CN106179178A - Process the brucite preparation method of phosphor in sewage - Google Patents
Process the brucite preparation method of phosphor in sewage Download PDFInfo
- Publication number
- CN106179178A CN106179178A CN201610637611.6A CN201610637611A CN106179178A CN 106179178 A CN106179178 A CN 106179178A CN 201610637611 A CN201610637611 A CN 201610637611A CN 106179178 A CN106179178 A CN 106179178A
- Authority
- CN
- China
- Prior art keywords
- znal
- brucite
- zno
- preparation
- dissolved
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The present invention relates to a kind of brucite preparation method processing phosphor in sewage, this ZnO ZnAl brucite preparation process is: first make ZnAl brucite by the method for hydrothermal synthesis method, finally load to, on ZnAl hydrotalcite nano piece, i.e. prepare described hydrotalcite material by circumfluence method by ZnO.This preparation method advantage is to prepare that houghite impurity is less, purity is higher, structure is more regular, Nano grade, better processing effect.The hydrotalcite material that the inventive method prepares has the advantage that (1) has the biggest surface area, and the Electrostatic Absorption for physics provides good environment；(2) bimetallic has a large amount of clean positive charge, provides good condition for complexation phosphonium ion；(3) existence hydroxy brings great amount of hydroxy group group, provides good condition for the absorption of phosphonium ion substituted hydroxy；(4) synthesize simple, non-secondary pollution and easily regenerate.
Description
Technical field
The present invention relates to a kind of brucite preparation method processing phosphor in sewage.
Background technology
Along with economic fast development, the continuous of population increases sharply, and industrialized step is the most progressively accelerated, mankind's activity
Domestic water containing macrometabolic element and industrial wastewater are also drained into rivers,lakes and seas by the expansion of scope.Among these, just there is life
Nitrogen required for thing growth, the nutrient substance such as phosphorus, therefore algae and plankton in water are able to the most numerous
Growing, this just defines " wawter bloom ", and this kind of phenomenon among ocean is " red tide ", and both phenomenons are referred to as water by educational circles
Body eutrophication.Having the analysis and research of researcher elemental composition various to algae to show, algae experience composition formula is represented by
C106H262O110N16P, thus mass fraction C, H, O, N and P of calculating component are respectively 35.8%, 2.4%, 49.6%, 6.3%
With 0.9%, it can be seen that the ratio of phosphorus is minimum among these, this absolutely proves that phosphorus is the key point controlling organism in water breeding.Also
There is scholar to think, in aquatic ecosystem, as phosphorus concentration as little as 30 g/L in water, also can stimulate the growth of algae.
Body eutrophication has become the primary water environmental problems that China faces, finds according to correlational study, and phosphorus is rich battalion
One of main contamination index of fosterization.China causes eutrophic lake to account for total the 56% of lake of adding up, worth note because phosphorus pollutes
Meaning, enters and surpasses the phosphorus of 66% in these eutrophy type lakes and all derive from life and industrial wastewater.Eutrophication water due to
The too high meeting of phosphorus content causes cyanophyceae raised growth so that water transparency reduces, and water body distributes bad smell, and oxygen in water subtracts
Few, a large amount of fish and shrimp are dead, ultimately result in aquatic ecosystem and collapse rapidly.Therefore, the phosphorus content controlling water body can effectively contain richness
The generation of nutrient laden.
Brucite feature is that internal surface area is big, positive charge is many, anion-exchange capacity is big, synthesis is simple, non-secondary pollution
And easily regeneration etc., therefore of increasing concern as adsorbent application in waste water dephosphorization field.
Himself there is interlayer anion commutativity, Acidity of Aikalinity, heat stability, memory effect, catalytic.Not only at Shui Chu
There is application prospect in reason field, has been widely used at other field.
Summary of the invention
It is an object of the invention to provide a kind of low cost, non-secondary pollution, can quickly, the water of phosphorus in efficient sewerage processing
Talcum preparation method.
The brucite preparation method of the process phosphor in sewage of the present invention, comprises the following steps:
(1) preparation of ZnAl hydrotalcite nano piece: weigh 30.14g zinc nitrate (Zn (NO respectively3)2·6H2And 10.18g nitric acid O)
Aluminum (Al (NO3)3·9H2O) being dissolved in 200mL deionized water, ultrasonic 15min makes it mix, hydrotropy, separately weighs 10g sodium hydroxide
And 5.3g sodium carbonate (Na (NaOH)2CO3) be dissolved in 100mL deionized water, ultrasonic 15min makes it be dissolved to water white transparency state.
