CN107298493A - The chloramines biodegrading process of estriol in a kind of water supply network - Google Patents
The chloramines biodegrading process of estriol in a kind of water supply network Download PDFInfo
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- CN107298493A CN107298493A CN201710329899.5A CN201710329899A CN107298493A CN 107298493 A CN107298493 A CN 107298493A CN 201710329899 A CN201710329899 A CN 201710329899A CN 107298493 A CN107298493 A CN 107298493A
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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
- C02F1/66—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
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
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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
- C02F2101/30—Organic compounds
- C02F2101/305—Endocrine disruptive agents
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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
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2307/00—Location of water treatment or water treatment device
- C02F2307/14—Treatment of water in water supply networks, e.g. to prevent bacterial growth
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a kind of chloramines biodegrading process of estriol in water supply network, including：The temperature of water supply network is adjusted to 20 DEG C 30 DEG C, the flow velocity of water supply network is adjusted to 0.7m/s 1.5m/s, phosphoric acid and sodium hydroxide is added, water supply network pH to 6.5 8.4 is adjusted；Ammonium chloride and sodium hypochlorite are sequentially added into pipe network again, it is 39 that chlorine nitrogen mass ratio in chloramines disinfection liquid, chloramines disinfection liquid is formed in pipe network：Total available chlorine concentration is 0.6 1.4mg/L in 1 pipe network, after degradation reaction, completes the degraded of estriol.The biodegrading process of estriol in water supply network of the present invention, pass through the regulation to water supply network temperature, flow velocity, estriol is realized and degraded using the pH and addition ammonium chloride and sodium hypochlorite of main body water in phosphoric acid and sodium hydroxide regulation water supply network, with operation is simple, industrialization is easily achieved, possesses wide application prospect.
Description
Technical field
The present invention relates to drinking water treatment method technical field, and in particular to the chloramines drop of estriol in a kind of water supply network
Solution method.
Background technology
Estriol (Estriol, E3) is a kind of typical environment incretion interferent, mainly passes through the urine of humans and animals
Enter environment with the excreta such as excrement, migrated between the surrounding mediums such as sewage treatment plant, soil, surface water and groundwater.Certainly
It is difficult to degrade under the conditions of so and extremely low concentration can be made to aquatic organism and human endocrine system, particularly reproductive system
Into severe jamming, the health of organism and human body is threatened.The natural water body of current countries and regions many in worldwide,
There is detection in sewage, surface water, underground water and drinking water.With the quickening of urbanization process, the pollution of drinking water source is asked
Topic becomes increasingly conspicuous, and the situation that China's water body is polluted by incretion interferents such as estriol is more serious.
Chloramines disinfection is a kind of sterilization process being widely adopted, frequently as the means of the secondary chlorination of water factory.Its advantage is
The growing amount of the DBPs such as haloform can be reduced and water supply network can be made to keep a certain amount of in a long time
Chlorine residue level.Have the disadvantage that oxidisability is weaker, disinfecting time is longer, easily produce nitrification.Simultaneously chloramines can with including female
Numerous incretion interferents including triol are reacted, and they are degraded.
Research in recent years to incretion interferent in drinking water disinfection and transportation is a lot, but most research collection
In under the simple reaction environment such as beaker deionized water or organic solvent, and to natural organic matter in water supply network, inorganic
The influence of metal ion, hydraulics and infrastructure etc. is not almost accounted for, poor with response situation in actual water supply network
It is not larger.And during for using chloramines disinfection technique, the experiment of estriol degradation rule is either under the simple environment of beaker, still
All not yet had been reported that under water supply network complex situations.
Application publication number CN103728382A (Application No. 201310596499.2) Chinese invention patent application is disclosed
A kind of analysis method of estriol, comprises the following steps：(1) solution is prepared：Precision weighs estriol crude product, puts volumetric flask
In, with methanol dilution and constant volume, shake up and both obtained；(2) chromatographic condition：Hydrophily octadecylsilane chemically bonded silica chromatographic column (5 μ
M, 4.6 × 250mm), mobile phase is acetonitrile-water, flow velocity 1.0mL/min, column temperature：30 DEG C, Detection wavelength：280nm, sample size is
20μL；(3) gradient elution：The volume ratio of acetonitrile and water is：At 0-10 minutes, 10-40:90-60；At 10-30 minutes, 20-
80:80-20；At 30-55 minutes, 60-80:40-20.But the technical scheme only discloses the analysis method of estriol, does not have
The technical scheme that estriol is removed is provided.
