CN103332807A - Degradation method for bisphenol A in water in tap water pipeline network - Google Patents
Degradation method for bisphenol A in water in tap water pipeline network Download PDFInfo
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- CN103332807A CN103332807A CN2013102677375A CN201310267737A CN103332807A CN 103332807 A CN103332807 A CN 103332807A CN 2013102677375 A CN2013102677375 A CN 2013102677375A CN 201310267737 A CN201310267737 A CN 201310267737A CN 103332807 A CN103332807 A CN 103332807A
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Abstract
The invention discloses a degradation method for bisphenol A in water in a tap water pipeline network. The method comprises the steps of regulating a flow velocity of water in a tap water pipeline network to 0.5-2m/s, and adding phosphoric acid and sodium hydroxide to regulate pH of the water in the tap water pipeline network to 6-9; adding sodium hypochlorite to the tap water pipeline network so that chlorine residue concentration in the water in the tap water pipeline network is 0.1-0.7mg/L, and implementing degradation reaction, thus finishing degradation of the bisphenol A. The degradation method, through regulating the flow velocity of the water in the tap water pipeline network, regulating the pH of the water in the tap water pipeline network by the phosphoric acid and the sodium hydroxide, and adding the sodium hypochlorite to realize degradation of the bisphenol A, can finish rapid degradation of the bisphenol A by controlling various conditions; the bisphenol A is rapid to be degraded, and water quality is consistent with hygienic standard for drinking water; the degradation method is simple to operate and easy to implement, simple for industrial implementation, and wide in application prospect.
Description
Technical field
The present invention relates to belong to the water treatment method field, particularly the degradation method of dihydroxyphenyl propane in the interior water of a kind of tap water pipe network.
Background technology
(bisphenol A BPA) is a kind of typical environment incretion interferent to dihydroxyphenyl propane, and it is widely used and a plurality of industries.BPA may be leaked in the environment in producing synthetic, transportation, use, BPA is a kind of compound with bio-toxicity and estrogen effect, belong to low toxicity material, skin, respiratory tract, digestive tube and cornea there is the medium tenacity pungency, can cause that leukemia and lymphoma incidence female, male rat raise, and have teratogenecity.In worldwide, be detected in the settling in the natural water body of a lot of branch countries and regions, the tap water of handling, sewage disposal plant effluent, lake, river etc. and the animal tissues at present.Along with industrial fast development in recent years, China's water body is subjected to the pollution condition of endocrine disrupters such as BPA even more serious.
Clorox sterilization is the disinfection way that China water factory generally adopts, its advantage be with low cost, sterilisation effect is obvious, shortcoming is that decay is very fast in the relatively poor water of water quality.Clorox can react with the multiple endocrine disrupter that comprises BPA simultaneously, and their chlorinations are degraded.
BPA and sodium hypochlorite reaction degraded in recent years is by a lot of scholar's research mistakes, but the two simple reaction and beaker experiment under the pure water environment has mostly only been considered in these researchs.And tap water also has different because the existence of natural organic matter, inorganic ion and pipe scale etc. makes that this reaction is more complex so the rule of BPA degraded generates product with chlorination in the actual pipe network.Therefore, the degradation rule of BPA in actual pipe network can not be well reacted in simple beaker experiment, more can't degrade effectively to BPA in the tap water in the tap water pipe network.
Application publication number CN101968474A discloses the method for dihydroxyphenyl propane in LC-MS/MS detection tap water and the beverage/food, comprise the steps: determining of (1) LC-MS/MS: I, LC-MS chromatographic condition: according to dihydroxyphenyl propane retention characteristic in chromatographic column, choose chromatographic column, and formulate chromatographiccondition; II, MS condition: adopt conventional dihydroxyphenyl propane mass spectroscopy condition; (2) typical curve is drawn; (3) sample detection: with detected result and typical curve contrast, calculate the content of dihydroxyphenyl propane in the sample.But this technical scheme only discloses the detection of dihydroxyphenyl propane in the tap water, the technical scheme that dihydroxyphenyl propane is removed in not supplying drinking water.
