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CN116870701B - Anti-fouling ultrafiltration membrane and application thereof in recycling of circulating water concentrated drainage - Google Patents

Anti-fouling ultrafiltration membrane and application thereof in recycling of circulating water concentrated drainage Download PDF

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CN116870701B
CN116870701B CN202311153035.4A CN202311153035A CN116870701B CN 116870701 B CN116870701 B CN 116870701B CN 202311153035 A CN202311153035 A CN 202311153035A CN 116870701 B CN116870701 B CN 116870701B
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ultrafiltration membrane
quaternary ammonium
fouling
alkenyl
ultrafiltration
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CN116870701A (en
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周卫华
陈谦
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Jiaxing Wattek Environmental Protection Technology Co ltd
Hangzhou Shangshanruoshui Environmental Protection Technology Co ltd
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Jiaxing Wattek Environmental Protection Technology Co ltd
Hangzhou Shangshanruoshui Environmental Protection Technology Co ltd
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    • 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
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • 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
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/48—Antimicrobial properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Water Supply & Treatment (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention discloses an anti-fouling ultrafiltration membrane and application thereof in recycling of circulating water concentrated drainage, and belongs to the technical field of ultrafiltration membranes. An anti-fouling ultrafiltration membrane comprising: the polyvinylidene fluoride ultrafiltration membrane and the alkenyl quaternary ammonium salt are grafted on the polyvinylidene fluoride ultrafiltration membrane, and the alkenyl quaternary ammonium salt is selected from alkenyl quaternary ammonium chloride or alkenyl pyridinium chloride. The anti-fouling ultrafiltration membrane has better antibacterial effect, hydrophilicity and pure water flux, and can be used in an ultrafiltration device for recycling the concentrated drainage of circulating water. The recycling method of the circulating water concentrated drainage comprises the following steps: filtering the circulating water concentrated drainage through a self-cleaning filter to obtain filtered effluent; introducing the filtered effluent into an ultrafiltration device adopting an anti-pollution ultrafiltration membrane, and performing ultrafiltration treatment in the presence of a slime control agent to obtain ultrafiltration effluent; and introducing the ultrafiltration effluent into a reverse osmosis device, regulating the pH value, and performing reverse osmosis treatment in the presence of a scale inhibitor to obtain reclaimed water and concentrated water, wherein the reclaimed water is reused in a circulating water system, and the concentrated water enters a concentrated water tank.

Description

Anti-fouling ultrafiltration membrane and application thereof in recycling of circulating water concentrated drainage
Technical Field
The invention belongs to the technical field of ultrafiltration membranes, and particularly relates to an anti-fouling ultrafiltration membrane and application thereof in recycling of circulating water concentrated drainage.
Background
In the current common use, the circulating water system with the maximum water consumption standard is of an open type, and various pollutants in the air, such as during the operation of the open type circulating water system; fly ash, impurities, soluble gases and the like can enter water in a circulating water system to different degrees, ions (such as calcium, magnesium, sulfate radical, chloride ions and the like), soluble solids and suspended matters in the circulating water can be increased along with the time, and the system can greatly breed microorganisms and generate scaling, corrosion and sticky mud adhesion in a pipeline of the system to cause the reduction of the heat exchange efficiency of the system. In order to prevent scaling caused by the rising of the salt content in the circulating water system after being continuously concentrated, a part of cooling water needs to be periodically discharged and a part of fresh water needs to be replenished, the discharged water is concentrated drainage, and the replenished water is system water replenishing. The water replenishing of the circulating water system accounts for 1.5% of the circulating water of the system, and the concentrated water draining accounts for 3-5% of the circulating water of the system. A common way to treat the concentrated wastewater of a circulating water system is to discharge directly or to enter a wastewater treatment system. In the prior art, the Chinese patent application No. 2009100909649 discloses a treatment and recycling method of industrial circulating water sewage, wherein the industrial circulating water sewage is treated by adopting a composite titanium oxide photocatalytic oxidation treatment technology, colloid, suspended matters and the like in the industrial circulating water sewage are removed by adopting an inorganic-organic composite flocculation precipitation and filtration method, and the produced water is treated by a hollow fiber ultrafiltration membrane and a reverse osmosis membrane so as to be recycled; the Chinese patent of application number 2021115831563 discloses a near zero emission treatment method for circulating water sewage, which comprises the steps of pretreating the sewage by a pretreatment process, then concentrating by a reverse osmosis process to obtain fresh water and concentrated water, further deeply treating the obtained concentrated water to reduce the treatment capacity of the subsequent concentrated water, wherein the fresh water reaches the recycling standard of circulating water supplementing water; and (3) carrying out evaporative crystallization treatment on the concentrated water after reduction to obtain evaporative condensate water for recycling and solid crystallization outward transportation treatment.
Disclosure of Invention
The invention aims to provide an anti-fouling ultrafiltration membrane with better antibacterial effect, hydrophilicity and pure water flux.
The technical scheme adopted by the invention for achieving the purpose is as follows:
an anti-fouling ultrafiltration membrane, the anti-fouling ultrafiltration membrane comprising:
polyvinylidene fluoride ultrafiltration membranes; and
the alkenyl quaternary ammonium salt is grafted on the polyvinylidene fluoride ultrafiltration membrane, and the alkenyl quaternary ammonium salt is selected from alkenyl quaternary ammonium chloride or alkenyl pyridinium chloride.
The quaternary ammonium salt can crack bacterial biomembrane, has better antibacterial effect, and the quaternary ammonium salt is grafted and copolymerized on the surface of the anti-fouling ultrafiltration membrane, so that the anti-fouling ultrafiltration membrane also has better antibacterial effect, can kill bacteria adhered on the surface of the ultrafiltration membrane, thereby improving the anti-microbial pollution performance of the surface of the ultrafiltration membrane, and has higher hydrophilicity and pure water flux compared with the polyvinylidene fluoride ultrafiltration membrane. In summary, the anti-fouling ultrafiltration membrane can obviously reduce microbial pollution, reduce maintenance cost and prolong service life.
In one embodiment, the alkenyl quaternary ammonium salt has a grafting ratio of 5-20%.
In a preferred embodiment, the alkenyl quaternary ammonium salt has a grafting ratio of 10-20%.
In one embodiment, the alkenyl quaternary ammonium chloride salt has the formula。
In a preferred embodiment, the alkenyl quaternary ammonium chloride salt has a grafting ratio of 10-16%.
In one embodiment, the alkenyl pyridinium chloride quaternary ammonium salt has the structural formula。
In a preferred embodiment, the grafting ratio of the alkenyl pyridinium chloride quaternary ammonium salt is 12-18%.
The invention also discloses a preparation method of the alkenyl quaternary ammonium chloride, which comprises the following steps:
adding cinnamoyl chloride and dimethylaminoethyl methacrylate into dichloromethane, reacting for 24-48h at 80-110 ℃, evaporating dichloromethane after the reaction is finished, washing with diethyl ether for 2-4 times, filtering, and drying to obtain alkenyl quaternary ammonium chloride salt.
In one embodiment, the molar ratio of cinnamoyl chloride to dimethylaminoethyl methacrylate is 1.2-1.6:1.
In one embodiment, the ratio of cinnamoyl chloride to dichloromethane is 1g:5-15mL.
The invention also discloses a preparation method of the alkenyl pyridine chloride quaternary ammonium salt, which comprises the following steps:
adding cinnamoyl chloride and 2-hydroxymethylpyridine into dichloromethane, reacting for 24-48h at 80-110 ℃, evaporating the solvent after the reaction is finished, washing with diethyl ether for 2-4 times, filtering, and drying to obtain pyridine chloride quaternary ammonium salt; and
Adding the pyridine chloride quaternary ammonium salt, a catalyst and a polymerization inhibitor into dichloromethane, uniformly stirring, dropwise adding isocyanoethyl methacrylate at 40-60 ℃, continuously stirring at 40-60 ℃ for reaction for 4-12h after the dropwise adding, evaporating dichloromethane by rotating, washing with diethyl ether for 2-4 times, and drying to obtain the alkenyl pyridine chloride quaternary ammonium salt.
In one embodiment, the molar ratio of cinnamoyl chloride to 2-hydroxymethylpyridine is 1.2-1.6:1.
In one embodiment, the ratio of cinnamoyl chloride to dichloromethane is 1g:5-15mL.
In one embodiment, the catalyst is dibutyltin dilaurate in an amount of 0.1-1wt% of the quaternary ammonium pyridinium chloride.
In one embodiment, the polymerization inhibitor is hydroquinone in an amount of 0.5 to 2wt% of the quaternary ammonium salt of pyridine chloride.
