CN103332807B - 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
- Publication number
- CN103332807B CN103332807B CN201310267737.5A CN201310267737A CN103332807B CN 103332807 B CN103332807 B CN 103332807B CN 201310267737 A CN201310267737 A CN 201310267737A CN 103332807 B CN103332807 B CN 103332807B
- Authority
- CN
- China
- Prior art keywords
- tap water
- pipe network
- water pipe
- water
- degradation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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 and belong to water treatment method field, particularly the degradation method of dihydroxyphenyl propane in water in a kind of tap water pipe network.
Background technology
Dihydroxyphenyl propane (bisphenol A, BPA) is a kind of typical environment incretion interferent, and it is widely used and multiple industry.BPA may be leaked in environment in production synthesis, transport, use procedure, BPA is a kind of compound with bio-toxicity and estrogen effect, belong to low toxicity material, medium tenacity pungency is had to skin, respiratory tract, digestive tube and cornea, the leukemia of female, male rat and lymphoma incidence can be caused to raise, there is teratogenecity.Be detected in the settling of the current natural water body, the tap water processed, sewage disposal plant effluent, lake, river etc. of a lot of point countries and regions in worldwide and animal tissues.Along with industrial fast development in recent years, China's water body is even more serious by the pollution condition of the endocrine disrupters such as BPA.
Hypochlorite disinfectant is the disinfection way that water factory of China generally adopts, and its advantage is that with low cost, sterilisation effect is obvious, and shortcoming is that decay is very fast in the poor water of water quality.Clorox can react with the multiple endocrine disrupter comprising BPA, by they chlorizating depolymerizations simultaneously.
BPA and sodium hypochlorite reaction are degraded by a lot of scholar's research mistake in recent years, but these researchs mostly only considered the two simple reaction under pure water environment and beaker experiments.And tap water makes this reaction more complex due to the existence of natural organic matter, inorganic ion and pipe scale etc. in actual pipe network, the rule of BPA degraded and chlorination generate product also to be had so different.Therefore, simple beaker experiments well can not react the degradation rule of BPA in actual pipe network, more effectively cannot degrade to BPA in tap water in tap water pipe network.
Application publication number CN101968474A discloses the method that LC-MS/MS detects dihydroxyphenyl propane in tap water and beverage/food, comprise the steps: the determination of (1) LC-MS/MS: I, LC-MS chromatographic condition: according to dihydroxyphenyl propane retention characteristic in the chromatography column, choose chromatographic column, and formulate chromatographiccondition; II, MS condition: adopt conventional dihydroxyphenyl propane mass spectroscopy condition; (2) Specification Curve of Increasing; (3) sample detection: by detected result and standard curve control, calculates the content of dihydroxyphenyl propane in sample.But this technical scheme only discloses the detection of dihydroxyphenyl propane in tap water, the technical scheme of the middle dihydroxyphenyl propane that do not supply drinking water removing.
Application publication number be the Chinese invention patent application of CN102198313A disclose a kind of food-grade microbiological probiotics degraded dihydroxyphenyl propane in application, described probiotic bacterium be in lactobacterium helveticus, Roy's formula Bacterium lacticum, short lactobacillus, moral formula Bacterium lacticum subspecies bulgaricus, lactobacterium casei and Bacillus subtilis natto any one or multiple.By the dihydroxyphenyl propane that above-mentioned food-grade microbiological probiotics can effectively be degraded in Yoghourt, but utilize this food-grade microbiological probiotics to degrade in tap water pipe network dihydroxyphenyl propane in tap water, thalline can be introduced on the one hand, there is certain risk, on the other hand, utilize food-grade microbiological probiotics to degrade in tap water pipe network dihydroxyphenyl propane in tap water, its cost is also higher.
Summary of the invention
The invention provides the degradation method of dihydroxyphenyl propane in water in a kind of tap water pipe network, can dihydroxyphenyl propane effectively in degradation water.
The degradation method of dihydroxyphenyl propane in water in tap water pipe network, comprises the following steps:
(1) by the flow rate regulation of water in tap water pipe network to 0.5m/s ~ 2m/s, add phosphoric acid and sodium hydroxide, regulate the pH of water in tap water pipe network to be 6 ~ 9;
(2) in tap water pipe network, add clorox again, make the residual chlorine concentration in tap water pipe network in water reach 0.1 ~ 0.7mg/L, after DeR, complete the degraded of dihydroxyphenyl propane.
