CN104176851A - Glyphosate wastewater purifying device and purifying method - Google Patents
Glyphosate wastewater purifying device and purifying method Download PDFInfo
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- CN104176851A CN104176851A CN201410319086.4A CN201410319086A CN104176851A CN 104176851 A CN104176851 A CN 104176851A CN 201410319086 A CN201410319086 A CN 201410319086A CN 104176851 A CN104176851 A CN 104176851A
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Abstract
The invention relates to a glyphosate wastewater purifying device. According to the device, a pH regulating tank is connected with a spraying layer of an air stripping tower (2-2) through an air stripping pump (7-1); the air stripping tower (2-2) is connected with a spraying layer at the upper end of an air stripping tower (2-1) via an air stripping pump (7-3); the top end of the air stripping tower (2-1) is connected with the bottom of the air stripping tower (2-2); the top end of the air stripping tower (2-2) is connected with an inlet in the bottom of an absorption tower (4); and the top of the absorption tower (4) is connected with the air stripping tower (2-1) after being connected with an air stripping fan (3). Ammonia gas obtained through first-level and second-level air stripping by adopting the equipment is neutralized via sulfuric acid to prepare ammonium sulfate for being used in the next step. The device has the advantages that the device is high in purifying rate, the air stripping efficiency of the purifying method is far higher than that of a traditional air stripping method and the ammonia gas air stripping efficiency can be up to 98%; the ammonia gas with large wastewater quantity and high concentration can be recycled; and an absorption and purification tower adopts second-level reverse spraying, the specific surface area of padding is large, the performance stability is guaranteed through the gas liquid ratio confirmed by experimental researches and the ammonia gas absorbing efficiency can be up to 95%.
Description
Technical field
The present invention relates to a kind of refining plant of glyphosate waste water, and utilize this device to purify waste water, belong to chemical industry equipment and chemical technique field.
Background technology
Glyphosate is a kind of good organic phosphates nonselective herbicide, is the natural disposition highy potent herbicide that goes out after the bud of a kind of efficient, low toxicity, low residue, broad weed-killing spectrum, has good interior suction, conductive performance.Nearly all annual and perennial weeds and thicket can be prevented and kill off, 76 kinds in 78 kinds of dark malignant weeds can be effectively killed, after medicine is partially absorbed by green plant, very strong to the underground organization destructive force of perennial weeds.This kind emerges rapidly along with the spread of global genetically modified crops.Therefore, glyphosate is consumption maximum in the world today, one of weedicide kind of the most violent also tool market competitiveness of growth.The simultaneously production of glyphosate is also accompanied by the generation of a large amount of waste water, the manufacturing enterprise of China mainly in Zhejiang, the provinces and cities in the environment sensitive waters such as the density of population such as Jiangsu, Shandong, Sichuan, Anhui large, environmental capacity is little, the Taihu Lake of special-protection-by-the-State, Chaohu, the Changjiang river.The pollution problem main manifestations of glyphosate production is waste water, and this waste water has the features such as quantity discharged is large, ammonia nitrogen concentration is high, toxicity is large, saltiness is high, difficult degradation compounds content is high, difficulty of governance is large.The application of pollutant control technology at present lags behind the development of product.Just be strict in current standards in " the organophosphorus pesticide industrial water pollution thing emission standard " of publicity, particularly to feature pollutent, and the cancellation of 10% glyphosate formulation, make glyphosate waste water administer one of the difficult problem that becomes puzzlement industry, environmental issue restriction gradually the existence of enterprise.High-concentration ammonia nitrogenous wastewater adopts traditional stripping process to carry out pre-treatment, not only stripping efficiency is low, and can only can not carry out stripping to organic ammonia nitrogen to inorganic free ammonia nitrogen, simultaneously a lot of ammonia nitrogen waste water saltiness are large, be difficult to carry out follow-up biochemical treatment, thereby cause many high-concentration ammonia nitrogenous wastewaters can not qualified discharge, be at present compared with the trade effluent of refractory reason.Therefore, production control cost, autonomous innovation, environmental protection, dwindle the production technology gap with overseas enterprise, and Cai Nengshi enterprise has competitive power at any time.