In one embodiment, the ratio of the quaternary ammonium pyridinium chloride to the methylene chloride is 1g to 5-15mL.
In one embodiment, the molar ratio of pyridinium chloride quaternary ammonium salt to isocyanatoethyl methacrylate is 1.0-1.2:1.
The invention also discloses a preparation method of the anti-fouling ultrafiltration membrane, which comprises the following steps:
washing and drying the polyvinylidene fluoride ultrafiltration membrane to obtain a dried polyvinylidene fluoride ultrafiltration membrane; and
Soaking the dried polyvinylidene fluoride ultrafiltration membrane in a solution containing benzophenone, pre-irradiating under ultraviolet light, adding alkenyl quaternary ammonium salt, performing copolymerization under ultraviolet light irradiation, rinsing after finishing, and drying to obtain the anti-fouling ultrafiltration membrane.
According to the preparation method, benzophenone is used as a photoinitiator, quaternary ammonium salt is used as a grafting monomer, and under the irradiation of ultraviolet light, the quaternary ammonium salt is grafted and copolymerized on the surface of the polyvinylidene fluoride ultrafiltration membrane, so that the anti-fouling ultrafiltration membrane is prepared, and the higher the grafting rate is, the better the antibacterial effect is; simultaneously, compared with the polyvinylidene fluoride ultrafiltration membrane, the anti-fouling ultrafiltration membrane has higher water flux.
In one embodiment, the polyvinylidene fluoride ultrafiltration membrane is washed and then dried by the following specific steps: and (3) placing the polyvinylidene fluoride ultrafiltration membrane in ethanol for ultrasonic cleaning for 30-60min, then placing the polyvinylidene fluoride ultrafiltration membrane in deionized water for ultrasonic cleaning for 30-60min, and drying to obtain the dried polyvinylidene fluoride ultrafiltration membrane.
In one embodiment, the benzophenone-containing solution is a methanol solution containing benzophenone at a concentration of 0.1 to 1.0mol/L.
In one embodiment, the alkenyl quaternary ammonium salt is selected from alkenyl quaternary ammonium chloride or alkenyl pyridinium chloride.
In a preferred embodiment, the alkenyl quaternary ammonium chloride salt has the formula。
In a preferred embodiment, the alkenyl pyridinium chloride quaternary ammonium salt has the formula。
In one embodiment, the alkenyl quaternary ammonium salt is added at a concentration of 5 to 20wt%.
In one embodiment, the pre-irradiation conditions are: the power of the ultraviolet light is 500-1000W, the light distance is 10-30cm, the irradiation temperature is 30-40 ℃ and the time is 5-10min.
In one embodiment, the conditions of the copolymerization are: the power of the ultraviolet light is 500-1000W, the light distance is 10-30cm, the irradiation temperature is 30-40 ℃ and the time is 10-30min.
In one embodiment, a method of preparing an anti-fouling ultrafiltration membrane, comprising:
placing the polyvinylidene fluoride ultrafiltration membrane in ethanol for ultrasonic cleaning for 30-60min, then placing the polyvinylidene fluoride ultrafiltration membrane in deionized water for ultrasonic cleaning for 30-60min, and drying to obtain a dried polyvinylidene fluoride ultrafiltration membrane; and
soaking the dried polyvinylidene fluoride ultrafiltration membrane in a methanol solution containing 0.1-1.0mol/L benzophenone, pre-irradiating for 5-10min under the ultraviolet light with the power of 500-1000W, the light distance of 10-30cm and the irradiation temperature of 30-40 ℃, adding alkenyl quaternary ammonium salt to the concentration of 5-20wt%, irradiating for 10-30min under the ultraviolet light with the power of 500-1000W and the light distance of 10-30cm and the irradiation temperature of 30-40 ℃, rinsing for 10-30min with methanol and deionized water sequentially after the completion, and drying to obtain the anti-fouling ultrafiltration membrane.
The invention also discloses application of the anti-fouling ultrafiltration membrane in preparing an ultrafiltration device.
The invention also discloses application of the ultrafiltration device in recycling of the circulating water concentrated drainage.
Another object of the present invention is to provide a method for recycling the concentrated wastewater of the circulating water, which can remove suspended particles, organic matters, slime, colloids and most of inorganic salts contained in the concentrated wastewater of the circulating water. The treated reclaimed water is used as the supplementing water of the circulating water system, thereby achieving the purposes of saving water, enhancing efficiency and reducing emission.
The technical scheme adopted by the invention for achieving the purpose is as follows:
a method for recycling a concentrated wastewater of circulating water, comprising:
filtering the circulating water concentrated drainage through a self-cleaning filter to obtain filtered effluent;
introducing the filtered effluent into an ultrafiltration device, and performing ultrafiltration treatment on the anti-fouling ultrafiltration membrane of the ultrafiltration device in the presence of a slime control agent to obtain ultrafiltration effluent; and
and (3) introducing ultrafiltration effluent into a reverse osmosis device, regulating the pH value, and performing reverse osmosis treatment in the presence of a scale inhibitor to obtain reclaimed water and concentrated water, wherein the reclaimed water is reused in a circulating water system, and the concentrated water enters a concentrated water tank.
The ultrafiltration device of the invention adopts the anti-fouling ultrafiltration membrane, which can obviously reduce biological pollution and reduce the fouling frequency of the ultrafiltration membrane, thereby reducing maintenance cost and prolonging service life. According to the method, the slime control agent is added into the inlet of the ultrafiltration device, so that the biological slime of the ultrafiltration device is prevented from being blocked, the slime control agent is not trapped by the ultrafiltration device, the slime control agent can enter ultrafiltration produced water, and the ultrafiltration produced water contains the slime control agent, so that the biological slime of the reverse osmosis device is prevented from being blocked. The method can realize recycling of the concentrated drainage of the circulating cooling water, and the obtained recycled water can be reused in a circulating water system, so that a part of water supplementing is replaced, the water supplementing usage amount is reduced, and the cost of fresh water supplementing is reduced; the method of the invention recovers the concentrated drainage, reduces the direct discharge amount of the concentrated drainage, and can directly reduce the wastewater treatment cost and the external drainage cost.
In one embodiment, the slime control agent includes a binding chlorine agent, the slime control agent having an effective chlorine concentration of 0.5-5mg/L.
In one embodiment, the binding chlorinating agent is a chloramine compound comprising monochloramine, dichloramine and trichlolamine in a weight ratio of 1:0.5 to 1:1 to 1.5.
In one embodiment, the slime control agent further comprises a buffer, an oxidizing agent, a stabilizer, and a solvent.
In one embodiment, the oxidizing agent is selected from at least one of sodium hypochlorite, hydrogen peroxide, or hypochlorous acid.
In one embodiment, the buffer is selected from at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, or sodium bicarbonate.
In one embodiment, the stabilizer is selected from one of zinc stearate or calcium stearate.
In one embodiment, the solvent is selected from one of water, ethanol, propanol, butanol, or petroleum ether.
In one embodiment, the slime control agent comprises: 1-10 parts of buffering agent, 20-50 parts of oxidant, 5-20 parts of stabilizer and 100-200 parts of solvent.
In one embodiment, the pH adjustor is selected from 20-31v/v% hydrochloric acid or 50-98v/v% sulfuric acid.
In one embodiment, the scale inhibitor comprises an organic phosphonic acid and a carboxylic acid based polymer. The scale inhibitor can effectively inhibit deposition and scaling of inorganic salts such as calcium carbonate, sulfate, silicate and the like on the surface of the membrane, and prolong the cleaning period of the reverse osmosis membrane.
In a preferred embodiment, the mass ratio of organophosphonic acid to carboxylic acid polymer is from 2 to 6:1.
In a preferred embodiment, the organic phosphonic acid is selected from at least one of diethylenetriamine pentamethylene phosphonic acid, aminotrimethylene phosphoric acid, hexamethylenediamine tetramethylene phosphonic acid, 2-butane-1, 2, 4-tricarboxylic acid, and hydroxyethylidene diphosphonic acid.
In a preferred embodiment, the carboxylic acid based polymer is selected from at least one of polyacrylic acid, polymaleic anhydride, polyaspartic acid, polyepoxysuccinic acid, acrylic acid/hydroxypropyl acrylate copolymer or acrylate/styrenesulfonic acid copolymer.
In one embodiment, a portion of the concentrate of the reverse osmosis membrane is returned to the reverse osmosis unit inlet and then enters the reverse osmosis unit for treatment. The operation can improve the recovery rate of the system, improve the flow velocity of the reverse osmosis membrane system and reduce the frequency of fouling.