(2) blend step (1) above two solution, reacts 30min under 65 DEG C of bath temperatures and stirring double condition, will
After reaction, liquid is centrifuged separating, and rotating speed is 3000 revs/min, and centrifugation time is 1min, is again divided by centrifuged deposit thing
Dissipate in deionized water, be then transferred in 200mL hydrothermal reaction kettle, hydro-thermal reaction 20 hours at a temperature of 120 DEG C, then take out through vacuum
Filter, deionized water wash, it is vacuum dried 20 hours at 80 DEG C, last grind into powder, is ZnAl hydrotalcite nano piece.
(3) ZnO-ZnAl(is called for short ZZA) prepared by brucite: weigh ZnAl brucite prepared by 0.9g said method respectively and receive
Rice sheet, 8.925g zinc nitrate (Zn (NO3)2·6H2And 4.2g hexamethylenetetramine (C O)6H12N4) be dissolved in 600ml deionized water,
Ultrasonic 8min makes its mix homogeneously.
(4) transfer to the mixed liquor in step (3) again, in the there-necked flask of 1000ml, return in mechanical agitation and condensing tube
In the case of stream, reacting 30min, then be centrifuged gained suspension separating, rotating speed is 3000 revs/min, and centrifugation time is
1min, centrifuged deposit thing is through vacuum filtration, then is washed with deionized, and is vacuum dried 20 hours, grind into powder at 80 DEG C,
It is ZnO-ZnAl brucite.
The ZnO-ZnAl brucite of the process phosphor in sewage of the present invention is layered double hydroxide, its stratiform having
Structure has the biggest surface area, and the Electrostatic Absorption for physics provides good environment, and bimetallic has a large amount of clean positive charge,
Good condition is provided for complexation phosphonium ion；Existence hydroxy brings great amount of hydroxy group group, inhales for phosphonium ion substituted hydroxy
Attached provide good condition, ZnO-ZnAl brucite can quickly, phosphorus in efficient sewerage processing, use cost is low, without secondary dirt
Dye.
Accompanying drawing explanation
Fig. 1 is ZnAl hydrotalcite nano piece precursor (a, c) of the present invention and the SEM image of ZnO-ZnAl brucite (b, d)；
Fig. 2 is the X-ray powder diffraction figure of ZnAl hydrotalcite nano piece；
Fig. 3 is the X-ray powder diffraction figure of ZnO-ZnAl；
Fig. 4 is ZnAl hydrotalcite nano piece precursor and the infrared spectroscopic imaging of ZnO-ZnAl brucite；
Fig. 5 is that ZnO-ZnAl dosage affects figure to actual waste water tp removal rate；
Fig. 6 is that the dosage of ZnO-ZnAl is to actual waste water KDAffect figure；
Fig. 7 is that the ZnO-ZnAl under different temperatures adsorbs phosphatic situation map.
Detailed description of the invention
Embodiment 1:
A kind of brucite preparation method processing phosphor in sewage, on the basis of synthetic ZnAl hydrotalcite nano piece precursor, logical
Cross circumfluence method ZnO load to be entered, specifically comprise the following steps that
Step 1: centrifuging prepares ZnAl hydrotalcite nano piece, weighs 30.14g zinc nitrate (Zn (NO respectively3)2·6H2O) and
10.18g aluminum nitrate (Al (NO3)3·9H2O) being dissolved in 200mL deionized water, ultrasonic 15min makes it mix, hydrotropy.
Step 2: separately weigh 10g sodium hydroxide (NaOH) and 5.3g sodium carbonate (Na2CO3) be dissolved in 100mL deionized water,
Ultrasonic 15min makes it dissolve straight water white transparency state.
Step 3: mixing above two solution, reacts 30min at 65 DEG C of bath temperatures with being stirred vigorously under double condition, will
After reaction, liquid is centrifuged separating, and rotating speed is 3000 revs/min, and centrifugation time is 1min, is again divided by centrifuged deposit thing
Dissipate in deionized water, be then transferred in 200mL hydrothermal reaction kettle, hydro-thermal reaction 20 hours at a temperature of 120 DEG C, then take out through vacuum
Filter, deionized water wash, it is vacuum dried 20 hours at 80 DEG C, last grind into powder, is ZnAl hydrotalcite nano piece.
