CN111187413A - Sulfonated polyethyleneimine, nanofiltration membrane and preparation method thereof - Google Patents
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Abstract
The invention relates to sulfonated polyethyleneimine, a nanofiltration membrane and a preparation method thereof, wherein the sulfonated polyethyleneimine is obtained by ring-opening reaction of polyethyleneimine and sultone sulfonate. And (3) preparing the loose nanofiltration membrane by interfacial polymerization by using sulfonated polyethyleneimine as a water-phase monomer. Due to the introduction of sulfonic acid groups, the polarity of the monomer is improved, the solubility of the monomer in an oil phase is reduced, so that the interfacial polymerization process is inhibited, and finally, the polyamide separation surface layer with a loose structure is obtained. Based on the unique structure and properties of sulfonated polyethyleneimine, the prepared nanofiltration membrane has the characteristics of high water flux, high dye retention and high salt penetration, and is suitable for treatment of printing and dyeing wastewater.
Description
Technical Field
The invention belongs to the field of separation membranes and preparation methods thereof, and particularly relates to sulfonated polyethyleneimine, a nanofiltration membrane and a preparation method thereof.
Background
With the rapid development of the current printing and dyeing industry, the environment-friendly method is urgently needed for treating and discharging the waste liquor. Most of the traditional treatment methods adopt adsorption or chemical precipitation and the like, but the separation efficiency is low and valuable inorganic salts (5-6 wt% of sodium chloride and sodium sulfate) in the wastewater cannot be recovered. Loose nanofiltration membranes are of great interest due to their high dye retention and low salt retention. At present, the preparation of the loose nanofiltration membrane is mostly focused on doping various inorganic nano materials, however, the agglomeration of the nano materials and the cost problem seriously restrict the further development of the nano materials.
The polyethyleneimine monomer has good hydrophilicity and abundant amido, and can be modified and surface grafted through Michael addition or Schiff base reaction. By utilizing the characteristics, the preparation of the loose nanofiltration membrane by using polyethyleneimine is reported at present. For example, a loose nanofiltration membrane is prepared by modifying a polyacrylonitrile ultrafiltration membrane by codeposition of polyethyleneimine and dopamine, and is used for dye desalination; the loose nanofiltration membrane is also prepared by using the crosslinking reaction of polyethyleneimine and tannic acid. Although the reaction of polyethyleneimine with polyphenols can be used for preparing the loose nanofiltration membrane, the selective separation coefficient of the dye and the salt of the loose nanofiltration membrane is still not high from the result, the reaction time of polyethyleneimine with polyphenols is long, and the uniformity for modifying the membrane surface is not enough. In addition, the price of polyphenols is also expensive from the viewpoint of production cost, which is disadvantageous for industrialization.
The method firstly obtains a sulfonated modified polyethyleneimine monomer by a simple one-step sulfonation method, then uses the monomer as a novel water-phase monomer, and adopts simple immersion to carry out interfacial polymerization to directly obtain the loose nanofiltration membrane.
Disclosure of Invention
The invention aims to solve the technical problems of providing sulfonated polyethyleneimine, a nanofiltration membrane and a preparation method thereof, and overcoming the defects of poor stability and high cost of the existing loose nanofiltration membrane prepared by crosslinking reaction of polyethyleneimine and polyphenols.
The sulfonated polyethyleneimine is obtained by ring-opening reaction of polyethyleneimine and sultone sulfonate.
The invention relates to a preparation method of sulfonated polyethyleneimine, which comprises the following steps:
and adding sultone sulfonate and ammonia water into the polyethyleneimine solution, stirring for reaction, filtering, and freeze-drying to obtain the sulfonated polyethyleneimine.
The preferred mode of the above preparation method is as follows:
the polyethyleneimine is one or more of branched or linear polyethyleneimine with molecular weight of 600Da, 1800Da, 1000Da, 1500Da, 5000Da, 10000Da and 70000 Da; the sulfolactone is 1, 3-propanesulfolactone and/or butanesulfolactone; the mass ratio of the sultone sulfonate to the polyethyleneimine is 1:100 to 100: 1.
The solvent of the polyethyleneimine solution is organic alcohol; the mass concentration of the polyethyleneimine solution is 0.2-90%; the adding amount of the ammonia water is 0.1-10% of the volume of the solvent.
Further, the organic alcohol is one or more of methanol, ethanol, propanol and butanol.
In the preparation method of the sulfonated polyethyleneimine, the stirring reaction temperature is 25-100 ℃, and the reaction time is 0.5-24 hours.
The sulfonation degree of the obtained sulfonated polyethyleneimine is 1-100%.