In one embodiment, the recycling rate of the circulating water concentrated drain water is more than 85%.
In one embodiment, a method for recycling a circulating water concentrate drain includes:
filtering the circulating water concentrated drainage through a self-cleaning filter to obtain filtered effluent;
adding the slime control agent into an automatic slime control agent adding device arranged at the inlet of the ultrafiltration device, and performing ultrafiltration treatment to obtain ultrafiltration effluent, wherein the ultrafiltration device adopts the anti-fouling ultrafiltration membrane; and
The ultrafiltration effluent enters a reverse osmosis device, a pH regulator is added into a pH regulator arranged at the inlet of the reverse osmosis device to regulate the pH to 5.0-7.0, a scale inhibitor is added into an automatic scale inhibitor adding device arranged at the inlet of the reverse osmosis device, reverse osmosis treatment is carried out to obtain reclaimed water and concentrated water, the reclaimed water is reused in a circulating water system, and the concentrated water enters a concentrated water tank.
The invention also discloses a scale inhibitor which comprises organic phosphonic acid, quaternary ammonium salt/AMPS copolymer and carboxylic acid polymer. The scale inhibitor has antibacterial property and can effectively prevent microbial contamination; the scale inhibitor has excellent scale inhibition performance, can effectively inhibit deposition and scaling of inorganic salts such as calcium carbonate salt, sulfate, silicate and the like on the surface of the membrane, and prolongs the cleaning period of the reverse osmosis membrane.
In one embodiment, the mass ratio of the organophosphonic acid, itaconic acid/quaternary ammonium salt/AMPS copolymer and carboxylic acid polymer is from 2 to 6:0.1 to 1.0:1.
In one embodiment, the organic phosphonic acid is selected from at least one of diethylenetriamine pentamethylene phosphonic acid, aminotrimethylene phosphoric acid, hexamethylenediamine tetramethylene phosphonic acid, 2-phosphonate butane-1, 2, 4-tricarboxylic acid, and hydroxyethylidene diphosphonic acid.
In one embodiment, the itaconic acid/quaternary ammonium salt/AMPS copolymer is an itaconic acid/alkenyl quaternary ammonium chloride/AMPS copolymer or an itaconic acid/alkenyl pyridinium chloride/AMPS copolymer. The itaconic acid/quaternary ammonium salt/AMPS copolymer has better antibacterial property, and the scale inhibitor prepared by the copolymer also has antibacterial property; in addition, when the itaconic acid/quaternary ammonium salt/AMPS copolymer is matched with diethylene triamine pentamethylene phosphonic acid and polyepoxysuccinic acid to prepare the scale inhibitor, the prepared scale inhibitor has excellent scale inhibition property.
In a preferred embodiment, the itaconic acid/alkenyl quaternary ammonium chloride/AMPS copolymer is a copolymer obtained by copolymerizing itaconic acid, the above alkenyl quaternary ammonium chloride and 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) as monomers.
In a preferred embodiment, the itaconic acid/alkenyl quaternary ammonium chloride/AMPS copolymer is prepared by:
adding deionized water into itaconic acid and AMPS at 70-95 ℃, stirring until the mixture is uniform, adding tert-butyl alcohol, introducing nitrogen to replace air, then respectively dropwise adding methanol solution of alkenyl quaternary ammonium chloride and aqueous solution of potassium persulfate at 70-95 ℃ under stirring, continuously stirring at 70-95 ℃ for 2-6h after the dropwise addition is completed within 0.5-2h, and cooling to room temperature to obtain the itaconic acid/alkenyl quaternary ammonium chloride/AMPS copolymer.
In a more preferred embodiment, the molar ratio of itaconic acid, AMPS and alkenyl quaternary ammonium chloride is from 1:0.5 to 1.0:0.1 to 0.2. The itaconic acid/alkenyl quaternary ammonium chloride/AMPS copolymer obtained by copolymerizing monomers in the molar ratio range has better scale inhibition performance when being matched with diethylenetriamine pentamethylene phosphonic acid and polyepoxysuccinic acid to prepare the scale inhibitor.
In a more preferred embodiment, the ratio of itaconic acid to deionized water is 1g to 10 to 50mL.
In a more preferred embodiment, t-butanol is used in an amount of 6 to 12% of the total mass of the monomers.
In a more preferred embodiment, the concentration of the alkenyl quaternary ammonium chloride salt in the methanolic solution of the alkenyl quaternary ammonium chloride salt is 20 to 30 weight percent.
In a more preferred embodiment, the potassium persulfate is used in an amount of from 1 to 5% by weight of the total mass of the monomer.
In a more preferred embodiment, the concentration of the aqueous potassium persulfate solution is from 20 to 30 weight percent.
In a preferred embodiment, the itaconic acid/alkenyl quaternary ammonium chloride/AMPS copolymer is a copolymer obtained by copolymerizing itaconic acid, the above-described alkenyl quaternary ammonium chloride and 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) as monomers.
In a preferred embodiment, the itaconic acid/alkenyl pyridinium chloride quaternary ammonium salt/AMPS copolymer is prepared by:
adding deionized water into itaconic acid and AMPS at 70-95 ℃, stirring until the mixture is uniform, adding tert-butyl alcohol, introducing nitrogen to replace air, then respectively dropwise adding methanol solution of alkenyl pyridine chloride quaternary ammonium salt and potassium persulfate aqueous solution at 70-95 ℃ under the stirring state, continuously stirring at 70-95 ℃ for 2-6h after the dropwise addition is completed within 0.5-2h, and cooling to room temperature to obtain the itaconic acid/alkenyl pyridine chloride quaternary ammonium salt/AMPS copolymer.
In a more preferred embodiment, the molar ratio of itaconic acid, AMPS and alkenylpyridinium chloride quaternary ammonium salt is 1:0.5-1.0:0.05-0.15. The itaconic acid/alkenyl pyridine chloride quaternary ammonium salt/AMPS copolymer obtained by copolymerizing monomers in the molar ratio range has better scale inhibition performance when being matched with diethylenetriamine pentamethylene phosphonic acid and polyepoxysuccinic acid to prepare the scale inhibitor.
In a more preferred embodiment, the ratio of itaconic acid to deionized water is 1g to 10 to 50mL.
In a more preferred embodiment, t-butanol is used in an amount of 6 to 12% of the total mass of the monomers.
In a more preferred embodiment, the concentration of the alkenyl pyridinium chloride quaternary ammonium salt in the methanolic solution is 20 to 30 weight percent.
In a more preferred embodiment, the potassium persulfate is used in an amount of from 1 to 5% by weight of the total mass of the monomer.
In a more preferred embodiment, the concentration of the aqueous potassium persulfate solution is from 20 to 30 weight percent.
In one embodiment, the carboxylic acid based polymer is selected from at least one of polyacrylic acid, polymaleic anhydride, polyaspartic acid, polyepoxysuccinic acid, acrylic acid/hydroxypropyl acrylate copolymer, or acrylic acid ester/styrenesulfonic acid copolymer.
The invention also discloses application of the scale inhibitor in recycling of the circulating water concentrated drainage.
The invention adopts the alkenyl quaternary ammonium salt to graft on the polyvinylidene fluoride ultrafiltration membrane, thereby having the following beneficial effects: the anti-fouling ultrafiltration membrane also has a better antibacterial effect, and can kill bacteria adhered to the surface of the ultrafiltration membrane, thereby improving the anti-microbial pollution performance of the surface of the ultrafiltration membrane; compared with the polyvinylidene fluoride ultrafiltration membrane, the anti-fouling ultrafiltration membrane has higher hydrophilicity and pure water flux. Therefore, the invention aims to provide an anti-fouling ultrafiltration membrane with better antibacterial effect, hydrophilicity and pure water flux.
The invention adopts the anti-pollution ultrafiltration membrane as the ultrafiltration membrane of the ultrafiltration device, thereby having the following beneficial effects: the method can obviously reduce biological pollution and reduce the fouling frequency of the ultrafiltration membrane, thereby reducing maintenance cost and prolonging service life; the recycling rate of the concentrated drainage of the treated circulating water is more than 85%. Accordingly, an object of the present invention is to provide a method for recycling concentrated wastewater of circulating water, which can remove suspended particles, organic matters, slime, colloids and most of inorganic salts contained in the concentrated wastewater of circulating water. The treated reclaimed water is used as the supplementing water of the circulating water system, thereby achieving the purposes of saving water, enhancing efficiency and reducing emission.
