CN107117701B - Method for controlling generation of bromate and trihalomethane in water treatment process - Google Patents

Method for controlling generation of bromate and trihalomethane in water treatment process Download PDF

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CN107117701B
CN107117701B CN201710358250.6A CN201710358250A CN107117701B CN 107117701 B CN107117701 B CN 107117701B CN 201710358250 A CN201710358250 A CN 201710358250A CN 107117701 B CN107117701 B CN 107117701B
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张孝洪
李贤舟
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Zhoushan Water Supply Co ltd
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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
    • C02F1/76—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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/008—Control or steering systems not provided for elsewhere in subclass C02F
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions

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  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

A method for controlling the production of bromate and trihalomethane in a water treatment process comprises the steps of coagulating sedimentation, filtering, ozone activated carbon advanced treatment and chlorine disinfection of a water body in sequence, and the process also comprises the step of adding chlorine for multiple times before the water body is subjected to the ozone-activated carbon advanced treatment. The method is based on the existing water treatment process, can realize the purpose of simultaneously controlling the generation amount of bromate and THMs only by increasing the chlorination point and controlling the chlorination amount, and has the advantages of low cost, easy realization, convenient control, higher operability and wide application range.

Description

Method for controlling generation of bromate and trihalomethane in water treatment process
Technical Field
The invention relates to the technical field of water treatment, in particular to a method for controlling the generation of bromate and trihalomethane in a water treatment process
Background
The global eutrophication problem is serious, China is no exception, the problem of the eutrophication of lakes and reservoirs is prominent, drinking water sources are polluted in different degrees, the conventional process of a water plant cannot ensure the water quality safety of the drinking water, and the ozone-biological activated carbon (O3-BAC) advanced treatment process is often added to improve the water quality of the tap water. In addition, some waterworks also use ozone pretreatment to remove micropollutants and control algae.
However, ozone pretreatment and O3The BAC advanced treatment process can effectively improve the removal effect of the organic matters, but for bromine-rich water, the bromine-rich water is treated by O3After oxidation, part of the bromide ion Br-Will be oxidized into bromate BrO3 -See equation (1), and BAC cannot effectively remove it, resulting in BrO3 -There is an overproof risk. BrO3 -Is a potential carcinogen, is regulated in drinking water regulations or standards of many countries, is no exception in China, and is regulated by the latest 'sanitary Standard test method for Drinking Water' GBT 5750-2006: BrO in drinking water when waterworks use ozone technology3 -The concentration of the solution can not exceed 0.01 mg/L.
O3+Br-＝BrO3 -(1)
Current control of BrO3 -The more common method is in O3Addition of ammonia to inhibit BrO prior to oxidation3 -However, for some special water bodies, the water body is a high ammonia nitrogen water body (generally, the concentration of ammonia nitrogen in water is higher than 0.5mg/L, and the high ammonia nitrogen water body), even if ammonia is added, the BrO is treated3 -The control effect of (A) is not ideal, and excessive ammonia can influence the periodic law of microorganisms in BAC, thereby influencing the removal effect of BAC on ammonia nitrogen and organic matters.
Disinfectant chlorine Cl commonly used in water plant2Can oxidize Br to generate hypobromous acid HOBr shown in formula (2) and formula (3),
Cl2+H2O＝HClO+ClO-(2)
HOCl+Br-＝HOBr+Cl-(3)，
HOBr can react with organic materials to produce organic brominated by-products, such as bromine-containing trihalomethane THMs, thereby reducing BrO3 -Is generated. However, THMs are also indexes defined by sanitary standards for drinking water (GB5746-2006), and BrO can be solved by only adding excessive chlorine once3 -But the THMs are out of limits.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for controlling the generation of bromate and trihalomethane in a water treatment process, and in order to achieve the aim, the solution scheme of the invention is as follows:
the method comprises the steps of coagulating sedimentation, filtering, ozone-activated carbon advanced treatment and chlorine disinfection of the water body to be detected in sequence, and also comprises the step of adding chlorine for multiple times in the water body before the water body is subjected to the ozone-activated carbon advanced treatment, wherein the step of adding chlorine for multiple times comprises the steps of adding chlorine before the water body is subjected to the coagulating sedimentation step, and adding chlorine before the water body is subjected to the filtering step after the water body is subjected to the coagulating sedimentation step.