Application publication number is that the Chinese invention patent application of CN102198313A discloses a kind of food-grade microorganisms probiotic bacterium in the application of degraded in the dihydroxyphenyl propane, described probiotic bacterium be in lactobacterium helveticus, Roy's formula Bacterium lacticum, short lactobacillus, moral formula Bacterium lacticum Bulgaria subspecies, lactobacterium casei and the Bacillus subtilis natto any one or multiple.With can effectively degrade dihydroxyphenyl propane in the sour milk of above-mentioned food-grade microorganisms probiotic bacterium, but utilize dihydroxyphenyl propane in the interior tap water of this food-grade microorganisms probiotic bacterium degraded tap water pipe network, can introduce thalline on the one hand, there is certain risk, on the other hand, utilize dihydroxyphenyl propane in the interior tap water of food-grade microorganisms probiotic bacterium degraded tap water pipe network, its cost is also higher.
Summary of the invention
The invention provides the degradation method of dihydroxyphenyl propane in the interior water of a kind of tap water pipe network, effectively the dihydroxyphenyl propane in the degradation water.
The degradation method of dihydroxyphenyl propane in the water in a kind of tap water pipe network may further comprise the steps:
(1) with the flow rate regulation of water in the tap water pipe network to 0.5m/s～2m/s, add phosphoric acid and sodium hydroxide, the pH that regulates water in the tap water pipe network is 6～9;
(2) in the tap water pipe network, add clorox again, make that the residual chlorine concentration in the interior water of tap water pipe network reaches 0.1～0.7mg/L, through after the DeR, finish the degraded of dihydroxyphenyl propane.
Described chlorine residue is free residual chlorine, refers to the oxidation state that contains, namely valency be 0 ,+1 ,+3 ,+4 ,+5 ,+7 oxidation state chlorine, the residual chlorine concentration in the potable water network in the water refers to Cl
2, HClO and ClO
-The concentration sum.
In the step (1), with the flow rate regulation of water in the tap water pipe network to 0.5m/s～2m/s, under the different in flow rate, the flow turbulence intensity difference, the exchange of substance complexity is different between materials such as BPA and pipe scale, and different water flow velocities has certain influence to the degradation rate of BPA, as preferably, the flow rate regulation of water in the tap water pipe network to 1m/s～1.8m/s, is fit to the degraded of BPA very much.Further preferred, with the flow rate regulation of water in the tap water pipe network to 1.8m/s.
As preferably, described phosphoric acid adds with the form of phosphate aqueous solution, described sodium hydroxide adds with the form of aqueous sodium hydroxide solution, phosphoric acid and sodium hydroxide all adopt the form of the aqueous solution, one side is conducive to phosphoric acid and sodium hydroxide joins in the tap water pipe network, on the other hand, adopts the form of the aqueous solution, can control the add-on of phosphoric acid and sodium hydroxide exactly, thus the dihydroxyphenyl propane in the water in the tap water pipe network that is conducive to degrade.
Further preferred, the concentration of described phosphate aqueous solution is 60～100g/L, 80g/L more preferably, the concentration of described aqueous sodium hydroxide solution is 3～10g/L, 7g/L more preferably, the phosphate aqueous solution of above-mentioned concentration and aqueous sodium hydroxide solution can be regulated the pH in the water in the tap water pipe network well, are conducive to the degraded of dihydroxyphenyl propane in the water in the tap water pipe network.
As preferably, when in the tap water pipe network, adding phosphoric acid and sodium hydroxide, add Sodium Bromide, the bromide ion concentration of regulating in the interior water of tap water pipe network is 0.01～0.06mg/L, the bromide anion of proper concn can generate hypobromous acid with residual chlorine reaction, hypobromous acid can react degraded BPA with BPA, can accelerate the BPA degraded so bromide anion exists, and above-mentioned bromide ion concentration is very beneficial for the degraded of BPA.Further preferred, the bromide ion concentration of regulating in the interior water of tap water pipe network is 0.06mg/L.