The content of the invention
The invention provides a kind of chloramines biodegrading process of estriol in water supply network, can be effectively in degradation water female three
Alcohol.
The chloramines biodegrading process of estriol, comprises the following steps in a kind of water supply network：
(1) temperature of water supply network is adjusted to 20 DEG C -30 DEG C, the flow velocity of water supply network is adjusted to 0.7m/s-1.5m/s, plus
Enter phosphoric acid and sodium hydroxide, adjust water supply network pH to 6.5-8.4；
(2) ammonium chloride and sodium hypochlorite are sequentially added into pipe network again, chloramines disinfection liquid, chloramines disinfection are formed in pipe network
Chlorine nitrogen mass ratio is 3-9 in liquid：Total available chlorine concentration is 0.6-1.4mg/L in 1 pipe network, after degradation reaction, completes female three
The degraded of alcohol；
Described total available chlorine concentration refers to the concentration sum of freedom chlorine residue, monochloro amine and dichlormaine；
Described freedom chlorine residue refers to hypochlorous acid and hypochlorite sum.
Below as the preferred technical solution of the present invention：
In step (1), the temperature of water supply network is adjusted to 20 DEG C -30 DEG C, on the one hand, under different temperatures, degradation reaction institute
The activation energy needed is different, and the reaction rate of estriol and chloramines is different, and said temperature is conducive to the degraded of estriol, another
Aspect, 20 DEG C -30 DEG C are common environment temperature, and estriol can smoothly degrade at this temperature, without increasing additional temperature
Control cost.Further preferably, the temperature of water supply network is adjusted to 25 DEG C -30 DEG C.
The speed of current in water supply network is adjusted to 0.7m/s-1.5m/s, the turbulent condition of water body different in flow rate is not yet
Together, the complexity of the mass exchange between material and pipe scale such as estriol is also different in water body, the degraded different in flow rate to estriol
Have a certain impact, preferably, the flow velocity of water supply network is adjusted into 1.0m/s-1.5m/s.
Preferably, the phosphoric acid and sodium hydroxide that add are added in form of an aqueous solutions, using the form one of the aqueous solution
Aspect is conducive to phosphoric acid and sodium hydroxide to be added in water supply network, on the other hand, can effectively control phosphoric acid and sodium hydroxide
Addition so that precisely regulation water supply network pH.
Further preferably, the concentration of described phosphate aqueous solution be 50-75g/L, further preferably, phosphate aqueous solution it is dense
Degree elects 75g/L as；The concentration of described sodium hydrate aqueous solution be 5-10g/L, further preferably, sodium hydrate aqueous solution it is dense
Degree elects 10g/L as, and the phosphate aqueous solution and sodium hydrate aqueous solution of above-mentioned concentration can be good at adjusting the pH of water supply network, have
Beneficial to the degraded of estriol in water supply network.
Phosphoric acid and sodium hydroxide are added, the pH to 6.5-8.4 of water supply network water body is adjusted.Under different pH environment estriol and
The existence form of chloramines, pH is smaller, and the estriol proportion of molecular state is bigger, and dichlormaine proportion is also bigger；Conversely, from
The estriol proportion of sub- state is bigger, and monochloro amine proportion is also bigger.The estriol and different shape of different existence forms
Chloramines degradation rate it is different.Preferably, regulation water supply network pH to 7.5-8.4, is especially suitable for the degraded of estriol, enters one
Step is preferred, adjusts water supply network pH to 8.4.
In step (2), chloramines disinfection agent is reacted with estriol, and estriol is dropped in main generation substitution reaction
Solution.
Preferably, the configuration use of chloramine solution adds ammonium chloride successively and being arranged in order for sodium hypochlorite forms.Institute
The ammonium chloride and sodium hypochlorite stated are added in form of an aqueous solutions, are conducive to ammonium chloride and hypochlorous acid in the form of the aqueous solution
Sodium is added in water supply network, while addition can also be controlled accurately.
Further preferably, the concentration of aqueous ammonium chloride solution is 5-10g/L, and aqueous sodium hypochlorite solution is the quality hundred of free chlorine
Divide the aqueous sodium hypochlorite solution that content is 6%-14%, free chlorine refers to hypochlorous acid (HClO) and hypochlorite (ClO-) sum.
Further preferably, the concentration of aqueous ammonium chloride solution is 7.5g/L, and aqueous sodium hypochlorite solution is that the weight/mass percentage composition of free chlorine is
10% aqueous sodium hypochlorite solution.