The chlorination frequency is preferably 2 times, and can be increased according to various indexes of the actual water body to be treated.
In the water body to be treated, the concentration of bromide ions is 50-1000 mug/L, the mass concentration ratio of the bromide ions to DOC is 1-50%, and the concentration of ammonia nitrogen is 0.05-1.0 mg/L.
The chlorine adding amount to the water body before the treatment (the first chlorine adding point) of the coagulating sedimentation step is a times of DOC1The sum of the concentration and b times of ammonia nitrogen concentration, wherein,
the value range of a is 0.5-3, the value range of b is 6-9, and the DOC is1The concentration of the ammonia nitrogen and the water is the concentration of the water before the water is subjected to the coagulating sedimentation step.
The chlorine adding amount to the water body before the treatment of the filtering step (the second chlorine adding point) is c times of DOC2The concentration of the component (A) in the solution,
c is 0.1-1, and the DOC2The concentration is the concentration of the water body after the treatment of the coagulating sedimentation step and before the treatment of the filtering step.
The chlorine adding amount of the water body after the advanced treatment by the ozone-activated carbon for chlorine disinfection (third chlorine adding point) is executed according to the chlorine adding amount when the raw water treatment process is normally operated.
The invention adopts a multi-point chlorination method and an ozone activated carbon advanced treatment process (O) in water3BAC advanced treatment process), active chlorine component is added to oxidize the bromide ions in the water body into hypobromous acid, so that the content of the bromide ions in O in the water body is reduced3The BAC advanced treatment process always has the probability of generating bromate by reacting with ozone, so the generation amount of the bromate is reduced, and meanwhile, as the invention adopts multiple times of chlorination and controls the chlorination, the generated hypobromous acid is smaller, the hypobromous acid is unstable and is easy to decompose under visible light, so the method of the invention can inhibit the generation of brominated by-products (such as bromine-containing trihalomethane THMs) generated by the reaction of the hypobromous acid and organic matters in water, thereby achieving the purpose of simultaneously controlling the production of the trihalomethane and the bromate.
Due to the adoption of the scheme, the invention has the beneficial effects that:
firstly, on the basis of determining the generation mechanism of bromate and trihalomethane, the invention reduces the generation amount of bromate in the ozone oxidation process of bromine-containing water body by carrying out multipoint chlorine addition at different stages of water treatment, and controls the generation amount of THMs by controlling the addition amount of chlorine during multipoint chlorine addition, so as to finally achieve the purpose that the treated water body meets the relevant regulation of the sanitary standard for drinking water GBT 5750-2006.
Secondly, the method adopted by the invention is based on the existing water treatment process, the aim of simultaneously controlling the generation amount of bromate and THMS can be realized only by increasing the chlorination point and controlling the chlorination amount, and two water quality indexes of soluble organic carbon (DOC) and ammonia nitrogen (NH3) in the water body can be measured by the national standard method, and the method is also simple and convenient, so the method adopted by the invention has the advantages of low cost, easy realization, convenient management and control, higher operability and wide application range.
Detailed Description
The invention provides a method for controlling the generation of bromate and trihalomethane in a water treatment process.
The method comprises the steps of adding chlorine for multiple times to the water body to be detected on the basis of performing a conventional water treatment process to control the generation of bromate and trihalomethane in the conventional water treatment process, wherein the conventional water treatment process comprises the steps of coagulating sedimentation, filtering, ozone-activated carbon advanced treatment and chlorine disinfection of the water body to be detected in sequence.
The invention will now be further illustrated by reference to the following examples.