Prepared by step 4:ZnO-ZnAl brucite, weigh respectively ZnAl hydrotalcite nano piece prepared by 0.9g said method,
8.925g zinc nitrate (Zn (NO3)2·6H2And 4.2g hexamethylenetetramine (C O)6H12N4) be dissolved in 600ml deionized water, ultrasonic
8min makes its mix homogeneously, is then transferred in the there-necked flask of 1000ml, in the case of mechanical agitation and condensing tube reflux, instead
Answering 30min, then be centrifuged gained suspension separating, rotating speed is 3000 revs/min, and centrifugation time is 1min, heavy after being centrifuged
Shallow lake thing is through vacuum filtration, then is washed with deionized, and is vacuum dried 20 hours, grind into powder, is ZnO-ZnAl at 80 DEG C
Brucite.
The hydrotalcite material structural characterization of above-mentioned process phosphor in sewage:
Crystal form: using RigakuSmartlab type x-ray powder diffraction instrument, the radiating light source that test uses is that Cu target K α penetrates
Line, voltage is 40kV, and electric current is 30mA, and instrumental error is ± 0.04o, angular range is 5-70o, scanning speed is 4o/ min, step
A length of 0.02o.When the angle of diffraction 2 θ is 11.6 °, 23.1 °, 34.5 °, 47.2 °, 56.6 ° and 61.8 °, corresponding houghite diffraction is brilliant
Face is respectively (003), (006), (012), (018), (110) and (113), all occurs in that strong and sharp-pointed diffraction maximum, such as Fig. 2,
Prove that its degree of crystallinity is high, owing to there is no other dephasign peaks, this also illustrates the purity of this ZnAl hydrotalcite nano piece also
The highest.By, on circumfluence method loading ZnO to ZnAl hydrotalcite nano piece, having obtained ZnO-ZnAl brucite.Fig. 3 is ZnO-ZnAl
The X-ray powder diffraction figure of brucite, in addition to occurring being similar to the characteristic diffraction peak of ZnAl hydrotalcite nano piece, have also appeared
In obviously ZnO characteristic diffraction peak, i.e. figure at a, b, c tri-, this illustrates ZnO and well loaded to ZnAl neatly
In stone nanometer sheet, and other dephasign peaks do not occur, the purity of this explanation ZnO-ZnAl brucite is the highest.
Qualitative analysis: characterized by infrared spectrum, uses Perkin Elmer company of U.S. Spectrum
One NTS type Fourier infrared spectrograph, sweep limits is 4000cm-1—400cm-1.Such as Fig. 4, in figure, both threads all occurs in that
Significantly houghite characteristic peak, ZnAl hydrotalcite nano piece precursor and ZnO-ZnAl brucite are at 3433cm-1Near have one
The hydroxyl stretching vibration peak of individual obvious interlayer water of crystallization, compares more than 3650cm-1Free hydroxyl, this vibration peak occurs in that one
Determining the skew of degree, this indicates that hydrogen bond is widely present in ZnAl hydrotalcite nano piece precursor and ZnO-ZnAl brucite.?
2926cm-1Near occur in that a faint peak, the reason that this peak causes is interlayer CO3 2-With H2The hydrogen bond of O acts on.
At 1636cm-1The neighbouring hydroxyl bending vibration peak that absworption peak is water of crystallization occurred.At 1380cm-1The peak of neighbouring appearance is
CO3 2-Stretching vibration absworption peak, essentially from the Na in preparation process2CO3, a small amount of CO come from environment2.From above point
Analysis finds, in the infrared spectrogram of ZnO-ZnAl brucite, the characteristic absorption peak of houghite is obtained for and is effectively maintained.
Phosphate optimum dosage in ZnO-ZnAl brucite Adsorption sewage treatment plant tail water:
(1) in eight 300ml tool plug conical flask, be separately added into 200 mL actual waste water, then be separately added into 0.001g, 0.002g,
The ZZA of 0.005g, 0.01g, 0.02g, 0.05g, 0.1g and 0.5g, pH are 6.5, at (25 ± 1) DEG C, and temperature constant magnetic stirring
1h, rotating speed is 180 r/min, filters suspension with 0.45 μm needle tubing filter, uses molybdenum-antimony anti-spectrophotometric method to measure in filtrate
Phosphorus content.