The sulfonated polyethyleneimine hydrophobic composite nanofiltration membrane is obtained by interfacial polymerization of a water-phase monomer and an oil-phase monomer on the surface of a porous support membrane, wherein the water-phase monomer contains sulfonated polyethyleneimine; the oil phase monomer comprises aromatic acid chloride.
The composite nanofiltration membrane consists of a polyamide separation surface layer and an ultrafiltration support basement membrane, and has the characteristics of high water flux, high dye retention and high salt penetration.
The invention relates to a preparation method of a sulfonated polyethyleneimine composite nanofiltration membrane, which comprises the following steps:
immersing the porous support membrane into the water phase solution for reaction, taking out and discharging the solution with excessive surface, immersing the porous support membrane into the oil phase solution for reaction, and performing heat treatment and soaking cleaning to obtain the sulfonated polyethyleneimine composite nanofiltration membrane; wherein the water phase solution: sulfonated polyethyleneimine water solution containing first reaction monomers; oil phase solution: an organic solution containing a second reactive monomer, an aromatic acid chloride.
The preferred mode of the above preparation method is as follows:
the porous support membrane is a macromolecular ultrafiltration membrane.
Further, the porous support membrane is one or more of a polysulfone ultrafiltration membrane, a polyether sulfone ultrafiltration membrane and a polyacrylonitrile ultrafiltration membrane.
The aromatic acyl chloride is one or more of benzene trimethyl acyl chloride, phthalic acid chloride, isophthaloyl dichloride, paraphthaloyl chloride and pyromellitic dianhydride; the mass concentration of the aromatic acyl chloride in the oil phase solution is 0.01-1%; the mass concentration of the sulfonated polyethyleneimine in the aqueous phase solution is 0.01-10.0%.
Immersing the mixture into the aqueous phase solution for reaction for 1-60 min; immersing the mixture into the oil phase solution for reaction for 0.1-60 min; the heat treatment is carried out at 60 deg.C for 1-60 min.
The invention provides an application of the sulfonated polyethyleneimine boresight composite filter membrane.
Advantageous effects
The method obtains the sulfonated and modified polyethyleneimine monomers by the ring-opening reaction of the polyethyleneimine monomers with different molecular weights and the sultone under the alkaline condition, has simple operation and mild condition, does not need complex purification process for the product, and can obtain the monomers with different sulfonation degrees by simply changing the addition proportion of the raw materials.
The sulfonated polyethyleneimine product is used as a water-phase monomer for preparing the loose nanofiltration membrane through interfacial polymerization. Due to the introduction of sulfonic acid groups, the polarity of the monomer is improved, the solubility of the monomer in an oil phase is reduced, and an interfacial polymerization process is inhibited, so that a polyamide layer with a loose structure can be obtained. Based on the unique structure and properties of sulfonated polyethyleneimine, the nanofiltration membrane prepared by using the sulfonated polyethyleneimine as an aqueous phase monomer has the characteristics of high water flux, high dye retention and high salt penetration. The selective separation of the printing and dyeing wastewater with high salt concentration is efficient and stable in long-time operation. The prepared nanofiltration membrane also shows high anti-pollution capability to common pollutants such as protein and the like. Therefore, the loose nanofiltration membrane has great application potential in the field of printing and dyeing wastewater treatment.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
1g of polyethyleneimine (PEI, molecular weight 600Da, purity: 99%, Shanghai Aladdin reagent Co.) was added to a 100mL round-bottomed flask, followed by slow addition of 50mL of anhydrous ethanol solution. The mixture is magnetically stirred until PEI is completely dissolved to obtain a colorless transparent solution, then 1g of 1, 3-propanesultone (purity: 99%, Shanghai Aladdin reagent company) and 0.416mL of ammonia water solution are added into the solution in sequence, and stirring reaction is continued at 50 ℃ for 24h to obtain an ethanol solution of viscous sulfonated polyethylene imine (SPEI). Finally, by filtration, freeze drying gives a SPEI solids sulfonation degree of 15.8% and storage in a desiccator.
Example 2
The difference from example 1 is that: the amount of the propane sultone added was 0.5g, and the degree of sulfonation was 7.5%.
Example 3
The difference from example 1 is that: the amount of the propane sultone added was 2g, and the degree of sulfonation was 32.7%.
Example 4
The difference from example 1 is that: the molecular weight of the polyethyleneimine is 1000 Da.
Example 5
The difference from example 1 is that: the molecular weight of the polyethyleneimine is 5000 Da.
Example 6
The difference from example 1 is that: the molecular weight of the polyethyleneimine is 10000 Da.