Described chlorine residue is free residual chlorine, refers to the oxidation state contained, and namely valency is the oxidation state chlorine of 0 ,+1 ,+3 ,+4 ,+5 ,+7, and the residual chlorine concentration in potable water network in water refers to Cl
2, HClO and ClO
-concentration sum.
In step (1), by the flow rate regulation of water in tap water pipe network to 0.5m/s ~ 2m/s, under different in flow rate, flow turbulence intensity is different, BPA etc. between material from pipe scale exchange of substance complexity different, the degradation rate of different water flow velocities to BPA has certain influence, as preferably, by the flow rate regulation of water in tap water pipe network to 1m/s ~ 1.8m/s, be applicable to very much the degraded of BPA.Further preferred, by the flow rate regulation of water in 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 tap water pipe network, on the other hand, adopts the form of the aqueous solution, the add-on of phosphoric acid and sodium hydroxide can be controlled exactly, thus be conducive to the dihydroxyphenyl propane in degraded tap water pipe network in water.
Further preferably, the concentration of described phosphate aqueous solution is 60 ~ 100g/L, more preferably 80g/L, the concentration of described aqueous sodium hydroxide solution is 3 ~ 10g/L, more preferably 7g/L, the phosphate aqueous solution of above-mentioned concentration and aqueous sodium hydroxide solution can regulate the pH in tap water pipe network in water well, are conducive to the degraded of dihydroxyphenyl propane in water in tap water pipe network.
As preferably, while add phosphoric acid and sodium hydroxide in tap water pipe network, add Sodium Bromide, the bromide ion concentration in tap water pipe network in water is regulated to be 0.01 ~ 0.06mg/L, the bromide anion of proper concn can generate hypobromous acid with residual chlorine reaction, hypobromous acid can react with BPA the BPA that degrades, therefore bromide anion existence can accelerate BPA degraded, and above-mentioned bromide ion concentration is very beneficial for the degraded of BPA.Further preferably, the bromide ion concentration in tap water pipe network in water is regulated to be 0.06mg/L.
Further preferably, described Sodium Bromide adds with the form of aqueous sodium bromide, the concentration of described aqueous sodium bromide is 60 ~ 100g/L, more preferably 82.4g/L, adopt the form of aqueous sodium bromide, be conducive to Sodium Bromide to join in tap water pipe network, and can accurately control its add-on, the more important thing is the degraded being conducive to dihydroxyphenyl propane in water in tap water pipe network.
Add phosphoric acid and sodium hydroxide, the pH regulating water in tap water pipe network is 6 ~ 9.Under different pH environment, BPA existence form is different, and pH is less, and molecular state BPA proportion is larger; Otherwise pH is larger, ionic state BPA proportion is larger, and different existence form BPA degradation rate is different.Regulation and stipulation tap water pH is 6 ~ 9.Add the pH of main body water in phosphoric acid and the adjustable tap water pipe network of sodium hydroxide.As preferably, the pH regulating water in tap water pipe network is 7.2 ~ 8, is applicable to very much the degraded of BPA, and further preferably, the pH regulating water in tap water pipe network is 8.
As preferably, in tap water pipe network, the temperature of water is 10 DEG C ~ 30 DEG C, on the one hand, said temperature is conducive to the degraded of dihydroxyphenyl propane in water in tap water pipe network, on the other hand, 10 DEG C ~ 30 DEG C is conventional envrionment temperature, therefore, degraded BPA can carry out at ambient temperature, need not increase extra temperature again and control cost.Further preferably, in described tap water pipe network, the temperature of water is 25 DEG C ~ 30 DEG C.
In step (2), can there is chlorination reaction with BPA in clorox, first produces the chlorination on phenyl ring, and then carbon-to-carbon rupture between propyl group and phenyl ring, and last phenyl ring open loop, BPA is degraded to small molecules the most at last.
As preferably, described clorox adds with the form of aqueous sodium hypochlorite solution, adopts aqueous sodium hypochlorite solution to be conducive to clorox and joins in tap water pipe network, can also control add-on exactly simultaneously.Further preferably, in described aqueous sodium hypochlorite solution, the weight percentage of free chlorine is the aqueous sodium hypochlorite solution of 5% ~ 15%, and free chlorine refers to hypochlorous acid (HClO) and hypochlorite (ClO
-) sum.Further preferably, in described aqueous sodium hypochlorite solution, the weight percentage of free chlorine is the aqueous sodium hypochlorite solution of 10%.
