CN112535955A - Decolorizing membrane and preparation method and application thereof - Google Patents
Decolorizing membrane and preparation method and application thereof Download PDFInfo
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- CN112535955A CN112535955A CN202011261168.XA CN202011261168A CN112535955A CN 112535955 A CN112535955 A CN 112535955A CN 202011261168 A CN202011261168 A CN 202011261168A CN 112535955 A CN112535955 A CN 112535955A
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Abstract
The invention provides a decolorizing membrane and a preparation method and application thereof, wherein the decolorizing membrane comprises a supporting layer and an active separation layer loaded on the supporting layer, the active separation layer comprises an interfacial polymerization product of an aqueous phase reactant and an oil phase reactant, the aqueous phase reactant comprises an amine-containing monomer and a polyphenol monomer, and the oil phase reactant comprises an acid halide functional group-containing monomer and an iron-containing compound. The preparation method of the decolorizing membrane comprises the steps of soaking a support membrane of a support layer with an aqueous phase reactant solution, taking out the support membrane to remove a surface solution, soaking the support membrane with an oil phase reactant solution to carry out interfacial polymerization reaction, taking out the support membrane to remove a surface organic solution, airing, and soaking with an alkaline solution to obtain the decolorizing membrane. The preparation method is easy to repeat and beneficial to industrial production, and the prepared decolorizing membrane is resistant to high temperature, pollution and alkali washing swelling, has high flux and pigment retention rate, and has stable flux in continuous operation and cleaning process.
Description
Technical Field
The invention belongs to the technical field of membrane separation, relates to a decolorizing membrane and a preparation method and application thereof, and particularly relates to an alkali-resistant eluting swelling decolorizing membrane and a preparation method and application thereof.
Background
With the development of industry, people pursue higher and higher appearance quality and grade of products, and how to decolor becomes a problem which is often encountered in industrial production of food industry, daily chemical industry, textile industry and the like. The membrane separation technology is a high-efficiency separation technology which utilizes the selective permeability of a membrane to separate a mixture under the action of concentration difference, pressure difference and the like to achieve the effects of extraction, purification or enrichment and the like, has the advantages of low energy consumption, low emission, high automation degree, small occupied area and the like, and is widely applied to the field of decolorization.
CN107803116A discloses a method for decolorizing vegetable wax by using commercial nanofiltration membrane, which comprises the following steps: providing a raw material liquid of vegetable wax and a selectively permeable first nanofiltration membrane, forming a first penetrating liquid and a first trapped liquid by contacting the raw material liquid with the first nanofiltration membrane, and finally enriching the pigment in the trapped liquid.
CN107325016A discloses a high-quality ornithine extraction method, which comprises the following steps: microfiltration, decolorization, concentration, pH adjustment, concentration and crystallization, water washing, drying and crystallization crushing. Wherein the organic decolorizing membrane system of the decolorizing treatment part adopts a nanofiltration membrane with the molecular weight cut-off of about 100-1000.
CN107937628A discloses a sugarcane sugar making system utilizing all components and a processing method thereof, wherein the system comprises a pretreatment unit, a multi-stage membrane filtration system and a concentrated solution processing unit. Wherein the decolorizing membrane is a separating membrane adopted in a multi-stage membrane filtration system.
CN109289557A discloses a decolorizing membrane, and a preparation method and an application thereof, wherein the decolorizing membrane comprises an active separation layer and a support layer, the active separation layer comprises an interfacial polymerization product of an aqueous phase reactant and an oil phase reactant, and the aqueous phase reactant comprises an amine-containing monomer and polyelectrolyte. The preparation method of the decolorizing membrane comprises the steps of soaking the support membrane of the support layer by using an aqueous phase reactant solution, taking out the support membrane to remove a surface solution, and soaking the support membrane by using an oil phase reactant solution to carry out interfacial polymerization reaction to obtain the decolorizing membrane.
The above-mentioned separation layers of the decolorizing membranes each contain a large amount of carboxyl groups, and the electronegativity of the carboxyl groups increases in an alkaline environment, resulting in an increase in electrostatic repulsive force between the carboxyl groups, thereby expanding the structure of the separation layer and failing to recover in a short time. The alkaline washing is the most common washing method in the use process of the nanofiltration membrane, and in the continuous filtration process, as the membrane pores expand after the alkaline washing, pollutants are more likely to enter the interior of the membrane pores to form irreversible pollution, so that the irreversible pollution is easy to accumulate, and the flux is gradually attenuated. In addition, the membrane pores are expanded, which causes negative effects such as a decrease in retention rate and an increase in pigment permeation. However, since the increase of carboxyl groups can improve the hydrophilicity and contamination resistance of the decolorizing film, most studies have been made to increase the number of carboxyl groups by means of modification or the like, while neglecting the problem of alkaline swelling.
