis membrane.
Example 2
The procedure for preparing the oxidized nanocrystals was the same as in example 1.
Uniformly stirring a solution consisting of 3wt% of oxidized nanocrystalline, 2wt% of glutaraldehyde, 15wt% of silk fibroin and the balance of water, coating the solution on a polysulfone ultrafiltration membrane, and carrying out heat treatment at 60 ℃ for 10min to obtain the gel nanocrystalline ultrafiltration membrane.
Dipping the gel nanocrystalline ultrafiltration membrane in an aqueous phase solution which is composed of 2.5wt% of o-phenylenediamine, 0.3wt% of triethylamine, 0.3wt% of camphorsulfonic acid and the balance of water and has the pH =7 for 40s, removing redundant solution through a rubber roller, dipping the gel nanocrystalline ultrafiltration membrane in an oil phase solution which is composed of 0.05wt% of p-trimesoyl chloride and the balance of ethylcyclohexane for 60s, and carrying out heat treatment at 80 ℃ for 10min to obtain the nascent reverse osmosis membrane.
And (2) immersing the nascent reverse osmosis membrane in a buffer solution which is composed of 1wt% of sodium periodate with the pH =5, 1wt% of tannic acid and the balance of tris hydrochloride for 8min, and washing with deionized water to obtain the nano compact composite reverse osmosis membrane.
Example 3
The procedure for preparing the oxidized nanocrystals was the same as in example 1.
Uniformly stirring a solution consisting of 5wt% of oxidized nanocrystalline, 2wt% of glutaraldehyde, 15wt% of silk fibroin and the balance of water, coating the solution on a polysulfone ultrafiltration membrane, and carrying out heat treatment at 60 ℃ for 10min to obtain the gel nanocrystalline ultrafiltration membrane.
Dipping the gel nanocrystalline ultrafiltration membrane in an aqueous phase solution which is composed of 2.5wt% of o-phenylenediamine, 0.3wt% of triethylamine, 0.3wt% of camphorsulfonic acid and the balance of water and has the pH =7 for 40s, removing redundant solution through a rubber roller, dipping the gel nanocrystalline ultrafiltration membrane in an oil phase solution which is composed of 0.05wt% of p-trimesoyl chloride and the balance of solvent ethylcyclohexane for 60s, and carrying out heat treatment at 80 ℃ for 10min to obtain the nascent reverse osmosis membrane.
And (2) immersing the nascent reverse osmosis membrane in a buffer solution which is composed of 2wt% of sodium periodate with the pH =5, 1wt% of tannic acid and the balance of tris (hydroxymethyl) aminomethane hydrochloride for 10min, and washing with deionized water to obtain the nano compact composite reverse osmosis membrane.
Example 4
And sequentially soaking the ground elephant grass blades in 1mol/L sulfuric acid solution and 2mol/L sodium hydroxide solution for 40min respectively, washing with deionized water, and sieving with a 30-mesh sieve to obtain the nanocrystalline.
Stirring 2,2,6, 6-tetramethyl piperidine oxide, sodium bromide, sodium hypochlorite and the nanocrystal at 25 ℃ for reaction for 3 hours, and centrifuging to obtain the oxidized nanocrystal. Wherein, the raw material components are 1.5wt% of 2,2,6, 6-tetramethyl piperidine oxide, 3wt% of sodium bromide, 2.5wt% of sodium hypochlorite, 3wt% of nanocrystalline and the balance of deionized water.
The other preparation processes are the same as the example 1, and the nano compact composite reverse osmosis membrane is obtained.
Example 5
And sequentially soaking the ground elephant grass blades in 1mol/L sulfuric acid solution and 2mol/L sodium hydroxide solution for 40min respectively, washing with deionized water, and sieving with a 30-mesh sieve to obtain the nanocrystalline.
Stirring 2,2,6, 6-tetramethyl piperidine oxide, sodium bromide, sodium hypochlorite and the nanocrystal at 25 ℃ for reaction for 3 hours, and centrifuging to obtain the oxidized nanocrystal. Wherein, the raw material components are 2wt% of 2,2,6, 6-tetramethyl piperidine oxide, 3wt% of sodium bromide, 2.5wt% of sodium hypochlorite, 5wt% of nanocrystalline and the balance of deionized water.
The other preparation processes are the same as the example 1, and the nano compact composite reverse osmosis membrane is obtained.