Drawings
FIG. 1 shows the grafting rate of alkenyl quaternary ammonium salt on the surface of polyvinylidene fluoride;
FIG. 2 is an infrared spectrum of the antibacterial ultrafiltration membranes of example 2 and example 5;
FIG. 3 shows the antibacterial efficiency of the bacterial ultrafiltration membrane and the polyvinylidene fluoride ultrafiltration membrane;
FIG. 4 is a water contact angle of an antibacterial ultrafiltration membrane and a polyvinylidene fluoride ultrafiltration membrane;
FIG. 5 is the pure water flux of the antibacterial and polyvinylidene fluoride ultrafiltration membranes;
FIG. 6 is an antimicrobial ratio of itaconic acid/quaternary ammonium salt/AMPS copolymer;
FIG. 7 is a scale inhibition rate of the scale inhibitor;
fig. 8 shows the reuse rate of the circulating water concentrate drainage.
Detailed Description
The present invention will be further described in detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent.
The experimental methods in the following examples are conventional methods unless otherwise specified. Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified. The polyvinylidene fluoride ultrafiltration membrane used in the embodiment of the invention is an external pressure type PVDF hollow fiber ultrafiltration membrane, the inner diameter is 0.9mm, the outer diameter is 1.5mm, and the average pore diameter is 0.03 mu m.
Example 1:
an alkenyl quaternary ammonium chloride salt, the preparation method comprising:
adding cinnamoyl chloride and dimethylaminoethyl methacrylate in a molar ratio of 1.5:1 into dichloromethane, wherein the cinnamoyl chloride and the dichloromethane The ratio of the dosage is 1g to 12mL, the reaction is carried out for 24 hours at 100 ℃, the methylene dichloride is distilled off after the reaction is finished, then the mixture is washed with diethyl ether for 3 times, filtered by suction and dried, and the alkenyl quaternary ammonium chloride salt is obtained. The structural formula of the alkenyl quaternary ammonium chloride is shown in the following formula a, 1 H NMR（400MHz，DMSO-d 6 ），7.83（d，1H），7.67（d，2H），7.46-7.32（t，3H），6.63（d，1H），6.54-6.45（d，2H），4.64（t，2H），3.55（t，2H），2.94（s，6H），2.11（s，3H）。
a, a
The preparation method of the anti-fouling ultrafiltration membrane comprises the following steps:
placing the polyvinylidene fluoride ultrafiltration membrane in ethanol for ultrasonic cleaning for 60min, then placing the polyvinylidene fluoride ultrafiltration membrane in deionized water for ultrasonic cleaning for 60min, and drying to obtain a dried polyvinylidene fluoride ultrafiltration membrane;
soaking a dried polyvinylidene fluoride ultrafiltration membrane in a methanol solution containing 0.8mol/L benzophenone, pre-irradiating for 5min under the ultraviolet light with the power of 800W and the light distance of 20cm and the irradiation temperature of 35 ℃, adding alkenyl quaternary ammonium chloride to the concentration of 5wt%, irradiating for 30min under the ultraviolet light with the power of 800W, the light distance of 20cm and the irradiation temperature of 35 ℃, rinsing for 15min with methanol and deionized water in sequence after the completion, and drying to obtain the anti-fouling ultrafiltration membrane.
Example 2:
the preparation method of the anti-fouling ultrafiltration membrane comprises the following steps:
placing the polyvinylidene fluoride ultrafiltration membrane in ethanol for ultrasonic cleaning for 30min, then placing the polyvinylidene fluoride ultrafiltration membrane in deionized water for ultrasonic cleaning for 30min, and drying to obtain a dried polyvinylidene fluoride ultrafiltration membrane;
Immersing a dried polyvinylidene fluoride ultrafiltration membrane in a methanol solution containing 0.5mol/L benzophenone, and pre-irradiating for 8min under ultraviolet light with power of 1000W, light distance of 20cm and irradiation temperature of 35 ℃; and
then adding the alkenyl quaternary ammonium chloride in the embodiment 1 until the concentration is 10wt%, irradiating for 20min under the ultraviolet light with the power of 1000W, the light distance of 20cm and the irradiation temperature of 35 ℃, rinsing for 20min by methanol and deionized water sequentially after the completion, and drying to obtain the anti-fouling ultrafiltration membrane.
Example 3:
the preparation method of the anti-fouling ultrafiltration membrane comprises the following steps:
placing the polyvinylidene fluoride ultrafiltration membrane in ethanol for ultrasonic cleaning for 45min, then placing the polyvinylidene fluoride ultrafiltration membrane in deionized water for ultrasonic cleaning for 45min, and drying to obtain a dried polyvinylidene fluoride ultrafiltration membrane;
immersing a dried polyvinylidene fluoride ultrafiltration membrane in a methanol solution containing 0.2mol/L benzophenone, and pre-irradiating for 10min under ultraviolet light with power of 500W, light distance of 20cm and irradiation temperature of 35 ℃; and
then adding the alkenyl quaternary ammonium chloride in the embodiment 1 until the concentration is 20wt%, irradiating for 15min under the ultraviolet light with the power of 500W, the light distance of 20cm and the irradiation temperature of 35 ℃, rinsing for 10min by methanol and deionized water sequentially after the completion, and drying to obtain the anti-fouling ultrafiltration membrane.
Example 4:
an alkenyl pyridinium chloride quaternary ammonium salt, the preparation method thereof comprises:
adding cinnamoyl chloride and 2-hydroxymethyl pyridine with the molar ratio of 1.5:1 into dichloromethane, reacting at 100 ℃ for 24 hours, rotationally steaming out dichloromethane after the reaction is finished, washing with diethyl ether for 3 times, filtering, and drying to obtain pyridine chloride quaternary ammonium salt;
adding pyridine quaternary ammonium chloride, dibutyl tin dilaurate (the dosage is 0.4wt% of the pyridine quaternary ammonium chloride) and hydroquinone (the dosage is 1wt% of the pyridine quaternary ammonium chloride) into methylene dichloride, stirring uniformly, dropwise adding isocyano ethyl methacrylate at 50 ℃, stirring at 50 ℃ for reaction for 6 hours, steaming out methylene dichloride, washing with diethyl ether for 3 times, and drying to obtain alkenyl pyridine quaternary ammonium chloride. The structural formula of the alkenyl quaternary ammonium chloride is shown in the following formula b, 1 H NMR（400MHz，DMSO-d 6 ），9.44（d，1H），9.12（t，1H），8.97（d，1H），8.32（t，1H），8.15（s，1H），7.80（d，1H），7.65（d，2H），7.53-7.40（t，3H），6.72（d，1H），6.50-6.42（d，2H），5.45（s，2H），4.54（t，2H），3.23（t，2H），2.06（s，3H）。
b
The preparation method of the anti-fouling ultrafiltration membrane comprises the following steps:
placing the polyvinylidene fluoride ultrafiltration membrane in ethanol for ultrasonic cleaning for 60min, then placing the polyvinylidene fluoride ultrafiltration membrane in deionized water for ultrasonic cleaning for 60min, and drying to obtain a dried polyvinylidene fluoride ultrafiltration membrane;
Immersing a dried polyvinylidene fluoride ultrafiltration membrane in a methanol solution containing 0.8mol/L benzophenone, and pre-irradiating for 5min under ultraviolet light with power of 800W, light distance of 20cm and irradiation temperature of 35 ℃; and
then adding alkenyl pyridine chloride quaternary ammonium salt to the concentration of 5wt%, irradiating for 30min under the ultraviolet light with the power of 800W, the light distance of 20cm and the irradiation temperature of 35 ℃, rinsing for 15min by methanol and deionized water in sequence after the completion of the irradiation, and drying to obtain the anti-fouling ultrafiltration membrane.
Example 5:
the preparation method of the anti-fouling ultrafiltration membrane comprises the following steps:
placing the polyvinylidene fluoride ultrafiltration membrane in ethanol for ultrasonic cleaning for 30min, then placing the polyvinylidene fluoride ultrafiltration membrane in deionized water for ultrasonic cleaning for 30min, and drying to obtain a dried polyvinylidene fluoride ultrafiltration membrane;
immersing a dried polyvinylidene fluoride ultrafiltration membrane in a methanol solution containing 0.5mol/L benzophenone, and pre-irradiating for 8min under ultraviolet light with power of 1000W, light distance of 20cm and irradiation temperature of 35 ℃; and
then adding the alkenyl pyridine chloride quaternary ammonium salt of the embodiment 4 to the concentration of 10 weight percent, irradiating for 20 minutes under the ultraviolet light with the power of 1000W, the light distance of 20cm and the irradiation temperature of 35 ℃, rinsing for 20 minutes by methanol and deionized water in sequence after the completion of the irradiation, and drying to obtain the anti-fouling ultrafiltration membrane.
