CN103357416A - Preparation method of supported iron-molybdate catalyst and application of catalyst to degradation of dye wastewater - Google Patents
Preparation method of supported iron-molybdate catalyst and application of catalyst to degradation of dye wastewater Download PDFInfo
- Publication number
- CN103357416A CN103357416A CN2012100808118A CN201210080811A CN103357416A CN 103357416 A CN103357416 A CN 103357416A CN 2012100808118 A CN2012100808118 A CN 2012100808118A CN 201210080811 A CN201210080811 A CN 201210080811A CN 103357416 A CN103357416 A CN 103357416A
- Authority
- CN
- China
- Prior art keywords
- molybdate
- catalyst
- iron
- supported iron
- ammonium molybdate
- 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
Images
Abstract
The invention relates to a preparation method of a supported iron-molybdate catalyst and an application of the supported iron molybdate catalyst to the degradation of dye wastewater. The supported iron-molybdate solid acid catalyst is synthesized from such raw materials as ammonium molybdate, ferric nitrate, diatomaceous earth, zeolite and a molecular sieve by adopting an aqueous precipitation method. The synthesis method of the supported iron-molybdate solid acid catalyst comprises the following steps of mixing a carrier with a solution of ammonium molybdate fully, adjusting the pH value of a medium by using aqueous ammonia until the medium is weakly alkaline; and dropwise adding a solution of ferric nitrate into the solution of ammonium molybdate, stirring the two solutions fully, ageing, filtering, washing, drying, and calcining in a muffle furnace for 2 hours at the temperature of 550 DEG C. The supported iron-molybdate solid acid catalyst can be used for degrading the methylene-blue simulated wastewater and the turquoise blue real wastewater quickly and effectively without adjusting the pH value of the dye and generating iron sludge, thus reagents are saved, and the separation becomes easy. The supported iron-molybdate solid acid catalyst can be recycled.
Description
Technical field
The present invention relates to a kind of application of synthetic and this catalyst in the Fenton-like reaction of solid acid catalyst.Relate to technically the fields such as inorganic synthetic chemistry and sewage disposal.
Background technology
The Fenton method is a kind of efficient, economic high-level oxidation technology in the organic pollutant degradation.Traditional Fenton method is a kind of employing H
2O
2Be oxidant, Fe
2+Homogeneous catalysis oxidizing process for catalyst.Under acid condition, H
2O
2The OH that produces has higher oxidation-reduction potential, and the rapidly pollutant in the oxidized waste water and non-selectivity can make to be difficult to biodegradable larger molecular organics in the waste water and to be cracked into the small organic molecule that is easy to be degraded by microorganisms, and perhaps permineralization is CO
2And H
2O
2, thereby homogeneous phase Fenton method has a wide range of applications in wastewater treatment.But, some shortcomings that homogeneous phase Fenton method exists so that its range of application be very limited: reaction will be carried out under the environment of pH ≈ about 3, the pH value that needs to regulate waste water before and after the reaction, need to expend a large amount of bronsted lowry acids and bases bronsted lowries, water outlet is because containing a large amount of iron ion Show Colors, and iron ion is difficult to reclaim and easily produce secondary pollution.Therefore exploitation can become study hotspot for the solid acid catalyst of catalyzing hydrogen peroxide degradable organic pollutant under nearly neutral environment.Result of study in recent years shows: solid acid catalyst can make the degradation reaction of waste water carry out under nearly neutral environment, in addition acid adding or alkali; Catalyst is easy to separate, and can repeatedly reuse, and reduces sludge quantity, makes more clean environment firendly of course of reaction.Therefore, by solid acid catalyst and H
2O
2The heterogeneous Fenton technology that consists of is expected to overcome the shortcoming of its existence when keeping the method high efficiency, economy.
Molybdate belongs to a branch of polyoxometallate, molybdate owing to have high-ratio surface and surface energy, many active sites, high selectivity gets more and more people's extensive concerning, be subject to extensive concern aspect luminescence generated by light and the catalysis, particularly metal molybdate has had a lot of reports as the catalyst of hydro carbons Selective Oxidation, and also fewer in the application study of field of waste water treatment.