As preferably, in tap water pipe network, add clorox, make the residual chlorine concentration in tap water pipe network in water reach 0.3 ~ 0.5mg/L, the BPA in tap water pipe network in water can be made to degrade effectively rapidly.
As preferably, the time of DeR is after 10min ~ 80min, DeR 10min ~ 80min, completes the degraded of BPA.Further preferably, the time of DeR is 30min ~ 65min, and more than 95% BPA can be degraded, and completes the degraded of BPA.
Get the water source without degraded dihydroxyphenyl propane, the tap water obtained through the inventive method process meets " drinking water sanitary standard " (GB5749-2006), can use in daily life.
Compared with prior art, tool of the present invention has the following advantages:
The degradation method of dihydroxyphenyl propane in water in tap water pipe network of the present invention, by the flow rate regulation to water in tap water pipe network, utilize the pH of water in phosphoric acid and sodium hydroxide adjustment tap water pipe network and add clorox and dihydroxyphenyl propane is degraded, the fast degradation of dihydroxyphenyl propane has been controlled by each condition, dihydroxyphenyl propane degradation rate is fast, operation is simple, be easy to industrializing implementation, possess wide application prospect.
Tap water after degradation method process of the present invention, physico-chemical parameter all controls to meet " drinking water sanitary standard " (GB5749-2006), ensures water quality safety, to meet the service requirements of daily life.
Accompanying drawing explanation
Fig. 1 be embodiment 1 and embodiment 2 tap water pipe network in the degradation curve of dihydroxyphenyl propane in water;
Fig. 2 be embodiment 1 and embodiment 3 tap water pipe network in the degradation curve of dihydroxyphenyl propane in water;
Fig. 3 be embodiment 1 and embodiment 4 tap water pipe network in the degradation curve of dihydroxyphenyl propane in water;
Fig. 4 be embodiment 1 and embodiment 5 tap water pipe network in the degradation curve of dihydroxyphenyl propane in water;
Fig. 5 be embodiment 1 and embodiment 6 tap water pipe network in the degradation curve of dihydroxyphenyl propane in water.
Embodiment
Embodiment 1
(1) water source without degraded dihydroxyphenyl propane is got, after testing, the concentration C of dihydroxyphenyl propane in this water source
0be 100 μ g/L, to pass in tap water pipe network, by the flow rate regulation of water in tap water pipe network to 1m/s, in tap water pipe network, the temperature of water controls at 25 DEG C, to add concentration be 80g/L phosphate aqueous solution and concentration is the aqueous sodium hydroxide solution of 7g/L, and the pH regulating water in tap water pipe network is 7.2;
(2) weight percentage adding free chlorine again in tap water pipe network is the aqueous sodium hypochlorite solution of 10%, makes the residual chlorine concentration in tap water pipe network in water reach 0.3mg/L, after DeR after a while, completes the degraded of dihydroxyphenyl propane.
Under different time t, from tap water pipe network, take out 200mL water sample to 250mL with in the brown bottle of lid, add 2mL aqueous ascorbic acid (100mg/L) and fix.Different time t(min) calculate from adding aqueous sodium hypochlorite solution after the water source without degraded dihydroxyphenyl propane is passed into tap water pipe network.As at 60min, from tap water pipe network, take out 200mL water sample to 250mL with 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 water sample, and under obtaining 60min, bisphenol A concentration in water in tap water pipe network.
High performance liquid chromatograph is utilized to measure bisphenol A concentration in water sample, C
0for the concentration C of dihydroxyphenyl propane in water source
0, C is the concentration of the dihydroxyphenyl propane in tap water pipe network in water, with C/C
0for Y-axis, the time is X-axis, draws dihydroxyphenyl propane degradation curve, consuming time be 60min curve as shown in Figure 1, BPA degradation rate is 90% need 65min.
Embodiment 2
In step (1), the pH regulating water in 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, pH=8.0 not only can fast and effeciently degrade dihydroxyphenyl propane, and meets the stable and user of water quality in tap water pipe network and use water requirement, therefore in tap water pipe network, the optimal ph of degraded dihydroxyphenyl propane is pH=8.0.