Preferably, addition ammonium chloride and sodium hypochlorite form chlorine nitrogen in chloramines disinfection liquid, chloramines disinfection liquid in pipe network
Mass ratio is 3-9：1, different chlorine nitrogen are more different with the ratio shared by dichlormaine than free chlorine, monochloro amine in lower solution, estriol
Degradation rate is also different, further preferably, and the mass ratio of chlorine nitrogen elects 8 as：1.
Preferably, the concentration for adding the total available chlorine after ammonium chloride and sodium hypochlorite in pipe network is 0.6-1.4mg/L,
The estriol in water supply network can be made effectively to be degraded.Further preferably, the concentration of total available chlorine is 1.0-1.4mg/L,
Most preferably, the concentration of total available chlorine elects 1.4mg/L as.
Preferably, the time of degradation reaction is 7h~20h, further preferably, the time of degradation reaction is 9h, and degraded is anti-
Answer after 9h, more than 90% estriol can be degraded, complete the degraded of estriol.
Most preferably, in a kind of water supply network estriol chloramines biodegrading process, comprise the following steps：
(1) temperature of water supply network is adjusted to 30 DEG C, the flow velocity of water supply network is adjusted to 1.5m/s, add phosphoric acid and hydrogen-oxygen
Change sodium, adjust water supply network pH to 8.4；
The phosphoric acid and sodium hydroxide of addition are added in form of an aqueous solutions, and the concentration of phosphate aqueous solution is 75g/L, hydrogen-oxygen
It is 10g/L to change sodium water solution concentration；
(2) ammonium chloride and sodium hypochlorite are sequentially added into pipe network again so that the chlorine nitrogen matter of the chloramines disinfection liquid in pipe network
Amount is than being 8：1, total available chlorine concentration is 1.4mg/L, after degradation reaction 9h~11h, completes the degraded of estriol；
Described ammonium chloride and sodium hypochlorite are added in form of an aqueous solutions, and the concentration of aqueous ammonium chloride solution is 7.5g/
L, aqueous sodium hypochlorite solution be free chlorine weight/mass percentage composition be 10% aqueous sodium hypochlorite solution, free chlorine refers to hypochlorous acid
With hypochlorite sum；
Described total available chlorine concentration refers to the concentration sum of freedom chlorine residue, monochloro amine and dichlormaine；
Described freedom chlorine residue refers to hypochlorous acid and hypochlorite sum.
Compared with prior art, the invention has the advantages that：
The biodegrading process of estriol in water supply network of the present invention, by the regulation to water supply network temperature, flow velocity, utilizes phosphorus
Acid and sodium hydroxide adjust the pH of main body water and addition ammonium chloride and sodium hypochlorite in water supply network and estriol are realized and degraded.
Control to complete the degraded of estriol by various conditions, with operation is simple, it is easy to accomplish industrialization, possess wide answer
Use prospect.
Brief description of the drawings
Fig. 1 be embodiment 1 and embodiment 2 water supply network water body in estriol degradation curve；
Fig. 2 be embodiment 1 and embodiment 3 water supply network water body in estriol degradation curve；
Fig. 3 be embodiment 1 and embodiment 4 water supply network water body in estriol degradation curve；
Fig. 4 be embodiment 1 and embodiment 5 water supply network water body in estriol degradation curve；
Fig. 5 be embodiment 1 and embodiment 6 water supply network water body in estriol degradation curve.
Embodiment
Embodiment 1
(1) water source without estriol of degrading is taken, after testing, the concentration of the water source estriol is 25 μ g/L, is passed into
In water supply network, the temperature of main body water in water supply network is adjusted to 25 DEG C, the flow velocity of main body water is adjusted to 1.0m/s in water supply network,
Add main body in the phosphate aqueous solution that concentration is 75g/L and the sodium hydrate aqueous solution that concentration is 10g/L, regulation water supply network
The pH of water is 7.5.
(2) weight percent of aqueous ammonium chloride solution and free chlorine that concentration is 7.5g/L is sequentially added into water supply network again
Content is 10% aqueous sodium hypochlorite solution so that chlorine nitrogen mass ratio is 8 in water supply network, and total available chlorine concentration reaches 1.0mg/
L, after degraded after a while, completes the degraded of estriol.React after 9h, the degradation rate of estriol is 96%.
