CN103695655A - Method for recycling precious metals from stainless steel acid pickling sludge - Google Patents
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Abstract
The invention provides a method for recycling precious metals from stainless steel acid pickling sludge, belonging to the field of non-ferrous metallurgy and waste utilization. The method mainly comprises the following steps: 1) thickening and filter pressing; 2) leaching; 3) iron removal and filter pressing; 4) P204 extraction: filtering and clarifying the mother liquid and feeding into a P204 extraction box; performing continuous saponification and counter-current extraction, and separating out an organic phase A and a filtrate A; extracting to remove impurity elements such as Zn, Cu, Mn, Ca and the like; 5) P507 extraction: feeding the filtrate A separated by the step 4) into a P507 extraction box, performing continuous saponification and counter-current extraction in the extraction box at room temperature, and separating out an organic phase B and a filtrate B; performing reverse extraction of the organic phase B by use of dilute hydrochloric acid to obtain a high-purity cobalt chloride solution, and enriching nickel in the filtrate B by use of dilute sulphuric acid to obtain a high-purity high-concentration nickel sulfate solution. The method provided by the invention finally obtains products such as copper sulfate, nickel sulfate, high-purity nickel, cobalt oxalate and the like, realizes resource recycling of precious metals in sludge, and has the comprehensive benefits of economic benefits, environmental benefits and social benefits.
Description
Technical field
the invention belongs to nonferrous metallurgy and recycling field, be specifically related to a kind of method that reclaims precious metal from acid-washing stainless steel mud.
Background technology
In producing stainless steel process, for obtaining good surface quality, need process through the pickled surface such as persulfuric acid, hydrofluoric acid before cold rolling, thereby produce the spent pickle liquor that contains in a large number the hazardous and noxious substances such as cobalt, nickel, copper.Most stainless steel enterprises are all used lime neutralization precipitation method to process, and the plurality of heavy metal mud of generation, belongs to industrial hazard waste.Heavy Metals in Sludge exists with forms such as carbonate, precipitations of hydroxide, if not treated, arbitrarily stacks or simple landfill, and heavy metal very easily leaches and is diffused in physical environment, and soil and surface water are produced to great effect, is detrimental to health.
Current domestic sludge creation producer mainly exports landfill to the processing mode of this metal sludge, great majority are deposited in refuse landfill, and this mode is cured the symptoms, not the disease, and not only take a large amount of soils, and serious environment pollution, bring very large harm to the mankind's living environment.
Except landfill, for sludge treatment, external method also has: soil utilization (for agroforestry), throw aside ocean and burn.First kind of way, soil utilization, can cause secondary pollution by the direct soil utilization of pickling mud, inadvisable; The second way, processes pickling mud row sea, can pollute ocean, inadvisable; The third mode, sludge incineration, this treatment process is high with state's accounting example such as Japanese, German, Austrian, general Large Sewage Treatment Plant mud is innoxious by burning, the heat energy recoverable producing, reducing sludge volume minimizing degree is very high, but subject matter is burning, investment is huge, operational administrative is complicated, and energy consumption and running cost are all very high.Meanwhile, burn the secondary pollution that the toxic gas producing can cause air.
Summary of the invention
The invention provides a kind of method that reclaims precious metal from acid-washing stainless steel mud, can from the acid-washing stainless steel mud of low taste, extract the noble metal of high added value, extract copper sulfate, single nickel salt, high purity nickel and cobalt oxalate, thereby effectively realized economic worth; The present invention is simple to operate, raw material is universal, and production cost is lower, obvious economic; The present invention fully utilizes incidental spent acid in pickling mud, has reduced the pollution of environment when having saved cost.
