CN105948155A - Treatment method of methylene blue dye waste water - Google Patents
Treatment method of methylene blue dye waste water Download PDFInfo
- Publication number
- CN105948155A CN105948155A CN201610318660.3A CN201610318660A CN105948155A CN 105948155 A CN105948155 A CN 105948155A CN 201610318660 A CN201610318660 A CN 201610318660A CN 105948155 A CN105948155 A CN 105948155A
- Authority
- CN
- China
- Prior art keywords
- methylene blue
- blue dye
- adsorbent
- waste water
- processing method
- 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.)
- Withdrawn
Links
Classifications
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- 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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic 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
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
Abstract
The invention discloses a treatment method of methylene blue dye waste water. The treatment method comprises the following steps: firstly, an aza-macrocyclic ligand, potassium iodide and potassium carbonate are dissolved in an organic solvent, mesoporous silica with a functional chlorine group is added under the protection of nitrogen, the mixture is subjected to a reflux reaction for 20-40 h while being constantly stirred and is cooled to the room temperature after the reaction ends, a product is obtained after filtration, washed with ethanol and water 2-5 times alternately and dried under a vacuum condition at the temperature of 60-80 DEG C for 12-16 h, and a modified silica adsorbent is obtained; then the modified silica adsorbent is added to the methylene blue dye waste water, the pH of the dye waste water is adjusted to range from 5 to 10, the mixture is stirred at the speed of 3,000-5,000 r/m for 24-28 h, left to stand still and filtered to remove the adsorbent adsorbing methylene blue dye, and the methylene blue dye in the waste water is removed. The method is simple, convenient and quick to operate, the treatment cost is low, the adopted adsorbent can adsorb a large amount of dye, and the methylene blue dye in the methylene blue dye waste water can be effectively removed.
Description
Technical field:
The present invention relates to Organic Dyestuff Wastewater Treatment field, be specifically related to a kind of methylene blue dye
The processing method of material waste water.
Background technology:
Waste water from dyestuff is the industrial wastewater that a kind of amount is big, wide, and ecological environment causes serious dirt
Dye.Along with the development of China's dyeing, the every annual emissions of China Dyestuffs waste water is about 1.3 ×
109m3, account for the 35% of industrial wastewater discharge total amount.Waste water from dyestuff is mainly derived from dyestuff and dyestuff
Intermediate produce and dyeing, its complicated component, high COD, high chroma, high salinity,
Change of water quality is big, be difficult to biodegradation, affects the photosynthesis of water plant after entering water body,
Thus destroy ecological balance in water, cause environmental problem.
Metaporous silicon dioxide material has regular pore passage structure and continuously adjustable aperture, bigger
Specific surface area and pore volume, good heat stability and chemical stability, absorption with separate,
The fields such as bulky molecular catalysis have a wide range of applications.Received by carrying transition metal oxide
Rice grain is to pure SiO2Mesoporous material is modified, and can improve the many property of mesoporous material
Can, such as skeleton stability, surface acidity, selective catalysis ability and ion-exchange capacity etc..By
Composite porous there is bigger specific surface area simultaneously and beneficially material quickly passes in this
Defeated continuous macropore structure, therefore before adsorbing separation field should have well application
Scape.But the most conventional Metaporous silicon dioxide material adsorbance is little, use environmental condition harsh.
Summary of the invention:
It is an object of the invention to provide the processing method of a kind of methylene blue dye wastewater, the method
Can effectively remove the organic dyestuff in waste water, the adsorbent amount used is big, environmental protection,
This processing method.
For achieving the above object, the present invention is by the following technical solutions:
The processing method of a kind of methylene blue dye wastewater, comprises the following steps:
(1) preparation of adsorbent:
Aza macrocyclic ligands, potassium iodide and potassium carbonate being dissolved in organic solvent, nitrogen is protected
Under, the mesoporous silicon oxide of addition chloro functionalization, continuously stirred lower back flow reaction 20-40h,
Reaction is cooled to room temperature after terminating, and is filtrated to get product, alternately washs 2-5 time with second alcohol and water,
It is vacuum dried 12-16h at 60-80 DEG C, obtains improved silica adsorbent；
(2) in methylene blue dye wastewater, the improved silica that step (1) prepares is added
Adsorbent, and by the pH regulator of waste water from dyestuff to 5-10, at the shape of 3000-5000 rev/min
Stir 24-48h under state, stand and be filtered to remove the adsorbent being adsorbed with methylene blue dye, i.e.