Take 200mL water samples into 250mL browns tool mouth vial from water supply network under different time t, add immediately
2g ascorbic acid terminates degradation reaction, and the concentration of estriol in water sample is then determined using high performance liquid chromatograph.
The concentration of estriol in water sample, C are determined using high performance liquid chromatograph0For the concentration of estriol in water source, C is confession
The concentration of estriol in grid water body, with C/C0For Y-axis, the time is X-axis, draws estriol degradation curve, is taken as 9h, song
Line is as shown in Figure 1.
Embodiment 2
In step (2), the weight of aqueous ammonium chloride solution and free chlorine that concentration is 7.5g/L is sequentially added into water supply network
Measure the aqueous sodium hypochlorite solution that percentage composition is 10% so that chlorine nitrogen mass ratio is 3 in water supply network, and total available chlorine concentration reaches
The degradation curve of 1.0mg/L, remaining be the same as Example 1, embodiment 1 and embodiment 2 is as shown in Figure 1.
As shown in figure 1, when chlorine nitrogen mass ratio is 3, after reaction 9h, the degradation rate of estriol is 78%.Chlorine nitrogen mass ratio is 3
When, the reaction long period still can not effectively degrade estriol, therefore the optimal chlorine nitrogen mass ratio of estriol degraded is 8.
Embodiment 3
In step (2), the weight of aqueous ammonium chloride solution and free chlorine that concentration is 7.5g/L is sequentially added into water supply network
Measure the aqueous sodium hypochlorite solution that percentage composition is 10% so that chlorine nitrogen mass ratio is 8 in water supply network, and total available chlorine concentration reaches
The degradation curve of 1.4mg/L, remaining be the same as Example 1, embodiment 1 and embodiment 3 is as shown in Figure 2.
As shown in Fig. 2 in embodiment 1, when total available chlorine concentration is 1.0mg/L, estriol degraded 90% needs 9h, and real
Apply in example 3, when total available chlorine concentration is 1.4mg/L, estriol degraded 96% only needs to 6.8h.Simultaneously in view of making water supply network
Certain chlorine residue level is kept in a long time, therefore the optimal total available chlorine concentration of estriol degraded is 1.4mg/L.
Embodiment 4
In step (1), the temperature of main body water in water supply network is adjusted to 30 DEG C, remaining be the same as Example 1, embodiment 1 and real
The degradation curve for applying example 4 is as shown in Figure 3.
As shown in figure 3, the temperature control of main body water is conducive to the degraded of estriol, embodiment 4 at 30 DEG C in water supply network
In, estriol degradation rate needs 8.2h for 96%.Because water temperature is 30 DEG C in southern summer maximum temperature in water supply network
Left and right, therefore, the optimum temperature that estriol is degraded in water supply network are 30 DEG C.
Embodiment 5
In step (1), the flow velocity of main body water in water supply network is adjusted to 1.5m/s, remaining be the same as Example 1, the He of embodiment 1
The degradation curve of embodiment 5 is as shown in Figure 4.
As shown in figure 4, the increase of 1.5m/s flow velocitys is conducive to reacting estriol after 9h in the degraded of estriol, embodiment 5
Degradation rate is higher than 96%, and slightly above flow velocity is 1.0m/s situations.Therefore, the optimum flow rate of estriol degraded is in water supply network
1.5m/s。
Embodiment 6
In step (1), the pH of main body water in water supply network is adjusted to 8.4, remaining be the same as Example 1, embodiment 1 and embodiment
6 degradation curve is as shown in Figure 5.
As shown in figure 5, the pH of main body water is adjusted to 8.4 in water supply network, be conducive in the degraded of estriol, embodiment 5,
Estriol degradation rate only needs 6.5h for 96%.The fast degradation of estriol can be promoted by improving pH, and meet water quality in pipe network
Stable requirement, therefore, the Optimal pH that estriol is degraded in water supply network are 8.4.
Claims (10)
1. the chloramines biodegrading process of estriol in a kind of water supply network, it is characterised in that comprise the following steps：
(1) temperature of water supply network is adjusted to 20 DEG C -30 DEG C, the flow velocity of water supply network is adjusted to 0.7m/s-1.5m/s, add phosphorus
Acid and sodium hydroxide, adjust water supply network pH to 6.5-8.4；
(2) ammonium chloride and sodium hypochlorite are sequentially added into pipe network again, is formed in pipe network in chloramines disinfection liquid, chloramines disinfection liquid
Chlorine nitrogen mass ratio is 3-9：1, total available chlorine concentration is 0.6-1.4mg/L in pipe network, after degradation reaction, completes estriol
Degraded；
Described total available chlorine concentration refers to the concentration sum of freedom chlorine residue, monochloro amine and dichlormaine；
Described freedom chlorine residue refers to hypochlorous acid and hypochlorite sum.