Summary of the invention
This invention, in conjunction with glyphosate production Technology, catalyzed oxidation technology and MVR technology, adopts multistage ammonia nitrogen blowing-off device, sums up and concludes, and carries out technological transformation repeatedly and innovation.Solve glyphosate waste water and processed the problems such as difficulty, waste of raw materials, environmental protection, reduced waste water Reducing exhaust emission environmental pollution, the ammonium sulfate simultaneously reclaiming is sold outward, reach reduction of discharging synergy, cleaner production, the object of optimizing the environment, has also realized the idea of development of national recycling economy, and comprehensive benefit is remarkable.Be specially:
A kind of glyphosate waste water refining plant, liquid caustic soda storage tank is connected with the flowrate control valve of pH regulator groove upper end pipeline through liquid caustic soda pump;
PH regulator bottom land end is connected with the spraying layer of stripping tower upper end through stripping pump, stripping tower bottom is connected with the spraying layer of stripping tower upper end through stripping pump, stripping tower top via line pipeline is connected with stripping tower bottom inlet, stripping tower top via line pipeline is connected with absorption tower bottom inlet, and top, absorption tower via line pipeline is connected with stripping tower after being connected with stripping blower fan again;
Sulfuric acid storage tank is connected with Yi Ce bottom, absorption tower through sulfuric acid pump, and the cable tubing of absorption tower offside is through absorbent recirculation pump
Be connected with the spraying layer on absorption tower, absorbent recirculation pump to the cable tubing of spraying layer is provided with to the cable tubing of ammonium sulfate storage tank.
Described absorption tower is divided into upper, middle, and lower part, and top is provided with two-layer spraying layer, and bottom is provided with sulfuric acid storage tank,
Middle portion is the entrance of stripping tower top via line pipeline and bottom, absorption tower, and the offside of this entrance is provided with air intake duct.In described absorption tower upper strata spraying layer spray nozzle density be lower floor's spraying layer spray nozzle density 0.5-2 doubly.
Described stripping tower, stripping tower bottom are respectively arranged with delivery of steam machine.
The lower end of the spraying layer on described stripping tower, stripping tower, absorption tower is also provided with filling filler.
The present invention also provides a kind of glyphosate waste water purifying method, comprises the steps:
Glyphosate waste water is delivered to pH regulator groove, regulate the pH to 11-12 of waste water, and after this waste water is adjusted to temperature and is 45-50 DEG C, pump into the spraying layer at stripping tower 2-2 top, waste water is dissipated to after spray fills on filler, through filling the denitrfying agent denitrogenation on filler, the gas after denitrogenation rises and passes into absorption tower on stripping tower 2-2 top, completes stripping one time;
Waste water after denitrogenation falls and the spraying layer to stripping tower 2-1 top through stripping pump pump through the filling filler on stripping tower top, waste water is dissipated to after spray fills on packing layer, through filling the denitrfying agent denitrogenation on packing layer, gas after denitrogenation rises and passes into stripping tower 2-1 on stripping tower 2-1 top, gas after denitrogenation rises and passes into absorption tower on stripping tower 2-2 top, complete secondary stripping, the waste water after denitrogenation is delivered to waste water treatment plant through draw-off pump;
Gas through a denitrogenation, secondary denitrogenation is delivered to behind absorption tower, pumping into mass concentration toward bottom, absorption tower is 5-25% dilute sulphuric acid, this dilute sulphuric acid pumps into the spraying layer on absorption tower through absorbent recirculation pump, simultaneously, in absorption tower, pass into air, dilute sulphuric acid contacts with the back flow of gas after denitrogenation after spray, generate ammonium sulfate, and pump is to ammonium sulfate storage tank.
Vapour-liquid ratio control in described absorption tower is 2000 ~ 2400:1
Described filling spice layer is the mixture of polypropylene and denitrfying agent.
During one time stripping, secondary stripping are processed, when total nitrogen concentration is higher than 1000mg/L in glyphosate waste water, pass into steam toward stripping tower 2-1, stripping tower 2-2 bottom; When total nitrogen concentration is lower than 1000mg/L in glyphosate waste water, adopt the stripping blower fan air blast stripping that circulates.