Eliminate the methylene blue dye in waste water.
Preferred as technique scheme, in step (1), described improved silica is inhaled
Mesoporous the two of chloro functionalization is modified by nucleophilic substitution for attached dose for aza macrocyclic ligands
Silicon oxide surface, nitrogen atom on the ring skeleton of described aza macrocyclic ligands, described chloro function
The mesoporous silicon oxide changed contains end chloro structure.
Preferred as technique scheme, in step (1), described aza macrocyclic ligands is
Cyclen, 1,4,8,11-tetraazacyclododecane tetradecane, 1,4,8,12-
Tetraazacyclododecane pentadecane, 1,4,7,10,13-five-nitrogen heterocyclic pentadecane, 1,4,7,10,13,16-
One in hexanitrogen heterocycle octadecane.
Preferred as technique scheme, in step (1), described organic solvent is tetrahydrochysene
One in furan, acetonitrile, toluene, organic solvent uses front metallic sodium and benzophenone to enter
Row Non-aqueous processing.
Preferred as technique scheme, in step (1), the consumption of described organic solvent
Mesoporous silicon oxide for every 1-3g chloro functionalization uses 200-400ml.
Preferred as technique scheme, in step (1), aza macrocyclic ligands, iodate
Potassium, potassium carbonate, the mass ratio of mesoporous silicon oxide of chloro functionalization be: (2-5):
(1.5-3.5): (6-11): (1-1.2).
Preferred as technique scheme, in step (2), described methylene blue dye gives up
The concentration of water is 500-1200mg/L.
Preferred as technique scheme, in step (2), described improved silica is inhaled
The consumption of attached dose is that every liter of methylene blue dye wastewater adds improved silica adsorbent
0.5-0.8g。
The method have the advantages that
The improved silica adsorbent that the present invention prepares, surface is modified with aza macrocyclic ligands,
The rate of adsorption is fast, it is easy to eluting and recycling, and its specific surface area is big, good hydrophilic property, can
Effectively to remove the dye molecule in methylene blue dye wastewater；
The adsorbance of this adsorbent is affected less by temperature and pH, has eco-friendly characteristic,
Water body is not resulted in secondary pollution.
Detailed description of the invention:
In order to be better understood from the present invention, below by embodiment, the present invention is further described,
Embodiment is served only for explaining the present invention, and the present invention will not constitute any restriction.
Embodiment 1
The processing method of a kind of methylene blue dye wastewater, comprises the following steps:
(1) preparation of adsorbent:
2g1,4,7,10-tetraazacyclododecanand, 1.5g potassium iodide and 6g potassium carbonate are dissolved
In 200ml oxolane, under nitrogen protection, add the mesoporous dioxy of 1g chloro functionalization
SiClx, continuously stirred lower back flow reaction 20h, reaction is cooled to room temperature after terminating, is filtrated to get
Product, with alternately washing 2-5 time of second alcohol and water, is vacuum dried 12h, obtains modification at 60 DEG C
Silica adsorbent；
(2) in every liter of methylene blue dye wastewater, prepared the changing of 0.5g step (1) is added
Property silica adsorbent, and by the pH regulator of waste water from dyestuff to 5-10, at 3000 revs/min
State under stir 24h, stand be filtered to remove the adsorbent being adsorbed with methylene blue dye, i.e.
Eliminate the methylene blue dye in waste water.
Embodiment 2
The processing method of a kind of methylene blue dye wastewater, comprises the following steps:
(1) preparation of adsorbent:
By 5g1,4,8,11-tetraazacyclododecane tetradecane, 1,4,8,12-tetraazacyclododecane pentadecane,
3.5g potassium iodide and 11g potassium carbonate are dissolved in 400ml acetonitrile, under nitrogen protection, add
The mesoporous silicon oxide of 1.2g chloro functionalization, continuously stirred lower back flow reaction 40h, reaction knot
It is cooled to room temperature after bundle, is filtrated to get product, with alternately washing 2-5 time of second alcohol and water, 80 DEG C
Lower vacuum drying 16h, obtains improved silica adsorbent；
(2) in every liter of methylene blue dye wastewater, prepared the changing of 0.8g step (1) is added
Property silica adsorbent, and by the pH regulator of waste water from dyestuff to 5-10, at 5000 revs/min
State under stir 48h, stand be filtered to remove the adsorbent being adsorbed with methylene blue dye, i.e.
