CN104229969A - Method for carrying out intensified reductive dechlorination on triclosan in sewage by using vitamin B12 - Google Patents
Method for carrying out intensified reductive dechlorination on triclosan in sewage by using vitamin B12 Download PDFInfo
- Publication number
- CN104229969A CN104229969A CN201310487706.0A CN201310487706A CN104229969A CN 104229969 A CN104229969 A CN 104229969A CN 201310487706 A CN201310487706 A CN 201310487706A CN 104229969 A CN104229969 A CN 104229969A
- Authority
- CN
- China
- Prior art keywords
- sewage
- triclosan
- vitamins
- nano zero
- valence iron
- 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.)
- Pending
Links
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention relates to a method for carrying out intensified reductive dechlorination on triclosan in sewage by using vitamin B12. According to the method, nano zero-valent iron and vitamin B12 are added to sewage containing triclosan under the condition that the pH value is 5-9, the reaction time is 5-10 hours, so that sewage is subjected to intensified reductive dechlorination, wherein the mass concentration of triclosan in sewage is 1-20mg/L; 0.1-1g of nano zero-valent iron is added to each liter of sewage; and 10-100mg of vitamin B12 is added to each liter of sewage. Compared with the prior art, the method disclosed by the invention is simple in reaction condition, mild in reaction, short in treatment time, high in triclosan removal rate, free of secondary pollution, suitable for treatment of sewage containing triclosan and other pharmaceutical wastewaters, and beneficial to resource utilization of the sewage.
Description
Technical field
The present invention relates to a kind of sewage water treatment method containing triclosan, especially relate to one and utilize vitamins B
12the method strengthening reduction dechlorination is carried out to triclosan in sewage.
Background technology
Medicine and Personal hygiene nursing materials (Pharmaceuticals and personal care products, PPCPs) be the ubiquitous organic micro-pollutant in water and sewage found after Insecticides (tech) & Herbicides (tech) and endocrine disrupter, it has caused extensive concern both domestic and external to the impact that environment causes.PPCPs once enter in human body, will be transformed into polarity, deliquescent meta-bolites and acid, along with urine and ight soil enter in municipal effluent.Research shows, traditional biological process is difficult to remove all PPCPs completely.Therefore, the PPCPs remained after Sewage Plant process can enter in surface water, underground water or seawater along with the discharge of Sewage Plant tail water, thus has an impact to the mankind and damage aquatic environment.
In the past few decades, foreign study person has entered a large amount of investigation to the existence of PPCPs in Sewage Plant and removal situation.The people such as Gracia-Lor have investigated existence and the removal situation of 50 kinds of target P PCPs in three sewage works of Spain, they detected 17 kinds of PPCPs and remain in sewage effluents, are mainly anodyne class, antiphlogistic drug class, antibiotics, hypolipidemic class, anti-allergy agent similar drug.Previous research finds, antiphlogistic drug, microbiotic, diuretic(s), hypolipidemic, anti-allergy agent, stimulants are the drug contamination things extensively existed in the water inlet of Sewage Plant abroad, due to the difference of selected target PPCPs and sewage source different, its concentration range can from hundreds of pg/L to hundreds of μ g/L.Relative to the investigation of drug contamination thing, also relatively less to the investigation of Personal hygiene nursing materials, only main chlorinated organics several frequently seen in Personal hygiene nursing materials to be studied (wherein triclosan and triclocarban are the Personal hygiene nursing materialss be often detected), because chlorinated organics is widely used in sanitas, opalizer, sterilant and sterilizing agent etc. in Personal hygiene nursing materials.Chlorinated organics can cause great harm to HUMAN HEALTH and environment, and usual chlorinated organics has carinogenicity, teratogenecity and mutagenicity, and is difficult to be removed completely by biology.Triclosan, as a kind of wide-spectrum bactericide, is widely used among the household chemicals such as soap, toothpaste, finds its ubiquity in the water inlet of Sewage Plant in investigation.The people such as Bendz, the people such as Yu,
investigate triclosan in Sewage Plant Deng the people such as people and Lishman, they find that the clearance of triclosan is different in Sewage Plant, is respectively 58%, 69%, 88% and 93%.In the U.S., the soap with germ resistance of 84% is all containing triclosan, and its consumption is up to 1500 tons/year.Triclosan has been employed 50 years as high yield chemical substance nearly in the U.S., but until its harm in recent years just causes people to pay close attention to.