The method enters equalizing tank by the water of condensation after evaporation after interchanger heat exchange is to 40-50 DEG C, and on-line control pH value 11～12 midway, adds active denitrfying agent, converts ammonia nitrogen to free ammonia, rises to ammonia separate denitrification column through pump.Stripping tower often adopts counter-current operation, and the filler of certain altitude is housed in tower, thereby is conducive to ammonia desorb from waste water to increase gas-liquid mass transfer area, shifts to gas phase, reaches the object of removal of ammonia and nitrogen.After secondary stripping, ammonia nitrogen in waste water meets production requirement, is back to production.Waste gas, after secondary stripping purifies, meets discharging standards.
The structure of stripping tower adopts gas-liquid contact apparatus, fills filler, in order to improve contact area in the inside of tower.Water of condensation after evaporation is entered to equalizing tank after interchanger heat exchange is to 40-50 DEG C, and on-line control pH value 11～12 midway, is showered into water with stripping pump filler and formation water droplet from the top of tower, drip successively along the gap of filler.At the bottom of tower, pass into steam, accelerate the effusion of ammonia; The hot exhaust gas of packing layer below is sent into the utilization of every first stage tower internal recycle through the circulation of stripping blower fan, saving heat energy utilization, and tower top tail gas enters ammonia absorption device.The whole mass transfer process that completes, makes ammonia transfer gas phase to by liquid phase, with air venting, completes stripping process, and decreasing ratio reaches more than 98%.
Ammonia from stripping tower is tangentially entered to type absorption purification tower from tower body below inlet mouth, then rise to equably first step packing material absorbing section.On the surface of filler, water or sulfuric acid generation chemical reaction in ammonia and liquid phase in gas phase, reaction generates (NH
4)
2sO
4, and flow into bottom stationary tank.The ammonia gas not absorbing completely continues to rise and enters first step spraying layer.In spraying layer, absorption liquid, from the ejection at a high speed of uniform nozzle, forms countless fine mist, fully mixes and contacts with gas, continues to occur chemical reaction.The second stage is different from first step spray nozzle density, and hydrojet pressure difference absorbs acidic gas concentration scope also different.The process contacting in spray section and packing section two is also the process of heat and mass transfer.Flow velocity and residence time by control dilute sulphuric acid ensure the abundant and stable of this process.Through (the NH of sulfuric acid absorption
4)
2sO
4, after multiple-effect evaporation, recycle.
The present invention has following beneficial effect
1. purification rate is high, and stripping efficiency far, higher than traditional blow-off method, can reach 98% to the stripping efficiency of ammonia
2. the ammonia recoverable that pair wastewater flow rate is large, concentration is high
3. type absorption purification tower adopts the reverse spray of secondary, and packing specific area is large, and the vapour-liquid ratio of being determined by experimental study has ensured stable performance, can reach 95% to the assimilated efficiency of ammonia.
4. the present invention will greatly reduce the discharge of waste water, reduces environmental pollution; The ammonium sulfate packaging reclaiming is taken out, and increases Business Economic Benefit.
Brief description of the drawings
Fig. 1 is a kind of glyphosate waste water refining plant structure iron, wherein, and 1.pH regulating tank, 2-1,2-2 stripping tower, 3 stripping blower fan, 4. absorption towers, 5. ammonium sulfate storage tank, 6. sulfuric acid storage tank, 7-1 stripping pump, 7-2 draw-off pump, 7-3 stripping pump, 7-4 absorbent recirculation pump, 7-5 liquid caustic soda pump, 7-6 sulfuric acid pump, 8. liquid caustic soda storage tank, 9. flowrate control valve, 10-1,10-2. steamer.
