CN111362497B - Method for treating brominated disinfection by-product precursor by combining magnetic ion exchange resin with nanofiltration - Google Patents

Method for treating brominated disinfection by-product precursor by combining magnetic ion exchange resin with nanofiltration Download PDF

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CN111362497B
CN111362497B CN202010200903.XA CN202010200903A CN111362497B CN 111362497 B CN111362497 B CN 111362497B CN 202010200903 A CN202010200903 A CN 202010200903A CN 111362497 B CN111362497 B CN 111362497B
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exchange resin
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CN111362497A (en
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楚文海
欧恬
李宏伟
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Tongji University
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • 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
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • 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
    • C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/04—Disinfection

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  • Hydrology & Water Resources (AREA)
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  • Environmental & Geological Engineering (AREA)
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Abstract

The invention discloses a method for treating a brominated disinfection by-product precursor by combining magnetic ion exchange resin with nanofiltration, which comprises the following steps: adjusting the pH of the bromine-containing raw water to 7-10 by using alkali liquor; adding magnetic ion exchange resin with the volume ratio of 5 ml/L-12 ml/L to the original water body for pretreatment, stirring for 5 min-10 min, and then reacting for 0.5 h-5 h; after the reaction is finished, adding activated carbon powder mixed with magnetic polymer nano composite particles into the mixture, wherein the mass ratio of the magnetic nano particles to the activated carbon powder is 1: 1-1: 5, stirring the mixture for 5-10 min at the rotating speed of 100-200 rpm, and then reacting for 0.2-0.5 h; standing the reaction mixed solution for 10-60 min, and taking the supernatant to pass through a nanofiltration membrane treatment unit; adding a disinfectant to react for 24 to 48 hours in a dark environment according to the content of the soluble organic carbon in the effluent; the magnetic ion exchange resin adopted by the invention has the characteristics of small particle size, high density, high adsorption efficiency, simple regeneration and the like, and can effectively slow down membrane pollution and obviously improve the removal effect of organic matters when being combined with a nanofiltration membrane.

Description

Method for treating brominated disinfection by-product precursor by combining magnetic ion exchange resin with nanofiltration
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a method for treating a brominated disinfection by-product precursor by combining magnetic ion exchange resin with nanofiltration.
Background
Drinking water safety is an important problem related to the national civilization, and water disinfection is an essential treatment measure for guaranteeing drinking water safety. Free chlorine is the most widely used drinking water disinfection method at present due to its advantages of low price, spectrum sterilization and continuous disinfection. Because the water contains organic matters and inorganic ions (such as bromide ions) which are difficult to remove, the disinfectant can also generate disinfection byproducts which are harmful to human bodies while inactivating germs. The current control method of disinfection byproducts can be summarized into three aspects: (1) source control, namely removing precursor substances in water before disinfection, wherein disinfection byproducts cannot be generated due to the lack of reactants; (2) process control, which mainly reduces the formation of disinfection by-products in the disinfection process by changing disinfection process parameters or disinfection modes; (3) end-point control, which refers to the removal of disinfection by-products that have been generated. Because the generation mechanism of the disinfection by-product is complex, the influence factors are more, and once the disinfection by-product is generated, the disinfection by-product is difficult to economically and effectively remove, the precursor is efficiently removed by enhancing the water treatment process (such as adding an advanced treatment process) before disinfection, so that the source control of the disinfection by-product is realized, and the method is an effective control method.
The advanced treatment technology of drinking water mainly comprises preoxidation, ozone activated carbon, membrane technology and the like. The nanofiltration membrane technology has the advantages of small occupied area, simplicity in operation, stability in operation and the like, can retain part of elements beneficial to human bodies in purified water, and has wide application prospects in drinking water treatment. Meanwhile, the nanofiltration membrane technology has obvious removal effect on indexes such as organic matters, conductivity, turbidity and the like, can effectively control the concentration of the organic matters, and can greatly reduce the dosage of the disinfectant in subsequent disinfection, so that the risk of disinfection by-products is greatly reduced.