Find that the traditional removal effect of biological process to chloride PPCPs is poor by the previous existence to PPCPs typical in Sewage Plant and removal condition survey research, and its removal effect is subject to the impact of influent quality and Sewage Plant treatment process.In recent years, nano material, due to its huge specific surface area and high reactivity, makes speed of reaction be improved, and is applied to contaminated soil and groundwater remediation and sewage disposal, and it is wherein relatively many to nano zero valence iron (nano-scale zero-valent, nZVI) research.NZVI is a kind of effective Dehalogenation reduction agent, just attracts attention as far back as the eighties in 20th century.Nano zero valence iron can the multiple Organohalogen compounds of catalytic reduction, as: the hardly degraded organic substance pollutents such as halogenated alkane, haloolefin, halogenated aromatic, be translated into nontoxic compound, improve its biodegradability simultaneously, can create favorable conditions for further biological degradation.Zhang etc. utilize nano zero valence iron degrade trichoroacetic acid(TCA), trieline and zellon time find, their clearances in 24 hours can reach 99%.The research of the people such as Lowry shows, the dechlorination effect of nano zero valence iron will be much better than micron order Zero-valent Iron, and polychlorobiphenyl dechlorination can be the chlordiphenyl that toxicity is lower by nano zero valence iron.Although nano zero valence iron has a lot of advantage, in the process of its application, also run into some problems, the less stable of such as nano zero valence iron.Have and report that nano zero valence iron is easy to oxidized and forms the oxide compound of iron or oxyhydroxide at Nanoscale Iron surface deposition, thus make nano zero valence iron produce passivation.Find the increase along with pH when the people such as Song utilize nano zero-valence Fe3+ reduction tetrachloroethane, speed of reaction is corresponding increase also, and its reason is that pH increases, and the ironing surface zone of oxidation of nanometer can be corresponding thickening, thus the corresponding grow of the oxidation capacity of system.In addition, aging effect and magnetic also can affect the activity of nano zero valence iron particle, have carried out correlative study in order to overcome above shortcoming to bimetallic catalytic reaction system (Ag, Pd, Ni, Cu, Pt and Zn).Research shows, Pd adds the removal effect that nZVI system can improve dioxin, trieline, zellon, but this method is too high and uneconomical concerning cost contaminated soil or water body, therefore the katalysis of transition metal coenzyme to nZVI system having again investigator to utilize to exist in natural surroundings is studied.Their research finds, the porphyrin existed in natural soil, vitamins B
12can have good katalysis to reduction reaction Deng transition metal coenzyme, these metal coenzyme can be produced in neutral conditions by anaerobic bacterium (producing acetic bacteria, methanogen).Vitamins B
12a corrin ring and cobalt atom is comprised as transition metal coenzyme.Vitamins B
12in Co
3+agent (titanium (III) citric acid, sulfide, dithiothreitol (DTT), halfcystine and sodium bisulfite) can be reduced and be reduced into Co
2+(vitamins B
12r) and Co
+(vitamins B
12s), and vitamins B
12reduzate can improve electron transmission efficiency thus have stronger dechlorination efficiency to chlorinatedorganic, promote further its degraded in biology-abiotic interactive system.Therefore, be necessary to carry out corresponding research work.
Summary of the invention
Object of the present invention is exactly removal speed in order to improve triclosan in sewage and removal effect, and provide that a kind of reaction conditions is simple, reaction temperature and, treatment time short, high to the clearance of triclosan, non-secondary pollution utilize vitamins B
12the method strengthening reduction dechlorination is carried out to triclosan in sewage.The method can remove the triclosan in sewage quickly and efficiently, reduces and contains triclosan sewage to the harm of environment, be conducive to the recycling of follow-up sewage.