Embodiment
embodiment 1
A kind of glyphosate waste water refining plant, liquid caustic soda storage tank 8 is connected with the flowrate control valve 9 of pH regulator groove 1 upper end pipeline through liquid caustic soda pump 7-5;
PH regulator groove 1 bottom is connected with the spraying layer of stripping tower 2-2 upper end through stripping pump 7-1, stripping tower 2-2 bottom is connected with the spraying layer of stripping tower 2-1 upper end through stripping pump 7-3, stripping tower 2-1 top via line pipeline is connected with stripping tower 2-2 bottom inlet, stripping tower 2-2 top via line pipeline is connected with absorption tower 4 bottom inlets, after absorption tower 4 top via line pipelines are connected with stripping blower fan 3, is connected with stripping tower 2-1 again;
Sulfuric acid storage tank 6 is connected with the bottom of absorption tower 4 one sides through sulfuric acid pump 7-6, the cable tubing of absorption tower 4 offsides is connected with the spraying layer on absorption tower 4 through absorbent recirculation pump 7-4, and absorbent recirculation pump 7-4 is provided with to the cable tubing of ammonium sulfate storage tank 5 to the cable tubing of spraying layer.
Absorption tower 4 is divided into upper, middle, and lower part, and top is provided with two-layer spraying layer, and bottom is provided with sulfuric acid storage tank, and middle portion is the entrance of stripping tower 2-2 top via line pipeline and 4 bottoms, absorption tower, and the offside of this entrance is provided with air intake duct.
Upper strata spraying layer spray nozzle density in described absorption tower 4 is 0.5-2 times of lower floor's spraying layer spray nozzle density.
Described stripping tower 2-1, stripping tower 2-2 bottom are respectively arranged with delivery of steam machine 10-1,10-2.
The lower end of the spraying layer on stripping tower 2-1, stripping tower 2-2, absorption tower 4 is provided with filling filler.
embodiment 2
A kind of glyphosate waste water purifying method, comprises the steps:
1) glyphosate waste water is delivered to pH regulator groove 1, in its glyphosate waste water, total nitrogen concentration is 5000mg/L, regulate the pH to 11 of waste water, and after this waste water is adjusted to temperature and is 45 DEG C, pump into the spraying layer at stripping tower 2-2 top, pass into steam toward stripping tower 2-2 bottom, waste water is dissipated to after spray fills on filler, through filling the denitrfying agent denitrogenation on filler, the gas after denitrogenation rises and passes into absorption tower 4 on stripping tower 2-2 top, completes stripping one time;
2) waste water after denitrogenation falls and the spraying layer to stripping tower 2-1 top through stripping pump 8-3 pump through the filling filler on stripping tower 2-2 top, pass into steam toward stripping tower 2-1 bottom, waste water is dissipated to after spray fills on packing layer, through filling the denitrfying agent denitrogenation on packing layer, gas after denitrogenation rises and passes into stripping tower 2-2 on stripping tower 2-1 top, gas after denitrogenation rises and passes into absorption tower 4 on stripping tower 2-2 top, complete secondary stripping, the waste water after denitrogenation is delivered to waste water treatment plant through draw-off pump 7-2;
3) deliver to behind absorption tower 4 through the gas of a denitrogenation, secondary denitrogenation, pumping into mass concentration toward 4 bottoms, absorption tower is 15% dilute sulphuric acid, this dilute sulphuric acid pumps into the spraying layer on absorption tower through absorbent recirculation pump 7-4, simultaneously, in absorption tower, pass into air, dilute sulphuric acid contacts with the back flow of gas after denitrogenation after spray, generate ammonium sulfate, and pump is to ammonium sulfate storage tank., the vapour-liquid ratio control in absorption tower is 2000:1.Stripping rate reaches 98.5%, and ammonia specific absorption reaches 96%.