Embodiment 3
In step (2), the weight percentage adding free chlorine in tap water pipe network is the aqueous sodium hypochlorite solution of 10%, make the residual chlorine concentration in tap water pipe network in water 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, in embodiment 1, under 0.3mg/L residual chlorine concentration, BPA degradation rate 90% 65min consuming time; And in embodiment 3, under 0.5mg/L residual chlorine concentration, BPA can be made to degrade in very short time, BPA90% degradation rate only needs 15min.And consider that in tap water pipe network, too high chlorine residue can affect tap water mouthfeel simultaneously, and dispensing cost can be increased, therefore the best residual chlorine concentration of BPA degraded is 0.5mg/L.
Embodiment 4
In step (1), in tap water pipe network, the temperature of water controls at 30 DEG C, 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, in tap water pipe network, the temperature of water controls at 30 DEG C, be conducive to BPA degraded, in embodiment 4 after 35min BPA degradation rate namely more than 90%.Because temperature in tap water pipe network is up to about 30 DEG C in south summer, in tap water pipe network, in water, the optimum temps of BPA degraded is 30 DEG C.
Embodiment 5
In step (1), by the flow rate regulation of water in tap water pipe network to 1.8m/s, all the other are with embodiment 1, 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 be conducive to BPA degraded, in embodiment 5 after 50min BPA degradation rate more than 90%, a little more than flow velocity 1.0m/s situation.Therefore, in tap water pipe network, in water, the optimum flow rate of dihydroxyphenyl propane degraded is 1.8m/s.
Embodiment 6
In step (1), while add phosphoric acid and sodium hydroxide in tap water pipe network, add the aqueous sodium bromide that concentration is 82.4g/L, regulate the bromide ion concentration 0.06mg/L in water in 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, and experiment proves that the degradation rate of bromide ion concentration more than 0.06mg/L, BPA be not in increase, and therefore, in tap water pipe network, the best bromide ion concentration of water is 0.06mg/L.
Get the water source without degraded dihydroxyphenyl propane, namely dihydroxyphenyl propane does not meet " drinking water sanitary standard " (GB5749-2006), process through embodiment 1 ~ 6 tap water obtained and meet " drinking water sanitary standard " (GB5749-2006), can use in daily life.
Comparative example 1
Get the water source without degraded dihydroxyphenyl propane, this water source is placed in reaction tank, the temperature of water controls at 25 DEG C, be the aqueous sodium hypochlorite solution of 10% to its weight percentage adding free chlorine, the residual chlorine concentration in tap water pipe network in water is made to reach 0.5mg/L, carry out DeR, after 1h, BPA degradation rate is 19%, after 2h, BPA degradation rate is 33%, after 3h, BPA degradation rate is 45%, after 4h, BPA degradation rate is 56%, after 5h, BPA degradation rate is 66%, after 6h, BPA degradation rate is 71%, after 7h, BPA degradation rate is 76%, after 8h, BPA degradation rate is 80%, 8h ~ 12h afterwards, degraded slowly, substantially last BPA degradation rate is 80%.
Claims (1)
1. the degradation method of dihydroxyphenyl propane in water in tap water pipe network, is characterized in that, comprise the following steps:
(1) by the flow rate regulation of water in tap water pipe network to 1m/s ~ 1.8m/s, in tap water pipe network, the temperature of water is 10 DEG C ~ 30 DEG C, adds phosphoric acid and sodium hydroxide, regulates the pH of water in tap water pipe network to be 7.2 ~ 8;
Described phosphoric acid adds with the form of phosphate aqueous solution, and described sodium hydroxide adds with the form of aqueous sodium hydroxide solution, and the concentration of described phosphate aqueous solution is 60 ~ 100g/L, and the concentration of described aqueous sodium hydroxide solution is 3 ~ 10g/L;
While add phosphoric acid and sodium hydroxide in tap water pipe network, add Sodium Bromide, regulate the bromide ion concentration in tap water pipe network in water to be 0.01 ~ 0.06mg/L, described Sodium Bromide adds with the form of aqueous sodium bromide, and the concentration of described aqueous sodium bromide is 60 ~ 100g/L;
(2) in tap water pipe network, add clorox again, make the residual chlorine concentration in tap water pipe network in water reach 0.3 ~ 0.5mg/L, after DeR, the time of DeR is 10min ~ 80min, completes the degraded of dihydroxyphenyl propane;