However, it is worth noting that the nanofiltration membrane technology also has certain limitations. On one hand, in the membrane treatment process, particles in the water body can generate physical and chemical interaction with the membrane, and are adsorbed and deposited on the surface or in membrane holes of the membrane, so that membrane pollution is caused, the operation pressure is increased, the membrane flux is reduced, and the operation cost is increased. On the other hand, from the control perspective of the disinfection byproducts, as the nanofiltration has a significant effect on removing organic matters, but has a limited effect on removing monovalent ions (such as bromide ions), the ratio of bromide ions to organic matters in the nanofiltration water increases, which causes the concentration of the brominated disinfection byproducts generated in the subsequent disinfection to increase. Compared with the similar chlorinated disinfection byproducts, the brominated disinfection byproducts have higher toxicity and bring potential risks to human health. Therefore, a method for treating brominated disinfection byproducts in raw water by a pretreatment unit cooperating with nanofiltration is urgently needed.
The magnetic ion exchange resin MIEX (magnetic ion exchange resin) technology is an ion exchange technology developed by the Australian Federal science and industry research institute, the southern Australia Water administration and the Orica company and is mainly applied to feedwater pretreatment. At present, the research of the MIEX resin as the pretreatment combined with the nanofiltration process mainly focuses on the aspects of membrane pollution control, organic matter removal, organic matter property change and the like, and the control attention on the disinfection byproducts is less. In a few studies that mention disinfection by-products, the by-product classes of interest are dominated by chlorinated trihalomethanes, haloacetic acids, with little coverage and very limited control studies on brominated disinfection by-products. In fact, compared with the chlorinated species, the generation mechanism of the brominated disinfection by-products, the reactivity of the precursor, the influencing factors and the like are different, and the optimal control conditions of the brominated disinfection by-products need to be determined through a large number of experimental researches.
Disclosure of Invention
The invention aims to provide a method for improving the use efficiency of a nanofiltration membrane and the treatment efficiency of brominated disinfection byproducts in a plateau water body in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a method for treating a brominated disinfection by-product precursor by combining magnetic ion exchange resin with nanofiltration comprises the following steps:
s1: adjusting the pH of the bromine-containing raw water to 7-10 by using alkali liquor;
s2: adding magnetic ion exchange resin with the volume ratio of 5 ml/L-12 ml/L to the original water body for pretreatment, stirring for 5 min-10 min, and then reacting for 0.5 h-5 h;
s3: after the reaction is finished, adding activated carbon powder mixed with magnetic polymer nano composite particles into the mixture, wherein the mass ratio of the magnetic nano particles to the activated carbon powder is 1: 1-1: 5, stirring the mixture for 5-10 min at the rotating speed of 100-200 rpm, and then reacting for 0.2-0.5 h;
s4: standing the reaction mixed solution for 10-60 min, and taking the supernatant to pass through a nanofiltration membrane treatment unit at the pressure of 0.3-1.0 MPa;
s5: adding a disinfectant to react for 24 to 48 hours in a dark environment according to the content of the soluble organic carbon in the effluent;
the intercepted molecular mass of the nanofiltration membrane is 200 Da-1000 Da;
the disinfectant is one or more of hypochlorous acid, sodium hypochlorite or calcium hypochlorite;
the preparation method of the magnetic polymer nano composite particle comprises the following steps:
1) dissolving 40-50 parts by weight of polyethylene in xylene, wherein the mass volume ratio of the polyethylene to the xylene is 1: 10-1: 12, and heating and melting the mixture at 120-140 ℃ for 1-2 h;
2) dissolving 20-30 parts by weight of metal carbonyl compound in the mixture obtained in the step 1);
3) at 25cm2Providing nitrogen atmosphere at the speed of/min, reacting the mixture obtained in the step 2) at 50-80 ℃ for 30min, cooling to room temperature, taking the precipitate, and drying in an oven at 100-120 ℃ to obtain the magnetic polymer nano composite particles.
Further, the metal carbonyl compound is Co2(CO)8、Fe(CO)5Or Ni (CO)4One or more of them.
Further, the alkali is one or more of sodium hydroxide or potassium hydroxide.
Further, the pH value of the water body after alkali adjustment is 8-9.
Further, the initial concentration of the bromide ions in the raw water body is 50-1000 mug/L.
Further, the stirring speed of the magnetic ion exchange resin in the reaction process is 100 rpm-500 rpm.
Further, the stirring speed of the magnetic ion exchange resin in the reaction process is 100 rpm-200 rpm.