embodiment 3
A kind of glyphosate waste water purifying method, is characterized in that, comprises the steps:
1) glyphosate waste water is delivered to pH regulator groove 1, in its glyphosate waste water, total nitrogen concentration is 800mg/L, regulate the pH to 12 of waste water, and after this waste water is adjusted to temperature and is 50 DEG C, pump into the spraying layer at stripping tower 2-2 top, waste water is dissipated to after spray fills on filler, through filling the denitrfying agent denitrogenation on filler, gas after denitrogenation rises and passes into absorption tower 4 on stripping tower 2-2 top, completes stripping one time;
2) waste water after denitrogenation falls and the spraying layer to stripping tower 2-1 top through stripping pump 8-3 pump through the filling filler on stripping tower 2-2 top, open stripping blower fan 3 and carry out air blast stripping, waste water is dissipated to after spray fills on packing layer, through filling the denitrfying agent denitrogenation on packing layer, gas after denitrogenation rises and passes into stripping tower 2-2 on stripping tower 2-1 top, gas after denitrogenation rises and passes into absorption tower 4 on stripping tower 2-2 top, complete secondary stripping, the waste water after denitrogenation is delivered to waste water treatment plant through draw-off pump 7-2;
3) deliver to behind absorption tower 4 through the gas of a denitrogenation, secondary denitrogenation, pumping into mass concentration toward 4 bottoms, absorption tower is 25% dilute sulphuric acid, this dilute sulphuric acid pumps into the spraying layer on absorption tower through absorbent recirculation pump 7-4, simultaneously, in absorption tower, pass into air, dilute sulphuric acid contacts with the back flow of gas after denitrogenation after spray, generates ammonium sulfate, and pump is to ammonium sulfate storage tank, the vapour-liquid ratio control in absorption tower is 2400:1.Stripping rate reaches 99%, and ammonia specific absorption reaches 95%.
Claims (9)
1. a glyphosate waste water refining plant, is characterized in that:
Liquid caustic soda storage tank (8) is connected with the flowrate control valve (9) of pH regulator groove (1) upper end pipeline through liquid caustic soda pump (7-5);
PH regulator groove (1) bottom is connected with the spraying layer of stripping tower (2-2) upper end through stripping pump (7-1), stripping tower (2-2) bottom is connected with the spraying layer of stripping tower (2-1) upper end through stripping pump (7-3), stripping tower (2-1) top via line pipeline is connected with stripping tower (2-2) bottom inlet, stripping tower (2-2) top via line pipeline is connected with absorption tower (4) bottom inlet, after top, absorption tower (4) via line pipeline is connected with stripping blower fan (3), is connected with stripping tower (2-1) again;
Sulfuric acid storage tank (6) is connected with the bottom of absorption tower (4) one sides through sulfuric acid pump (7-6), the cable tubing of absorption tower (4) offside is connected with the spraying layer of absorption tower (4) through absorbent recirculation pump (7-4), and absorbent recirculation pump (7-4) to the cable tubing of spraying layer is provided with to the cable tubing of ammonium sulfate storage tank (5).
2. glyphosate waste water refining plant according to claim 1, it is characterized in that: absorption tower (4) are divided into upper, middle, and lower part, top is provided with two-layer spraying layer, bottom is provided with sulfuric acid storage tank, middle portion is the entrance of stripping tower (2-2) top via line pipeline and absorption tower (4) bottom, and the offside of this entrance is provided with air intake duct.
3. glyphosate waste water refining plant according to claim 2, is characterized in that: the upper strata spraying layer spray nozzle density in absorption tower (4) is 0.5-2 times of lower floor's spraying layer spray nozzle density.
4. glyphosate waste water refining plant according to claim 1, is characterized in that: stripping tower (2-1), stripping tower (2-2) bottom are respectively arranged with delivery of steam machine (10-1), (10-2).
5. glyphosate waste water refining plant according to claim 1, is characterized in that: the lower end of the spraying layer of stripping tower (2-1), stripping tower (2-2), absorption tower (4) is provided with filling filler.
6. a glyphosate waste water purifying method, is characterized in that, comprises the steps:
1) glyphosate waste water is delivered to pH regulator groove (1), regulate the pH to 11-12 of waste water, and after this waste water is adjusted to temperature and is 45-50 DEG C, pump into the spraying layer at stripping tower (2-2) top, waste water is dissipated to after spray fills on filler, through filling the denitrfying agent denitrogenation on filler, the gas after denitrogenation rises and passes into absorption tower (4) on stripping tower (2-2) top, completes stripping one time;
2) waste water after denitrogenation falls and the spraying layer to stripping tower (2-1) top through stripping pump (8-3) pump through the filling filler on stripping tower (2-2) top, waste water is dissipated to after spray fills on packing layer, through filling the denitrfying agent denitrogenation on packing layer, gas after denitrogenation rises and passes into stripping tower (2-2) on stripping tower (2-1) top, gas after denitrogenation rises and passes into absorption tower (4) on stripping tower (2-2) top, complete secondary stripping, the waste water after denitrogenation is delivered to waste water treatment plant through draw-off pump (7-2);
3) after the gas of a denitrogenation, secondary denitrogenation is delivered to absorption tower (4), pumping into mass concentration toward bottom, absorption tower (4) is 5-25% dilute sulphuric acid, this dilute sulphuric acid pumps into the spraying layer on absorption tower through absorbent recirculation pump (7-4), simultaneously, in absorption tower, pass into air, dilute sulphuric acid contacts with the back flow of gas after denitrogenation after spray, generate ammonium sulfate, and pump is to ammonium sulfate storage tank.