Example 1:
DOC and NH measured by water body to be treated in A water plant3Concentration (also DOC before coagulating sedimentation process)1And NH3Concentration) of 2.5mg/L and 0.5mg/L, respectively, Br in water-At a concentration of 62. mu.g/L and Br-(mg/L) and DOC1(mg/L) at a mass concentration ratio of 2.48%,
firstly, chlorine is added to a water body to be treated at a first chlorine adding point, wherein the value of a is 2, the value of b is 6, and thus the chlorine adding amount of the first chlorine adding point is 2 × 2.5.5 mg/L and 6 × 0.5.5 mg/L is 8.0mg/L, namely the chlorine adding amount of the first chlorine adding point is 8.0 mg/L;
step two: performing coagulating sedimentation treatment on the water body treated in the first step, wherein the step is a conventional water treatment step of a water plant and is not described herein again;
step three: measuring DOC in the water body after the coagulating sedimentation step before the filtering step2The concentration is 1.5mg/L, and the chlorination step of a second chlorination point is carried out on the water body before the water body is treated by the filtering process, wherein the value of c is 0.4, so that the chlorination amount of the second chlorination point is 0.4 × 1.5.5-0.6 mg/L, namely the chlorination amount of the second chlorination point is 0.6 mg/L;
step four: the water body treated by the second chlorination point chlorination step is sequentially subjected to a filtering step and an O step3BAC advanced treatment step treatment, which is not described herein since it is a conventional water treatment step in water plants;
step five: and C, performing chlorine disinfection in the raw water treatment process of the water plant A on the water body treated in the step four, wherein the chlorine dosage in the chlorine disinfection step in the raw water treatment process of the water plant A is 2.0mg/L, so that the chlorine dosage of the third chlorine adding point is 2.0 mg/L.
The water body treated by the steps is sampled and then is kept stand for 24 hours, then the measurement is carried out (24 hours are used for summarizing the time for conveying tap water from a water plant to a user), the measurement result is shown in table 1, and the test standard is 'sanitary standard test method for drinking water' GBT 5750-2006.
Comparative example 1:
the chlorination step of the first chlorination site and the chlorination step of the second chlorination site in example 1 were removed, which is the water treatment process of this comparative example, and the treated water was sampled, left to stand for 24 hours, and then measured (24 hours is used to refer to the time for transporting tap water from the water plant to the user), and the measurement results are shown in table 1, and the test standard is "test method for sanitary Standard for Drinking Water" GBT 5750-2006.
TABLE 1
Figure BDA0001299668810000041
As is clear from Table 1, BrO in example 13 -The concentration, CF, BDCM and other trihalomethanes are all lower than the limit requirement of sanitary Standard for Drinking Water (GB5749-2006), while the BrO in comparative example 13 -The concentration and the CF concentration both exceed the limit requirement of sanitary Standard for Drinking Water (GB5749-2006), namely do not reach the standard.
Example 2:
DOC and NH measured by water body to be treated in water plant B3Concentration (also DOC before coagulating sedimentation process)1And NH3Concentration) of 5.5mg/L and 0.5mg/L, respectively, Br in water-At a concentration of 70. mu.g/L and Br-(mg/L) and DOC1(mg/L) at a mass concentration ratio of 1.27%,
firstly, chlorine is added to a water body to be treated at a first chlorine adding point, wherein the value of a is 1, the value of b is 6, and thus the chlorine adding amount at the first chlorine adding point is 1 × 5.5mg/L +6 × 0.5.5 mg/L is 8.5mg/L, namely the chlorine adding amount at the first chlorine adding point is 8.5 mg/L;
step two: performing coagulating sedimentation treatment on the water body treated in the first step, wherein the step is a conventional water treatment step of a water plant and is not described herein again;
step three: measuring DOC in the water body after the coagulating sedimentation step before the filtering step2The concentration is 3.5mg/L, and the water body is subjected to a second chlorination point chlorination step before being treated by a filtering process, wherein the value of c is 0.2, so that the chlorination amount of the second chlorination point is 0.2 × 3.5.5-0.7 mg/L, namely the chlorination amount of the second chlorination point is 0.7 mg/L;
step four: the water body treated by the second chlorination point chlorination step is sequentially subjected to a filtering step and an O step3BAC advanced treatment step treatment, which is not described herein since it is a conventional water treatment step in water plants;
step five: and C, performing chlorine disinfection in the raw water treatment process of the water plant B on the water body treated in the step four, wherein the chlorine dosage in the chlorine disinfection step in the raw water treatment process of the water plant B is 1.5mg/L, so that the chlorine dosage of the third chlorine adding point is 1.5 mg/L.
The water body treated by the process is sampled and then is kept stand for 24 hours for determination (24 hours is used for generally indicating the time for conveying tap water from a water plant to a user), the determination result is shown in table 2, and the test standard is 'sanitary standard test method for drinking water' GBT 5750-2006.