, will be for 2. the chloramines biodegrading process of estriol in the water supply network described in as requested 1, it is characterised in that in step (1)
The temperature of grid is adjusted to 25 DEG C -30 DEG C.
3. the chloramines biodegrading process of estriol in the water supply network described in as requested 1, it is characterised in that in step (1), will be for
The flow velocity of grid is adjusted to 1.0m/s-1.5m/s.
4. the chloramines biodegrading process of estriol in the water supply network described in as requested 1, it is characterised in that in step (1), is added
Phosphoric acid and sodium hydroxide add in form of an aqueous solutions.
5. the chloramines biodegrading process of estriol in the water supply network described in as requested 4, it is characterised in that phosphate aqueous solution it is dense
Spend for 50-75g/L, the concentration of sodium hydrate aqueous solution is 5-10g/L.
6. the chloramines biodegrading process of estriol in the water supply network described in as requested 1, it is characterised in that in step (1), regulation
Water supply network pH to 7.5-8.4.
7. the chloramines biodegrading process of estriol in the water supply network described in as requested 1, it is characterised in that described in step (2)
Ammonium chloride and sodium hypochlorite add in form of an aqueous solutions.
8. the chloramines biodegrading process of estriol in the water supply network described in as requested 7, it is characterised in that in step (2), chlorination
The concentration of aqueous ammonium be 5-10g/L, aqueous sodium hypochlorite solution be free chlorine weight/mass percentage composition be 6%-14% secondary chlorine
Acid sodium aqueous solution, free chlorine refers to hypochlorous acid and hypochlorite sum.
9. the chloramines biodegrading process of estriol in the water supply network described in as requested 1, it is characterised in that in step (2), is added
The concentration of total available chlorine after ammonium chloride and sodium hypochlorite in pipe network is 1.0-1.4mg/L.
10. the chloramines biodegrading process of estriol in the water supply network described in as requested 1, it is characterised in that in step (2), drop
The time of solution reaction is 7h~20h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111480656A (en) * | 2020-04-30 | 2020-08-04 | 同济大学 | Method suitable for efficiently preparing high-concentration disinfectant monochloramine in water works |
| USD918654S1 (en) | 2019-06-06 | 2021-05-11 | Sharkninja Operating Llc | Grill plate |
| US20210206636A1 (en) * | 2018-04-03 | 2021-07-08 | Honbusankei Co., Ltd. | Manufacturing method for obtaining novel chlorine oxide composition from degraded hypochlorite |
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| CN101182085A (en) * | 2006-11-17 | 2008-05-21 | 中山大学 | Ultraviolet-chlorination agent sequentially disinfecting technology for reclaimed water |
| CN103332807A (en) * | 2013-06-28 | 2013-10-02 | 浙江大学 | Degradation method for bisphenol A in water in tap water pipeline network |
| CN103523897A (en) * | 2013-10-31 | 2014-01-22 | 哈尔滨工业大学 | Water treatment compound agent for removing organic pollutants in oxidation mode with high-activity singlet oxygen and water treatment method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101182085A (en) * | 2006-11-17 | 2008-05-21 | 中山大学 | Ultraviolet-chlorination agent sequentially disinfecting technology for reclaimed water |
| CN103332807A (en) * | 2013-06-28 | 2013-10-02 | 浙江大学 | Degradation method for bisphenol A in water in tap water pipeline network |
| CN103523897A (en) * | 2013-10-31 | 2014-01-22 | 哈尔滨工业大学 | Water treatment compound agent for removing organic pollutants in oxidation mode with high-activity singlet oxygen and water treatment method thereof |
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| US20210206636A1 (en) * | 2018-04-03 | 2021-07-08 | Honbusankei Co., Ltd. | Manufacturing method for obtaining novel chlorine oxide composition from degraded hypochlorite |
| USD918654S1 (en) | 2019-06-06 | 2021-05-11 | Sharkninja Operating Llc | Grill plate |
| CN111480656A (en) * | 2020-04-30 | 2020-08-04 | 同济大学 | Method suitable for efficiently preparing high-concentration disinfectant monochloramine in water works |
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Application publication date: 20171027 |