CN113371901B - Method for controlling bromate and brominated disinfection byproducts in drinking water - Google Patents
Method for controlling bromate and brominated disinfection byproducts in drinking water Download PDFInfo
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- CN113371901B CN113371901B CN202110423210.1A CN202110423210A CN113371901B CN 113371901 B CN113371901 B CN 113371901B CN 202110423210 A CN202110423210 A CN 202110423210A CN 113371901 B CN113371901 B CN 113371901B
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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
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
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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
- C02F7/00—Aeration of stretches of water
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Abstract
The invention discloses a method for controlling bromate and brominated disinfection byproducts in drinking water, which comprises the following steps: s110, adjusting the pH value of a raw water body containing bromide ions and soluble organic matters to 4-7 by using acid liquor to obtain pretreated raw water; s120, adding preoxidized hydrogen persulfate into the pretreated raw water, wherein the molar concentration ratio of the hydrogen persulfate to bromide ions is 1:0.5-2, and simultaneously applying aeration; s130, adding ozone with the concentration of 0.5-4mg/L into the aerated water body; and S140, adding chloramine into the water body treated by the ozone in the step S130, and reacting for 24-48h in a dark place. The beneficial effects are that: high-toxicity bromate and brominated disinfection byproducts generated in the subsequent disinfection process are reduced, the water quality of purified water is improved, and the safety of drinking water treatment is ensured; the process is convenient to operate and low in implementation cost, and compared with a microbial capacitance deionization technology and a membrane filtration deionization technology, water treatment equipment and water plant structures do not need to be added, so that the construction cost of a water plant can be saved.
Description
Technical Field
The invention relates to the technical field of drinking water treatment, in particular to a method for controlling bromate and brominated disinfection byproducts in drinking water.
Background
In drinking water treatment, residues such as halogen ions and organic substances remain in treated water, and the residues react with a disinfectant to generate disinfection byproducts, which are widely noticed due to potential correlation with the increase of the incidence of diseases such as bladder cancer, rectal cancer and poor pregnancy. In particular, the toxicity of bromate and brominated disinfection byproducts is 2 to 3 orders of magnitude higher than that of the conventional disinfection byproducts brought into the water quality management standard, seriously threatens the health of drinking water, and the generation of the bromate and the brominated disinfection byproducts is controlled. There are three main methods of controlling disinfection by-products: 1. precursor substances in water are removed before source control disinfection, reactants are lacked, and disinfection byproducts cannot be generated; 2. process control is primarily directed to reducing the formation of disinfection byproducts during the disinfection process by changing the disinfection process parameters or the mode of disinfection. Changing disinfection process parameters on the basis of ensuring disinfection and sterilization effects, and reducing the disinfection dose of chlorine by replacing original chlorine disinfection with combined disinfection, thereby controlling the quantity of disinfection byproducts; 3. the terminal control removes the generated disinfection by-products, and the existence of the precursor and the residual chlorine can also continue to generate the disinfection by-products in the pipe network conveying process, so that the disinfection by-products cannot be eradicated. Therefore, before disinfection, the precursor is efficiently removed by adding pretreatment measures in combination with the conditions of reagents of a water plant, so that the source control of the nitrogenous disinfection byproducts is realized, and the water treatment process capable of effectively realizing the source control is not available at present.
Disclosure of Invention
The invention aims to provide a method for controlling bromate and brominated disinfection byproducts in drinking water in order to solve the problems, and the preferable technical scheme in the technical schemes provided by the invention comprises the following steps: the method can remove bromide ions of raw water from the source, reduce the generation of disinfection byproducts, improve the safety of drinking water, and has the technical effects of convenient operation, low process cost and the like, which are explained in detail below.
In order to realize the purpose, the invention provides the following technical scheme:
the invention provides a method for controlling bromate and brominated disinfection byproducts in drinking water, which comprises the following steps:
s110, adjusting the pH value of a raw water body containing bromide ions and soluble organic matters to 4-7 by using acid liquor to obtain pretreated raw water;
s120, adding preoxidized hydrogen persulfate into the pretreated raw water, wherein the molar concentration ratio of the hydrogen persulfate to bromide ions is 1:0.5-2, and simultaneously applying aeration;
s130, adding ozone with the concentration of 0.5-4mg/L into the aerated water body;
and S140, adding chloramine into the water body treated by the ozone in the step S130, and reacting for 24-48h in a dark place.
Preferably, in step S110, the acid solution is one or a combination of hydrochloric acid and sulfuric acid.