The particle surface current potential is zero when solution reaches certain pH value, and this specific pH value is isoelectric point.Solid acid catalyst with low isoelectric point, the acidity on its surface is stronger, catalytic activity is higher.It is reported that many molybdenum systems that contain have lower isoelectric point, such as 10wt.%MoO
3/ Al
2O
3, 7.6wt.%MoO
3/ ZrO
2And 0.5wt.%Mo/SiO
2Isoelectric point be respectively 3.7,2.5,2.9.And iron molybdate Fe
2(MoO4)
3Isoelectric point be 2.9, have more intense surface acidity, and this material has good stability, be expected to become the solid acid catalyst of function admirable, realize the degraded of waste water under nearly neutral environment.
In addition, if catalyst fines is directly applied to the degraded of aqueous dye solutions, the suspension system of then disperseing exists and is difficult to separate and reclaim, the easy shortcoming such as cohesion, so that poor reproducibility, running cost is higher.Therefore the immobilized and integrated reaction and separation of catalyst becomes one of challenging problem in the field of heterogeneous catalysis.The present invention is directed to this shortcoming, iron molybdate is carried on porous diatomite, molecular sieve and the zeolite, increased the specific area of catalyst, carrier acts synergistically with iron molybdate, has improved catalytic activity and the settleability of iron molybdate.
The method of synthetic molybdate has a variety of, and is wherein common with the precipitation method and hydro-thermal method such as solid phase method, aqueous phase precipitation method, hydro-thermal method, sol-gal process, ultrasonic method etc., and this patent adopts simple aqueous phase precipitation method successfully to synthesize ultra micro rice iron molybdate.
Summary of the invention
The object of the invention is to solve the difficulty that prior art runs into, adopt the synthetic highly active iron molybdate solid acid catalyst of aqueous phase precipitation method, to realize the degraded of waste water from dyestuff under nearly neutral environment.
In acidity, neutrality and weak alkaline medium, ammonium molybdate and ferric nitrate are mixed according to a certain ratio, generate the iron molybdate precipitation, with this washing of precipitate, drying, roasting, namely be worth the iron molybdate catalyst.
Reaction equation is as follows: 3Mo
7O
24 6-+ 2Fe
3+=Fe
2(MoO
4)
3↓
Technical scheme of the present invention is as follows:
1. the preparation of iron molybdate
Amount ratio according to certain takes by weighing respectively ammonium molybdate and ferric nitrate solid, prepares certain density ammonium molybdate and iron nitrate solution.
In ammonium molybdate solution, add ammoniacal liquor, regulate pH value to solution and be alkalescent.Iron nitrate solution is dropwise joined in the above-mentioned mixed liquor, and the vigorous stirring certain hour gets yellow-green precipitate under the room temperature, filters, with distilled water washing, drying, high-temperature calcination in Muffle furnace.
2. the preparation of solid-carrying type iron molybdate
Carrier diatomite, zeolite or molecular sieve are carried out preliminary treatment, i.e. washing, suction filtration, drying, cooling, for subsequent use.
Amount ratio according to certain takes by weighing respectively ammonium molybdate and ferric nitrate solid, prepares certain density ammonium molybdate and iron nitrate solution.
In ammonium molybdate aqueous solution, add a certain amount of diatomite, stir to get suspension, add ammoniacal liquor and regulate the pH value to alkalescent.Certain density iron nitrate aqueous solution is dropwise joined in the above-mentioned mixed liquor, and the vigorous stirring certain hour gets precipitation under the room temperature, filters, with distilled water washing, drying, high-temperature calcination in Muffle furnace.
3. catalytic degradation
In small beaker, add a certain amount of dye solution and a certain amount of catalyst, after premixed reaches adsorption equilibrium, add hydrogen peroxide.In the catalytic degradation experimentation, behind every certain interval of time, take out part solution, catalyst granules is removed in centrifugal filtration, then with the variation of spectrophotometer monitoring absorbance, tries to achieve the degradation rate of different time.Survey the COD value of different degradation times with the quick oven method.