From Fig. 5 and Fig. 6, phosphatic clearance and KDChange all increase with the increase of dosage, dosage
During being increased to 0.01g by 0.002g, phosphatic clearance is then increased 70% by 12%, phosphoric residue concentration then by
0.88mg/L reduces to 0.3mg/L, K meanwhileDIncreases slowly.Water outlet during 0.01g ZZA dosage, has reached China
Urban wastewater treatment firm pollutant emission standard one-level A standard.During 0.01g increases to 0.04g, phosphatic clearance increases
Long slow, solid-liquid partition coefficient KD increases very fast.Therefore experimental result draws, in 200ml waste water, ZnO-ZnAl brucite adsorbs
Phosphate optimum dosage in actual waste water is 0.01g.
As shown in Figure 7, when the ZZA phosphatic adsorption temp of absorption is set as 15 DEG C, 25 DEG C and 35 DEG C, reach after absorption 48h
To adsorption equilibrium, its maximum adsorption capacity is respectively 30.54mg/g, 32.40mg/g and 33.54mg/g, consequently found that necessarily
Within the temperature range of, along with the rising of adsorption temp, the maximum adsorption capacity of ZnO-ZnAl brucite also increases, this be because of
Rising for temperature increases the rate of adsorption, thus adds adsorbance, indicates the absorption of ZnO-ZnAl brucite phosphatic
Reaction is probably an endothermic reaction.
Claims (1)
1. the brucite preparation method processing phosphor in sewage, it is characterised in that: it comprises the following steps:
(1) preparation of ZnAl hydrotalcite nano piece: weigh 30.14g zinc nitrate respectively and 10.18g aluminum nitrate be dissolved in 200mL go from
In sub-water, ultrasonic 15min makes it mix, hydrotropy, separately weighs 10g sodium hydroxide and 5.3g sodium carbonate is dissolved in 100mL deionized water
In, ultrasonic 15min makes it be dissolved to water white transparency state；
(2) blend step (1) above two solution, reacts 30min under 65 DEG C of bath temperatures and stirring double condition, will reaction
Rear liquid is centrifuged separating, and rotating speed is 3000 revs/min, and centrifugation time is 1min, is again scattered in by centrifuged deposit thing
In deionized water, it is then transferred in 200mL hydrothermal reaction kettle, hydro-thermal reaction 20 hours at a temperature of 120 DEG C, then through vacuum filtration,
Deionized water wash, is vacuum dried 20 hours at 80 DEG C, grind into powder, is ZnAl hydrotalcite nano piece；
(3) prepared by ZnO-ZnAl brucite: weigh ZnAl hydrotalcite nano piece, 8.925g nitre prepared by 0.9g said method respectively
Acid zinc and 4.2g hexamethylenetetramine are dissolved in 600ml deionized water, and ultrasonic 8min makes its mix homogeneously；
Again the mixed liquor in step (3) is transferred in the there-necked flask of 1000ml, in the feelings that mechanical agitation and condensing tube reflux
Under condition, reacting 30min, then be centrifuged gained suspension separating, rotating speed is 3000 revs/min, and centrifugation time is 1min, from
Heart postprecipitation thing is through vacuum filtration, then is washed with deionized, and is vacuum dried 20 hours, grind into powder, is at 80 DEG C
ZnO-ZnAl brucite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610637611.6A CN106179178A (en) | 2016-08-08 | 2016-08-08 | Process the brucite preparation method of phosphor in sewage |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610637611.6A CN106179178A (en) | 2016-08-08 | 2016-08-08 | Process the brucite preparation method of phosphor in sewage |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106179178A true CN106179178A (en) | 2016-12-07 |
Family
ID=57513582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610637611.6A Pending CN106179178A (en) | 2016-08-08 | 2016-08-08 | Process the brucite preparation method of phosphor in sewage |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106179178A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107963824A (en) * | 2017-11-29 | 2018-04-27 | 中国科学院海洋研究所 | A kind of triazole corrosion inhibitor compound of base containing pyrazoline of hydrotalcite intercalation chlorion probe modification and its application |
| CN109734137A (en) * | 2019-02-08 | 2019-05-10 | 桂林理工大学 | A kind of method and application preparing cobalt nickel bimetal hydroxide with glass sample bottle |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013069742A1 (en) * | 2011-11-11 | 2013-05-16 | 堺化学工業株式会社 | Hydrotalcite and method for producing same |