Object of the present invention can be achieved through the following technical solutions:
One utilizes vitamins B
12the method strengthening reduction dechlorination is carried out to triclosan in sewage, to containing in the sewage of triclosan, adds nano zero valence iron and vitamins B
12, reaction times 5-10 hour, the temperature of reaction is not limit, and carries out strengthening reduction dechlorination to the triclosan in sewage.Vitamins B
12the bimetallic system formed with nano zero valence iron strengthens reduction mechanism to triclosan: nano zero valence iron is corroded generation hydrogen in water, and hydrogen is by vitamins B
12adsorb and embed vitamins B
12lattice in form strong reducible agent vitamins B
12.H
2, last strong reducible agent vitamins B
12.H
2vitamins B will be adsorbed on
12the triclosan deoxidization, degradation of-nano zero-valence iron surface.Triclosan is through vitamins B
12the bimetallic system formed with nano zero valence iron is reduced into 2-hydroxyl-phenyl ether, and its toxicity reduces greatly, well can be removed by sewage disposal conventional further to 2-hydroxyl-phenyl ether.
Further, in described sewage, the mass concentration of triclosan is 1 ~ 20 milligrams per liter, and the input amount of described nano zero valence iron adds 0.1 ~ 1 gram, described vitamins B in often liter of sewage
12input amount for adding 10 ~ 100 milligrams in often liter of sewage.
Further, nano zero valence iron and vitamins B is being added
12before, the pH value regulating sewage is 5 ~ 9.
Further, nano zero valence iron and vitamins B is being added
12before, the pH value regulating sewage is 8 ~ 9.
Again further, nano zero valence iron and vitamins B is being added
12before, the pH value regulating sewage is 9.
Further, the grain diameter of described nano zero valence iron is 50 ~ 70 nanometers.
At vitamins B
12input amount for adding in 10 ~ 100 nanogram ranges in often liter of sewage, vitamins B
12add-on is larger, and under biconditional operation condition, triclosan clearance is higher.
Compared with prior art, the present invention has the following advantages and beneficial effect:
1, applied widely, reaction conditions is simple.The present invention adds vitamins B to containing in the waste water of triclosan
12and nano zero valence iron, temperature of reaction is not limit, and can reach good removal effect under normal temperature and pressure.
2, speed of reaction is fast.Add vitamins B
12after improve reduction dechlorination speed, just can to being that the sewage of the triclosan of 1-20 milligrams per liter have good removal effect containing mass concentration in 5-10 hour.
3, processing cost is low.Relative to other catalytic reduction metals as Ag, Pd, Ni, Cu, Pt and Zn, vitamins B
12just exist in natural surroundings, easily obtain, therefore expense is low, has a good application prospect.
4, environmental friendliness.Vitamins B in the present invention
12carry out strengthening reduction dechlorination to triclosan to remove, the toxicity of dechlorination product is significantly reduced, is conducive to the recycling of sewage.
5, target compound scope is suitable for wide.The present invention, except being applicable to the sewage containing triclosan, is also applicable to the sewage of chlorinated organics.
Accompanying drawing explanation
Fig. 1 is that the pH value of sewage and reaction times are on the impact of triclosan clearance;
Fig. 2 is for dropping into vitamins B
12concentration and the reaction times on the impact of triclosan clearance.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
The analyzing and testing of triclosan adopts Agilent7890A-5975C VL MSD gas chromatograph-mass spectrometer: chromatographic column adopts HP-5MS (30 meters × 0.25 millimeter × 0.25 micron); Injector temperature 270 degrees Celsius; Starting temperature 80 degrees Celsius, keeps 3 minutes; Rise to 300 degrees Celsius with the speed of 20 centigrade per minutes, keep 7 minutes; Carrier gas is helium.Flow rate of carrier gas 1 milliliter of per minute; Splitting ratio 10: 1, sample size 1 microlitre.Mass Spectrometry Conditions: ionization mode EI, ionizing energy 70 electron-volts, ion source temperature 280 degrees Celsius.Transmission line temperature: 250 degrees Celsius, sweep limit: 41-450 atomic mass unit, mass spectrum java standard library: NIST storehouse.