4. the regeneration of solid catalyst
After the catalysis experiment finishes, filter, with filtrate and catalyst separation, water and ethanol is washing catalyst precipitation several times successively, and gained is deposited in 105 ℃ of dryings, can reuse.
Advantage of the present invention:
1. building-up process is simple, and is pollution-free.
2. it is little to prepare catalyst granules, and specific surface is large, and catalytic efficiency is high.
2. can in pH 2~9 scopes, realize the degraded of dyestuff, need not add acid-base accommodation pH, not produce iron mud.
3. catalyst is reusable.
Description of drawings
Fig. 1 is the XRD figure of non-loaded iron molybdate.
Fig. 2 is the SEM figure of non-loaded iron molybdate.
Fig. 3 is the SEM figure of tripolite loading type iron molybdate.
The specific embodiment
Be further described when of the present invention below in conjunction with embodiment.
Embodiment 1: the preparation of non-loaded iron molybdate catalyst
Ratio n according to amount of substance
Mo: n
Fe=2: 1, take by weighing respectively ammonium molybdate and ferric nitrate solid, prepare certain density ammonium molybdate and iron nitrate solution.
With 8~12mL 2mol/L ammoniacal liquor, add in the 100mL ammonium molybdate aqueous solution, regulate pH value to solution and be alkalescent.The 100mL iron nitrate aqueous solution is dropwise joined in the mixed liquor, and vigorous stirring 2h gets precipitation under the room temperature, filter, and with distilled water washing, 105 ℃ of dryings, 550 ℃ of calcining 2h in Muffle furnace.
Embodiment 2: the preparation of tripolite loading iron molybdate catalyst
Behind diatomite 30g washing suction filtration 3 times, in 130 ℃ of dry 1h, according to m
Carrier: m
Catalyst=4: 1 relation, it is for subsequent use to get 12g diatomite.
Ratio n according to amount of substance
Mo: n
Fe=2: 1, take by weighing respectively ammonium molybdate and ferric nitrate solid, prepare certain density ammonium molybdate and iron nitrate solution.
With 8~12mL 2mol/L ammoniacal liquor, be added in the diatomaceous suspension of 100mL ammonium molybdate and 12g, stir.The 100mLmol/L iron nitrate solution is dropwise joined in the above-mentioned mixed liquor, and vigorous stirring 2h gets precipitation under the room temperature, and precipitation ageing 3 hours is filtered, with the distilled water washing, and 105 ℃ of dry 12h, 550 ℃ of calcining 2h in Muffle furnace.
Embodiment 3: the preparation of zeolite-loaded iron molybdate catalyst
With zeolite (80 orders, 100 orders, 120 orders) washing, the oven dry of different size, for subsequent use.
Ratio n according to amount of substance
Mo: n
Fe=2: 1, take by weighing respectively ammonium molybdate and ferric nitrate solid, prepare certain density ammonium molybdate and iron nitrate solution.
With 8~12mL 2mol/L ammoniacal liquor, be added in the suspension of 100mL ammonium molybdate and 12g zeolite, stir.The 100mL iron nitrate solution is dropwise joined in the mixed liquor, and vigorous stirring 2h gets precipitation under the room temperature, and precipitation ageing 3 hours is filtered, with the distilled water washing, and 105 ℃ of dry 12h, 550 ℃ of calcining 2h in Muffle furnace.
Embodiment 4: the preparation of molecular sieve carried iron molybdate catalyst
Ratio n according to amount of substance
Mo: n
Fe=2: 1, take by weighing respectively ammonium molybdate and ferric nitrate solid, prepare certain density ammonium molybdate and iron nitrate solution.
With 8~12mL 2mol/L ammoniacal liquor, be added in the suspension of 100mL ammonium molybdate and 12g molecular sieve (model is ZSM-5), stir.The ferric nitrate of 100mL is dropwise joined in the mixed liquor, and vigorous stirring 2h gets precipitation under the room temperature, and precipitation ageing 3 hours is filtered, with the distilled water washing, and 105 ℃ of dry 12h, 550 ℃ of calcining 2h in Muffle furnace.