Comparative example 1
And sequentially soaking the ground elephant grass blades in 1mol/L sulfuric acid solution and 2mol/L sodium hydroxide solution for 40min respectively, washing with deionized water, and sieving with a 30-mesh sieve to obtain the nanocrystalline.
Uniformly stirring a solution consisting of 1wt% of nanocrystalline, 0.5wt% of glutaraldehyde, 15wt% of silk fibroin and the balance of water, coating the solution on a polysulfone ultrafiltration membrane, and carrying out heat treatment at 60 ℃ for 10min to obtain the nanocrystalline ultrafiltration membrane.
The nanocrystalline ultrafiltration membrane is immersed in an aqueous phase solution which is composed of 2.5wt% of o-phenylenediamine, 0.3wt% of triethylamine, 0.3wt% of camphorsulfonic acid and the balance of water and has the pH =7 for 40s, then the excess solution is removed by a rubber roller, and the nanocrystalline ultrafiltration membrane is immersed in an oil phase solution which is composed of 0.05wt% of terephthaloyl chloride and the balance of solvent ethylcyclohexane for 60s, and the primary reverse osmosis membrane is obtained after heat treatment at 80 ℃ for 10 min.
Comparative example 2
And sequentially soaking the ground elephant grass blades in 1mol/L sulfuric acid solution and 2mol/L sodium hydroxide solution for 40min respectively, washing with deionized water, and sieving with a 30-mesh sieve to obtain the nanocrystalline.
Stirring 2,2,6, 6-tetramethyl piperidine oxide, sodium bromide, sodium hypochlorite and the nanocrystal at 25 ℃ for reaction for 3 hours, and centrifuging to obtain the oxidized nanocrystal. Wherein, the raw material components are respectively 0.5wt% of 2,2,6, 6-tetramethyl piperidine oxide, 1wt% of sodium bromide, 1wt% of sodium hypochlorite, 1wt% of nanocrystalline and the balance of deionized water.
Uniformly stirring a solution consisting of 1wt% of oxidized nanocrystalline, 0.5w% of glutaraldehyde, 15wt% of silk fibroin and the balance of water, coating the solution on a polysulfone ultrafiltration membrane, and carrying out heat treatment at 60 ℃ for 10min to obtain the gel nanocrystalline ultrafiltration membrane.
Immersing the gel nanocrystalline ultrafiltration membrane in an aqueous phase solution which is composed of 2.5wt% of o-phenylenediamine, 0.3wt% of triethylamine, 0.3wt% of camphorsulfonic acid and the balance of water and has the pH =7 for 40s, removing redundant solution through a rubber roller, immersing in an oil phase solution which is composed of 0.05wt% of p-trimesoyl chloride and the balance of solvent ethylcyclohexane for 60s, and carrying out heat treatment at 80 ℃ for 10min to obtain the composite reverse osmosis membrane.
TABLE 1 flux, salt rejection, and contact angle of the reverse osmosis membranes of examples and comparative examples
As can be seen from table 1: the nano compact composite reverse osmosis membrane prepared by the method has a nano compact water channel and high stability, and the two-layer structure forms strong chelation, so that the hydrophilicity is good.
The foregoing is illustrative of the preferred embodiments of the present invention, and it is to be understood that the invention is not limited thereto, and that various modifications and enhancements which fall within the spirit and scope of the invention are possible.
Claims (7)
1. A preparation method of a nano compact composite reverse osmosis membrane is characterized by comprising the following steps: the method comprises the following steps:
(1) sequentially soaking the ground elephant grass blades in 1mol/L sulfuric acid solution and 2mol/L sodium hydroxide solution for 40min respectively, washing with deionized water, and sieving with a 30-mesh sieve to obtain nano crystals;
(2) sequentially adding 2,2,6, 6-tetramethylpiperidine oxide, sodium bromide, sodium hypochlorite and the nanocrystalline prepared in the step (1) into deionized water, stirring and reacting at 25 ℃ for 3 hours, and centrifuging to obtain oxidized nanocrystalline;
(3) adding the oxidized nanocrystalline and glutaraldehyde prepared in the step (2) into silk fibroin solution, uniformly stirring, coating on a polysulfone ultrafiltration membrane, and carrying out heat treatment at 60 ℃ for 10min to obtain a gel nanocrystalline ultrafiltration membrane;
(4) immersing the ultrafiltration membrane prepared in the step (3) in an aqueous phase solution with the pH =7 for 40s, removing redundant solution through a rubber roller, immersing in an oil phase solution for 60s, and performing heat treatment at 80 ℃ for 10min to obtain a primary reverse osmosis membrane;
(5) and (3) immersing the nascent reverse osmosis membrane prepared in the step (4) in a trihydroxymethyl aminomethane hydrochloride buffer solution with the pH =5 and containing sodium periodate and tannic acid, and washing with deionized water to obtain the nano compact composite reverse osmosis membrane.