Technical solution of the present invention is as follows:
A method that reclaims noble metal from acid-washing stainless steel mud, the method comprises the following steps:
1) dense, press filtration: low-grade acid-washing stainless steel mud is sent into center driving high-efficiency concentrator, and to carry out mud dense, and the mud after dense is carried out to processed;
2) leach: continue to add mass concentration 98% sulphuric acid soln in mud, regulate pH value to 1.5～1.7, by steam heating, control temperature under 70～90 ℃ of conditions, stir 4～8h(reach leach object completely); Again by pressure filter press filtration separatory;
3) deironing press filtration: add oxidant hydrogen peroxide that the ferrous iron in solution is oxidized to ferric iron in filtrate, after question response is complete, by obtaining mother liquor after press filtration;
4) P204 extraction: mother liquor after filtration, be sent in P204 extraction box after clarification, is isolated organic phase A and filtrate A after continuous saponification and counter-current extraction; Through extraction, remove wherein the impurity elements such as Zn, Cu, Mn, Ca;
5) P507 extraction: the filtrate A of step 4 separation enters in P507 extraction box, at room temperature continuous saponification in extraction box, counter-current extraction, separated organic phase B and liquor B; Organic phase A is first used the dilute hydrochloric acid back extraction of 6mol/L to obtain highly purified cobalt chloride solution, and liquor B is carried out enrichment with 0.5mol/l dilute sulphuric acid to nickel again, obtains high-purity high-concentration nickel sulfate solution.
Further design of the present invention is:
Step 5 is obtained to high-purity high-concentration nickel sulfate solution and pump into vacuum-evaporation appts, liquid after evaporation is put into cooling crystallization machine and carry out crystallisation by cooling, then put into horizontal centrifuge and carry out centrifuge dripping, obtain crystalline sulfuric acid nickel product.
The high density high-purity sulphuric acid nickel solution that step 5 is obtained adds additive boric acid to boric acid concentration 5g/L, then regulates pH to 2～2.5, and this solution is added to electrolysis in electro deposited nickel equipment, negative electrode output high-purity nickel; Anolyte returns to P507 extraction box.
In the high-purity cobalt chloride solution of high density obtaining to step 5, add ammonium oxalate to regulate pH value to 1.0～1.5, control 36～42 ℃ of temperature, solution is to substantially colourless, and through centrifugation, 90 ℃ of pure water washings (are used AgNO
3solution detects washing lotion without white precipitate), obtain wet cobalt oxalate, then in 120～130 ℃ through flash distillation, obtain product cobalt oxalate.
The organic phase A that step 4 obtains adopts segmentation back extraction to obtain copper-bath with dilute sulphuric acid, copper-bath is pumped in vacuum-evaporation appts and evaporated, 40～50 ℃ of vaporization temperatures product, (product proportion is at 1.5～1.6 g/cm3), when temperature is down to 28～35 ℃, product is sent into horizontal centrifuge and carry out centrifuge dripping, obtain cupric sulfate crystals.
In step 1), in thickener, all add the flocculation agent polyacrylamide PAM that accounts for mud 0.3 ‰, filter cake moisture content is lower than 12%.
In step 3) deironing pressure-filtering process, first regulate pH value to adopting sodium carbonate, sulfuric acid or sodium sulfate to 3.0～3.5(), temperature, under 25 ℃ of conditions, then adds oxygenant, then adds sodium carbonate to regulate pH value to remain on 3.0～3.5, press filtration after reaction.
In step 4 and step 5, extraction agent is selected respectively P204 and P507, and thinner is all selected 260# solvent oil.
beneficial effect of the present invention:
1. the present invention can extract the noble metal of high added value from the acid-washing stainless steel mud of low taste, has extracted copper sulfate, single nickel salt, high purity nickel and cobalt oxalate, thereby has effectively realized economic worth;
2. the present invention is simple to operate, raw material universal, and production cost is lower, obvious economic;
3. the present invention fully utilizes incidental spent acid in pickling mud, has reduced the pollution of environment when having saved cost, solves to a certain extent the problem of shortage of resources.
Accompanying drawing explanation
Fig. 1 is processing technological flow schematic diagram of the present invention.
Embodiment
embodiment mono-:
Raw material: get low-grade stainless steel sludge 5000kg, Ni 0.8% wherein, Co 0.03%, Cu0.5%, by the processing step described in Fig. 1, concrete steps are as follows:
1, first mud is passed into and in center driving high-efficiency concentrator, carries out densely, in thickener, add the flocculation agent polyacrylamide (PAM) that accounts for mud weight 3 ‰, after through 100m2 pressure filter, press filtration makes the water ratio 11% of filter cake.