Therefore, it is very useful to develop a decolorizing membrane for pigment removal which has both high hydrophilicity and resistance to alkali washing swelling.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a decolorizing membrane and a preparation method and application thereof, and particularly provides an alkali-resistant elution swelling decolorizing membrane and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present disclosure provides a decolorizing membrane that includes a support layer and an active separation layer supported on the support layer, the active separation layer including an interfacial polymerization product of an aqueous phase reactant and an oil phase reactant, the aqueous phase reactant including an amine-containing monomer and a polyphenol monomer.
According to the invention, a polyphenol monomer contained in the decolorizing membrane can generate Michael addition covalent bonding reaction with an amine-containing monomer, so that a separation layer and a support layer prepared by interfacial polymerization have higher bonding force; meanwhile, the existence of a large number of phenolic hydroxyl groups can enhance the hydrophilicity and the pollution resistance of the membrane; in addition, hydroxyl groups are weaker in electronegativity than carboxyl groups, and the degree of electronegativity enhancement in an alkaline environment is lower, which contributes to reducing the degree of swelling of the membrane structure.
In the present invention, the amine-containing monomer includes any one of an aromatic organic compound having at least two amine functional groups, an aliphatic organic compound having at least two amine functional groups, or an alicyclic organic compound having at least two amine functional groups, or a combination of at least two thereof.
Preferably, the amine-containing monomer comprises any one of piperazine, polyetheramine, ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, polyvinylamine, polyethyleneimine, cyclohexanediamine, phenylenediamine, or benzenetriamine, or a combination of at least two thereof. Combinations of the at least two, such as piperazine and polyetheramine, ethylenediamine and propylenediamine, diethylenetriamine and triethylenetetramine, polyvinylamine and polyethyleneimine, and cyclohexanediamine, and the like.
In the present invention, the polyphenol containing monomer includes any one of dopamine, tannic acid, catechol, or gallic acid or a combination of at least two thereof. Combinations of at least two of the foregoing, such as dopamine and tannic acid, catechol and gallic acid, and the like.
In the present invention, the oil phase reactant includes an acid halide functional group-containing monomer and an iron-containing compound.
Preferably, the acyl halide functional group-containing monomer includes any one of or a combination of at least two of an aromatic organic substance having at least two acyl halide functional groups, an aliphatic organic substance having at least two acyl halide functional groups, or an alicyclic organic substance having at least two acyl halide functional groups.
Preferably, the acyl halide functional group-containing monomer includes any one of or a combination of at least two of phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesoyl chloride, methyl isophthaloyl chloride, 1,3, 5-cyclohexanetrioyl chloride, biphenyl triacyl chloride, biphenyl tetracoyl chloride, 5-oxoformyl chloride-isophthaloyl chloride, or 5-isocyanate-isophthaloyl chloride. Combinations of the at least two, such as phthaloyl chloride and isophthaloyl chloride, terephthaloyl chloride and trimesoyl chloride, methyl isophthaloyl and 1,3, 5-cyclohexanetrioyl chloride, and biphenyltriacyl chloride, and the like.
In the present invention, the iron-containing compound is an iron-containing compound that is soluble in an organic solvent.
Preferably, the iron-containing compound comprises iron acetylacetonate and/or ferrocene.
In the invention, the support layer is a porous ultrafiltration support membrane.
Preferably, the porous ultrafiltration support membrane has a molecular weight cut-off of 10000-.
Preferably, the material of the porous ultrafiltration support membrane comprises any one or a combination of at least two of polyethylene, polyamide, polyimide, polyetherimide, polytetrafluoroethylene, polyvinylidene fluoride, polysulfone or polyethersulfone. Combinations of at least two of the foregoing, such as polyethylene and polyamide, polyimide and polyetherimide, polytetrafluoroethylene and polyvinylidene fluoride, and polysulfone, and the like.