Further, the formula for calculating the dosage of the disinfectant is as follows:
Cl2＝(1-5)×DOC+8×NH3-N + a, wherein said Cl2、DOC、NH3And the unit of N is mg/L, and a is an error adjusting item with a numerical value in the range of 0-20.
Further, the temperature of the reaction was 20 ± 2 ℃ protected from light.
Compared with the prior art, the invention has the beneficial effects that:
1) the magnetic ion exchange resin adopted by the invention is specially designed aiming at the characteristics of organic matters in drinking water, compared with the traditional resin, the magnetic ion exchange resin has the advantages of large specific surface area, large adsorption capacity, high mass transfer efficiency and the like, and has better removal effect on bromide ions while efficiently removing organic pollutants in a water body, so that the membrane pollution is reduced, the membrane operation period is prolonged, and the yield of brominated disinfection byproducts in nano-filtered water can be effectively controlled; and the resin is easier to recycle and regenerate due to the magnetism. Compared with other nanofiltration pretreatment technologies such as coagulation and advanced oxidation, the technology does not introduce new chemical substances, does not produce unknown intermediate products, and is more environment-friendly and safer.
2) According to the method, after the magnetic ion exchange resin is adopted for pretreatment in the nanofiltration pretreatment process, the precursor of the brominated disinfection by-product generated in the subsequent disinfection process is further treated by adopting the mixture of the activated carbon powder and the magnetic polymer nano composite particles, the activated carbon can further remove halogen element ions and the pungent smell of gas, the disinfection residual taste in water is reduced, the magnetic polymer nano composite particles are dissolved in water to form gel, and the loss of the chelating and capturing capacity of the organic precursor of the brominated disinfection by-product generated in the subsequent disinfection process due to the oxidation of metal ions can be effectively avoided through the protection of carbonyl on the metal ions; the metal carbonyl compound can further react with pollutants such as heavy metal ions, organic matters, COD and the like in the original water body under the protection of the gel, so that the metal carbonyl compound is flocculated in the gel, and the metal ions can react with Cl in the water body-、Br-And the chelating of halogen elements reduces the nanofiltration burden of a nanofiltration membrane treatment unit. The magnetic polymer nano composite particles can be reused after acid washing, so that the treatment cost of the original water body bromination disinfection by-product treatment is reduced.
3) The reaction condition of the invention is mild, the pH value is 7-10, the pH value of the common natural water body is neutral or alkalescent, and the pH value does not need to be adjusted when the pretreatment of a water plant is actually carried out, thereby saving the manpower, material resources and financial resources.
4) The invention provides a method for removing a precursor of a disinfection by-product by a nanofiltration combination process from the aspect of source control, which can effectively control the disinfection by-product of water delivered by a water plant, thereby improving the safety of drinking water.
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The method for treating the brominated disinfection by-product precursor in the raw water body by combining the pretreatment of the magnetic ion exchange resin and the nanofiltration comprises the following steps:
adjusting the pH value of raw water containing bromide ions with the initial concentration of 60 mu g/L to 7.0 by using sodium hydroxide, then adding magnetic ion exchange resin with the volume ratio of 5mL/L to the raw water for pretreatment, stirring at the rotating speed of 100rpm for 5min during pretreatment, then performing pretreatment for 0.5h, after the reaction is finished, adding activated carbon powder mixed with magnetic polymer nano composite particles into the activated carbon powder, wherein the mass ratio of the magnetic nano particles to the activated carbon powder is 1:1, stirring at the rotating speed of 100rpm for 5min, and then reacting for 0.2 h; standing for 10min after reaction, and allowing the supernatant to pass through a nanofiltration membrane treatment unit with the molecular weight cutoff of 200Da and the operating pressure of 0.3 MPa. Adding a disinfectant hypochlorous acid according to the content of soluble organic carbon and ammonia nitrogen in the outlet water of the nanofiltration treatment unit, immediately sealing by using a screw cap with a polytetrafluoroethylene gasket, fully mixing, storing in a thermostat, reacting for 24 hours in a dark place, and simultaneously keeping the temperature at 20 ℃, thereby controlling the generation of brominated disinfection byproducts.