Further preferred, described Sodium Bromide adds with the form of aqueous sodium bromide, the concentration of described aqueous sodium bromide is 60～100g/L, 82.4g/L more preferably, adopt the form of aqueous sodium bromide, be conducive to Sodium Bromide and join in the tap water pipe network, and can accurately control its add-on, the more important thing is to be conducive to the degraded of dihydroxyphenyl propane in the water in the tap water pipe network.
Add phosphoric acid and sodium hydroxide, the pH that regulates water in the tap water pipe network is 6～9.BPA existence form difference under the different pH environment, pH is more little, and molecular state BPA proportion is more big; Otherwise pH is more big, and ionic state BPA proportion is more big, different existence form BPA degradation rate differences.Regulation and stipulation tap water pH is 6～9.Add phosphoric acid and sodium hydroxide and can regulate the pH of main body water in the running water pipe net.As preferably, the pH that regulates water in the tap water pipe network is 7.2～8, is fit to very much the degraded of BPA, and further preferred, the pH that regulates water in the tap water pipe network is 8.
As preferably, the temperature of water is 10 ℃～30 ℃ in the tap water pipe network, on the one hand, said temperature is conducive to the degraded of dihydroxyphenyl propane in the water in the tap water pipe network, on the other hand, 10 ℃～30 ℃ are envrionment temperature commonly used, therefore, degraded BPA can carry out at ambient temperature, need not increase extra temperature again and control cost.Further preferred, the temperature of water is 25 ℃～30 ℃ in the described tap water pipe network.
In the step (2), chlorination reaction can take place with BPA in clorox, at first produces the chlorination on the phenyl ring, and then carbon-to-carbon rupture between propyl group and phenyl ring, last phenyl ring open loop, and BPA is degraded to small molecules the most at last.
As preferably, the form of the described clorox hypochlorous sodium aqueous solution adds, and adopts aqueous sodium hypochlorite solution to be conducive to clorox and joins in the tap water pipe network, can also control add-on exactly simultaneously.Further preferred, the weight percentage of free chlorine is 5%～15% aqueous sodium hypochlorite solution in the described aqueous sodium hypochlorite solution, and free chlorine refers to hypochlorous acid (HClO) and hypochlorite (ClO
-) sum.Further preferred, the weight percentage of free chlorine is 10% aqueous sodium hypochlorite solution in the described aqueous sodium hypochlorite solution.
As preferably, in the tap water pipe network, add clorox, make that the residual chlorine concentration in the interior water of tap water pipe network reaches 0.3～0.5mg/L, can make that the BPA in the interior water of tap water pipe network degrades effectively rapidly.
As preferably, the time of DeR is 10min～80min, behind DeR 10min～80min, finishes the degraded of BPA.Further preferred, the time of DeR is 30min～65min, and 95% above BPA can be degraded, and finishes the degraded of BPA.
Get the water source without the degraded dihydroxyphenyl propane, handle the tap water that obtains through the inventive method and meet " drinking water sanitary standard " (GB5749-2006), can use in daily life.
Compared with prior art, the present invention has following advantage:
The degradation method of dihydroxyphenyl propane in the water in the tap water pipe network of the present invention, by the flow rate regulation of water in the tap water pipe network, pH and the adding clorox that utilizes phosphoric acid and sodium hydroxide to regulate water in the tap water pipe network are degraded to dihydroxyphenyl propane, finish the quick degraded of dihydroxyphenyl propane by each condition control, the dihydroxyphenyl propane degradation rate is fast, operation is simple, be easy to industrializing implementation, possess wide application prospect.
Through the tap water after the degradation method processing of the present invention, physico-chemical parameter is all controlled and is met " drinking water sanitary standard " (GB5749-2006), guarantees water quality safety, to satisfy the service requirements of daily life.