Example 7
The sulfonated polyethyleneimine nanofiltration membrane is prepared by adopting sulfonated dopamine as a monomer according to the following steps:
dissolving sulfonated polyethyleneimine (SPEI, prepared in example 1) in deionized water to obtain an aqueous phase solution with the concentration of 0.15 wt%, and performing ultrasonic treatment for 10min to completely dissolve the sulfonated polyethyleneimine; soaking the wet polysulfone support membrane into the water phase solution for 20min, taking out and blowing to dry for later use; the cyclohexane oil phase solution concentration of trimesoyl chloride (purity: 99%, Shanghai Aladdin reagent company) is 0.15 wt%; immersing the support membrane into the oil phase solution, reacting for 1min, and taking out; and (3) carrying out heat treatment on the composite film in an oven at 60 ℃ for 30 min. And rinsing with deionized water for several times to obtain the composite nanofiltration membrane containing sulfonated polyethyleneimine.
Example 8
The difference from example 7 is that: sulfonated polyethyleneimine is prepared as in example 2.
Example 9
The difference from example 7 is that: sulfonated polyethyleneimine is prepared as in example 3.
Example 10
The difference from example 7 is that: sulfonated polyethyleneimine is prepared as in example 4.
Example 11
The difference from example 7 is that: sulfonated polyethyleneimine is prepared as in example 5.
Example 12
The difference from example 7 is that: sulfonated polyethyleneimine is prepared as in example 6.
Example 13
The difference from example 7 is that: the concentration of the aqueous phase was 0.1 wt%.
Example 14
The difference from example 7 is that: the concentration of the aqueous phase was 0.3 wt%.
Example 15
The difference from example 7 is that: the oil phase concentration was 0.1 wt%.
Example 16
The difference from example 7 is that: the oil phase concentration was 0.25 wt%.
Comparative example 1
The comparative example provides an unsulfonated polyethyleneimine nanofiltration membrane prepared according to the following steps:
dissolving polymine with the molecular weight of 600Da in deionized water, wherein the concentration is 0.15 wt%, and performing ultrasonic treatment for 10min to completely dissolve the polymine; soaking the wet polysulfone support membrane into the water phase solution for 20min, taking out and blowing to dry for later use; preparing 0.15 wt% cyclohexane oil phase solution of trimesoyl chloride; immersing the support membrane into the oil phase solution, reacting for 1min, and taking out; and (3) carrying out heat treatment on the composite film in an oven at 60 ℃ for 30 min. And rinsing with deionized water for several times to obtain the composite nanofiltration membrane.
Test example 1
SPEI loose nanofiltration membranes of examples 7-9 were tested for water flux, sodium sulfate salt, and Congo red rejection at an operating pressure of 0.6MPa, a sodium sulfate salt concentration of 1g/L, and a Congo red concentration of 0.1 g/L. The flux and retention results are shown in table 1.
Table 1:
as can be seen from table 1, sulfonated polyethyleneimines of different sulfonation degrees have a significant effect on the properties of the resulting membrane. When the SPEI sulfonation degree is 15.8%, the loose nanofiltration membrane shows higher water flux, and the dye retention rate and the low salt retention rate are suitable for treating dye wastewater.
Test example 2
SPEI loose nanofiltration membranes of examples 10-12 were tested for water flux, sodium sulfate salt, and Congo red rejection at an operating pressure of 0.6MPa, a sodium sulfate salt concentration of 1g/L, and a Congo red concentration of 0.1 g/L. The flux and retention results are shown in table 2.
Table 2:
as can be seen from table 2, different molecular weight polyethyleneimines have a significant effect on the properties of the resulting film. When the molecular weight of the used polyethyleneimine is 600Da, the nanofiltration membrane shows better loose nanofiltration performance.
Test example 3
SPEI loose nanofiltration membranes of examples 13-14 were tested for water flux, sodium sulfate salt, and Congo red rejection at an operating pressure of 0.6MPa, a sodium sulfate salt concentration of 1g/L, and a Congo red concentration of 0.1 g/L. The flux and retention results are shown in table 3.
Table 3:
as can be seen from table 3, different concentrations of sulfonated polyethyleneimine in the aqueous phase have a significant effect on the performance of the resulting membrane. When the water phase concentration of the sulfonated polyethyleneimine is 0.15 wt%, the nanofiltration membrane shows better loose nanofiltration performance.
Test example 4
SPEI loose nanofiltration membranes of examples 15-16 were tested for water flux, sodium sulfate salt, and Congo red rejection at an operating pressure of 0.6MPa, a sodium sulfate salt concentration of 1g/L, and a Congo red concentration of 0.1 g/L. The flux and retention results are shown in table 4.
Table 4:
as can be seen from table 4, different concentrations of sulfonated polyethyleneimine in the aqueous phase have a significant effect on the performance of the resulting membrane. When the concentration of the oil phase TMC is 0.15 wt%, the nanofiltration membrane shows better loose nanofiltration performance.