Eliminate the methylene blue dye in waste water.
Embodiment 3
The processing method of a kind of methylene blue dye wastewater, comprises the following steps:
(1) preparation of adsorbent:
3g 1,4,8,12-tetraazacyclododecane pentadecane, 2g potassium iodide and 7g potassium carbonate are dissolved in
In 250ml toluene, under nitrogen protection, add the mesoporous silicon oxide of 1.05g chloro functionalization,
Continuously stirred lower back flow reaction 25h, reaction is cooled to room temperature after terminating, is filtrated to get product,
With alternately washing 2-5 time of second alcohol and water, at 65 DEG C, it is vacuum dried 13h, obtains modified titanium dioxide
Silicon adsorbent；
(2) in every liter of methylene blue dye wastewater, prepared the changing of 0.6g step (1) is added
Property silica adsorbent, and by the pH regulator of waste water from dyestuff to 5-10, at 3500 revs/min
State under stir 30h, stand be filtered to remove the adsorbent being adsorbed with methylene blue dye, i.e.
Eliminate the methylene blue dye in waste water.
Embodiment 4
The processing method of a kind of methylene blue dye wastewater, comprises the following steps:
(1) preparation of adsorbent:
By 3.5g 1,4,7,10,13-five-nitrogen heterocyclic pentadecane, 2.5g potassium iodide and 8g carbonic acid
Potassium is dissolved in 300ml oxolane, under nitrogen protection, adds 1.1g chloro functionalization
Mesoporous silicon oxide, continuously stirred lower back flow reaction 30h, reaction is cooled to room temperature after terminating,
It is filtrated to get product, with alternately washing 2-5 time of second alcohol and water, at 70 DEG C, is vacuum dried 14h,
Obtain improved silica adsorbent；
(2) in every liter of methylene blue dye wastewater, prepared the changing of 0.65g step (1) is added
Property silica adsorbent, and by the pH regulator of waste water from dyestuff to 5-10, at 4000 revs/min
State under stir 35h, stand be filtered to remove the adsorbent being adsorbed with methylene blue dye, i.e.
Eliminate the methylene blue dye in waste water.
Embodiment 5
The processing method of a kind of methylene blue dye wastewater, comprises the following steps:
(1) preparation of adsorbent:
By 4g 1,4,7,10,13,16-hexanitrogen heterocycle octadecane, 3g potassium iodide and 9g potassium carbonate
It is dissolved in 350ml toluene, under nitrogen protection, adds mesoporous the two of 1.15g chloro functionalization
Silicon oxide, continuously stirred lower back flow reaction 35h, reaction is cooled to room temperature after terminating, filters
To product, with alternately washing 2-5 time of second alcohol and water, it is vacuum dried 15h at 75 DEG C, is changed
Property silica adsorbent；
(2) in every liter of methylene blue dye wastewater, prepared the changing of 0.7g step (1) is added
Property silica adsorbent, and by the pH regulator of waste water from dyestuff to 5-10, at 4500 revs/min
State under stir 40h, stand be filtered to remove the adsorbent being adsorbed with methylene blue dye, i.e.
Eliminate the methylene blue dye in waste water.
Embodiment 6
The processing method of a kind of methylene blue dye wastewater, comprises the following steps:
(1) preparation of adsorbent:
By 4.5g Cyclen, 3.2g potassium iodide and 10g potassium carbonate
It is dissolved in 400ml toluene, under nitrogen protection, adds mesoporous the two of 1.18g chloro functionalization
Silicon oxide, continuously stirred lower back flow reaction 40h, reaction is cooled to room temperature after terminating, filters
To product, with alternately washing 2-5 time of second alcohol and water, it is vacuum dried 15.5h at 75 DEG C, obtains
Improved silica adsorbent；
(2) in every liter of methylene blue dye wastewater, prepared the changing of 0.75g step (1) is added
Property silica adsorbent, and by the pH regulator of waste water from dyestuff to 5-10, at 5000 revs/min
State under stir 45h, stand be filtered to remove the adsorbent being adsorbed with methylene blue dye, i.e.
Eliminate the methylene blue dye in waste water.