In another aspect, the present invention provides a method for preparing the decolorizing film, comprising the steps of:
and soaking the support membrane of the support layer by using an aqueous phase reactant solution, taking out the support membrane to remove a surface solution, soaking the support membrane by using an oil phase reactant solution to perform interfacial polymerization reaction, taking out the support membrane to remove a surface organic solution, and soaking the support membrane by using an alkaline solution after drying to obtain the decolorizing membrane.
Polyphenol monomers contained in the decolorizing membrane participate in interfacial polymerization reaction to form ester bonds, and the crosslinking degree of a separation layer can be regulated and controlled through subsequent alkali soaking treatment and damage; meanwhile, the polyphenol monomer can be coordinated and combined with the iron-containing compound in the oil phase solution. The decolorizing membrane adopts a mode of preparing a composite membrane by interfacial polymerization, a support layer, an active separation layer, a polyphenol monomer, an amine-containing monomer, an acyl halide organic matter and an iron-containing compound in the active separation layer are separately designed and then coupled, and the preparation method is easy to repeat and is beneficial to industrial production. In order to stabilize the interfacial polymerization layer, the support layer needs to be removed to remove the surface solution after the support membrane is immersed in the water phase and the support membrane is immersed in the oil phase for the interfacial polymerization reaction.
In the present invention, the alkaline solute contained in the alkaline solution is a compound that can be dissolved in water and makes the solution pH greater than 11;
preferably, the basic solute comprises any one of sodium hydroxide, potassium hydroxide, ammonia, triethylamine, pyridine, hydroxylamine 2-methylpyridine or 3-methylpyridine or a combination of at least two of the above. Combinations of the at least two, such as sodium and potassium hydroxide, ammonia and triethylamine, pyridine and hydroxylamine 2-methylpyridine and 3-methylpyridine, and the like.
Preferably, the pH of the alkaline solution is 11.0-12.5, such as 11.0, 11.5, 12.0 or 12.5, etc.
Preferably, the method for preparing the aqueous phase reactant solution is a physical blending method.
Preferably, the aqueous reactant solution contains 0.1 to 3g (e.g., 0.1g, 0.2g, 0.3g, 0.4g, 0.6g, 0.8g, 1g, 2g, or 3g, etc.) of solute per 100g of aqueous reactant solution.
Preferably, the solvent of the oil phase reactant solution is benzene, petroleum ether, n-hexane, cyclohexane, p-xylene.
Preferably, the oil phase reactant solution contains 0.1-3g (e.g., 0.1g, 0.2g, 0.3g, 0.4g, 0.6g, 0.8g, 1g, 2g, or 3g, etc.) of solute per 100 mL.
Preferably, the time for impregnating the support film of the support layer with the aqueous phase reactant solution is 1-60min, such as 1min, 5min, 10min, 20min, 30min, 40min, 50min or 60min, etc., preferably 1-20 min.
Preferably, the interfacial polymerization is carried out for a time ranging from 2 to 300s, such as 2s, 10s, 20s, 50s, 100s, 150s, 180s, 200s, 250s or 300s, etc., preferably from 2 to 180 s.
Preferably, the time for soaking in the alkaline solution is 15-60min, such as 15min, 20min, 30min, 40min, 50min or 60min, etc., preferably 15-30 min.
Preferably, after the alkaline solution is soaked, the membrane is subjected to heat treatment and is soaked in deionized water.
Preferably, the temperature of the heat treatment is 25-80 ℃, such as 25 ℃, 30 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃ or 80 ℃.
Preferably, the time of the heat treatment is 5-120min, such as 5min, 20min, 40min, 60min, 80min, 100min, 120 min.
Preferably, the heat treatment mode is oven heating or heating plate heating.
Preferably, the soaking time in deionized water is 2-24h, such as 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24 h.
The heat treatment is to complete the interfacial polymerization reaction, and the soaking in deionized water is to hydrolyze the unreacted acyl chloride on the support membrane.