Preferably, in step S110, the pH of the pretreated raw water is 5.
Preferably, in step S120, the peroxodisulfate has a pre-oxidation time of 1 to 12 hours.
Preferably, in the step S120, the intensity of the applied aeration is 1-5L/min, and the aeration time is 10-40 min.
Preferably, in the step S130, the adding concentration of the ozone is 1-3mg/L, and the contact reaction time of the ozone and the water body is 1-6 h.
Preferably, in the step S130, the adding concentration of the ozone is 2mg/L, and the contact reaction time of the ozone and the water body is 2 hours.
Preferably, in step S140, the chloramine is added in an amount such that the chloramine remains in an amount of 0.5 to 1.5mg/L after 24 hours of reaction.
Preferably, in step S140, the chloramine is added in an amount such that the remaining chloramine amount is 1mg/L after 24 hours of reaction.
Preferably, in step S140, the temperature of the light-shielding reaction between the ozone-treated water body and chloramine is 18 ℃ to 22 ℃.
In conclusion, the beneficial effects of the invention are as follows: 1. the hydrogen persulfate and the ozone adopted by the process are both environment-friendly reagents, and the hydrogen persulfate oxidizes bromide ions to generate bromine simple substances, and then the bromine simple substances can be taken out from the water body through aeration, so that the bromide ions in the original water body can be removed from the source, high-toxicity bromate and brominated disinfection byproducts generated in the subsequent disinfection process are reduced, the water quality of purified water is improved, and the safety of drinking water treatment is ensured;
2. the process is convenient to operate and low in implementation cost, and compared with a microbial capacitance deionization technology and a membrane filtration deionization technology, water treatment equipment and water plant structures do not need to be added, so that the construction cost of a water plant can be saved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a graph showing the reduction in bromate and brominated disinfection by-products formed in water in examples 1 and 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It should be apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a method for controlling bromate and brominated disinfection byproducts in drinking water, which comprises the following steps:
s110, adjusting the pH value of a raw water body containing bromide ions and soluble organic matters to 4-7 by using acid liquor to obtain pretreated raw water;
s120, adding preoxidized hydrogen persulfate into the pretreated raw water, wherein the molar concentration ratio of the hydrogen persulfate to bromide ions is 1:0.5-2, and simultaneously applying aeration;
s130, adding ozone with the concentration of 0.5-4mg/L into the aerated water body;
and S140, adding chloramine into the water body treated by the ozone in the step S130, and reacting for 24-48h in a dark place.
In the method, the reaction equation of the peroxydisulfate and bromide ions is as follows:
the method for measuring the brominated disinfection by-products comprises the following steps: firstly, carrying out liquid-liquid extraction on a water sample subjected to preoxidation, namely: a water sample passes through a 0.45-micrometer microporous filter membrane, and a certain amount of ascorbic acid is added into the water sample to eliminate residual chloramine in the water, wherein the adding amount (by molar concentration) of the ascorbic acid is 1-2 times of that of the residual chloramine in the water; then 2mL of methyl tert-butyl ether is added as an extractant 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 introduction bottle, the sample introduction bottle is placed in an automatic sample injector, then a gas chromatography-mass spectrometry instrument is used for measurement, and the test result is shown in figure 1.
Wherein, the parameter setting of above-mentioned instrument is as follows: an RTX-5MS capillary column (the column length is 30m, the inner diameter is 0.25mm, the membrane is 2.5 mu m later) is adopted, the detection carrier gas is high-purity helium, the flow control mode of the carrier gas is pressure control, the column head pressure is 100-140KPa, the flow rate of the carrier gas is 34mL/min, the sample injection amount is 1 mu l, the sample injection mode is non-split flow, the sample injection port temperature is 220 ℃, the temperature of a mass spectrum detector is 250 ℃, the ion source is an electron impact ion source (EI), the electron energy is 70ev, the scanning mass range is 50-300m/z, the detection mode is selected ion detection (SIM), the initial temperature of a temperature raising program is 40 ℃, the temperature is kept for 3min, the temperature is raised to 260 ℃ at the speed of 10 ℃/min, and the temperature is kept for 3 min.
The detection method of bromate is as follows: an ion chromatograph (model ICS-1100) was used, equipped with an autosampler, conductivity detector, AS23 column, and anion suppressor. The temperature of the conductivity detection cell is 30 ℃, the flow rate of the mobile phase is NaHCO3-NaCO3, the flow rate of the mobile phase is 1mL/min, the sample injection volume is 100 mu L, and the current of the suppressor is 25 mA.