Description of drawings
Fig. 1 is the degradation curve of dihydroxyphenyl propane in the interior water of the tap water pipe network of embodiment 1 and embodiment 2;
Fig. 2 is the degradation curve of dihydroxyphenyl propane in the interior water of the tap water pipe network of embodiment 1 and embodiment 3;
Fig. 3 is the degradation curve of dihydroxyphenyl propane in the interior water of the tap water pipe network of embodiment 1 and embodiment 4;
Fig. 4 is the degradation curve of dihydroxyphenyl propane in the interior water of the tap water pipe network of embodiment 1 and embodiment 5;
Fig. 5 is the degradation curve of dihydroxyphenyl propane in the interior water of the tap water pipe network of embodiment 1 and embodiment 6.
Embodiment
Embodiment 1
(1) get without the degraded dihydroxyphenyl propane the water source, after testing, the concentration C of dihydroxyphenyl propane in this water source
0Be 100 μ g/L, to feed in the tap water pipe network, to 1m/s, the control of the temperature of water is at 25 ℃ in the tap water pipe network with the flow rate regulation of water in the tap water pipe network, adding concentration is that 80g/L phosphate aqueous solution and concentration are the aqueous sodium hydroxide solution of 7g/L, and the pH that regulates water in the tap water pipe network is 7.2;
(2) weight percentage that adds free chlorine again in the tap water pipe network is 10% aqueous sodium hypochlorite solution, makes that the residual chlorine concentration in the water reaches 0.3mg/L in the tap water pipe network, after DeR after a while, finishes the degraded of dihydroxyphenyl propane.
Under different time t, from the tap water pipe network, take out the 200mL water sample and have to 250mL in the brown bottle of lid, add 2mL aqueous ascorbic acid (100mg/L) and fix.Different time t(min) from beginning to calculate without adding aqueous sodium hypochlorite solution behind the water source feeding tap water pipe network of degraded dihydroxyphenyl propane.As at 60min, from the tap water pipe network, take out the 200mL water sample and have to 250mL in the brown bottle of lid, add 2mL aqueous ascorbic acid (100mg/L) and fix.And then utilize high performance liquid chromatograph to measure bisphenol A concentration in the water sample, obtain under the 60min bisphenol A concentration in the water in the tap water pipe network.
Utilize high performance liquid chromatograph to measure bisphenol A concentration in the water sample, C
0Concentration C for dihydroxyphenyl propane in the water source
0, C is the concentration of the dihydroxyphenyl propane in the water in the tap water pipe network, with C/C
0Be Y-axis, the time is X-axis, draws the dihydroxyphenyl propane degradation curve, consuming time be the 60min curve as shown in Figure 1, the BPA degradation rate is 90% need 65min.
Embodiment 2
In the step (1), the pH that regulates water in the tap water pipe network is 8, and all the other are with embodiment 1, and its dihydroxyphenyl propane degradation curve as shown in Figure 1.
As shown in Figure 1, the pH=8.0 dihydroxyphenyl propane of not only can fast and effeciently degrading, and meet stable and user's water requirement of water quality in the tap water pipe network, so the optimal ph of degraded dihydroxyphenyl propane is pH=8.0 in the tap water pipe network.
Embodiment 3
In the step (2), the weight percentage that adds free chlorine in the tap water pipe network is 10% aqueous sodium hypochlorite solution, make the residual chlorine concentration in the interior water of tap water pipe network reach 0.5mg/L, all the other are with embodiment 1, and the dihydroxyphenyl propane degradation curve of embodiment 1 and embodiment 3 as shown in Figure 2.
As shown in Figure 2, among the embodiment 1, under the 0.3mg/L residual chlorine concentration, BPA degradation rate 90% 65min consuming time; And among the embodiment 3, under the 0.5mg/L residual chlorine concentration, can make BPA in the degraded of utmost point short period of time, the BPA90% degradation rate only needs 15min.And too high chlorine residue meeting influences the tap water mouthfeel in considering in the tap water pipe network simultaneously, and can increase the dispensing cost, so the best residual chlorine concentration of BPA degraded is 0.5mg/L.