Embodiment 1
First vitamins B is adopted
12to the strengthening reduction dechlorination method of triclosan in sewage, process is containing the sewage of 10 milligrams per liter of triclosans.
The initial pH value regulating sewage is 5, adds vitamins B in system simultaneously
1250 milligrams per liter of sewage, nano zero valence iron 0.5 gram of often liter of sewage, stirs, and wherein, the grain diameter of nano zero valence iron is 50 ~ 70 nanometers.
Embodiment 2
Difference from Example 1 is, the initial pH value of sewage be regulated to be 6.
Embodiment 3
Difference from Example 1 is, the initial pH value of sewage be regulated to be 7.
Embodiment 4
Difference from Example 1 is, the initial pH value of sewage be regulated to be 8.
Embodiment 5
Difference from Example 1 is, the initial pH value of sewage be regulated to be 9.
In embodiment 1 ~ 5, will detect the clearance of triclosan in sewage when each embodiment is carried out when the differential responses time, result as shown in Figure 1.As seen from Figure 1, in reaction 5 hours, under five pH conditions, when pH rises to 7 from 5, the clearance of triclosan reduces gradually; But when pH continues to raise, the reduction dechlorination clearance of triclosan also raises gradually, and when pH=8 and 9, the reduction dechlorination clearance difference of triclosan is little, and under pH=9 condition, clearance is greater than 99%.
Embodiment 6
First vitamins B is adopted
12to the strengthening reduction dechlorination method of triclosan in sewage, process is containing the sewage of 10 milligrams per liter of triclosans.
The initial pH value regulating sewage is 8, in containing the sewage of 10 milligrams per liter of triclosans, add the vitamins B that concentration is 10 milligrams per liter
12, nano zero valence iron add-on is 0.5 gram of often liter of sewage, stirs, and wherein, the grain diameter of nano zero valence iron is 50 ~ 70 nanometers.
Embodiment 7
Difference from Example 6 is, adds the vitamins B that concentration is 30 milligrams per liter in sewage
12.
Embodiment 8
Difference from Example 6 is, adds the vitamins B that concentration is 50 milligrams per liter in sewage
12.
Embodiment 9
Difference from Example 6 is, adds the vitamins B that concentration is 70 milligrams per liter in sewage
12.
Embodiment 10
Difference from Example 6 is, adds the vitamins B that concentration is 100 milligrams per liter in sewage
12.
In embodiment 6 ~ 10, will detect the clearance of triclosan in sewage when each embodiment is carried out when the differential responses time, result as shown in Figure 2.As seen from Figure 2, along with vitamins B
12add concentration and be increased to 50 milligrams per liter from 10 milligrams per liter, the reduction dechlorination clearance of triclosan increases gradually, but when dosage continues to be increased to 100 milligrams per liter, final reduction dechlorination clearance change is little.
Embodiment 11
One utilizes vitamins B
12carry out to triclosan in sewage the method strengthening reduction dechlorination, the pH value regulating sewage is 5, and the mass concentration to triclosan is in the sewage of 1 milligrams per liter, adds nano zero valence iron and vitamins B
12, the input amount of nano zero valence iron adds 0.1 gram, vitamins B in often liter of sewage
12input amount for adding 10 milligrams in often liter of sewage.In 5 hours reaction times, the temperature of reaction is not limit, and carries out strengthening reduction dechlorination to the triclosan in sewage.Wherein, the grain diameter of nano zero valence iron is 50 ~ 70 nanometers.
Embodiment 12
One utilizes vitamins B
12carry out to triclosan in sewage the method strengthening reduction dechlorination, the pH value regulating sewage is 9, and the mass concentration to triclosan is in the sewage of 20 milligrams per liter, adds nano zero valence iron and vitamins B
12, the input amount of nano zero valence iron adds 1 gram, vitamins B in often liter of sewage
12input amount for adding 100 milligrams in often liter of sewage.In 10 hours reaction times, the temperature of reaction is not limit, and carries out strengthening reduction dechlorination to the triclosan in sewage.Wherein, the grain diameter of nano zero valence iron is 50 ~ 70 nanometers.