The preparation method of the magnetic polymer nano composite particles comprises the following steps:
1) according to the weight components, 40 parts of polyethylene is dissolved in xylene, the mass volume ratio of the polyethylene to the xylene is 1:10, and the polyethylene and the xylene are heated and melted for 1 hour at 120 ℃;
2) taking 20 parts by weight of Co2(CO)8Dissolving in the mixture obtained in the step 1);
3) at 25cm2Providing nitrogen atmosphere at a speed of/min, allowing the mixture obtained in the step 2) to react at 50 ℃ for 30min, cooling to room temperature, taking the precipitate, and drying in an oven at 100 ℃ to obtain the magnetic high componentA sub-nanocomposite particle.
Example 2
The method for controlling the generation of the brominated disinfection by-product precursor in the raw water body by combining the pretreatment of the magnetic ion exchange resin and nanofiltration comprises the following steps:
adjusting the pH value of raw water containing bromide ions with the initial concentration of 100 mu g/L to 8.0 by using potassium hydroxide, then adding magnetic ion exchange resin with the volume ratio of 8.5mL/L to the raw water for pretreatment, stirring at the rotating speed of 150rpm for 8min during pretreatment, then carrying out pretreatment reaction for 2.75h, after the reaction is finished, adding activated carbon powder mixed with magnetic polymer nano composite particles into the mixture, wherein the mass ratio of the magnetic polymer nano composite particles to the activated carbon powder is 1:2.5, stirring at the rotating speed of 150rpm for 8min, and then reacting for 0.35 h; standing for 35min after reaction, and allowing the supernatant to pass through a nanofiltration membrane treatment unit with the molecular weight cutoff of 600Da and the operating pressure of 0.7 MPa. Adding effective chlorine according to the content of soluble organic carbon and ammonia nitrogen in the outlet water of the nanofiltration treatment unit, immediately sealing by using a screw cap with a polytetrafluoroethylene gasket, fully mixing, storing in a thermostat, reacting for 32 hours in a dark place, and simultaneously keeping the temperature at 20 ℃, thereby controlling the generation of brominated disinfection byproducts.
The preparation method of the magnetic polymer nano composite particles comprises the following steps:
1) according to the weight components, 45 parts of polyethylene is dissolved in xylene, the mass volume ratio of the polyethylene to the xylene is 1:11, and the polyethylene and the xylene are heated and melted for 1.5 hours at the temperature of 130 ℃;
2) taking 25 parts by weight of Fe (CO)5Dissolving in the mixture obtained in the step 1);
3) at 25cm2Providing nitrogen atmosphere at the speed of/min, reacting the mixture obtained in the step 2) at 65 ℃ for 30min, cooling to room temperature, taking the precipitate, and drying in an oven at 110 ℃ to obtain the magnetic polymer nano composite particles.
Example 3
The method for treating the brominated disinfection by-product precursor in the raw water body by combining the magnetic ion exchange resin with nanofiltration comprises the following steps:
adjusting the pH value of raw water containing bromide ions with the initial concentration of 200 mug/L to 9.0 by using sodium hydroxide, then adding magnetic ion exchange resin with the volume ratio of 10mL/L to the raw water for pretreatment, stirring at the rotating speed of 200rpm for 10min during pretreatment, then carrying out pretreatment reaction for 3.5h, after the reaction is finished, adding activated carbon powder mixed with magnetic polymer nano composite particles into the mixture, wherein the mass ratio of the magnetic nano particles to the activated carbon powder is 1:3.5, stirring at the rotating speed of 175rpm for 9min, and then reacting for 0.4 h; standing for 45min after reaction, and allowing the supernatant to pass through a nanofiltration membrane treatment unit with the intercepted molecular mass of 800Da and the operating pressure of 0.85 MPa. Adding effective chlorine according to the content of soluble organic carbon and ammonia nitrogen in the outlet water of the nanofiltration treatment unit, immediately sealing by using a screw cap with a polytetrafluoroethylene gasket, fully mixing, storing in a thermostat, reacting for 36 hours in a dark place, and simultaneously keeping the temperature at 20 ℃, thereby controlling the generation of brominated disinfection byproducts.
The preparation method of the magnetic polymer nano composite particles comprises the following steps:
1) according to the weight components, 48 parts of polyethylene is dissolved in xylene, the mass volume ratio of the polyethylene to the xylene is 1:11.5, and the polyethylene is heated and melted for 1.7 hours at 135 ℃;
2) taking 28 parts by weight of Ni (CO)4Dissolving in the mixture obtained in the step 1);
3) at 25cm2Providing nitrogen atmosphere at the speed of/min, reacting the mixture obtained in the step 2) at 70 ℃ for 30min, cooling to room temperature, taking the precipitate, and drying in an oven at 115 ℃ to obtain the magnetic polymer nano composite particles.