Example 6:
the preparation method of the anti-fouling ultrafiltration membrane comprises the following steps:
placing the polyvinylidene fluoride ultrafiltration membrane in ethanol for ultrasonic cleaning for 45min, then placing the polyvinylidene fluoride ultrafiltration membrane in deionized water for ultrasonic cleaning for 45min, and drying to obtain a dried polyvinylidene fluoride ultrafiltration membrane;
immersing a dried polyvinylidene fluoride ultrafiltration membrane in a methanol solution containing 0.2mol/L benzophenone, and pre-irradiating for 10min under ultraviolet light with power of 500W, light distance of 20cm and irradiation temperature of 35 ℃; and
then adding the alkenyl pyridine chloride quaternary ammonium salt of the embodiment 4 to the concentration of 20wt%, irradiating for 15min under the ultraviolet light with the power of 500W, the light distance of 20cm and the irradiation temperature of 35 ℃, rinsing for 10min by methanol and deionized water sequentially after the completion, and drying to obtain the anti-fouling ultrafiltration membrane.
Example 7:
a scale inhibitor comprising: diethylene triamine pentamethylene phosphonic acid and polyepoxysuccinic acid in a mass ratio of 5:1.
Example 8:
a scale inhibitor comprising: diethylene triamine pentamethylene phosphonic acid, itaconic acid/alkenyl quaternary ammonium chloride/AMPS copolymer and polyepoxysuccinic acid in the mass ratio of 5:0.3:1.
This example was prepared using itaconic acid/alkenyl quaternary ammonium chloride/AMPS copolymer by the following method:
Adding deionized water into itaconic acid and AMPS at 80 ℃, stirring until the mixture is uniform, adding tert-butyl alcohol, introducing nitrogen to replace air, then respectively dropwise adding a methanol solution of alkenyl quaternary ammonium chloride and a potassium persulfate aqueous solution obtained in example 1 at 80 ℃ under a stirring state, continuously stirring at 80 ℃ for reaction for 4 hours after the completion of dropwise adding, cooling to room temperature, adding methanol, standing and precipitating, and filtering to obtain the itaconic acid/alkenyl quaternary ammonium chloride/AMPS copolymer. The molar ratio of itaconic acid to AMPS to alkenyl quaternary ammonium chloride is 1:0.8:0.1; the dosage ratio of itaconic acid to deionized water is 1g to 40mL; the amount of t-butanol is 10% of the total mass of the monomers; in the methanol solution of the alkenyl quaternary ammonium chloride, the concentration of the alkenyl quaternary ammonium chloride is 25wt%; the amount of potassium persulfate was 4% by weight based on the total mass of the monomers, and the concentration of the aqueous potassium persulfate solution was 25% by weight.
Example 9:
a scale inhibitor comprising: diethylene triamine pentamethylene phosphonic acid, itaconic acid/alkenyl quaternary ammonium chloride/AMPS copolymer and polyepoxysuccinic acid in the mass ratio of 5:0.3:1.
This example was prepared using itaconic acid/alkenyl quaternary ammonium chloride/AMPS copolymer by the following method:
adding deionized water into itaconic acid and AMPS at 80 ℃, stirring until the mixture is uniform, adding tert-butyl alcohol, introducing nitrogen to replace air, then respectively dropwise adding a methanol solution of alkenyl quaternary ammonium chloride and a potassium persulfate aqueous solution obtained in example 1 at 80 ℃ under a stirring state, continuously stirring at 80 ℃ for reaction for 4 hours after the completion of dropwise adding, cooling to room temperature, adding methanol, standing and precipitating, and filtering to obtain the itaconic acid/alkenyl quaternary ammonium chloride/AMPS copolymer. The molar ratio of itaconic acid to AMPS to alkenyl quaternary ammonium chloride is 1:0.8:0.2; the dosage ratio of itaconic acid to deionized water is 1g to 40mL; the amount of t-butanol is 10% of the total mass of the monomers; in the methanol solution of the alkenyl quaternary ammonium chloride, the concentration of the alkenyl quaternary ammonium chloride is 25wt%; the amount of potassium persulfate was 4% by weight based on the total mass of the monomers, and the concentration of the aqueous potassium persulfate solution was 25% by weight.
Example 10:
a scale inhibitor comprising: diethylene triamine pentamethylene phosphonic acid, itaconic acid/alkenyl quaternary ammonium chloride/AMPS copolymer and polyepoxysuccinic acid in the mass ratio of 5:0.3:1.
This example was prepared using itaconic acid/alkenyl quaternary ammonium chloride/AMPS copolymer by the following method:
adding deionized water into itaconic acid and AMPS at 80 ℃, stirring until the mixture is uniform, adding tert-butyl alcohol, introducing nitrogen to replace air, then respectively dropwise adding a methanol solution of alkenyl quaternary ammonium chloride and a potassium persulfate aqueous solution obtained in example 1 at 80 ℃ under a stirring state, continuously stirring at 80 ℃ for reaction for 4 hours after the completion of dropwise adding, cooling to room temperature, adding methanol, standing and precipitating, and filtering to obtain the itaconic acid/alkenyl quaternary ammonium chloride/AMPS copolymer. The molar ratio of itaconic acid to AMPS to alkenyl quaternary ammonium chloride is 1:0.8:0.05; the dosage ratio of itaconic acid to deionized water is 1g to 40mL; the amount of t-butanol is 10% of the total mass of the monomers; in the methanol solution of the alkenyl quaternary ammonium chloride, the concentration of the alkenyl quaternary ammonium chloride is 25wt%; the amount of potassium persulfate was 4% by weight based on the total mass of the monomers, and the concentration of the aqueous potassium persulfate solution was 25% by weight.
Example 11:
a scale inhibitor comprising: diethylene triamine pentamethylene phosphonic acid, itaconic acid/alkenyl quaternary ammonium chloride/AMPS copolymer and polyepoxysuccinic acid in the mass ratio of 5:0.3:1.
This example was prepared using itaconic acid/alkenyl quaternary ammonium chloride/AMPS copolymer by the following method:
adding deionized water into itaconic acid and AMPS at 80 ℃, stirring until the mixture is uniform, adding tert-butyl alcohol, introducing nitrogen to replace air, then respectively dropwise adding a methanol solution of alkenyl quaternary ammonium chloride and a potassium persulfate aqueous solution obtained in example 1 at 80 ℃ under a stirring state, continuously stirring at 80 ℃ for reaction for 4 hours after the completion of dropwise adding, cooling to room temperature, adding methanol, standing and precipitating, and filtering to obtain the itaconic acid/alkenyl quaternary ammonium chloride/AMPS copolymer. The molar ratio of itaconic acid to AMPS to alkenyl quaternary ammonium chloride is 1:0.8:0.25; the dosage ratio of itaconic acid to deionized water is 1g to 40mL; the amount of t-butanol is 10% of the total mass of the monomers; in the methanol solution of the alkenyl quaternary ammonium chloride, the concentration of the alkenyl quaternary ammonium chloride is 25wt%; the amount of potassium persulfate was 4% by weight based on the total mass of the monomers, and the concentration of the aqueous potassium persulfate solution was 25% by weight.
Example 12:
a scale inhibitor comprising: diethylene triamine pentamethylene phosphonic acid, itaconic acid/alkenyl pyridine chloride quaternary ammonium salt/AMPS copolymer and polyepoxysuccinic acid in the mass ratio of 5:0.3:1.
This example was prepared using itaconic acid/alkenyl quaternary ammonium chloride/AMPS copolymer by the following method:
Adding deionized water into itaconic acid and AMPS at 80 ℃, stirring until the mixture is uniform, adding tert-butyl alcohol, introducing nitrogen to replace air, then respectively dropwise adding a methanol solution of alkenyl pyridine chloride quaternary ammonium salt and a potassium persulfate aqueous solution in a stirring state at 80 ℃, continuing stirring at 80 ℃ for 4 hours after the completion of dropwise adding, cooling to room temperature, adding methanol, standing and precipitating, and filtering to obtain the itaconic acid/alkenyl pyridine chloride quaternary ammonium salt/AMPS copolymer. The molar ratio of itaconic acid to AMPS to alkenyl pyridine chloride quaternary ammonium salt is 1:0.8:0.05; the dosage ratio of itaconic acid to deionized water is 1g to 40mL; the amount of t-butanol is 10% of the total mass of the monomers; in the methanol solution of the alkenyl pyridine chloride quaternary ammonium salt, the concentration of the alkenyl pyridine chloride quaternary ammonium salt is 25wt%; the amount of potassium persulfate was 4% by weight based on the total mass of the monomers, and the concentration of the aqueous potassium persulfate solution was 25% by weight.