2, to adding mass concentration in filter cake, be 98% the vitriol oil, after making pH value reach 1.6, maintain the temperature at 90 ℃, after 80rpm stirring velocity uniform stirring 4h, by the press filtration of 100m2 pressure filter, separating filtrate.The content of iron in determination and analysis filtrate.
3, filtrate at ambient temperature, with soda ash (or Sodium sulfate anhydrous.min(99)), regulate, in the situation that in maintenance filtrate, pH is 3.5, adding mass concentration is that 30% hydrogen peroxide (hydrogen peroxide add-on be about filtrate gross weight 0.5～1%) is oxidized to ferric iron by ferrous iron amount by ferrous iron, then add sodium carbonate regulating solution to make pH value remain on 3.5, at this moment, in solution, can generate the precipitation of yellow modumite, continue to use pressure filter press filtration, retain filtrate.
4, after filtrate is filtered, clarified, pass into P204 extraction box, extraction agent is selected P204, and thinner is 260# solvent oil.After continuous saponification and counter-current extraction, isolate organic phase A and filtrate A; Through extraction, remove wherein the impurity elements such as Zn, Cu, Mn, Ca;
5, organic phase A adopts segmentation back extraction to obtain copper-bath with 1.25mol/l dilute sulphuric acid, copper-bath is pumped into evaporation in vacuum-evaporation appts (vacuum tightness-0.1MP), 40～50 ℃ of vaporization temperatures product, (product proportion is at 1.5～1.6 g/cm3), when temperature is down to 28～35 ℃, product is sent into horizontal centrifuge and carry out centrifuge dripping, obtain 56.5kg cupric sulfate crystals.
6, filtrate A enters P507 extraction box, continuous saponification, counter-current extraction, and extraction agent P507, thinner is selected 260# solvent oil.Separated organic phase B and the liquor B of obtaining; Organic phase A utilizes the dilute hydrochloric acid back extraction of 6mol/L to obtain high-purity cobalt chloride solution.Liquor B utilizes the enrichment of 0.5mol/l dilute sulphuric acid to obtain high-purity sulphuric acid nickel solution.
7, high-purity sulphuric acid nickel solution directly enters in electro deposited nickel equipment, adds additive boric acid, to the concentration of boric acid in high-purity sulphuric acid nickel solution be 5g/L, with dilute sulphuric acid regulator solution pH value to 2～2.5, negative electrode output high-purity nickel is 28kg.
High-purity cobalt chloride solution, by after adding ammonium oxalate to regulate pH value to reach 1.2, is controlled 36～42 ℃ of temperature, and solution is to substantially colourless, and through centrifugation, 90 ℃ of pure water washings (are used AgNO
3solution detects washing lotion without white precipitate), obtain wet cobalt oxalate, then through flash distillation (120～130 ℃ of temperature), obtain high-purity cobalt oxalate 3.11kg.
embodiment bis-:
Raw material: get low-grade stainless steel sludge 5000kg, Ni 0.9% wherein, Co 0.025%, and Cu0.8%, by the processing step described in Fig. 1.
1, first mud is passed into and in center driving high-efficiency concentrator, carries out densely, in dense engineering, add the flocculation agent polyacrylamide (PAM) that accounts for mud weight 3 ‰, after through 100m2 pressure filter, press filtration makes the water ratio 9% of filter cake.
2, add dense 98% vitriol oil that crosses of quality, after making pH value reach 1.5, maintain the temperature at 80～100 ℃, after the uniform stirring 6h with the speed of 80rpm, by the press filtration of 100m2 pressure filter, separating filtrate.Measure and analyze the content of iron in filtrate.
3, at ambient temperature, keeping adding in situation that in filtrate, pH is 3.2 mass concentration is that 30% hydrogen peroxide (hydrogen peroxide add-on be about filtrate gross weight 0.5～1%) is oxidized Fe element, add sodium carbonate to make pH remain on 3.2 later, at this moment, in solution, can generate the precipitation of yellow modumite, continue to use pressure filter press filtration, retain filtrate.
4, after filtrate is filtered, clarified, pass into P204 extraction box, extraction agent is selected P204, and thinner is 260# solvent oil.Recycling back extraction obtains copper-bath, and this solution obtains 87.5kg cupric sulfate crystals after transpiration cooling.