Example 4
The method for controlling the generation of the brominated disinfection by-product precursor in the raw water body by combining the pretreatment of the magnetic ion exchange resin and nanofiltration comprises the following steps:
adjusting the pH value of raw water containing bromide ions with the initial concentration of 200 mug/L to 10.0 by using sodium hydroxide, then adding magnetic ion exchange resin with the volume ratio of 12mL/L to the raw water for pretreatment, stirring at the rotating speed of 500rpm for 10min during pretreatment, then carrying out pretreatment reaction for 5h, after the reaction is finished, adding activated carbon powder mixed with magnetic polymer nano composite particles into the activated carbon powder, wherein the mass ratio of the magnetic nano particles to the activated carbon powder is 1:5, stirring at the rotating speed of 200rpm for 9min, and then reacting for 0.5 h; standing for 60min after reaction, and then passing the supernatant through a nanofiltration membrane treatment unit, wherein the intercepted molecular mass of the nanofiltration membrane is 1000Da, and the operating pressure of the nanofiltration treatment unit is 1.0 MPa. Adding effective chlorine according to the content of soluble organic carbon and ammonia nitrogen in the outlet water of the nanofiltration treatment unit, immediately sealing by using a screw cap with a polytetrafluoroethylene gasket, fully mixing, storing in a thermostat, reacting for 48 hours in a dark place, and simultaneously keeping the temperature at 20 ℃, thereby controlling the generation of brominated disinfection byproducts.
The preparation method of the magnetic polymer nano composite particles comprises the following steps:
1) according to the weight components, 50 parts of polyethylene is dissolved in xylene, the mass volume ratio of the polyethylene to the xylene is 1:12, and the polyethylene and the xylene are heated and melted for 2 hours at the temperature of 140 ℃;
2) 30 parts by weight of Co2(CO)8Dissolving in the mixture obtained in the step 1);
3) at 25cm2Providing nitrogen atmosphere at the speed of/min, reacting the mixture obtained in the step 2) at 80 ℃ for 30min, cooling to room temperature, taking the precipitate, and drying in an oven at 120 ℃ to obtain the magnetic polymer nano composite particles.
Test example
The following experiments were conducted using the products of examples 1 to 3 as materials, respectively.
The determination method of the brominated disinfection by-products comprises the following steps: firstly, carrying out liquid-liquid extraction on a water sample subjected to preoxidation, namely: after a water sample passes through a 0.45-micron microporous filter membrane, 2g of anhydrous sodium sulfate (or anhydrous sodium chloride) is immediately added into a test tube containing 10ml of the water sample, and the test tube is placed on a test tube oscillator for oscillation, so that the anhydrous sodium sulfate is fully dissolved, and the liquid level of the water sample rises to some extent; then 2ml of methyl tert-butyl ether (as an extractant) is added and placed on a test tube oscillator to oscillate for 2min, the mixture is kept stand for 5min, 1ml of the extractant solution on the upper layer is absorbed by a pipette and placed in a sample injection bottle, the sample injection bottle is placed in an automatic sample injector, and then a gas chromatography-electronic capture detector combined instrument is used for measurement, and the test results are shown in table 1.