Example 13:
a scale inhibitor comprising: diethylene triamine pentamethylene phosphonic acid, itaconic acid/alkenyl pyridine chloride quaternary ammonium salt/AMPS copolymer and polyepoxysuccinic acid in the mass ratio of 5:0.3:1.
This example was prepared using itaconic acid/alkenyl quaternary ammonium chloride/AMPS copolymer by the following method:
Adding deionized water into itaconic acid and AMPS at 80 ℃, stirring until the mixture is uniform, adding tert-butyl alcohol, introducing nitrogen to replace air, then respectively dropwise adding a methanol solution of alkenyl pyridine chloride quaternary ammonium salt and a potassium persulfate aqueous solution in a stirring state at 80 ℃, continuing stirring at 80 ℃ for 4 hours after the completion of dropwise adding, cooling to room temperature, adding methanol, standing and precipitating, and filtering to obtain the itaconic acid/alkenyl pyridine chloride quaternary ammonium salt/AMPS copolymer. The molar ratio of itaconic acid to AMPS to alkenyl pyridine chloride quaternary ammonium salt is 1:0.8:0.15; the dosage ratio of itaconic acid to deionized water is 1g to 40mL; the amount of t-butanol is 10% of the total mass of the monomers; in the methanol solution of the alkenyl pyridine chloride quaternary ammonium salt, the concentration of the alkenyl pyridine chloride quaternary ammonium salt is 25wt%; the amount of potassium persulfate was 4% by weight based on the total mass of the monomers, and the concentration of the aqueous potassium persulfate solution was 25% by weight.
Example 14:
a scale inhibitor comprising: diethylene triamine pentamethylene phosphonic acid, itaconic acid/alkenyl pyridine chloride quaternary ammonium salt/AMPS copolymer and polyepoxysuccinic acid in the mass ratio of 5:0.3:1.
This example was prepared using itaconic acid/alkenyl quaternary ammonium chloride/AMPS copolymer by the following method:
Adding deionized water into itaconic acid and AMPS at 80 ℃, stirring until the mixture is uniform, adding tert-butyl alcohol, introducing nitrogen to replace air, then respectively dropwise adding a methanol solution of alkenyl pyridine chloride quaternary ammonium salt and a potassium persulfate aqueous solution in a stirring state at 80 ℃, continuing stirring at 80 ℃ for 4 hours after the completion of dropwise adding, cooling to room temperature, adding methanol, standing and precipitating, and filtering to obtain the itaconic acid/alkenyl pyridine chloride quaternary ammonium salt/AMPS copolymer. The molar ratio of itaconic acid to AMPS to alkenyl pyridine chloride quaternary ammonium salt is 1:0.8:0.02; the dosage ratio of itaconic acid to deionized water is 1g to 40mL; the amount of t-butanol is 10% of the total mass of the monomers; in the methanol solution of the alkenyl pyridine chloride quaternary ammonium salt, the concentration of the alkenyl pyridine chloride quaternary ammonium salt is 25wt%; the amount of potassium persulfate was 4% by weight based on the total mass of the monomers, and the concentration of the aqueous potassium persulfate solution was 25% by weight.
Example 15:
a scale inhibitor comprising: diethylene triamine pentamethylene phosphonic acid, itaconic acid/alkenyl pyridine chloride quaternary ammonium salt/AMPS copolymer and polyepoxysuccinic acid in the mass ratio of 5:0.3:1.
This example was prepared using itaconic acid/alkenyl quaternary ammonium chloride/AMPS copolymer by the following method:
Adding deionized water into itaconic acid and AMPS at 80 ℃, stirring until the mixture is uniform, adding tert-butyl alcohol, introducing nitrogen to replace air, then respectively dropwise adding a methanol solution of alkenyl pyridine chloride quaternary ammonium salt and a potassium persulfate aqueous solution in a stirring state at 80 ℃, continuing stirring at 80 ℃ for 4 hours after the completion of dropwise adding, cooling to room temperature, adding methanol, standing and precipitating, and filtering to obtain the itaconic acid/alkenyl pyridine chloride quaternary ammonium salt/AMPS copolymer. The molar ratio of itaconic acid to AMPS to alkenyl pyridine chloride quaternary ammonium salt is 1:0.8:0.2; the dosage ratio of itaconic acid to deionized water is 1g to 40mL; the amount of t-butanol is 10% of the total mass of the monomers; in the methanol solution of the alkenyl pyridine chloride quaternary ammonium salt, the concentration of the alkenyl pyridine chloride quaternary ammonium salt is 25wt%; the amount of potassium persulfate was 4% by weight based on the total mass of the monomers, and the concentration of the aqueous potassium persulfate solution was 25% by weight.
Example 16:
a method for recycling a concentrated wastewater of circulating water, comprising:
filtering the circulating water concentrated drainage through a self-cleaning filter to obtain filtered effluent;
feeding filtered effluent into an ultrafiltration device, adding a slime control agent into an automatic slime control agent adding device arranged at an inlet of the ultrafiltration device, and performing ultrafiltration treatment to obtain ultrafiltration effluent; and
The ultrafiltration effluent enters a reverse osmosis device, a pH regulator is added into a pH regulator arranged at the inlet of the reverse osmosis device to regulate the pH to 6-6.5, a scale inhibitor is added into an automatic scale inhibitor adding device arranged at the inlet of the reverse osmosis device, reverse osmosis treatment is carried out to obtain reclaimed water and concentrated water, the reclaimed water is reused in a circulating water system, and the concentrated water enters a concentrated water tank.
Wherein the ultrafiltration device employs the anti-fouling ultrafiltration membrane of example 2.
The slime control agent comprises a bonding chlorine agent, wherein the effective chlorine concentration in the slime control agent is 2mg/L; the binding chlorine agent is a chloramine compound, the chloramine compound comprises monochloramine, dichloramine and trichloroamine, and the weight ratio of the monochloramine to the dichloramine to the trichloroamine is 1:1:1; the slime control agent further comprises 5 parts by weight of sodium hydroxide, 35 parts by weight of hydrogen peroxide, 10 parts by weight of zinc stearate and 160 parts by weight of water.
The pH regulator was 20v/v% hydrochloric acid.
The scale inhibitor used was the scale inhibitor of example 7.
Example 17:
a method for recycling concentrated drainage of circulating water, which is different from example 16 in that: the ultrafiltration device employed the anti-fouling ultrafiltration membrane of example 5.
Example 18:
a method for recycling concentrated drainage of circulating water, which is different from example 16 in that: the scale inhibitor used was the scale inhibitor of example 8.
Example 19:
a method for recycling concentrated drainage of circulating water, which is different from example 16 in that: the ultrafiltration device adopts the anti-fouling ultrafiltration membrane of the example 5, and the scale inhibitor adopts the scale inhibitor of the example 8.
Example 20:
a method for recycling concentrated drainage of circulating water, which is different from example 16 in that: the scale inhibitor used was the scale inhibitor of example 12.
Example 21:
a method for recycling concentrated drainage of circulating water, which is different from example 16 in that: the ultrafiltration device adopts the anti-fouling ultrafiltration membrane of the example 5, and the scale inhibitor adopts the scale inhibitor of the example 12.
Test example 1:
performance test of anti-fouling ultrafiltration membrane
1. Grafting ratio
The grafting ratio of the alkenyl quaternary ammonium salt is calculated by the following formula: grafting ratio (%) = (weight of film after grafting-weight of film before grafting)/weight of film before grafting×100%.
FIG. 1 shows the grafting ratio of alkenyl quaternary ammonium salt on the surface of polyvinylidene fluoride, wherein PVDF-Q1 represents example 1, PVDF-Q2 represents example 2, PVDF-Q3 represents example 3, PVDF-Q4 represents example 4, PVDF-Q5 represents example 5, and PVDF-Q6 represents example 6. As can be seen from FIG. 1, in the anti-fouling ultrafiltration membranes obtained in examples 1 to 6, the grafting rate of the alkenyl quaternary ammonium salt on the surface of polyvinylidene fluoride is 5 to 20 percent.