The nanofiltration membrane of comparative example 1 was subjected to tests for water flux and sodium sulfate salt rejection, wherein the operating pressure was 0.6MPa, the sodium sulfate salt concentration was 1g/L, and the flux and salt rejection are shown in table 5.
Table 5:
as can be seen from Table 5, the interfacial polymerization prepared nanofiltration membrane using sulfonated PEI as the aqueous phase showed very high water flux and low salt rejection. It is demonstrated that the monomer properties can be significantly altered by introducing sulfonic acid groups, resulting in reversal of membrane performance.
Water flux (J) in the above examples and comparative examplesw，L/m2h) Calculated according to the following formula:
wherein V represents the volume of solution (L) permeated through the membrane, and A is the effective filtration area (m) of the membrane2) △ t is filtration time (h)
Salt rejection and dye rejection were calculated using the following formulas:
wherein C ispIs the conductivity or maximum UV absorption value, C, of the permeatefIs the conductivity or maximum uv absorption value of the feedstock solution.
Claims (10)
1. Sulfonated polyethyleneimine, which is characterized in that the sulfonated polyethyleneimine is obtained by ring-opening reaction of polyethyleneimine and sultone sulfonate.
2. A method of preparing a sulfonated polyethyleneimine, comprising:
and adding sultone sulfonate and ammonia water into the polyethyleneimine solution, stirring for reaction, filtering, and freeze-drying to obtain the sulfonated polyethyleneimine.
3. The preparation method according to claim 2, wherein the polyethyleneimine is one or more of branched or linear polyethyleneimine with molecular weight of 600Da, 1800Da, 1000Da, 1500Da, 5000Da, 10000Da, 70000 Da; the sulfolactone is 1, 3-propanesulfolactone and/or butanesulfolactone; the mass ratio of the sultone sulfonate to the polyethyleneimine is 1:100 to 100: 1.
4. The method according to claim 2, wherein the solvent of the polyethyleneimine solution is an organic alcohol; the mass concentration of the polyethyleneimine solution is 0.2-90%; the adding amount of the ammonia water is 0.1-10% of the volume of the solvent.
5. A sulfonated polyethyleneimine hydrophobic composite nanofiltration membrane, which is obtained by interfacial polymerization of an aqueous phase monomer and an oil phase monomer on the surface of a porous support membrane, wherein the aqueous phase monomer comprises the sulfonated polyethyleneimine as claimed in claim 1; the oil phase monomer comprises aromatic acid chloride.
6. A preparation method of a sulfonated polyethyleneimine composite nanofiltration membrane comprises the following steps:
immersing the porous support membrane into the water phase solution for reaction, taking out and discharging the solution with excessive surface, immersing the porous support membrane into the oil phase solution for reaction, and performing heat treatment and soaking cleaning to obtain the sulfonated polyethyleneimine composite nanofiltration membrane; wherein the water phase solution: an aqueous solution containing sulfonated polyethyleneimine; oil phase solution: an organic solution containing an aromatic acid chloride.
7. The preparation method according to claim 6, wherein the porous support membrane is one or more of a polysulfone ultrafiltration membrane, a polyethersulfone ultrafiltration membrane and a polyacrylonitrile ultrafiltration membrane.
8. The preparation method according to claim 6, wherein the aromatic acyl chloride is one or more of benzene tricarboxy chloride, phthalic acid dichloride, isophthaloyl dichloride, terephthaloyl dichloride and pyromellitic acid dichloride; the mass concentration of the aromatic acyl chloride in the oil phase solution is 0.01-1%; the mass concentration of the sulfonated polyethyleneimine in the aqueous phase solution is 0.01-10.0%.
9. The preparation method according to claim 6, wherein the immersion in the aqueous solution is carried out for 1-60 min; immersing the mixture into the oil phase solution for reaction for 0.1-60 min; the heat treatment is carried out at 60 deg.C for 1-60 min.
10. Use of the sulfonated polyethyleneimine borrelight composite filter membrane according to claim 5.
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Cited By (4)
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| CN114452840A (en) * | 2022-01-28 | 2022-05-10 | 中山大学 | Graphene oxide modified separation membrane based on electrostatic spraying and preparation and application thereof |
| CN114471197A (en) * | 2022-03-10 | 2022-05-13 | 中国科学院过程工程研究所 | Mixed charged nanofiltration membrane as well as preparation method and application thereof |
| CN114797492A (en) * | 2021-01-19 | 2022-07-29 | 欧美新材料(浙江)有限公司 | Hyperbranched polyethyleneimine, water phase, composite nanofiltration membrane and preparation method thereof |
| CN114849501A (en) * | 2022-05-30 | 2022-08-05 | 沃顿科技股份有限公司 | Preparation method of nanofiltration membrane and nanofiltration membrane prepared by same |
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