Claims (8)
1. the processing method of a methylene blue dye wastewater, it is characterised in that comprise the following steps:
(1) preparation of adsorbent:
Aza macrocyclic ligands, potassium iodide and potassium carbonate are dissolved in organic solvent, under nitrogen protection,
Adding the mesoporous silicon oxide of chloro functionalization, continuously stirred lower back flow reaction 20-40h, reaction terminates
After be cooled to room temperature, be filtrated to get product, with alternately washing 2-5 time of second alcohol and water, at 60-80 DEG C very
Empty dry 12-16h, obtains improved silica adsorbent；
(2) in methylene blue dye wastewater, add the improved silica absorption that step (1) prepares
Agent, and by the pH regulator of waste water from dyestuff to 5-10, stir when 3000-5000 rev/min
24-48h, stands and is filtered to remove the adsorbent being adsorbed with methylene blue dye, i.e. eliminate in waste water
Methylene blue dye.
The processing method of a kind of methylene blue dye wastewater the most as claimed in claim 1, its feature exists
In, in step (1), described improved silica adsorbent is that aza macrocyclic ligands passes through nucleophilic displacement of fluorine
The meso-porous titanium dioxide silicon face of chloro functionalization, the ring skeleton of described aza macrocyclic ligands are modified in reaction
Upper nitrogen atom, the mesoporous silicon oxide of described chloro functionalization contains end chloro structure.
The processing method of a kind of methylene blue dye wastewater the most as claimed in claim 1, its feature exists
In, in step (1), described aza macrocyclic ligands is Isosorbide-5-Nitrae, 7,10-tetraazacyclododecanands, Isosorbide-5-Nitrae, 8,11-
Tetraazacyclododecane tetradecane, 1,4,8,12-tetraazacyclododecane pentadecane, 1,4,7,10,13-five-nitrogen heterocyclic 15
One in alkane, 1,4,7,10,13,16-hexanitrogen heterocycle octadecane.
The processing method of a kind of methylene blue dye wastewater the most as claimed in claim 1, its feature exists
In, in step (1), described organic solvent is the one in oxolane, acetonitrile, toluene, organic
Solvent uses front metallic sodium and benzophenone to carry out Non-aqueous processing.
The processing method of a kind of methylene blue dye wastewater the most as claimed in claim 1, its feature exists
In, in step (1), the consumption of described organic solvent is the mesoporous dioxy of every 1-3g chloro functionalization
SiClx uses 200-400ml.
The processing method of a kind of methylene blue dye wastewater the most as claimed in claim 1, its feature exists
In, in step (1), aza macrocyclic ligands, potassium iodide, potassium carbonate, mesoporous the two of chloro functionalization
The mass ratio of silicon oxide is: (2-5): (1.5-3.5): (6-11): (1-1.2).
The processing method of a kind of methylene blue dye wastewater the most as claimed in claim 1, its feature exists
In, in step (2), the concentration of described methylene blue dye wastewater is 500-1200mg/L.
The processing method of a kind of methylene blue dye wastewater the most as claimed in claim 1, its feature exists
In, in step (2), the consumption of described improved silica adsorbent is that every liter of methylene blue dye gives up
Water adds improved silica adsorbent 0.5-0.8g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610318660.3A CN105948155A (en) | 2016-05-12 | 2016-05-12 | Treatment method of methylene blue dye waste water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610318660.3A CN105948155A (en) | 2016-05-12 | 2016-05-12 | Treatment method of methylene blue dye waste water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105948155A true CN105948155A (en) | 2016-09-21 |
Family
ID=56911526
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610318660.3A Withdrawn CN105948155A (en) | 2016-05-12 | 2016-05-12 | Treatment method of methylene blue dye waste water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105948155A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108217813A (en) * | 2018-01-16 | 2018-06-29 | 广西师范学院 | The method of dyestuff methylene blue in sial composite oxides absorption water |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013066489A1 (en) * | 2011-11-04 | 2013-05-10 | Ppg Industries Ohio, Inc. | Precipitated silica sorbents |
| CN104353411A (en) * | 2014-11-19 | 2015-02-18 | 上海电力学院 | Preparation method of water treatment strong adsorbent |