As a preferred technical scheme of the invention, the preparation method specifically comprises the following steps:
(1) preparing an aqueous phase reactant solution containing amine-containing monomers and polyphenol monomers by adopting a physical blending method, so that 0.1-3g of solute is contained in every 100g of the aqueous phase reactant solution;
(2) preparing an oil phase reactant solution containing an acyl halide functional group-containing monomer and an iron-containing compound by using an organic solvent, so that 0.1-3g of solute is contained in each 100mL of the oil phase reactant solution;
(3) cleaning a support membrane of the support layer;
(4) soaking the support membrane of the support layer with the aqueous phase reactant solution for 1-60min, taking out the support membrane to remove the surface solution, and soaking the support membrane with the oil phase reactant solution for 2-300s to perform interfacial polymerization;
(5) taking out the support film to remove the organic solution on the surface, and soaking for 15-60min by using an alkaline solution;
(6) and (3) soaking the film in an alkaline solution, then carrying out heat treatment on the film at 25-80 ℃ in an oven or a heating plate manner for 5-120min, and soaking the film in deionized water for 2-24h to obtain the decolorization film.
By introducing a large amount of phenolic hydroxyl and iron ions in the interfacial polymerization process, the alkali-resistant washing swelling performance is greatly improved while strong hydrophilicity and pollution resistance are ensured, and the polyamide nanofiltration membrane is beneficial to improving the stability of the decolorizing membrane in the use process and meets the industrial application.
In a further aspect, the present invention provides the use of a decolorizing membrane as described above for decolorizing a product.
Preferably, the product is a product in the food industry, the daily chemical industry, the environmental protection industry or the textile industry.
Compared with the prior art, the invention at least has the following beneficial effects:
the polyphenol monomer contained in the decolorizing membrane of the invention: on one hand, the composite membrane can generate Michael addition covalent bonding reaction with amine-containing monomers and firmly adhere to the surface of a supporting membrane, so that a separation layer and a supporting layer prepared by interfacial polymerization have higher bonding force, and the stability of the composite membrane is improved; on the other hand, the polymer can participate in interfacial polymerization reaction to form an ester bond, and can be destroyed through subsequent alkali soaking treatment to regulate and control the crosslinking degree of a separation layer; on the other hand, the iron-containing compound in the oil phase solution can be subjected to coordination bonding, and the coordination bonding force is kept stable in an alkaline environment, so that the anti-swelling performance of the separation layer in the alkaline washing process can be enhanced;
meanwhile, the existence of a large number of phenolic hydroxyl groups can enhance the hydrophilicity and the pollution resistance of the membrane; in addition, hydroxyl groups are weaker in electronegativity than carboxyl groups, and the degree of electronegativity enhancement in an alkaline environment is lower, which contributes to reducing the degree of swelling of the membrane structure.
Meanwhile, iron ions provided by the iron-containing compound in the organic phase can be subjected to coordination and combination with phenolic hydroxyl in the separating layer polymer, and can also be subjected to coordination and combination with carboxyl generated by the reaction of the amine-containing monomer and the organic acyl halide, and the coordination and combination force is kept stable in an alkaline environment, so that the anti-swelling performance of the separating layer in the alkaline washing process can be enhanced.
In addition, the decolorizing membrane adopts a mode of preparing the composite membrane by interfacial polymerization, the support layer, the active separation layer, the polyphenol monomer, the amine-containing monomer, the acyl halide organic matter and the iron-containing compound in the active separation layer are separately designed and then coupled, and the preparation method is easy to repeat and is beneficial to industrial production.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
This example provides a decolorizing membrane that includes a support layer and an active separation layer supported on the support layer, the active separation layer comprising an interfacial polymerization product of an aqueous phase reactant comprising an amine-containing monomer and a polyphenol monomer and an oil phase reactant comprising an acid halide-containing functional group monomer and an iron-containing compound. The preparation method comprises the following steps:
preparing an aqueous reactant solution containing piperazine and tannic acid by a physical blending method so that 0.5g of solute is contained in each 100g of the aqueous reactant solution; selecting a normal hexane solvent to prepare an oil phase reactant solution containing trimesoyl chloride and ferric acetylacetonate, so that 0.2g of solute is contained in each 100mL of the oil phase reactant solution; impregnating the polyethersulfone ultrafiltration membrane with the aqueous phase reactant solution for 5min, taking out the ultrafiltration membrane to remove the surface solution, and impregnating the ultrafiltration membrane with the oil phase reactant solution for 60s to perform interfacial polymerization; taking out the support membrane to remove the organic solution on the surface, and soaking for 20min by using an alkaline solution containing sodium hydroxide solute and having a pH value of 11.0; and after the soaking in the alkaline solution is finished, performing heat treatment on the film at 50 ℃ for 10min in a heating plate mode, and soaking the film in deionized water for 2h to obtain the decolorizing film.