Comparative example 2:
the chlorination step of the first chlorination site and the chlorination step of the second chlorination site in example 2 were removed, which is the water treatment process of this comparative example, and the treated water was sampled, left to stand for 24 hours, and then measured (24 hours is used to refer to the time for transporting tap water from the water plant to the user), and the measured results are shown in table 2, and the test standard is "sanitary standard test for drinking water" GBT 5750-2006.
TABLE 2
Figure BDA0001299668810000051
As is clear from Table 2, BrO in example 23 -The concentration, CF, BDCM and other trihalomethanes are all lower than the limit requirement of sanitary Standard for Drinking Water (GB5749-2006), while the BrO in comparative example 23 -The concentration and the CF concentration both exceed the limit requirement of sanitary Standard for Drinking Water (GB5749-2006), namely do not reach the standard.
Example 3:
DOC and NH measured by water body to be treated of C water plant3Concentration (also DOC before coagulating sedimentation process)1And NH3Concentration) of 8.5mg/L and 0.2mg/L, respectively, Br in water-At a concentration of 93. mu.g/L and Br-(mg/L) and DOC1(mg/L) is 1.09%,
firstly, the water body to be treated is added with chlorine at a first chlorination point, wherein the value of a is 0.6, the value of b is 7, and the chlorine adding amount at the first chlorination point is 0.6 × 8.5.5 mg/L +7 × 0.2.2 mg/L-6.5 mg/L, namely the chlorine adding amount at the first chlorination point is 6.5mg/L,
step two: performing coagulating sedimentation treatment on the water body treated in the first step, wherein the step is a conventional water treatment step of a water plant and is not described herein again;
step three: measuring DOC in the water body after the coagulating sedimentation step before the filtering step2The concentration is 5.5mg/L, and the water body is subjected to a second chlorination point chlorination step before being treated by a filtering process, wherein the value of c is 0.4, so that the chlorination amount of the second chlorination point is 0.4 × 5.5.5-2.2 mg/L, namely the chlorination amount of the second chlorination point is 2.2 mg/L;
step four: the water body treated by the second chlorination point chlorination step is sequentially subjected to a filtering step and an O step3BAC advanced treatment step treatment, which is not described herein since it is a conventional water treatment step in water plants;
step five: and C, performing chlorine disinfection on the water body treated in the fourth step in the raw water treatment process of the water plant C, wherein the chlorine dosage in the chlorine disinfection step in the raw water treatment process of the water plant C is 2.0mg/L, so that the chlorine dosage of the third chlorine adding point is 2.0 mg/L.
The water body treated by the process is sampled and then is kept stand for 24 hours for determination (24 hours is used for generally indicating the time for conveying tap water from a water plant to a user), the determination result is shown in table 3, and the test standard is 'sanitary standard test method for drinking water' GBT 5750-2006.
Comparative example 3:
the chlorination step of the first chlorination site and the chlorination step of the second chlorination site in example 3 were removed, which is the water treatment process of this comparative example, and the treated water was sampled, left to stand for 24 hours, and then measured (24 hours is used to refer to the time for transporting tap water from the water plant to the user), and the measured results are shown in table 3, and the test standard is "sanitary standard test for drinking water" GBT 5750-2006.
TABLE 3
Figure BDA0001299668810000061
As is clear from Table 3, BrO in example 33 -The concentration, CF, BDCM and other trihalomethanes are all lower than the sanitary Standard for Drinking Water (GB)5749-3 -The concentration and the CF concentration both exceed the limit requirement of sanitary Standard for Drinking Water (GB5749-2006), namely do not reach the standard.