The specific embodiment is as follows:
example 1
Adjusting the pH value of a raw water body containing 5mg/L soluble organic carbon with the initial concentration of 5mg/L and 1mg/L bromide ion concentration to be 5 by using 0.1mol/L hydrochloric acid, then adding 0.4mg/L potassium hydrogen persulfate solution, simultaneously aerating with the aeration intensity of 3.5L/min for 15min, and then adding 2mg/L ozone for reaction for 3 h; adding 10mg/L chloramine, measuring the concentration of the residual chloramine after reacting for 24 hours, and calculating the consumed chloramine amount; adding 1mg/L chloramine according to the concentration of the consumed chloramine, adding the chloramine, immediately sealing a container by using a screw cap with a polytetrafluoroethylene gasket, fully mixing, storing in a thermostat, and reacting for 24 hours in a dark place while keeping the temperature at 20 ℃, thereby controlling bromate and brominated disinfection byproducts.
Example 2:
adjusting the pH value of a raw water body containing 2mg/L soluble organic carbon and 0.2mg/L bromide ion to 6.2 by using 0.1mol/L hydrochloric acid, then adding 0.6mg/L potassium hydrogen persulfate solution, aerating at the same time, wherein the aeration intensity is 4L/min, aerating for 20 minutes, and adding 3mg/L ozone to react for 2 hours; adding 10mg/L chloramine, measuring the concentration of the residual chloramine after reacting for 24 hours, and calculating the consumed chloramine amount; adding chloramine according to the concentration of consumed chloramine, adding 1mg/L chloramine, immediately sealing by using a screw cap with a polytetrafluoroethylene gasket, fully mixing, storing in a thermostat, and reacting for 24 hours in a dark place while keeping the temperature at 20 ℃, thereby controlling bromate and brominated disinfection byproducts.
Example 3:
adjusting the pH value of a raw water body containing 2mg/L soluble organic carbon and 0.2mg/L bromide ions to 5.6 by using 0.1mol/L hydrochloric acid, then adding 0.5mg/L potassium hydrogen persulfate solution, aerating at the same time, wherein the aeration intensity is 4L/min, aerating for 20 minutes, and adding 2mg/L ozone to react for 2 hours; adding 10mg/L chloramine, measuring the concentration of the residual chloramine after reacting for 36 hours, and calculating the consumed chloramine amount; adding 1mg/L chloramine according to the concentration of the consumed chloramine, adding the chloramine, immediately sealing by using a screw cap with a polytetrafluoroethylene gasket, fully mixing, storing in a thermostat, and reacting for 24 hours in a dark place while keeping the temperature at 20 ℃, thereby controlling bromate and brominated disinfection byproducts.
Example 4:
adjusting the pH value of a raw water body containing 2mg/L soluble organic carbon with initial concentration and 0.2mg/L bromide ion concentration to 6.6 by using 0.1mol/L sulfuric acid, then adding 0.6mg/L potassium hydrogen persulfate solution, simultaneously carrying out aeration with the aeration intensity of 4L/min for 20 minutes, and then adding 2mg/L ozone for reaction for 5 hours; adding 10mg/L chloramine, measuring the concentration of the residual chloramine after reacting for 48 hours, and calculating the consumed chloramine amount; adding 1mg/L chloramine according to the concentration of the consumed chloramine, adding the chloramine, immediately sealing by using a screw cap with a polytetrafluoroethylene gasket, fully mixing, storing in a thermostat, and reacting for 24 hours in a dark place while keeping the temperature at 20 ℃, thereby controlling bromate and brominated disinfection byproducts.
The reduction rates of bromate and brominated disinfection byproducts in water bodies treated in examples 1 to 4 are shown in fig. 1, and it can be seen from fig. 1 that the method for effectively controlling bromate and brominated disinfection byproducts in drinking water by using hydrogen persulfate/ozone/chloramine combined disinfection has a good control effect on bromate, dibromoacetonitrile, tribromoacetonitrile and dibromoacetamide, wherein the reduction rate of the bromate generation amount is 40.2-55.5%, the reduction rate of the dibromoacetonitrile generation amount is 38.9-48.7%, the reduction rate of the tribromoacetonitrile generation amount is 38.1-47.2, and the reduction rate of the dibromoacetamide generation amount is 35.6-40.1%, which are far lower than the safe threshold value of drinking water, so that the method has a good inhibition effect on bromate and brominated disinfection byproducts in water bodies treated by the method disclosed by the invention.