Example 2
This example provides a decolorizing membrane that includes a support layer and an active separation layer supported on the support layer, the active separation layer comprising an interfacial polymerization product of an aqueous phase reactant comprising an amine-containing monomer and a polyphenol monomer and an oil phase reactant comprising an acid halide-containing functional group monomer and an iron-containing compound. The preparation method comprises the following steps:
preparing an aqueous phase reactant solution containing piperazine and catechol by a physical blending method so that 1g of solute is contained in each 100g of the aqueous phase reactant solution; preparing an oil phase reactant solution containing trimesoyl chloride and ferrocene by using a petroleum ether solvent, so that 0.3g of solute is contained in each 100mL of the oil phase reactant solution; impregnating the polysulfone ultrafiltration membrane with the aqueous phase reactant solution for 20min, taking out the ultrafiltration membrane to remove the surface solution, and impregnating the ultrafiltration membrane with the oil phase reactant solution for 30s to perform interfacial polymerization reaction; taking out the support membrane to remove the organic solution on the surface, and soaking for 60min by using an alkaline solution containing an ammonia water solute and having a pH value of 12.0; and after the alkaline solution is soaked, performing heat treatment on the film at 70 ℃ for 6min in an oven heating mode, and soaking the film in deionized water for 24h to obtain the decolorizing film.
Example 3
This example provides a decolorizing membrane that includes a support layer and an active separation layer supported on the support layer, the active separation layer comprising an interfacial polymerization product of an aqueous phase reactant comprising an amine-containing monomer and a polyphenol monomer and an oil phase reactant comprising an acid halide-containing functional group monomer and an iron-containing compound. The preparation method comprises the following steps:
preparing an aqueous phase reactant solution containing piperazine and gallic acid by a physical blending method, so that 0.2g of solute is contained in every 100g of the aqueous phase reactant solution; selecting a normal hexane solvent to prepare an oil phase reactant solution containing trimesoyl chloride and ferric acetylacetonate, so that 0.1g of solute is contained in each 100mL of the oil phase reactant solution; dipping the polyetherimide ultrafiltration membrane for 1min by using the aqueous phase reactant solution, taking out the ultrafiltration membrane to remove the surface solution, and dipping the ultrafiltration membrane for 180s by using the oil phase reactant solution to perform interfacial polymerization; taking out the support membrane to remove the organic solution on the surface, and soaking for 30min by using alkaline solution containing pyridine solute and having a pH value of 12.5; and after the soaking in the alkaline solution is finished, performing heat treatment on the film at 25 ℃ for 120min in an oven drying mode, and soaking the film in deionized water for 24h to obtain the decolorizing film.
Example 4
This example provides a decolorizing membrane that includes a support layer and an active separation layer supported on the support layer, the active separation layer comprising an interfacial polymerization product of an aqueous phase reactant comprising an amine-containing monomer and a polyphenol monomer and an oil phase reactant comprising an acid halide-containing functional group monomer and an iron-containing compound. The preparation method comprises the following steps:
preparing an aqueous reactant solution containing piperazine and tannic acid by a physical blending method so that 0.4g of solute is contained in each 100g of the aqueous reactant solution; selecting a normal hexane solvent to prepare an oil phase reactant solution containing trimesoyl chloride and ferric acetylacetonate, so that 0.4g of solute is contained in each 100mL of the oil phase reactant solution; dipping the polyetherimide ultrafiltration membrane for 30min by using the aqueous phase reactant solution, taking out the ultrafiltration membrane to remove the surface solution, and dipping the ultrafiltration membrane for 2s by using the oil phase reactant solution to perform interfacial polymerization reaction; taking out the support membrane to remove the organic solution on the surface, and soaking for 15min by using an alkaline solution containing sodium hydroxide solute and having a pH value of 11.0; and after the soaking in the alkaline solution is finished, performing heat treatment on the film for 20min at 40 ℃ in an oven drying mode, and soaking the film in deionized water for 36h to obtain the decolorizing film.