5, surplus solution enters P507 by utilizing the dilute hydrochloric acid back extraction of 6mol/L to obtain high-purity cobalt chloride solution, and surplus solution utilizes the enrichment of 0.5mol/l dilute sulphuric acid to obtain high-purity sulphuric acid nickel solution.High-purity sulphuric acid nickel solution directly enters in electro deposited nickel equipment, adds additive boric acid, to the concentration of boric acid in high-purity sulphuric acid nickel solution be 5g/L, with dilute sulphuric acid regulator solution pH value to 2～2.5, negative electrode output high-purity nickel is 35kg.
High-purity cobalt chloride solution, by add-on ammonium oxalate, after making pH value reach 1.5, is controlled 36～42 ℃ of temperature, and solution is to substantially colourless, and through centrifugation, 90 ℃ of pure water washings (are used AgNO
3solution detects washing lotion without white precipitate), obtain wet cobalt oxalate, then through flash distillation (120～130 ℃ of temperature), obtain high-purity cobalt oxalate 2.5kg.
embodiment tri-:
Raw material: get low-grade stainless steel sludge 5000kg, Ni 0.6% wherein, Co 0.05%, and Cu0.5%, by the processing step described in Fig. 1.
1, first mud is passed into and in thickener, carries out densely, in dense engineering, add the flocculation agent polyacrylamide (PAM) that accounts for mud weight 3 ‰, after through 100m2 pressure filter, press filtration makes the water ratio 12% of filter cake.
2, add dense 98% sulfuric acid that crosses of quality, after making pH value reach 1.5, maintain the temperature at 80 ℃, after the uniform stirring 8h with 80rpm speed, by the press filtration of 100m2 pressure filter.
3, at ambient temperature, keeping adding in situation that in filtrate, pH is 3.0 mass concentration is that 30% hydrogen peroxide (hydrogen peroxide add-on be about filtrate gross weight 0.5～1%) is oxidized Fe element, add sodium carbonate to make pH remain on 3.0 later, at this moment, in solution, can generate the precipitation of yellow modumite, continue to use pressure filter press filtration, retain filtrate.
4, after filtrate is filtered, clarified, pass into P204 extraction box, extraction agent is selected P204, and thinner is 260# solvent oil.Recycling back extraction obtains copper-bath, and this solution obtains 50kg cupric sulfate crystals after transpiration cooling.
5, surplus solution enters P507 by utilizing the dilute hydrochloric acid back extraction of 6mol/L to obtain high-purity cobalt chloride solution, and surplus solution utilizes the enrichment of 0.5mol/l dilute sulphuric acid to obtain high-purity sulphuric acid nickel solution.
6, high-purity sulphuric acid nickel solution directly enters in electro deposited nickel equipment, adds additive boric acid, to the concentration of boric acid in high-purity sulphuric acid nickel solution be 5g/L, with dilute sulphuric acid, regulator solution pH value to 2～2.5, negative electrode output high-purity nickel is 22.5kg.
High-purity cobalt chloride solution, by add-on ammonium oxalate, after making pH value reach 1.0, is controlled 36～42 ℃ of temperature, and solution is to substantially colourless, and through centrifugation, 90 ℃ of pure water washings (are used AgNO
3solution detects washing lotion without white precipitate), obtain wet cobalt oxalate, then through flash distillation (120～130 ℃ of temperature), obtain high-purity cobalt oxalate 5.6kg.