Embodiment 5: the catalytic degradation of methylene blue simulated wastewater
In the 100mL small beaker, add methylene blue solution and the 0.25g tripolite loading iron molybdate catalyst of 60mL 100mg/L, behind the premixed 30min, add hydrogen peroxide 0.10mL, reaction 20min.In the catalytic degradation experimentation, behind every certain interval of time, take out part solution, catalyst granules is removed in centrifugal filtration, then uses the absorbance of spectrophotometer test dye, obtains degradation rate.Color takes off to the greatest extent substantially during 20min, according to percent of decolourization=(A
0-A)/A
0, the colour removal rate is 99% when can be calculated reaction 20min.The COD clearance that records this moment with the quick oven method is 68%.
Embodiment 6: the degraded of emerald green blue dyestuff actual industrial waste water
In the 100mL small beaker, add the blue waste water of certain density kingfisher and 0.25g support type diatom soil load iron molybdate catalyst, behind the premixed 30min, add hydrogen peroxide 0.10mL, reaction 20min, color takes off to the greatest extent substantially.The clearance that records COD this moment with the quick oven method is 60%.
Claims (5)
1. the synthetic method of a solid-carrying type iron molybdate acidic catalyst.It is characterized in that following experimental procedure:
(1) according to certain amount ratio, takes by weighing respectively ammonium molybdate and ferric nitrate solid, prepare certain density ammonium molybdate and iron nitrate solution.
(2) carrier diatomite, zeolite or molecular sieve are carried out preliminary treatment, i.e. washing, suction filtration, drying, cooling, for subsequent use.
(3) prepare certain density ammonium molybdate aqueous solution, add a certain amount of diatomite, stir to get suspension, add ammoniacal liquor and regulate the pH value to alkalescent.
(4) certain density iron nitrate aqueous solution is dropwise joined in the above-mentioned mixed liquor, the vigorous stirring certain hour gets precipitation under the room temperature, filters, with distilled water washing, drying.
(5) high-temperature calcination in Muffle furnace.
2. according to the synthetic method of support type iron molybdate catalyst claimed in claim 1, it is characterized in that in the described step (2): ammonium molybdate is as the molybdenum source, and ferric nitrate is as source of iron, the ratio n of the two amount of substance
Mo: n
Fe=2: 1.The consumption of carrier is 12g, and the ratio of carrier and catalyst is 4: 1 in the product.
3. according to the synthetic method of support type iron molybdate catalyst claimed in claim 1, it is characterized in that reaction medium is alkalescent, the concentration of ammoniacal liquor is 2mol/L, and consumption is 8~10mL.
4. according to the synthetic method of support type iron molybdate catalyst claimed in claim 1, after it is characterized in that washing of precipitate, filtering, 105 ℃ of dry 12h, 550 ℃ of calcining 2h in Muffle furnace.