Example 4:
DOC and NH measured by water body to be treated in water plant3Concentration (also DOC before coagulating sedimentation process)1And NH3Concentration) of 3.4mg/L and 0.6mg/L, respectively, Br in water-At a concentration of 50. mu.g/L and Br-(mg/L) and DOC1(mg/L) at a mass concentration ratio of 1.47%,
firstly, chlorine is added to a water body to be treated at a first chlorine adding point, wherein the value of a is 1, the value of b is 6, and thus the chlorine adding amount at the first chlorine adding point is 1.5 × 3.4.4 mg/L +6.5 × 0.6.6 mg/L is 9mg/L, namely the chlorine adding amount at the first chlorine adding point is 9 mg/L;
step two: performing coagulating sedimentation treatment on the water body treated in the first step, wherein the step is a conventional water treatment step of a water plant and is not described herein again;
step three: measuring DOC in the water body after the coagulating sedimentation step before the filtering step2The concentration is 2.5mg/L, and the chlorination step of a second chlorination point is carried out on the water body before the water body is treated by the filtering process, wherein the value of c is 0.2, so that the chlorination amount of the second chlorination point is 0.2 × 2.5.5-0.5 mg/L, namely the chlorination amount of the second chlorination point is 0.5 mg/L;
step four: the water body treated by the second chlorination point chlorination step is sequentially subjected to a filtering step and an O step3BAC advanced treatment step treatment, which is not described herein since it is a conventional water treatment step in water plants;
step five: and D, performing chlorine disinfection on the water body treated in the fourth step in the raw water treatment process of the water plant, wherein the chlorine dosage in the chlorine disinfection step in the raw water treatment process of the water plant is 3.5mg/L, so that the chlorine dosage of the third chlorine adding point is 3.5 mg/L.
The water body treated by the process is sampled and then is kept stand for 24 hours for determination (24 hours is used for generally indicating the time for conveying tap water from a water plant to a user), the determination result is shown in table 4, and the test standard is 'sanitary standard test method for drinking water' GBT 5750-2006.
Comparative example 4:
the chlorination step of the first chlorination site and the chlorination step of the second chlorination site in example 4 were removed, which is the water treatment process of this comparative example, and the treated water was sampled, left to stand for 24 hours, and then measured (24 hours is used to refer to the time for transporting tap water from the water plant to the user), and the measured results are shown in table 4, and the test standard is "sanitary standard test for drinking water" GBT 5750-2006.
TABLE 4
Figure BDA0001299668810000071
As is clear from Table 4, BrO in example 43 -The concentration, CF, BDCM and other trihalomethanes are all lower than the limit requirement of sanitary Standard for Drinking Water (GB5749-2006), while the BrO in comparative example 43 -The concentration is also lower than the limit requirement of sanitary Standard for Drinking Water (GB5749-2006), but both CF and BDCM concentrations exceed the limit requirement of sanitary Standard for Drinking Water (GB5749-2006), i.e. do not reach the standard, which results in that the concentration of bromate reaches the standard due to the single point addition of excess chlorine in comparative example 4, while trichloromethane and monobromo dichloromethane do not reach the standard.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. It will be readily apparent to those skilled in the art that various modifications can be made to the embodiments and the generic principles defined herein may be applied to other embodiments without the use of inventive faculty, e.g., increasing the number of chlorinations, depending on the actual condition of the body of water being treated. Therefore, the present invention is not limited to the above-described embodiments. Those skilled in the art should appreciate that many modifications and variations are possible in light of the above teaching without departing from the scope of the invention.

Claims (3)

1. A method for controlling the generation of bromate and trihalomethane in a water treatment process comprises the steps of coagulating sedimentation, filtering, ozone activated carbon advanced treatment and chlorine disinfection of a water body to be treated, and is characterized in that: the method also comprises the step of adding chlorine for a plurality of times in the water body before the water body is subjected to the advanced treatment of ozone activated carbon, the step of adding chlorine for a plurality of times comprises the steps of adding chlorine before the water body is subjected to the coagulating sedimentation step, adding chlorine before the water body is subjected to the filtering step after the water body is subjected to the coagulating sedimentation step,
the chlorine adding amount to the water body before the coagulating sedimentation step is 0.5-3 times DOC1And 6-9 times of ammonia nitrogen concentration, and the DOC1The concentration of the ammonia nitrogen and the water is the concentration of the water before the water is subjected to the coagulating sedimentation step.
2. The method of claim 1, wherein: in the water body to be treated, the concentration of bromide ions is 50-1000 mug/L, the mass concentration ratio of the bromide ions to DOC is 1-50%, and the concentration of ammonia nitrogen is 0.05-1.0 mg/L.
3. The method of claim 1, wherein: the chlorine adding amount to the water body before the filtering step is 0.1-1 time DOC2Concentration of said DOC2The concentration is the concentration of the water body after the treatment of the coagulating sedimentation step and before the treatment of the filtering step.
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