7. glyphosate waste water purifying method according to claim 6, is characterized in that, the vapour-liquid ratio control in absorption tower is 2000 ~ 2400:1.
8. glyphosate waste water purifying method according to claim 6, is characterized in that, described filling spice layer is the mixture of polypropylene and denitrfying agent.
9. glyphosate waste water purifying method according to claim 6, is characterized in that, during one time stripping, secondary stripping are processed, when total nitrogen concentration is higher than 1000mg/L in glyphosate waste water, passes into steam toward stripping tower (2-1), stripping tower (2-2) bottom; When total nitrogen concentration is lower than 1000mg/L in glyphosate waste water, adopt stripping blower fan (3) the air blast stripping that circulates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410319086.4A CN104176851A (en) | 2014-07-07 | 2014-07-07 | Glyphosate wastewater purifying device and purifying method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410319086.4A CN104176851A (en) | 2014-07-07 | 2014-07-07 | Glyphosate wastewater purifying device and purifying method |
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| Publication Number | Publication Date |
|---|---|
| CN104176851A true CN104176851A (en) | 2014-12-03 |
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ID=51958241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410319086.4A Pending CN104176851A (en) | 2014-07-07 | 2014-07-07 | Glyphosate wastewater purifying device and purifying method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445787A (en) * | 2014-12-16 | 2015-03-25 | 湖北泰盛化工有限公司 | Catalytic oxidation device for glyphosate mother liquor |
| CN104828798A (en) * | 2015-05-20 | 2015-08-12 | 湖北泰盛化工有限公司 | Device and method for extracting sodium dihydrogen phosphate dihydrate by using crude brine in glyphosate production process through glycine method |
| CN104844414A (en) * | 2015-05-20 | 2015-08-19 | 湖北泰盛化工有限公司 | Equipment and process for recovering glyphosate solvent during production with glycine method |
| CN106800344A (en) * | 2017-01-14 | 2017-06-06 | 冯志祥 | A kind of complete processing system of ammonia nitrogen |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445290A (en) * | 2008-12-09 | 2009-06-03 | 武汉科梦科技发展有限公司 | Environment-friendly high-performance waste water ammonia-removal process and device thereof |
| CN102241422A (en) * | 2011-04-22 | 2011-11-16 | 杭州恒易环保科技有限公司 | Circulating closed ammonia nitrogen stripping system |
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2014
- 2014-07-07 CN CN201410319086.4A patent/CN104176851A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445290A (en) * | 2008-12-09 | 2009-06-03 | 武汉科梦科技发展有限公司 | Environment-friendly high-performance waste water ammonia-removal process and device thereof |
| CN102241422A (en) * | 2011-04-22 | 2011-11-16 | 杭州恒易环保科技有限公司 | Circulating closed ammonia nitrogen stripping system |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445787A (en) * | 2014-12-16 | 2015-03-25 | 湖北泰盛化工有限公司 | Catalytic oxidation device for glyphosate mother liquor |
| CN104828798A (en) * | 2015-05-20 | 2015-08-12 | 湖北泰盛化工有限公司 | Device and method for extracting sodium dihydrogen phosphate dihydrate by using crude brine in glyphosate production process through glycine method |
| CN104844414A (en) * | 2015-05-20 | 2015-08-19 | 湖北泰盛化工有限公司 | Equipment and process for recovering glyphosate solvent during production with glycine method |
| CN106800344A (en) * | 2017-01-14 | 2017-06-06 | 冯志祥 | A kind of complete processing system of ammonia nitrogen |
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Application publication date: 20141203 |
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