| CN105413624A (en) * | 2015-12-09 | 2016-03-23 | 中国科学院新疆理化技术研究所 | Preparation method for modified silicone absorption materials for treating anionic dye in waste water |
-
2016
- 2016-05-12 CN CN201610318660.3A patent/CN105948155A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013066489A1 (en) * | 2011-11-04 | 2013-05-10 | Ppg Industries Ohio, Inc. | Precipitated silica sorbents |
| CN104353411A (en) * | 2014-11-19 | 2015-02-18 | 上海电力学院 | Preparation method of water treatment strong adsorbent |
| CN105413624A (en) * | 2015-12-09 | 2016-03-23 | 中国科学院新疆理化技术研究所 | Preparation method for modified silicone absorption materials for treating anionic dye in waste water |
Non-Patent Citations (2)
| Title |
|---|
| M. MAKOWSKA-JANUSIK，ET AL: "Mesoporous Silica Functionalized by Cyclam-Metal Groups: Spectroscopic Studies and Numerical Modeling", 《JOURNAL OF INORGANIC AND ORGANOMETALLIC POLYMERS AND MATERIALS》 * |
| 张金花: "介孔二氧化硅MCM-41的吸附性能与生物安全性研究", 《天津工业大学硕士学位论文》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108217813A (en) * | 2018-01-16 | 2018-06-29 | 广西师范学院 | The method of dyestuff methylene blue in sial composite oxides absorption water |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jiang et al. | Effective dye purification using tight ceramic ultrafiltration membrane | |
| Tian et al. | Highly efficient removal of both cationic and anionic dyes from wastewater with a water-stable and eco-friendly Fe-MOF via host-guest encapsulation | |
| CN104492287B (en) | A kind of polymer porous film for inlaying molecular sieve with adsorption function | |
| Liu et al. | A heteropore covalent organic framework for adsorptive removal of Cd (II) from aqueous solutions with high efficiency | |
| CN112679731B (en) | Covalent organic framework material containing sulfonic acid group and preparation and application thereof | |
| CN107486130A (en) | Prussian-blue takes off the application in ammonium material preparation method and the de- ammonium of sewage | |
| CN105617981B (en) | The application in the treatment of waste water of the method for modifying of a kind of meerschaum and modified meerschaum | |
| CN109225138A (en) | The modified activated carbon and preparation method thereof of AOCs in a kind of efficient absorption PTA waste water | |
| CN104759263B (en) | A kind of multi-walled carbon nano-tubes doping salicylic acid is blended the preparation method of blotting membrane | |
| Zhang et al. | Ball-milled biochar incorporated polydopamine thin-film composite (PDA/TFC) membrane for high-flux separation of tetracyclic antibiotics from wastewater | |
| CN112774637B (en) | Preparation method and application of magnetic carboxyl functionalized covalent organic framework adsorbent with core-shell structure | |
| Luo et al. | Glycidol-functionalized macroporous polymer for boron removal from aqueous solution | |
| CN104324690A (en) | Magnetic two-peak mesoporous carbon containing iron-nickel double metals, preparation method and application thereof | |
| WO2022193674A1 (en) | Magadiite/polypyrrole adsorption material for treating rhodamine b wastewater and preparation method and application of magadiite/polypyrrole adsorption material | |
| CN106824136A (en) | A kind of adsorbent for Industrial Wastewater Treatment and preparation method thereof | |
| CN110449132A (en) | A kind of preparation method and applications of modified carbon nano-tube adsorbent | |
| Zhang et al. | Evaluation of functional group content of N-methylimidazolium anion exchange resin on the adsorption of methyl orange and alizarin red | |
| CN109908870A (en) | A kind of novel lattice vacancy HKUST-1 adsorbent and its preparation method and application | |
| CN105883804A (en) | Preparation method of porous carbon nanomaterial for adsorbing methylene blue | |
| CN112979977A (en) | For CO2Trapped bimetallic MOFs material, preparation method and application | |
| CN106943995A (en) | A kind of modified clinoptilolite and preparation method and remove waste water in Pb ions application | |
| CN105948155A (en) | Treatment method of methylene blue dye waste water | |
| CN104069683B (en) | A kind of nano-metal-oxide ferrum, aluminum, the composite modified quartz sand filter media of titanium and preparation method thereof | |
| CN103587003A (en) | Resource recycling method of waste polymeric microfiltration/ultrafiltration membrane | |
| CN104162409B (en) | A kind of effective raising active carbon is to the method for modifying of micro-ammonia absorption property |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20160921 |