5. when being applied to the degraded of methylene blue simulated wastewater and emerald green blue actual waste water according to support type iron molybdate catalyst claimed in claim 1, need not regulate the pH value, directly realize fast degradation.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2012100808118A CN103357416A (en) | 2012-03-26 | 2012-03-26 | Preparation method of supported iron-molybdate catalyst and application of catalyst to degradation of dye wastewater |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2012100808118A CN103357416A (en) | 2012-03-26 | 2012-03-26 | Preparation method of supported iron-molybdate catalyst and application of catalyst to degradation of dye wastewater |
Publications (1)
Publication Number | Publication Date |
---|---|
CN103357416A true CN103357416A (en) | 2013-10-23 |
Family
ID=49360174
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2012100808118A Pending CN103357416A (en) | 2012-03-26 | 2012-03-26 | Preparation method of supported iron-molybdate catalyst and application of catalyst to degradation of dye wastewater |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN103357416A (en) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104357875A (en) * | 2014-10-31 | 2015-02-18 | 上海应用技术学院 | Method for preparing iron molybdate by using cationic membrane electrolysis process |
CN104388681A (en) * | 2014-11-14 | 2015-03-04 | 金堆城钼业股份有限公司 | Treatment method for recycling high-concentration molybdenum calcine washing wastewater |
CN104445410A (en) * | 2014-11-14 | 2015-03-25 | 金堆城钼业股份有限公司 | Method for washing commercial molybdenum oxide |
CN105056965A (en) * | 2015-07-20 | 2015-11-18 | 长安大学 | Biological carbon sphere supported FeMoO4 Fenton catalyst, preparation method and application |
CN105906027A (en) * | 2016-06-11 | 2016-08-31 | 华南理工大学 | Method for degrading organic wastewater through excitation of peroxysulphate under effect offerrous molybdate |
CN111320208A (en) * | 2020-02-20 | 2020-06-23 | 华南理工大学 | Method for preparing POMs (polyoxymethylene) by photoinduced in-situ aggregation |
CN111644178A (en) * | 2020-05-28 | 2020-09-11 | 中交四航工程研究院有限公司 | Composite catalyst for degrading dye wastewater through electro-Fenton, and preparation method and application thereof |
CN112981991A (en) * | 2019-12-13 | 2021-06-18 | 苏州麻朵纺织科技有限公司 | Natural soaping agent and soaping method for blue vegetable dye dyed textiles |
CN114146681A (en) * | 2021-11-30 | 2022-03-08 | 广州东联环保科技有限公司 | Composite material for treating nitrogen-containing sewage and preparation method and application thereof |
CN114618509A (en) * | 2022-03-21 | 2022-06-14 | 上海尼普敦环境科技有限公司 | Carbon dioxide hydrogenation reduction catalyst and preparation method thereof |
CN115532274A (en) * | 2022-10-13 | 2022-12-30 | 北京林业大学 | Z-shaped Fe 2 (MoO 4 ) 3 /MoO 3 Heterojunction visible-light-driven photocatalyst and preparation method and application thereof |
CN115814808A (en) * | 2021-10-27 | 2023-03-21 | 中国矿业大学 | Iron-molybdenum-doped hydrothermal carbon composite material, preparation method thereof and wastewater degradation method |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101628236A (en) * | 2009-08-03 | 2010-01-20 | 浙江理工大学 | Preparation method of kieselguhr load type compound photocatalyst with iron ions doped titanium dioxide |
-
2012
- 2012-03-26 CN CN2012100808118A patent/CN103357416A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101628236A (en) * | 2009-08-03 | 2010-01-20 | 浙江理工大学 | Preparation method of kieselguhr load type compound photocatalyst with iron ions doped titanium dioxide |
Non-Patent Citations (1)
Title |
---|
S.H. TIAN ET AL.,: "Degradation of acid orange II at neutral pH using Fe2(MoO4)3 as a heterogeneous Fenton-like catalyst", 《CHEMICAL ENGINEERING JOURNAL》 * |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104357875A (en) * | 2014-10-31 | 2015-02-18 | 上海应用技术学院 | Method for preparing iron molybdate by using cationic membrane electrolysis process |
CN104388681A (en) * | 2014-11-14 | 2015-03-04 | 金堆城钼业股份有限公司 | Treatment method for recycling high-concentration molybdenum calcine washing wastewater |
CN104445410A (en) * | 2014-11-14 | 2015-03-25 | 金堆城钼业股份有限公司 | Method for washing commercial molybdenum oxide |
CN105056965A (en) * | 2015-07-20 | 2015-11-18 | 长安大学 | Biological carbon sphere supported FeMoO4 Fenton catalyst, preparation method and application |