Embodiment 4
In the step (1), the control of the temperature of water is at 30 ℃ in the tap water pipe network, and all the other are with embodiment 1, and the dihydroxyphenyl propane degradation curve of embodiment 1 and embodiment 4 as shown in Figure 3.
As shown in Figure 3, the control of the temperature of water is conducive to the BPA degraded at 30 ℃ in the tap water pipe network, among the embodiment 4 behind the 35min BPA degradation rate namely surpass 90%.Because temperature is up to about 30 ℃ in south summer in the tap water pipe network, the optimum temps that BPA degrades in the water in the tap water pipe network is 30 ℃.
Embodiment 5
In the step (1), to 1.8m/s, all the other are with embodiment 1 with the flow rate regulation of water in the tap water pipe network, and the dihydroxyphenyl propane degradation curve of embodiment 1 and embodiment 5 as shown in Figure 4.
As shown in Figure 4, the increase of 1.8m/s flow velocity is conducive to BPA degraded, among the embodiment 5 behind the 50min BPA degradation rate surpass 90%, a little more than flow velocity 1.0m/s situation.Therefore, the optimum flow rate that dihydroxyphenyl propane is degraded in the water in the tap water pipe network is 1.8m/s.
Embodiment 6
In the step (1), when in the tap water pipe network, adding phosphoric acid and sodium hydroxide, adding concentration is the aqueous sodium bromide of 82.4g/L, regulate the bromide ion concentration 0.06mg/L in the water in the tap water pipe network, all the other are with embodiment 1, and the dihydroxyphenyl propane degradation curve of embodiment 1 and embodiment 6 as shown in Figure 5.
As shown in Figure 5, the rising of bromide ion concentration is conducive to the degraded of BPA, experimental results show that bromide ion concentration surpasses 0.06mg/L, and the degradation rate of BPA is not increasing, and therefore, the best bromide ion concentration of water is 0.06mg/L in the tap water pipe network.
Get the water source without the degraded dihydroxyphenyl propane, be that dihydroxyphenyl propane does not meet " drinking water sanitary standard " (GB5749-2006), handle the tap water that obtains through embodiment 1～6 and meet " drinking water sanitary standard " (GB5749-2006), can use in daily life.
Comparative Examples 1
Get the water source without the degraded dihydroxyphenyl propane; this water source is placed reaction tank; the temperature control of water is at 25 ℃; it is 10% aqueous sodium hypochlorite solution to its weight percentage that adds free chlorine; make the residual chlorine concentration in the interior water of tap water pipe network reach 0.5mg/L; carry out DeR; the BPA degradation rate is 19% behind the process 1h; the BPA degradation rate is 33% behind the process 2h; the BPA degradation rate is 45% behind the process 3h, is 56% through BPA degradation rate behind the 4h, is 66% through BPA degradation rate behind the 5h; the BPA degradation rate is 71% behind the process 6h; the BPA degradation rate is 76% behind the process 7h, is 80% through BPA degradation rate behind the 8h, afterwards the 8h～12h; it is very slow to degrade, and last basically BPA degradation rate is 80%.
Claims (10)
1. the degradation method of dihydroxyphenyl propane in the water in the tap water pipe network is characterized in that, may further comprise the steps:
(1) with the flow rate regulation of water in the tap water pipe network to 0.5m/s～2m/s, add phosphoric acid and sodium hydroxide, the pH that regulates water in the tap water pipe network is 6～9;
(2) in the tap water pipe network, add clorox again, make that the residual chlorine concentration in the interior water of tap water pipe network reaches 0.1～0.7mg/L, through after the DeR, finish the degraded of dihydroxyphenyl propane.
2. the degradation method of dihydroxyphenyl propane in the water in the tap water pipe network according to claim 1 is characterized in that, in the step (1), with the flow rate regulation of water in the tap water pipe network to 1m/s～1.8m/s.