Example 5
This example provides a decolorizing membrane that includes a support layer and an active separation layer supported on the support layer, the active separation layer comprising an interfacial polymerization product of an aqueous phase reactant comprising an amine-containing monomer and a polyphenol monomer and an oil phase reactant comprising an acid halide-containing functional group monomer and an iron-containing compound. The preparation method comprises the following steps:
preparing an aqueous phase reactant solution containing cyclohexanediamine and catechol by a physical blending method so that 0.1g of solute is contained in every 100g of the aqueous phase reactant solution; selecting a normal hexane solvent to prepare an oil phase reactant solution containing trimesoyl chloride and ferric acetylacetonate, so that 1.5g of solute is contained in each 100mL of the oil phase reactant solution; dipping the polyetherimide ultrafiltration membrane for 10min by using the aqueous phase reactant solution, taking out the ultrafiltration membrane to remove the surface solution, and dipping the ultrafiltration membrane for 150s by using the oil phase reactant solution to perform interfacial polymerization; taking out the support membrane to remove the organic solution on the surface, and soaking for 40min by using an alkaline solution containing an ammonia water solute and having a pH value of 11.5; and after the alkaline solution is soaked, carrying out heat treatment on the film at 30 ℃ for 60min in an oven mode, and soaking the film in deionized water for 36h to obtain the decolorizing film.
Example 6
This example provides a decolorizing membrane that includes a support layer and an active separation layer supported on the support layer, the active separation layer comprising an interfacial polymerization product of an aqueous phase reactant comprising an amine-containing monomer and a polyphenol monomer and an oil phase reactant comprising an acid halide-containing functional group monomer and an iron-containing compound. The preparation method comprises the following steps:
preparing an aqueous phase reactant solution containing ethylenediamine and tannic acid by a physical blending method so that each 100g of the aqueous phase reactant solution contains 3g of solute; preparing an oil phase reactant solution containing phthaloyl chloride and ferrocene by using a petroleum ether solvent, so that each 100mL of the oil phase reactant solution contains 3g of solute; dipping the polyetherimide ultrafiltration membrane by using the aqueous phase reactant solution for 60min, taking out the ultrafiltration membrane to remove the surface solution, and dipping the ultrafiltration membrane by using the oil phase reactant solution for 300s to perform interfacial polymerization; taking out the support membrane to remove the organic solution on the surface, and soaking for 50min by using alkaline solution containing pyridine solute and having a pH value of 12.0; and after the soaking in the alkaline solution is finished, performing heat treatment on the film at 80 ℃ for 5min in a heating plate heating mode, and soaking the film in deionized water for 12h to obtain the decolorization film.
Comparative example 1
This comparative example provides a decolorizing membrane that includes an active separation layer that includes an interfacial polymerization product of an aqueous phase reactant that includes an amine-containing monomer and an oil phase reactant that includes an acid halide-containing functional group monomer, and a support layer. The preparation method comprises the following steps:
preparing an aqueous phase reactant solution containing piperazine by a physical blending method so that 0.5g of solute is contained in every 100g of the aqueous phase reactant solution; selecting a normal hexane solvent to prepare an oil phase reactant solution containing trimesoyl chloride, so that 0.2g of solute is contained in each 100mL of the oil phase reactant solution; impregnating the polyethersulfone ultrafiltration membrane with the aqueous phase reactant solution for 5min, taking out the ultrafiltration membrane to remove the surface solution, and impregnating the ultrafiltration membrane with the oil phase reactant solution for 60s to perform interfacial polymerization; taking out the support membrane to remove the organic solution on the surface, and soaking for 20min by using an alkaline solution containing sodium hydroxide solute and having a pH value of 11.0; and after the soaking of the interfacial polymerization reaction alkaline solution is finished, performing heat treatment on the film at 50 ℃ for 10min in a heating plate mode, and soaking the film in deionized water for 2h to obtain the decolorization film.
Comparative example 2
The present comparative example provides a decolorizing membrane, comprising a support layer and an active separation layer supported on the support layer, the active separation layer comprising an interfacial polymerization product of an aqueous phase reactant comprising an amine-containing monomer and an oil phase reactant comprising an acid halide functional group-containing monomer and an iron-containing compound. The preparation method comprises the following steps:
preparing an aqueous phase reactant solution containing piperazine by a physical blending method so that 0.5g of solute is contained in every 100g of the aqueous phase reactant solution; selecting a normal hexane solvent to prepare an oil phase reactant solution containing trimesoyl chloride and ferric acetylacetonate, so that 0.2g of solute is contained in each 100mL of the oil phase reactant solution; impregnating the polyethersulfone ultrafiltration membrane with the aqueous phase reactant solution for 5min, taking out the ultrafiltration membrane to remove the surface solution, and impregnating the ultrafiltration membrane with the oil phase reactant solution for 60s to perform interfacial polymerization; taking out the support membrane to remove the organic solution on the surface, and soaking for 20min by using an alkaline solution containing sodium hydroxide solute and having a pH value of 11.0; and after the soaking in the alkaline solution is finished, performing heat treatment on the film at 50 ℃ for 10min in a heating plate mode, and soaking the film in deionized water for 2h to obtain the decolorizing film.