2. Infrared absorption spectrum
Testing infrared absorption spectrum diagram of anti-fouling ultrafiltration membrane sample by using Fourier transform infrared spectrometer, wherein the measurement range is 400-4000cm -1 。
Fig. 2 is an infrared spectrum of the anti-fouling ultrafiltration membranes of example 2 and example 5, and (a) and (b) are respectively infrared spectra of the anti-fouling ultrafiltration membranes of example 4 and example 5. 1735cm in FIG. 2 (a) -1 Characteristic absorption peak of c=o appears in the vicinity, at 1650cm -1 Characteristic absorption peak of C=C appears nearby, and the absorption peak is 650-850cm -1 Characteristic absorption peaks of C-H on benzene rings appear in the range, which shows that alkenyl quaternary ammonium chloride is successfully grafted on the prepared polyvinylidene fluoride ultrafiltration membrane through ultraviolet light irradiation; at 3400cm in FIG. 2 (b) -1 Characteristic absorption peak of-NH-appears nearby, 3035cm -1 Characteristic absorption peak of C-H on pyridine ring appears nearby at 1720cm -1 Characteristic absorption peak of c=o appears near 1630cm -1 Characteristic absorption peak of C=C appears nearby, and the absorption peak is 650-850cm -1 Characteristic absorption peaks of C-H on benzene ring appear in the range, which shows that alkenyl pyridine chloride quaternary ammonium salt is successfully grafted on the prepared polyvinylidene fluoride ultrafiltration membrane through ultraviolet light irradiation.
3. Antibacterial property
Cutting the anti-fouling ultrafiltration membrane sample into a circular sheet with the diameter of 2cm, and then irradiating for 30min by an ultraviolet lamp for sterilization. Then the anti-fouling ultrafiltration membrane sample and 10mL of 5.0X10 5 The CFU/mL escherichia coli bacterial liquid is put into a sterilized 50mL triangle flask, the constant temperature oscillation is carried out at 37 ℃ and 150r/min, 1mL of contact bacterial liquid is taken every 15min to dilute by adopting a progressive dilution method, 0.1mL of contact bacterial liquid with different gradients is taken to be coated on a flat plate, and the flat plate is put into a constant temperature incubator to be cultured for 24 hours at 37 ℃. Counting viable bacteria on a flat plate with the colony number of about 25-250, calculating the bacterial liquid concentration of the escherichia coli bacterial liquid, and calculating the antibacterial rate of the grafted film with different quaternization degrees according to the dilution multiple, wherein the antibacterial rate is calculated according to the following formula: antibacterial ratio (%) = (concentration of antibacterial pre-bacterial liquid-concentration of antibacterial pre-bacterial liquid)/concentration of antibacterial pre-bacterial liquid×100%.
FIG. 3 shows the antibacterial activity of the anti-fouling ultrafiltration membrane and the polyvinylidene fluoride ultrafiltration membrane, wherein PVDF-Q1 represents the anti-fouling ultrafiltration membrane of example 1, PVDF-Q2 represents the anti-fouling ultrafiltration membrane of example 2, PVDF-Q3 represents the anti-fouling ultrafiltration membrane of example 3, PVDF-Q4 represents the anti-fouling ultrafiltration membrane of example 4, PVDF-Q5 represents the anti-fouling ultrafiltration membrane of example 5, PVDF-Q6 represents the anti-fouling ultrafiltration membrane of example 6, and PVDF represents the polyvinylidene fluoride ultrafiltration membrane. As can be seen from fig. 3, the anti-fouling ultrafiltration membranes of examples 1 to 6 have a better antibacterial effect and the antibacterial effect increases with time, which shows that the introduction of the quaternary ammonium salt can significantly improve the anti-biological pollution performance of the polyvinylidene fluoride ultrafiltration membrane, that is, the anti-fouling ultrafiltration membrane grafted and copolymerized with the quaternary ammonium salt can significantly reduce microbial pollution.
4. Contact angle of water
The contact angle of the anti-fouling ultrafiltration membrane sample is measured by a contact angle tester, five points are selected for each sample to be tested, the average water consumption is 3 mu L, and the average value is taken.
FIG. 4 is a graph showing water contact angles of an anti-fouling ultrafiltration membrane and a polyvinylidene fluoride ultrafiltration membrane, wherein PVDF-Q1 represents an anti-fouling ultrafiltration membrane of example 1, PVDF-Q2 represents an anti-fouling ultrafiltration membrane of example 2, PVDF-Q3 represents an anti-fouling ultrafiltration membrane of example 3, PVDF-Q4 represents an anti-fouling ultrafiltration membrane of example 4, PVDF-Q5 represents an anti-fouling ultrafiltration membrane of example 5, PVDF-Q6 represents an anti-fouling ultrafiltration membrane of example 6, and PVDF represents a polyvinylidene fluoride ultrafiltration membrane. As can be seen from fig. 4, the water contact angle of the anti-fouling ultrafiltration membranes of examples 1 to 6 was reduced compared with the polyvinylidene fluoride ultrafiltration membrane, which indicates that the introduction of the quaternary ammonium salt can significantly improve the hydrophilicity of the polyvinylidene fluoride ultrafiltration membrane, which is advantageous for improving the pure water flux.
5. Pure water flux
The anti-fouling ultrafiltration membrane sample is cleaned by deionized water and then is arranged on a self-made cup-type filter, after being pre-pressed for 10min under the conditions of room temperature and 0.1MPa of operation pressure, the filtrate in unit time is collected, each sample is repeatedly measured for 6 times, and the average value is taken. The pure water flux of the membrane is calculated as follows: pure water flux (L.m) -2 h -1 ) Volume of filtrate/(active area of membrane x running time).
FIG. 5 is a graph of pure water flux for an anti-fouling ultrafiltration membrane and a polyvinylidene fluoride ultrafiltration membrane, wherein PVDF-Q1 represents the anti-fouling ultrafiltration membrane of example 1, PVDF-Q2 represents the anti-fouling ultrafiltration membrane of example 2, PVDF-Q3 represents the anti-fouling ultrafiltration membrane of example 3, PVDF-Q4 represents the anti-fouling ultrafiltration membrane of example 4, PVDF-Q5 represents the anti-fouling ultrafiltration membrane of example 5, PVDF-Q6 represents the anti-fouling ultrafiltration membrane of example 6, and PVDF represents the polyvinylidene fluoride ultrafiltration membrane. As can be seen from fig. 5, the anti-fouling ultrafiltration membranes of examples 1 to 6 have higher pure water flux than the polyvinylidene fluoride ultrafiltration membrane, which shows that the introduction of the quaternary ammonium salt can significantly improve the pure water flux of the polyvinylidene fluoride ultrafiltration membrane, but the improvement of the pure water flux of the polyvinylidene fluoride ultrafiltration membrane is not significant with the increase of the grafting ratio, which is probably because the quaternary ammonium salt polymer grafted to the membrane surface can cover part of the membrane pores, thereby resulting in the insignificant improvement of the pure water flux of the polyvinylidene fluoride ultrafiltration membrane.
Test example 2:
performance test of scale inhibitor
1. Molecular weight analysis
Gel permeation chromatography was used to determine the molecular weight and distribution of the copolymer.
Example 8 itaconic acid/alkenylquaternary ammonium chloride/AMPS copolymer having a number average molecular weight of 1513 and a dispersibility index of about 1.26; example 9 the itaconic acid/alkenyl quaternary ammonium chloride/AMPS copolymer has a number average molecular weight of 1658 and a dispersibility index of about 1.19; example 12 itaconic acid/alkenyl pyridinium chloride quaternary ammonium salt/AMPS copolymer having a number average molecular weight value of 1435 and a dispersibility index of about 1.34; example 13 itaconic acid/alkenylquaternary ammonium chloride/AMPS copolymer has a number average molecular weight of 1592 and a dispersibility index of about 1.22.
2. Antibacterial property
The sample of itaconic acid/quaternary ammonium salt/AMPS copolymer was sterilized by irradiation with an ultraviolet lamp for 30 minutes. Then 10. Mu.L of a 5mg/mL itaconic acid/quaternary ammonium salt/AMPS copolymer sample solution and 10mL of 5.0X10 5 CFU/mL staphylococcus aureus or escherichia coli bacterial liquid is put into a sterilized 50mL triangle flask, the constant temperature oscillation is carried out for 5min at 37 ℃ and 150r/min, 1mL of contact bacterial liquid is diluted by adopting a progressive dilution method, 0.1mL of contact bacterial liquid with different gradients is coated on a flat plate, and the flat plate is put into a constant temperature incubator and cultured for 24h at 37 ℃. Counting viable bacteria on a flat plate with the colony number of about 25-250, calculating the bacterial liquid concentration of the escherichia coli bacterial liquid, and calculating the antibacterial rate of the grafted film with different quaternization degrees according to the dilution multiple, wherein the antibacterial rate is calculated according to the following formula: antibacterial ratio (%) = (concentration of antibacterial pre-bacterial liquid-concentration of antibacterial pre-bacterial liquid)/concentration of antibacterial pre-bacterial liquid×100%.