CN105906027A (en) * | 2016-06-11 | 2016-08-31 | 华南理工大学 | Method for degrading organic wastewater through excitation of peroxysulphate under effect offerrous molybdate |
CN112981991A (en) * | 2019-12-13 | 2021-06-18 | 苏州麻朵纺织科技有限公司 | Natural soaping agent and soaping method for blue vegetable dye dyed textiles |
CN111320208A (en) * | 2020-02-20 | 2020-06-23 | 华南理工大学 | Method for preparing POMs (polyoxymethylene) by photoinduced in-situ aggregation |
CN111644178A (en) * | 2020-05-28 | 2020-09-11 | 中交四航工程研究院有限公司 | Composite catalyst for degrading dye wastewater through electro-Fenton, and preparation method and application thereof |
CN115814808A (en) * | 2021-10-27 | 2023-03-21 | 中国矿业大学 | Iron-molybdenum-doped hydrothermal carbon composite material, preparation method thereof and wastewater degradation method |
CN114146681A (en) * | 2021-11-30 | 2022-03-08 | 广州东联环保科技有限公司 | Composite material for treating nitrogen-containing sewage and preparation method and application thereof |
CN114618509A (en) * | 2022-03-21 | 2022-06-14 | 上海尼普敦环境科技有限公司 | Carbon dioxide hydrogenation reduction catalyst and preparation method thereof |
CN115532274A (en) * | 2022-10-13 | 2022-12-30 | 北京林业大学 | Z-shaped Fe 2 (MoO 4 ) 3 /MoO 3 Heterojunction visible-light-driven photocatalyst and preparation method and application thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103357416A (en) | Preparation method of supported iron-molybdate catalyst and application of catalyst to degradation of dye wastewater | |
CN110437458B (en) | Reusable Fenton-like catalyst [ NH ]2-MIL-101(Fe)]Preparation and application methods of | |
CN102225792B (en) | Magnetic oxide supporting active carbon catalytic microwave degradation method of surfactant | |
CN102500356A (en) | Preparation method for carbon nanotube-nano-bismuth vanadate composite photocatalyst | |
CN104415754A (en) | Synthesizing method of immobilized multi-phase Fenton catalyst | |
CN104001496A (en) | BiVO4 nanosheet composite photocatalyst, and preparation method and application thereof | |
CN102489290A (en) | Preparation method of nano bismuth vanadate photocatalyst loaded on active carbon fiber | |
CN102773105B (en) | Supported bismuth tungstate photocatalyst and preparation method thereof | |
CN103357413A (en) | Method for preparing binary-oxide composite solid acid catalyst and method for treating degradation-resistant organic pollutants by catalyzing oxidization of H2O2 | |
CN105964308A (en) | Preparation method of carrier material for catalyst for sewage treatment | |
CN101318749B (en) | Photocatalysis oxidation method for treating waste water of anthraquinone dye | |
CN102407128B (en) | Preparation method and application of Gd, Pr or Yb doped fenton catalyst | |
CN103846099B (en) | A kind of support type polyoxometallate and preparation method thereof | |
CN107684926B (en) | Photocatalyst for treating dye in high-salinity wastewater and preparation method thereof | |
CN104549385A (en) | Graphene oxide composite FePO4 heterogeneous visible light Fenton catalyst and preparation method thereof | |
CN102489291B (en) | Method for preparing expanded graphite load nanometer bismuth vanadate photochemical catalyst | |
CN103157504A (en) | Novel mesoporous Fe2O3-SnO2-ZSM-5 solid acid prepared by impregnation method, and application study for catalyzing degradation of organic pollutants | |
CN102513091A (en) | Preparation method for graphene self-assembled nanometer bismuth vanadate photocatalyst | |
CN103990477B (en) | The preparation method of a kind of silver orthophosphate/silver vanadate composite photo-catalyst | |
CN107473326B (en) | Acidic TiO2Combined method for degrading dye wastewater by hydrosol regeneration aerobic granular sludge | |
CN103803695A (en) | Method for Fenton-like light-catalyzed reaction system for zero-valent iron and TiO2 photocatalytic coupling | |
CN103055844B (en) | Preparation method for catalyst composition for efficiently treating methylene blue dye wastewater | |
CN104028287A (en) | Preparation method of magnesium ferrite/silver phosphate compound photocatalyst | |
CN106311217B (en) | Preparation method of activated carbon functionalized tungsten oxide | |
CN104437468A (en) | Catalyst composition for treating wastewater containing methylene blue dye as well as preparation method and application of catalyst composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C05 | Deemed withdrawal (patent law before 1993) | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20131023 |