TABLE 1 reduction of brominated disinfection by-products in water
Examples Decline rate (%) of tribromomethane Decrease ratio of dibromoacetaldehyde (%) Reduction ratio (%) of dibromoacetonitrile
Example 1 68.4 55.6 49.1
Example 2 69.2 60.7 54.9
Example 3 73.4 63.5 56.8
Example 4 69.0 58.8 55.3
The rate of decrease in the table is the difference between the concentration of the disinfection by-product produced during disinfection of the water prior to treatment and the concentration of the disinfection by-product produced during disinfection after treatment, divided by the concentration of the disinfection by-product produced during disinfection of the water prior to treatment. As can be seen from Table 1, compared with the method for treating the brominated disinfection byproducts by combining the magnetic ion exchange resin with the nanofiltration membrane without treatment, the method has a good control effect on the brominated disinfection byproducts, the reduction rate of tribromomethane is 68.4-73.4%, the reduction rate of dibromoacetaldehyde is 55.6-63.5%, the reduction rate of dibromoacetonitrile is 49.1-56.8%, and the removal effect is obvious, so that the method for treating the brominated disinfection byproducts by combining the magnetic ion exchange resin with the nanofiltration provided by the invention has a good control effect on the generation of the brominated disinfection byproducts.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (9)

1. A method for treating a brominated disinfection by-product precursor by combining magnetic ion exchange resin with nanofiltration is characterized by comprising the following steps:
s1: adjusting the pH of the bromine-containing raw water to 7-10 by using alkali liquor;
s2: adding magnetic ion exchange resin with the volume ratio of 5 ml/L-12 ml/L to the original water body for pretreatment, stirring for 5 min-10 min, and then reacting for 0.5 h-5 h;
s3: after the reaction is finished, adding activated carbon powder mixed with magnetic polymer nano composite particles into the mixture, wherein the mass ratio of the magnetic nano particles to the activated carbon powder is 1: 1-1: 5, stirring the mixture for 5-10 min at the rotating speed of 100-200 rpm, and then reacting for 0.2-0.5 h;
s4: standing the reaction mixed solution for 10-60 min, and taking the supernatant to pass through a nanofiltration membrane treatment unit at the pressure of 0.3-1.0 MPa;
s5: adding a disinfectant to react for 24 to 48 hours in a dark environment according to the content of the soluble organic carbon in the effluent;
the intercepted molecular mass of the nanofiltration membrane is 200 Da-1000 Da;
the disinfectant is one or more of hypochlorous acid, sodium hypochlorite or calcium hypochlorite;
the preparation method of the magnetic polymer nano composite particle comprises the following steps:
1) dissolving 40-50 parts by weight of polyethylene in xylene, wherein the mass volume ratio of the polyethylene to the xylene is 1: 10-1: 12, and heating and melting the mixture at 120-140 ℃ for 1-2 h;
2) dissolving 20-30 parts by weight of metal carbonyl compound in the mixture obtained in the step 1);
3) at 25cm2Providing nitrogen atmosphere at the speed of/min, reacting the mixture obtained in the step 2) at 50-80 ℃ for 30min, cooling to room temperature, taking the precipitate, and drying in an oven at 100-120 ℃ to obtain the magnetic polymer nano composite particles.
2. The method of claim 1, wherein the metal carbonyl compound is Co2(CO)8、Fe(CO)5Or Ni (CO)4One or more of them.
3. The method for treating the brominated precursor of a disinfection by-product through combination of magnetic ion exchange resin and nanofiltration according to claim 1, wherein the alkali is one or more of sodium hydroxide or potassium hydroxide.
4. The method for treating the brominated disinfection by-product precursor by combining magnetic ion exchange resin with nanofiltration according to claim 1, wherein the pH value of the water body after alkali adjustment is 8-9.
5. The method for treating the brominated disinfection by-product precursor by combining magnetic ion exchange resin with nanofiltration according to claim 1, which is characterized in that: the initial concentration of bromide ions in the raw water body is 50 mug/L-1000 mug/L.
6. The method for treating the brominated precursor of the disinfection byproducts through the combination of the magnetic ion exchange resin and the nanofiltration of claim 1, wherein the stirring speed of the magnetic ion exchange resin in the reaction process is 100 rpm-500 rpm.
7. The method for treating the brominated precursor of the disinfection byproducts through the combination of the magnetic ion exchange resin and the nanofiltration of claim 6, wherein the stirring speed of the magnetic ion exchange resin in the reaction process is 100rpm to 200 rpm.
8. The method for treating the brominated disinfection by-product precursor by combining the magnetic ion exchange resin with the nanofiltration according to claim 1, wherein the dosage of the disinfectant is calculated according to the following formula:
Cl2＝(1-5)×DOC+8×NH3-N + a, wherein said Cl2、DOC、NH3And the unit of N is mg/L, and a is an error adjusting item with a numerical value in the range of 0-20.
9. The method for treating the brominated disinfection by-product precursor by combining the magnetic ion exchange resin with the nanofiltration according to claim 1, wherein the temperature for adding the disinfectant in a dark environment is 20 +/-2 ℃.
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CN102381800A (en) * 2011-09-20 2012-03-21 哈尔滨工程大学 Method for treatment of oily sewage at bottom of bilge of vessel and method for preparation of magnetic activated carbon for decontamination of oily sewage
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