Claims (6)
1. one kind utilizes vitamins B
12the method strengthening reduction dechlorination is carried out to triclosan in sewage, it is characterized in that, to containing in the sewage of triclosan, add nano zero valence iron and vitamins B
12, reaction times 5-10 hour, carries out strengthening reduction dechlorination to the triclosan in sewage.
2. one according to claim 1 utilizes vitamins B
12carry out to triclosan in sewage the method strengthening reduction dechlorination, it is characterized in that, in described sewage, the mass concentration of triclosan is 1 ~ 20 milligrams per liter, and the input amount of described nano zero valence iron is for adding 0.1 ~ 1 gram, described vitamins B in often liter of sewage
12input amount for adding 10 ~ 100 milligrams in often liter of sewage.
3. one according to claim 1 utilizes vitamins B
12the method strengthening reduction dechlorination is carried out to triclosan in sewage, it is characterized in that, adding nano zero valence iron and vitamins B
12before, the pH value regulating sewage is 5 ~ 9.
4. one according to claim 3 utilizes vitamins B
12the method strengthening reduction dechlorination is carried out to triclosan in sewage, it is characterized in that, adding nano zero valence iron and vitamins B
12before, the pH value regulating sewage is 8 ~ 9.
5. one according to claim 4 utilizes vitamins B
12the method strengthening reduction dechlorination is carried out to triclosan in sewage, it is characterized in that, adding nano zero valence iron and vitamins B
12before, the pH value regulating sewage is 9.
6. one according to claim 1 utilizes vitamins B
12carry out to triclosan in sewage the method strengthening reduction dechlorination, it is characterized in that, the grain diameter of described nano zero valence iron is 50 ~ 70 nanometers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310487706.0A CN104229969A (en) | 2013-10-17 | 2013-10-17 | Method for carrying out intensified reductive dechlorination on triclosan in sewage by using vitamin B12 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310487706.0A CN104229969A (en) | 2013-10-17 | 2013-10-17 | Method for carrying out intensified reductive dechlorination on triclosan in sewage by using vitamin B12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104229969A true CN104229969A (en) | 2014-12-24 |
Family
ID=52218990
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310487706.0A Pending CN104229969A (en) | 2013-10-17 | 2013-10-17 | Method for carrying out intensified reductive dechlorination on triclosan in sewage by using vitamin B12 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104229969A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104860369A (en) * | 2015-04-22 | 2015-08-26 | 苏州大学 | Method for adsorption recovery of triclosan in sewage by using penicillium |
| CN108568304A (en) * | 2017-10-12 | 2018-09-25 | 湖南大学 | A kind of electro-catalysis dehalogenation catalyst |
| CN110526377A (en) * | 2019-09-02 | 2019-12-03 | 北京高能时代环境技术股份有限公司 | A method of repairing chloro-carbon solvent polluted underground water |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006072944A2 (en) * | 2005-01-03 | 2006-07-13 | Yeda Research And Development Co. Ltd. | Zero valent metal composite for catalyticaly treating contaminated water |
| CN103240267A (en) * | 2013-04-28 | 2013-08-14 | 华中师范大学 | Soil restoration method based on oxygen activation of iron powder and polyphosphoric acid molecules |
-
2013
- 2013-10-17 CN CN201310487706.0A patent/CN104229969A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006072944A2 (en) * | 2005-01-03 | 2006-07-13 | Yeda Research And Development Co. Ltd. | Zero valent metal composite for catalyticaly treating contaminated water |
| CN103240267A (en) * | 2013-04-28 | 2013-08-14 | 华中师范大学 | Soil restoration method based on oxygen activation of iron powder and polyphosphoric acid molecules |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104860369A (en) * | 2015-04-22 | 2015-08-26 | 苏州大学 | Method for adsorption recovery of triclosan in sewage by using penicillium |