The hydrogen persulfate and the ozone adopted by the process are environment-friendly reagents, and the hydrogen persulfate oxidizes bromide ions to generate bromine, and then the bromine can be taken out from the water body through aeration, so that the bromide ions in the original water body can be removed from the source, high-toxicity bromate and brominated disinfection byproducts generated in the subsequent disinfection process are reduced, the water quality of purified water is improved, and the safety of drinking water treatment is ensured; the process is convenient to operate and low in implementation cost, and compared with a microbial capacitance deionization technology and a membrane filtration deionization technology, water treatment equipment and water plant structures do not need to be added, so that the construction cost of a water plant can be saved.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. A method for controlling bromate and brominated disinfection byproducts in drinking water is characterized by comprising the following steps:
s110, adjusting the pH value of a raw water body containing bromide ions and soluble organic matters to 4-7 by using acid liquor to obtain pretreated raw water;
s120, adding preoxidized hydrogen persulfate into the pretreated raw water, wherein the molar concentration ratio of the hydrogen persulfate to bromide ions is 1:0.5-2, and simultaneously applying aeration;
s130, adding ozone with the concentration of 0.5-4mg/L into the aerated water body;
and S140, adding chloramine into the water body treated by the ozone in the step S130, and reacting for 24-48h in a dark place.
2. The method for controlling bromate and brominated disinfection byproducts in drinking water according to claim 1, which is characterized in that: in the step S110, the acid solution is one or a combination of hydrochloric acid and sulfuric acid.
3. The method for controlling bromate and brominated disinfection byproducts in drinking water according to claim 1, which is characterized in that: in step S110, the pH of the pretreated raw water is 5.
4. The method for controlling bromate and brominated disinfection byproducts in drinking water as claimed in claim 1, wherein the method comprises the following steps: in the step S120, the peroxodisulfate has a pre-oxidation time of 1-12 h.
5. The method for controlling bromate and brominated disinfection byproducts in drinking water according to claim 1, which is characterized in that: in the step S120, the intensity of aeration is 1-5L/min, and the aeration time is 10-40 min.
6. The method for controlling bromate and brominated disinfection byproducts in drinking water according to claim 1, which is characterized in that: in the step S130, the adding concentration of the ozone is 1-3mg/L, and the contact reaction time of the ozone and the water body is 1-6 h.
7. The method of claim 6 for controlling bromate and brominated disinfection byproducts in drinking water, wherein the method comprises the following steps: in the step S130, the adding concentration of the ozone is 2mg/L, and the contact reaction time of the ozone and the water body is 2 h.
8. The method for controlling bromate and brominated disinfection byproducts in drinking water according to claim 1, which is characterized in that: in the step S140, the light-shielding reaction temperature of the water body after the ozone treatment and the chloramine is 18 ℃ to 22 ℃.
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| CN105967384A (en) * | 2016-05-24 | 2016-09-28 | 同济大学 | Method for controlling generation of iodo-trihalomethanes in drinking water |
| CN111362497A (en) * | 2020-03-20 | 2020-07-03 | 同济大学 | Method for treating brominated disinfection by-product precursor by combining magnetic ion exchange resin with nanofiltration |
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| US20090272698A1 (en) * | 2008-05-01 | 2009-11-05 | John Hill | Bromate suppression |
| CN104150562A (en) * | 2014-08-23 | 2014-11-19 | 哈尔滨工业大学 | Method for disinfecting filtered water from water plant with cooperation between medium-pressure ultraviolet catalyzing peroxymonosulfate and chloramine |
| CN105712549B (en) * | 2016-02-26 | 2018-07-27 | 同济大学 | A kind of method that bromo nitrogenous disinfection byproducts are formed in inhibition water |
| US20180065874A1 (en) * | 2016-09-02 | 2018-03-08 | Peroxychem Llc | Reduction of disinfection byproduct formation in drinking water |
| CN110498499A (en) * | 2019-08-01 | 2019-11-26 | 同济大学 | A kind of disinfectant reducing Disinfection Byproducts in Drinking Water concentration |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105967384A (en) * | 2016-05-24 | 2016-09-28 | 同济大学 | Method for controlling generation of iodo-trihalomethanes in drinking water |
| CN111362497A (en) * | 2020-03-20 | 2020-07-03 | 同济大学 | Method for treating brominated disinfection by-product precursor by combining magnetic ion exchange resin with nanofiltration |
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