Comparative example 3
This comparative example provides a decolorizing membrane comprising a support layer and an active separation layer supported on the support layer, the active separation layer comprising an interfacial polymerization product of an aqueous phase reactant comprising an amine-containing monomer and a polyphenol monomer and an oil phase reactant comprising an acid halide-containing functional group monomer. The preparation method comprises the following steps:
preparing an aqueous reactant solution containing piperazine and tannic acid by a physical blending method so that 0.5g of solute is contained in each 100g of the aqueous reactant solution; selecting a normal hexane solvent to prepare an oil phase reactant solution containing trimesoyl chloride, so that 0.2g of solute is contained in each 100mL of the oil phase reactant solution; impregnating the polyethersulfone ultrafiltration membrane with the aqueous phase reactant solution for 5min, taking out the ultrafiltration membrane to remove the surface solution, and impregnating the ultrafiltration membrane with the oil phase reactant solution for 60s to perform interfacial polymerization; taking out the support membrane to remove the organic solution on the surface, and soaking for 20min by using an alkaline solution containing sodium hydroxide solute and having a pH value of 11.0; and after the soaking in the alkaline solution is finished, performing heat treatment on the film at 50 ℃ for 10min in a heating plate mode, and soaking the film in deionized water for 2h to obtain the decolorizing film.
The decolorization membranes obtained in examples 1 to 6 and comparative examples 1 to 3 were tested for water flux and sodium sulfate rejection at 25 ℃, and for maximum transmembrane pressure difference, Brix rejection (soluble solid content rejection), pigment removal, membrane fouling, and alkali wash swelling rate of each decolorization membrane when molasses feed liquid was treated at 60 ℃ and a constant flow rate of 0.13 mL/min. The test results are shown in table 1.
TABLE 1
From the results in Table 1, it can be seen that:
compared with the decolorizing membranes prepared in comparative examples 1 to 3, the decolorizing membranes prepared in examples 1 to 6 have more stable performance, higher flux (small maximum transmembrane pressure difference) and pigment removal rate, stronger pollution resistance and stronger alkali-resistant washing and swelling capacity.
The applicant states that the present invention is illustrated by the above examples to the decolorized membrane of the present invention and the method of preparation and application thereof, but the present invention is not limited to the above examples, that is, it does not mean that the present invention must be practiced by relying on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
Claims (10)
1. A decolorizing membrane, comprising a support layer and an active separation layer supported on the support layer, wherein the active separation layer comprises an interfacial polymerization product of an aqueous phase reactant and an oil phase reactant, and the aqueous phase reactant comprises an amine-containing monomer and a polyphenol monomer.
2. The decolorizing membrane of claim 1, wherein said amine-containing monomer comprises any one or a combination of at least two of an aromatic organic compound having at least two amine functional groups, an aliphatic organic compound having at least two amine functional groups, or a cycloaliphatic organic compound having at least two amine functional groups;
preferably, the amine-containing monomer comprises any one of piperazine, polyetheramine, ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, polyvinylamine, polyethyleneimine, cyclohexanediamine, phenylenediamine, or benzenetriamine, or a combination of at least two thereof.
3. The decolorizing membrane of claim 1 or 2, wherein said polyphenol containing monomers comprise any one or a combination of at least two of dopamine, tannic acid, catechol, or gallic acid.
4. The decolorizing membrane of any of claims 1-3, wherein said oil phase reactants comprise an acid halide functional group-containing monomer and an iron-containing compound;
preferably, the acyl halide functional group-containing monomer comprises any one of or a combination of at least two of an aromatic organic substance having at least two acyl halide functional groups, an aliphatic organic substance having at least two acyl halide functional groups, or a cycloaliphatic organic substance having at least two acyl halide functional groups;
preferably, the acyl halide functional group-containing monomer includes any one of or a combination of at least two of phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesoyl chloride, methyl isophthaloyl chloride, 1,3, 5-cyclohexanetrioyl chloride, biphenyl triacyl chloride, biphenyl tetracoyl chloride, 5-oxoformyl chloride-isophthaloyl chloride, or 5-isocyanate-isophthaloyl chloride.