Described clorox adds with the form of aqueous sodium hypochlorite solution, and in described aqueous sodium hypochlorite solution, the weight percentage of free chlorine is the aqueous sodium hypochlorite solution of 5% ~ 15%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310267737.5A CN103332807B (en) | 2013-06-28 | 2013-06-28 | Degradation method for bisphenol A in water in tap water pipeline network |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310267737.5A CN103332807B (en) | 2013-06-28 | 2013-06-28 | Degradation method for bisphenol A in water in tap water pipeline network |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103332807A CN103332807A (en) | 2013-10-02 |
| CN103332807B true CN103332807B (en) | 2015-04-29 |
Family
ID=49241036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310267737.5A Expired - Fee Related CN103332807B (en) | 2013-06-28 | 2013-06-28 | Degradation method for bisphenol A in water in tap water pipeline network |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103332807B (en) |
Families Citing this family (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 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2249843B1 (en) * | 1973-11-05 | 1977-05-27 | Alsace Mines Potasse | |
| JP3919259B2 (en) * | 1995-07-24 | 2007-05-23 | オルガノ株式会社 | Ultrapure water production equipment |
| DE102007031113A1 (en) * | 2007-06-29 | 2009-01-02 | Christ Water Technology Ag | Treatment of water with hypobromite solution |
-
2013
- 2013-06-28 CN CN201310267737.5A patent/CN103332807B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103332807A (en) | 2013-10-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Oehmen et al. | Mercury removal from water streams through the ion exchange membrane bioreactor concept | |
| Polo-López et al. | Solar disinfection of fungal spores in water aided by low concentrations of hydrogen peroxide | |
| Gernjak et al. | Pilot-plant treatment of olive mill wastewater (OMW) by solar TiO2 photocatalysis and solar photo-Fenton | |
| Gombos et al. | Removal of organic matters in wastewater treatment by ferrate (VI)-technology | |
| Ping et al. | Integrated experimental investigation and mathematical modeling of brackish water desalination and wastewater treatment in microbial desalination cells | |
| De la Obra Jiménez et al. | Continuous flow disinfection of WWTP secondary effluents by solar photo-Fenton at neutral pH in raceway pond reactors at pilot plant scale | |
| Aguas et al. | Solar photocatalytic disinfection of agricultural pathogenic fungi (Curvularia sp.) in real urban wastewater | |
| CN105668880A (en) | Method for controlling chlorinated nitrogenous disinfection byproduct in water | |
| Goncharuk et al. | The use of redox potential in water treatment processes | |
| CN101774711B (en) | Method for reducing chlorite as disinfection by-product of drinking water | |
| Xia et al. | Direct delivery of CO2 into a hydrogen-based membrane biofilm reactor and model development | |
| Ruiz-Aguirre et al. | Integration of membrane distillation with solar photo-Fenton for purification of water contaminated with Bacillus sp. and Clostridium sp. spores | |
| CN103332807B (en) | Degradation method for bisphenol A in water in tap water pipeline network | |
| Bustos et al. | Disinfection of primary municipal wastewater effluents using continuous UV and ozone treatment | |
| Moslemi et al. | Bromate formation in a hybrid ozonation-ceramic membrane filtration system | |
| CA2797228A1 (en) | Wastewater treatment apparatus to achieve class b biosolids using chlorine dioxide | |
| CN105712549A (en) | Method for inhibiting forming of bromo nitrogenous disinfection byproducts in water | |
| Verma et al. | An investigation on the ion exchange membrane bioreactor with a spiral wound contactor for nitrate removal from contaminated groundwater | |
| Dong et al. | Bromide ion enhancing the phytodegradation of emerging phenolic pollutants and its mechanisms mediating wheat resistance to phenolic pollutants stress | |
| Tian et al. | Biological efficacy and toxic effect of emergency water disinfection process based on advanced oxidation technology | |
| CN203373231U (en) | Water purification device | |
| Yuan et al. | A review of hydrogen-based membrane biofilm reactor to remove oxidized pollutants from water | |
| Fernàndez-Ibañez et al. | Can solar water-treatment really help in the fight against water shortages? | |
| Qiu et al. | Aquatic transformation of phosphite under natural sunlight and simulated irradiation | |
| CN104944538A (en) | Pseudomonas aeruginosa and sphingomonas paucimobilis inactivating method based on water supply network growth ring |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150429 Termination date: 20190628 |