Claims (8)
1. from acid-washing stainless steel mud, reclaim a method for noble metal, the method comprises the following steps:
1) dense, press filtration: low-grade acid-washing stainless steel mud is sent into center driving high-efficiency concentrator, and to carry out mud dense, and the mud after dense is carried out to processed;
2) leach: continue to add mass concentration 98% sulphuric acid soln in mud, regulate pH value to 1.5～1.7, by steam heating, control temperature and stir 4～8h under 70～90 ℃ of conditions; Again by pressure filter press filtration separatory;
3) deironing press filtration: add oxidant hydrogen peroxide that the ferrous iron in solution is oxidized to ferric iron in filtrate, after question response is complete, by obtaining mother liquor after press filtration;
4) P204 extraction: mother liquor after filtration, be sent in P204 extraction box after clarification, is isolated organic phase A and filtrate A after continuous saponification and counter-current extraction; Through extraction, remove wherein the impurity elements such as Zn, Cu, Mn, Ca;
5) P507 extraction: the filtrate A of step 4 separation enters in P507 extraction box, at room temperature continuous saponification in extraction box, counter-current extraction, separated organic phase B and liquor B; Organic phase A is first used the dilute hydrochloric acid back extraction of 6mol/L to obtain highly purified cobalt chloride solution, and liquor B is carried out enrichment with 0.5mol/l dilute sulphuric acid to nickel again, obtains high-purity high-concentration nickel sulfate solution.
2. method according to claim 1, it is characterized in that: step 5 is obtained to high-purity high-concentration nickel sulfate solution and pump into vacuum-evaporation appts, liquid after evaporation is put into cooling crystallization machine and carry out crystallisation by cooling, then put into horizontal centrifuge and carry out centrifuge dripping, obtain crystalline sulfuric acid nickel product.
3. method according to claim 1, it is characterized in that: the high density high-purity sulphuric acid nickel solution that step 5 is obtained adds additive boric acid to boric acid concentration 5g/L, regulate again pH to 2～2.5, this solution is added to electrolysis in electro deposited nickel equipment, negative electrode output high-purity nickel; Anolyte returns to P507 extraction box.
4. method according to claim 1, it is characterized in that: in the high-purity cobalt chloride solution of high density obtaining to step 5, add ammonium oxalate to regulate pH value to 1.0～1.5, control 36～42 ℃ of temperature, solution is to substantially colourless, through centrifugation, 90 ℃ of pure water washings, obtain wet cobalt oxalate, again in 120～130 ℃ through flash distillation, obtain product cobalt oxalate.
5. method according to claim 1, it is characterized in that: the organic phase A that step 4 obtains adopts segmentation back extraction to obtain copper-bath with dilute sulphuric acid, copper-bath is pumped in vacuum-evaporation appts and evaporated, 40～50 ℃ of vaporization temperatures product, when temperature is down to 28～35 ℃, product is sent into horizontal centrifuge and carry out centrifuge dripping, obtain cupric sulfate crystals.
6. method according to claim 1, is characterized in that: in step 1, in thickener, all add the flocculation agent polyacrylamide PAM that accounts for mud 0.3 ‰, filter cake moisture content is lower than 12%.
7. method according to claim 1, is characterized in that: in step 3 deironing pressure-filtering process, first regulate pH value to 3.0～3.5, temperature, under 25 ℃ of conditions, then adds oxygenant, then adds sodium carbonate to regulate pH value to remain on 3.0～3.5, press filtration after reaction.
8. according to the arbitrary described method of claim 1-7, it is characterized in that: in step 4 and step 5, extraction agent is selected respectively P204 and P507, thinner is all selected 260# solvent oil.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104711427A (en) * | 2015-02-12 | 2015-06-17 | 江苏恒嘉再生资源有限公司 | Method for preparing and recovering sponge copper metal in pickling sludge |