| CN103691441A (en) * | 2013-12-02 | 2014-04-02 | 湖南理工学院 | Preparation method for photocatalytic material with strong adsorption and high visible light degradation of performance |
-
2016
- 2016-08-08 CN CN201610637611.6A patent/CN106179178A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013069742A1 (en) * | 2011-11-11 | 2013-05-16 | 堺化学工業株式会社 | Hydrotalcite and method for producing same |
| CN103691441A (en) * | 2013-12-02 | 2014-04-02 | 湖南理工学院 | Preparation method for photocatalytic material with strong adsorption and high visible light degradation of performance |
Non-Patent Citations (2)
| Title |
|---|
| 杨斌: "锌铝水滑石纳米复合材料的制备及其在锌镍电池中的应用研究", 《中国博士学位论文全文数据库 工程科技I辑》 * |
| 郑允民: "ZnAl类水滑石复合材料及其煅烧产物的制备和性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107963824A (en) * | 2017-11-29 | 2018-04-27 | 中国科学院海洋研究所 | A kind of triazole corrosion inhibitor compound of base containing pyrazoline of hydrotalcite intercalation chlorion probe modification and its application |
| CN109734137A (en) * | 2019-02-08 | 2019-05-10 | 桂林理工大学 | A kind of method and application preparing cobalt nickel bimetal hydroxide with glass sample bottle |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhou et al. | Novel hollow microspheres of hierarchical zinc–aluminum layered double hydroxides and their enhanced adsorption capacity for phosphate in water | |
| CN104874365B (en) | Carboxymethyl cellulose ion insertion hydrotalcite-like composite material and preparation method and application | |
| CN101757892B (en) | Preparation method of bagasse active carbon/ferric oxide | |
| CN105032348B (en) | A kind of redox graphene/nano zirconium dioxide composite adsorption dephosphorization agent and preparation method | |
| US9822024B2 (en) | Methods and systems for wastewater treatment and resource recovery | |
| CN100542976C (en) | Method with flyash and kaolin production compound aluminium silicate polymer ferric flocculant | |
| CN110217850B (en) | Method for photocatalytic degradation of antibiotics in water body | |
| CN101754932A (en) | Process for the production of barium sulfate | |
| CN107138131A (en) | A kind of preparation method of the oxidation of coal aluminium composite material of efficient absorption Cr (VI) | |
| CN113797890B (en) | Method for preparing catalytic and adsorption material from deep sea clay | |
| Castro et al. | Phosphate adsorption by montmorillonites modified with lanthanum/iron and a laboratory test using water from the Jacarepaguá Lagoon (RJ, Brazil) | |
| CN101691250A (en) | Adsorbing agent for adsorbing phosphate groups and adsorption method | |
| CN106179178A (en) | Process the brucite preparation method of phosphor in sewage | |
| CN110479221A (en) | A kind of preparation method and application of red mud/polypyrrole composite adsorbing material | |
| Wu et al. | Mechanochemical syntheses of oxygen-rich bismuth oxychlorides Bi x O y Cl z to enhance ciprofloxacin degradation under visible light irradiation | |
| CN113231041B (en) | Preparation method and application of artificial humus/iron mineral coprecipitation composite material | |
| Nawaz et al. | Photocatalytic performance of black titanium dioxide for phenolic compounds removal from oil refinery wastewater: nanoparticles vs nanowires | |
| CN102527325B (en) | Aluminum-modified attapulgite adsorbent and preparation method and application | |
| CN109201018A (en) | A kind of preparation method and purposes of the mesoporous carbon film of La doped | |
| CN105948198A (en) | Treatment method of sulfate wastewater | |
| CN103936077B (en) | A kind of preparation method of niobic acid manganese nano flower | |
| CN113354046A (en) | Carbon nitride modified nano Fe3O4Application of material as algae inhibitor and method | |
| CN103920451B (en) | The preparation method of a kind of zinc-aluminum hydrotalcite hollow sub-microsphere and the processing method of methyl orange system dyeing waste water | |
| CN113072159A (en) | Circulating dechlorination process and system | |
| CN109317157A (en) | A kind of ternary Z-type complex sound catalyst and its preparation method and application for antibiotic waste water of degrading |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20161207 |