| CN108568304A (en) * | 2017-10-12 | 2018-09-25 | 湖南大学 | A kind of electro-catalysis dehalogenation catalyst |
| CN108568304B (en) * | 2017-10-12 | 2020-10-09 | 湖南大学 | Electrocatalytic dehalogenation catalyst |
| CN110526377A (en) * | 2019-09-02 | 2019-12-03 | 北京高能时代环境技术股份有限公司 | A method of repairing chloro-carbon solvent polluted underground water |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Pan et al. | Mitigating antibiotic pollution using cyanobacteria: removal efficiency, pathways and metabolism | |
| Chen et al. | Assessment of degradation characteristic and mineralization efficiency of norfloxacin by ionizing radiation combined with Fenton-like oxidation | |
| Oluwole et al. | Pharmaceuticals and personal care products in water and wastewater: a review of treatment processes and use of photocatalyst immobilized on functionalized carbon in AOP degradation | |
| Quan et al. | Technology and principle of removing triclosan from aqueous media: A review | |
| Trovó et al. | Photodegradation of the pharmaceuticals amoxicillin, bezafibrate and paracetamol by the photo-Fenton process—application to sewage treatment plant effluent | |
| Giraldo et al. | Degradation of the antibiotic oxolinic acid by photocatalysis with TiO2 in suspension | |
| Liu et al. | Ferrous ions promoted aerobic simazine degradation with Fe@ Fe2O3 core–shell nanowires | |
| Wang et al. | Is the phototransformation of pharmaceuticals a natural purification process that decreases ecological and human health risks? | |
| Robinson-Lora et al. | Efficient metal removal and neutralization of acid mine drainage by crab-shell chitin under batch and continuous-flow conditions | |
| Davies et al. | The upsurge of photocatalysts in antibiotic micropollutants treatment: Materials design, recovery, toxicity and bioanalysis | |
| Zhong et al. | Performance and mechanism in degradation of typical antibiotics and antibiotic resistance genes by magnetic resin-mediated UV-Fenton process | |
| CN104229972A (en) | Method for removing carbamazepine in sewage by virtue of strong oxidation of Fenton technology | |
| CN103787484A (en) | Method for removing diclofenac contained in sewage by utilizing copper-iron heterogeneous fenton technology | |
| Georgin et al. | Main advances and future prospects in the remediation of the antibiotic amoxicillin with a focus on adsorption technology: A critical review | |
| Feng et al. | Cu2O-promoted degradation of sulfamethoxazole by α-Fe2O3-catalyzed peroxymonosulfate under circumneutral conditions: synergistic effect, Cu/Fe ratios, and mechanisms | |
| Iqbal et al. | Advanced Photocatalysis as a Viable and Sustainable Wastewater Treatment Process: A Comprehensive Review | |
| Zheng et al. | EB-radiolysis of carbamazepine: in pure-water with different ions and in surface water | |
| Mavronikola et al. | Mineralisation of the antibiotic amoxicillin in pure and surface waters by artificial UVA‐and sunlight‐induced Fenton oxidation | |
| CN104229969A (en) | Method for carrying out intensified reductive dechlorination on triclosan in sewage by using vitamin B12 | |
| Kusuma et al. | Advanced oxidation processes: a promising route for abatement of emerging contaminants in water | |
| Jalloul et al. | Antibiotics contaminated irrigation water: an overview on its impact on edible crops and visible light active titania as potential photocatalysts for irrigation water treatment | |
| Gutiérrez-Zapata et al. | Addition of hydrogen peroxide enhances abiotic sunlight-induced processes to simultaneous emerging pollutants and bacteria abatement in simulated groundwater using CPC solar reactors | |
| Ashraf et al. | Phyto-mediated photocatalysis: a critical review of in-depth base to reactive radical generation for erythromycin degradation | |
| Yu et al. | Contamination by antibiotics and their degradation and removal methods | |
| CN103466745B (en) | A kind of method utilizing ferrous ion to promote sulfa antibiotics removal by radiation in waste water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20141224 |