3. the degradation method of dihydroxyphenyl propane in the water in the tap water pipe network according to claim 1, it is characterized in that, in the step (1), described phosphoric acid adds with the form of phosphate aqueous solution, described sodium hydroxide adds with the form of aqueous sodium hydroxide solution, the concentration of described phosphate aqueous solution is 60～100g/L, and the concentration of described aqueous sodium hydroxide solution is 3～10g/L.
4. the degradation method of dihydroxyphenyl propane in the water in the tap water pipe network according to claim 1, it is characterized in that, in the step (1), when in the tap water pipe network, adding phosphoric acid and sodium hydroxide, add Sodium Bromide, the bromide ion concentration of regulating in the interior water of tap water pipe network is 0.01～0.06mg/L.
5. the degradation method of dihydroxyphenyl propane in the interior water of tap water pipe network according to claim 4 is characterized in that described Sodium Bromide adds with the form of aqueous sodium bromide, and the concentration of described aqueous sodium bromide is 60～100g/L.
6. the degradation method of dihydroxyphenyl propane in the interior water of tap water pipe network according to claim 1 is characterized in that in the step (1), the pH that regulates water in the tap water pipe network is 7.2～8.
7. the degradation method of dihydroxyphenyl propane in the interior water of tap water pipe network according to claim 1 is characterized in that in the step (1), the temperature of water is 10 ℃～30 ℃ in the tap water pipe network.
8. the degradation method of dihydroxyphenyl propane in the water in the tap water pipe network according to claim 1, it is characterized in that, in the step (2), the form of the described clorox hypochlorous sodium aqueous solution adds, and the weight percentage of free chlorine is 5%～15% aqueous sodium hypochlorite solution in the described aqueous sodium hypochlorite solution.
9. the degradation method of dihydroxyphenyl propane in the interior water of tap water pipe network according to claim 1 is characterized in that, in the step (2), adds clorox in the tap water pipe network, makes that the residual chlorine concentration in the interior water of tap water pipe network reaches 0.3～0.5mg/L.
10. the degradation method of dihydroxyphenyl propane in the interior water of tap water pipe network according to claim 1 is characterized in that in the step (2), the time of DeR is 10min～80min.
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| CN201310267737.5A CN103332807B (en) | 2013-06-28 | 2013-06-28 | Degradation method for bisphenol A in water in tap water pipeline network |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107298493A (en) * | 2017-05-11 | 2017-10-27 | 浙江大学 | The chloramines biodegrading process of estriol in a kind of water supply network |
| CN109607748A (en) * | 2019-01-09 | 2019-04-12 | 东华大学 | The method for removing glucocorticoid pollutant in water removal using sodium hypochlorite |
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| JPS5079163A (en) * | 1973-11-05 | 1975-06-27 | ||
| JPH0994585A (en) * | 1995-07-24 | 1997-04-08 | Japan Organo Co Ltd | Method for producing ultrapure water and apparatus therefor |
| CN101720307A (en) * | 2007-06-29 | 2010-06-02 | 克里斯特水处理技术股份公司 | Adopt the water treatment of hypobromite solution |
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2013
- 2013-06-28 CN CN201310267737.5A patent/CN103332807B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5079163A (en) * | 1973-11-05 | 1975-06-27 | ||
| JPH0994585A (en) * | 1995-07-24 | 1997-04-08 | Japan Organo Co Ltd | Method for producing ultrapure water and apparatus therefor |
| CN101720307A (en) * | 2007-06-29 | 2010-06-02 | 克里斯特水处理技术股份公司 | Adopt the water treatment of hypobromite solution |
Non-Patent Citations (1)
| Title |
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| 汪雪姣等: "次氯酸钠氧化消除水中BPA的影响因素和动力学", 《环境科学》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107298493A (en) * | 2017-05-11 | 2017-10-27 | 浙江大学 | The chloramines biodegrading process of estriol in a kind of water supply network |
| CN109607748A (en) * | 2019-01-09 | 2019-04-12 | 东华大学 | The method for removing glucocorticoid pollutant in water removal using sodium hypochlorite |
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