5. The decolorizing membrane of any of claims 1-4, wherein said iron-containing compound is an iron-containing compound that is soluble in an organic solvent;
preferably, the iron-containing compound comprises iron acetylacetonate and/or ferrocene.
6. The decolorizing membrane of any of claims 1-5, wherein said support layer is a porous ultrafiltration support membrane;
preferably, the molecular weight cut-off of the porous ultrafiltration support membrane is 10000-;
preferably, the material of the porous ultrafiltration support membrane comprises any one or a combination of at least two of polyethylene, polyamide, polyimide, polyetherimide, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, polysulfone or polyethersulfone.
7. The method for preparing a decolorizing film as recited in claims 1-6, characterized in that said method comprises the steps of:
and soaking the support membrane of the support layer by using an aqueous phase reactant solution, taking out the support membrane to remove a surface solution, soaking the support membrane by using an oil phase reactant solution to perform interfacial polymerization reaction, taking out the support membrane to remove a surface organic solution, and soaking the support membrane by using an alkaline solution after drying to obtain the decolorizing membrane.
8. The method for producing a decolorizing membrane as claimed in claim 7, wherein said alkaline solution contains an alkaline solute which is a compound capable of dissolving in water and having a solution pH of more than 11;
preferably, the alkaline solute comprises any one of sodium hydroxide, potassium hydroxide, ammonia water, triethylamine, pyridine, hydroxylamine 2-methylpyridine or 3-methylpyridine or a combination of at least two of the above;
preferably, the pH value of the alkaline solution is 11.0-12.5;
preferably, the preparation method of the aqueous phase reactant solution is a physical blending method;
preferably, the aqueous reactant solution contains 0.1 to 3g of solute per 100g of aqueous reactant solution;
preferably, the solvent of the oil phase reactant solution is benzene, petroleum ether, n-hexane, cyclohexane, p-xylene;
preferably, the oil phase reactant solution contains 0.1-3g of solute per 100 mL;
preferably, the time for soaking the support membrane of the support layer by the aqueous phase reactant solution is 1-60min, preferably 1-20 min;
preferably, the interfacial polymerization is carried out for a time ranging from 2 to 300s, preferably from 2 to 180 s;
preferably, the time for soaking in the alkaline solution is 15-60min, preferably 15-30 min;
preferably, after the alkaline solution is soaked, the membrane is subjected to heat treatment and is soaked in deionized water;
preferably, the temperature of the heat treatment is 25-80 ℃;
preferably, the time of the heat treatment is 5-120 min;
preferably, the heat treatment mode is oven heating or heating plate heating;
preferably, the soaking time in the deionized water is 2-24 h.
9. The method for preparing a decolorizing film according to claim 7 or 8, characterized in that it comprises in particular the steps of:
(1) preparing an aqueous phase reactant solution containing amine-containing monomers and polyphenol monomers by adopting a physical blending method, so that 0.1-3g of solute is contained in every 100g of the aqueous phase reactant solution;
(2) preparing an oil phase reactant solution containing an acyl halide functional group-containing monomer and an iron-containing compound by using an organic solvent, so that 0.1-3g of solute is contained in each 100mL of the oil phase reactant solution;
(3) cleaning a support membrane of the support layer;
(4) soaking the support membrane of the support layer with the aqueous phase reactant solution for 1-60min, taking out the support membrane to remove the surface solution, and soaking the support membrane with the oil phase reactant solution for 2-300s to perform interfacial polymerization;
(5) taking out the support film to remove the organic solution on the surface, and soaking for 15-60min by using an alkaline solution;
(6) and soaking the film in an alkaline solution, then carrying out heat treatment on the film at 25-80 ℃ in an oven or a heating plate manner for 5-120min, and soaking the film in deionized water for 2-24h to obtain the decolorization film.
10. Use of a decolorizing membrane according to any of claims 1-6 for decolorizing a product;
preferably, the product is a product in the food industry, the daily chemical industry, the environmental protection industry or the textile industry.
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