FIG. 6 is an antimicrobial ratio of itaconic acid/quaternary ammonium salt/AMPS copolymer, wherein CP-1 represents example 8 itaconic acid/alkenyl quaternary ammonium chloride/AMPS copolymer, CP-2 represents example 9 itaconic acid/alkenyl quaternary ammonium chloride/AMPS copolymer, CP-3 represents example 12 itaconic acid/alkenyl pyridinium chloride/AMPS copolymer, and CP-4 represents example 13 itaconic acid/alkenyl pyridinium chloride/AMPS copolymer. As can be seen from FIG. 6, the itaconic acid/alkenyl quaternary ammonium chloride/AMPS copolymers of examples 8 to 9 and the itaconic acid/alkenyl quaternary ammonium chloride/AMPS copolymers of examples 12 to 13 have a good antibacterial effect.
3. Scale inhibition performance
The calcium carbonate scale inhibition performance of the scale inhibitor is measured by referring to GB/T16632-2019 method for measuring the scale inhibition performance of a water treatment agent. Test conditions: c (Ca) 2+ ) =400 mg/L (calculated as calcium carbonate), C (HCO 3 - ) =800 mg/L (calculated as calcium carbonate), the test temperature was 60 ℃, the time was 10h, and the addition concentration of the scale inhibitor was 4mg/L. Determination of Ca in solution Using EDTA 2+ Concentration. Finally, the static scale inhibition rate is calculated according to the following formula: scale inhibition (%) = (C) 2 -C 1 ）/（C 2 -C 0 ) X 100%; wherein C is 0 Represents the content of calcium ions in the supernatant without adding the scale inhibitor, mg/L; c (C) 1 Represents the content of calcium ions in supernatant added with the scale inhibitor, mg/L; c (C) 2 Represents the content of original calcium ions in the experimental water sample, mg/L.
FIG. 7 is a graph showing the scale inhibition ratio of the scale inhibitor, wherein DA-1 represents the scale inhibitor of example 7, DA-2 represents the scale inhibitor of example 8, DA-3 represents the scale inhibitor of example 9, DA-4 represents the scale inhibitor of example 10, DA-5 represents the scale inhibitor of example 11, DA-6 represents the scale inhibitor of example 12, DA-7 represents the scale inhibitor of example 12, DA-8 represents the scale inhibitor of example 13, and DA-9 represents the scale inhibitor of example 14. As can be seen from FIG. 7, the scale inhibiting performance of the scale inhibitors of examples 8-9 and examples 12-13 is significantly better than that of example 7, which demonstrates that the presence of the itaconic acid/quaternary ammonium salt/AMPS copolymer in the scale inhibitor can improve the scale inhibiting performance of the scale inhibitor. As can be seen from fig. 7, the scale inhibition performance of the scale inhibitors of examples 8 to 9 is significantly better than that of examples 10 to 11, and the scale inhibition performance of the scale inhibitors of examples 10 to 11 is slightly higher than that of example 7, which shows that the scale inhibition performance of the prepared scale inhibitor is better when the itaconic acid/alkenyl quaternary ammonium chloride/AMPS copolymer is prepared by copolymerizing itaconic acid, AMPS and alkenyl quaternary ammonium chloride in a molar ratio of 1:0.5 to 1.0:0.1 to 0.2, and the scale inhibitor is prepared by compounding diethylenetriamine pentamethylene phosphonic acid and polyepoxysuccinic acid. As can be seen from fig. 7, the scale inhibition performance of the scale inhibitors of examples 12 to 13 is significantly better than that of examples 14 to 15, and the scale inhibition performance of the scale inhibitors of examples 14 to 15 is slightly higher than that of example 7, which indicates that the scale inhibition performance of the prepared scale inhibitor is better when the itaconic acid/alkenyl pyridine chloride quaternary ammonium salt/AMPS copolymer obtained by copolymerizing itaconic acid, AMPS and alkenyl pyridine chloride quaternary ammonium salt in a molar ratio of 1:0.5 to 1.0:0.05 to 0.15 is used for preparing the scale inhibitor by combining diethylenetriamine pentamethylene phosphonic acid and polyepoxysuccinic acid.
Test example 3:
test of recycling method of concentrated drainage of circulating water
The method of example 16-example 21 is adopted in the test example to recycle the concentrated water discharge of the water cooling unit circulating water of a certain thermal power plant. The quality of the recycled water obtained by the method of example 16 to example 21, which is the concentrated wastewater of the circulating water, is shown in Table 1. It can be seen that the effect of treating the circulating water concentrate by the methods of examples 16 to 21 is very remarkable. The recycling rate of the concentrated recycled water drain is shown in Table 8, and it can be seen that the method of example 16-example 21 is used to treat the concentrated recycled water drain, and the recycling rate of the concentrated recycled water drain is shown in FIG. 8, wherein S16 represents the method of example 16, S17 represents the method of example 17, S18 represents the method of example 18, S19 represents the method of example 19, S20 represents the method of example 20, and S21 represents the method of example 21. As can be seen from fig. 8, the recycling rate of the circulating water concentrated drain water is 85% or more.
TABLE 1 quality of recovered Water
Conventional operations in the operation steps of the present invention are well known to those skilled in the art, and are not described herein.
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made without departing from the spirit and scope of the invention.

Claims (10)

1. The preparation method of the anti-fouling ultrafiltration membrane is characterized by comprising the following steps of: the preparation method comprises the following steps:
washing and drying the polyvinylidene fluoride ultrafiltration membrane to obtain a dried polyvinylidene fluoride ultrafiltration membrane; and
immersing a dried polyvinylidene fluoride ultrafiltration membrane in a solution containing benzophenone, pre-irradiating under ultraviolet light, adding alkenyl quaternary ammonium salt, performing copolymerization under ultraviolet light irradiation, rinsing after finishing, and drying to obtain an anti-fouling ultrafiltration membrane;
wherein the alkenyl quaternary ammonium salt is selected from alkenyl quaternary ammonium chloride or alkenyl pyridinium chloride.
2. The method for preparing the anti-fouling ultrafiltration membrane according to claim 1, wherein the method comprises the following steps: the solution containing the diphenyl ketone is methanol solution containing the diphenyl ketone, and the concentration of the diphenyl ketone solution is 0.1-1.0mol/L.
3. The method for preparing the anti-fouling ultrafiltration membrane according to claim 1, wherein the method comprises the following steps: the alkenyl quaternary ammonium salt is added to a concentration of 5-20wt%.
4. The method for preparing the anti-fouling ultrafiltration membrane according to claim 1, wherein the method comprises the following steps: the grafting rate of the alkenyl quaternary ammonium salt on the anti-fouling ultrafiltration membrane is 5-20%.
5. The anti-fouling ultrafiltration membrane prepared by the preparation method of the anti-fouling ultrafiltration membrane of claim 1.
6. Use of an anti-fouling ultrafiltration membrane according to claim 5 for the preparation of an ultrafiltration device.
7. The use of the ultrafiltration device according to claim 6 for recycling of the concentrate drainage of circulating water.
8. A method for recycling concentrated drainage of circulating water is characterized by comprising the following steps: the method comprises the following steps:
filtering the circulating water concentrated drainage through a self-cleaning filter to obtain filtered effluent;
introducing filtered effluent into an ultrafiltration device, wherein the ultrafiltration device adopts the anti-fouling ultrafiltration membrane of claim 5, and ultrafiltration treatment is carried out in the presence of a slime control agent to obtain ultrafiltration effluent; and
and (3) introducing ultrafiltration effluent into a reverse osmosis device, regulating the pH value, and performing reverse osmosis treatment in the presence of a scale inhibitor to obtain reclaimed water and concentrated water, wherein the reclaimed water is reused in a circulating water system, and the concentrated water enters a concentrated water tank.
9. The method for recycling concentrated wastewater of circulating water according to claim 8, wherein: the slime control agent comprises a bonding chlorine agent, and the effective chlorine concentration in the slime control agent is 0.5-5mg/L.
10. The method for recycling concentrated wastewater of circulating water according to claim 8, wherein: the pH is adjusted by a pH regulator, wherein the pH regulator is selected from 20-31v/v% hydrochloric acid or 50-98v/v% sulfuric acid.
CN202311153035.4A 2023-09-08 2023-09-08 Anti-fouling ultrafiltration membrane and application thereof in recycling of circulating water concentrated drainage Active CN116870701B (en)

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