| CN104711428A (en) * | 2015-02-12 | 2015-06-17 | 江苏恒嘉再生资源有限公司 | Method for preparing and recovering noble metal in pickling sludge |
| CN104745821A (en) * | 2015-02-12 | 2015-07-01 | 江苏恒嘉再生资源有限公司 | Method for recovering nickel and copper metals in acid pickling sludge |
| CN105567978A (en) * | 2016-01-28 | 2016-05-11 | 浙江新时代中能循环科技有限公司 | Method for recycling copper, zinc, cobalt and nickel from various kinds of nonferrous metal containing waste |
| CN107502757A (en) * | 2017-08-04 | 2017-12-22 | 浙江正道环保科技有限公司 | A kind of method of the reclaiming nickel sulfate from nickel bath slag and sludge |
| CN108570555A (en) * | 2018-05-03 | 2018-09-25 | 北京矿冶科技集团有限公司 | A method of directly producing LITHIUM BATTERY nickel sulfate from nickel cobalt enriched substance |
| CN109852794A (en) * | 2019-03-11 | 2019-06-07 | 西安蓝晓科技新材料股份有限公司 | A method of being used to prepare LITHIUM BATTERY nickel sulfate |
| GB2578645A (en) * | 2018-11-02 | 2020-05-20 | Darlow Lloyd & Sons Ltd | Method and apparatus for treating waste material |
| CN111285492A (en) * | 2019-12-31 | 2020-06-16 | 安徽珍昊环保科技有限公司 | Method for recovering heavy metal resources in stainless steel pickling wastewater neutralized sludge |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101618892A (en) * | 2009-07-31 | 2010-01-06 | 东南大学 | Recovery and comprehensive utilization method of heavy metals in stainless steel pickling wastewater sludge |
| CN102808194A (en) * | 2012-07-04 | 2012-12-05 | 嘉兴科菲冶金科技股份有限公司 | Process for purifying cobalt by electro-depositing cobalt chloride solution through cyclone electrolysis technology and reclaiming residual chlorine |
-
2014
- 2014-01-10 CN CN201410011379.6A patent/CN103695655A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101618892A (en) * | 2009-07-31 | 2010-01-06 | 东南大学 | Recovery and comprehensive utilization method of heavy metals in stainless steel pickling wastewater sludge |
| CN102808194A (en) * | 2012-07-04 | 2012-12-05 | 嘉兴科菲冶金科技股份有限公司 | Process for purifying cobalt by electro-depositing cobalt chloride solution through cyclone electrolysis technology and reclaiming residual chlorine |
Non-Patent Citations (1)
| Title |
|---|
| 桂锦智: "从废合金中提取钴、镍、铜工艺的改进", 《中国物资再生》 * |
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| CN104711427A (en) * | 2015-02-12 | 2015-06-17 | 江苏恒嘉再生资源有限公司 | Method for preparing and recovering sponge copper metal in pickling sludge |
| CN104711428A (en) * | 2015-02-12 | 2015-06-17 | 江苏恒嘉再生资源有限公司 | Method for preparing and recovering noble metal in pickling sludge |
| CN104745821A (en) * | 2015-02-12 | 2015-07-01 | 江苏恒嘉再生资源有限公司 | Method for recovering nickel and copper metals in acid pickling sludge |
| CN104745821B (en) * | 2015-02-12 | 2017-01-25 | 江苏恒嘉再生资源有限公司 | Method for recovering nickel and copper metals in acid pickling sludge |
| CN104711428B (en) * | 2015-02-12 | 2017-05-03 | 江苏恒嘉再生资源有限公司 | Method for preparing and recovering metal in pickling sludge |
| CN105567978A (en) * | 2016-01-28 | 2016-05-11 | 浙江新时代中能循环科技有限公司 | Method for recycling copper, zinc, cobalt and nickel from various kinds of nonferrous metal containing waste |
| CN107502757A (en) * | 2017-08-04 | 2017-12-22 | 浙江正道环保科技有限公司 | A kind of method of the reclaiming nickel sulfate from nickel bath slag and sludge |
| CN108570555A (en) * | 2018-05-03 | 2018-09-25 | 北京矿冶科技集团有限公司 | A method of directly producing LITHIUM BATTERY nickel sulfate from nickel cobalt enriched substance |
| GB2578645A (en) * | 2018-11-02 | 2020-05-20 | Darlow Lloyd & Sons Ltd | Method and apparatus for treating waste material |
| GB2578645B (en) * | 2018-11-02 | 2021-11-24 | Darlow Lloyd & Sons Ltd | Method and apparatus for treating waste material |
| CN109852794A (en) * | 2019-03-11 | 2019-06-07 | 西安蓝晓科技新材料股份有限公司 | A method of being used to prepare LITHIUM BATTERY nickel sulfate |
| CN109852794B (en) * | 2019-03-11 | 2022-02-15 | 西安蓝晓科技新材料股份有限公司 | Method for preparing battery-grade nickel sulfate |
| CN111285492A (en) * | 2019-12-31 | 2020-06-16 | 安徽珍昊环保科技有限公司 | Method for recovering heavy metal resources in stainless steel pickling wastewater neutralized sludge |
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Application publication date: 20140402 |