2. The method of claim 1, wherein: in the step (2), the solution comprises the following raw materials: 1 to 5 weight percent of nanocrystalline, 0.5 to 2 weight percent of 2,2,6, 6-tetramethylpiperidine oxide, 1 to 3 weight percent of sodium bromide, 0.5 to 4 weight percent of sodium hypochlorite and the balance of deionized water solution.
3. The method of claim 1, wherein: in the step (3), the silk fibroin solution comprises the following raw materials: 1-5 wt% of oxidized nanocrystalline, 0.5-3 wt% of glutaraldehyde, 15wt% of silk fibroin and the balance of water.
4. The method of claim 1, wherein: in the step (4), the aqueous phase solution comprises the following raw materials: 2.5wt% o-phenylenediamine, 0.3wt% triethylamine, 0.3wt% camphorsulfonic acid, and the balance water.
5. The method of claim 1, wherein: in the step (4), the oil phase solution comprises the following raw materials: 0.05wt% of p-trimesoyl chloride and the balance of solvent ethylcyclohexane.
6. The method of claim 1, wherein: in the step (5), the buffer solution comprises the following raw materials: 0.5-2 wt% of sodium periodate, 0.5-1 wt% of tannic acid and the balance of tris hydrochloride buffer solution.
7. The method of claim 1, wherein: the dipping time in the step (5) is 5min to 10 min.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130180917A1 (en) * | 2010-08-23 | 2013-07-18 | The Research Foundation Of State University Of New York | High flux microfiltration membranes with virus and metal ion adsorption capability for liquid purification |
| CN106040014A (en) * | 2016-06-29 | 2016-10-26 | 浙江大学 | Nanometer crystal cellulose composite antioxidant nano-filtration membrane and method for preparing same |
| CN106345307A (en) * | 2016-09-23 | 2017-01-25 | 浙江大学 | Hollow fiber composite nano-filtration membrane and preparation method thereof |
| CN110141974A (en) * | 2019-05-17 | 2019-08-20 | 李文国 | A kind of nano-cellulose-composite nanometer filtering film (CNF-NF) and preparation method thereof |
| CN112452164A (en) * | 2020-10-22 | 2021-03-09 | 哈尔滨工业大学 | Two-step modified composite nanofiltration membrane containing cellulose nanocrystal intermediate layer and dopamine in-situ modification layer and preparation method thereof |
-
2021
- 2021-10-12 CN CN202111185430.1A patent/CN113786742A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130180917A1 (en) * | 2010-08-23 | 2013-07-18 | The Research Foundation Of State University Of New York | High flux microfiltration membranes with virus and metal ion adsorption capability for liquid purification |
| CN106040014A (en) * | 2016-06-29 | 2016-10-26 | 浙江大学 | Nanometer crystal cellulose composite antioxidant nano-filtration membrane and method for preparing same |
| CN106345307A (en) * | 2016-09-23 | 2017-01-25 | 浙江大学 | Hollow fiber composite nano-filtration membrane and preparation method thereof |
| CN110141974A (en) * | 2019-05-17 | 2019-08-20 | 李文国 | A kind of nano-cellulose-composite nanometer filtering film (CNF-NF) and preparation method thereof |
| CN112452164A (en) * | 2020-10-22 | 2021-03-09 | 哈尔滨工业大学 | Two-step modified composite nanofiltration membrane containing cellulose nanocrystal intermediate layer and dopamine in-situ modification layer and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| ETHAN D. SMITH ET. AL: "Functionalized Cellulose Nanocrystal Nanocomposite Membranes with Controlled Interfacial Transport for Improved Reverse Osmosis Performance", NANOMATERIALS, vol. 9, no. 1, pages 29 - 25 * |
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