CN102120658B - Treatment and recycling method of ammonia nitrogen in electrolytic manganese production end wastewater - Google Patents
Treatment and recycling method of ammonia nitrogen in electrolytic manganese production end wastewater Download PDFInfo
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- CN102120658B CN102120658B CN 201110033536 CN201110033536A CN102120658B CN 102120658 B CN102120658 B CN 102120658B CN 201110033536 CN201110033536 CN 201110033536 CN 201110033536 A CN201110033536 A CN 201110033536A CN 102120658 B CN102120658 B CN 102120658B
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- ammonia nitrogen
- electrolytic manganese
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Abstract
The invention provides a treatment and recycling method of ammonia nitrogen in the electrolytic manganese production end wastewater. The method comprises the following steps: pretreatments such as dechromisation, demanganization and filtration are performed to the electrolytic manganese production end wastewater, the pH value is adjusted to about 10 to ensure that NH<4+> is converted to NH3.H2O, the self-made exchange resin with copper cations is used to adsorb NH3 in the wastewater, and when the resin is saturated, H2SO4 is used as regenerant to desorb and regenerate the saturated resin under the weakly acidic condition that the pH value is about 4. By utilizing the method, after the electrolytic manganese production end wastewater is treated, the ammonia nitrogen concentration of the wastewater is below the national discharge requirement and the ammonia and nitrogen in the wastewater can be separated and recycled, thus the effective treatment and resource recycling of the high concentration ammonia nitrogen wastewater in the electrolytic manganese industry can be realized and the method has remarkable environmental, economic and social benefits.
Description
Technical field
The present invention relates to processing and the recovery and utilization technology of electrolytic manganese production tail end wastewater middle and high concentration ammonia nitrogen, is to adopt homemade cupric Zeo-karb to realize the high density NH in the waste water specifically
4 +Optionally separate and recycle.
Background technology
Electrolytic manganese is a kind of important industrial raw material, is widely used in the departments such as metallurgy, chemical industry, light industry, electronic material, " without manganese Cheng Gang not ", and in Iron And Steel Industry, the consumption of electrolytic manganese is only second to iron.The electrolytic manganese production of China mainly is to add sulfuric acid extracting sulfuric acid manganese with manganese carbonate ore at present, then carrying out electrolysis obtains, 1 ton of electrolytic manganese of every production, about 4 ~ 5 tons of waste discharge, the ammonia nitrogen waste water of its middle and high concentration is mainly derived from the workshops such as press filtration, purification, electrolysis, produces auxiliary boiler house and Tailings Dam percolate, the about 1000～2000mg/L of concentration of using.
At present, most of " reduction-neutralization precipitation method " technique that adopts of domestic Electrolytic Manganese Wastewater is administered, and it is removed for the chromium in the waste water, mn ion, to the removal of ammonia nitrogen without any effect.The domestic overwhelming majority's electrolytic manganese factory is not just processed directly discharging to ammonia nitrogen, cause great environmental pollution, along with electrolytic manganese industry is in recent years increasingly sharpened to the pollution condition of environment, relevant criterion is formulated announcement successively, country has listed ammonia nitrogen in " 12 " priority control pollutent register, and the pollution control of ammonia nitrogen becomes current very urgent task.
The present invention is directed to the characteristics of Electrolytic Manganese Wastewater, adopt the removal of a cover Coal Gas Washing Cycling Water ammonia nitrogen and the new technology of recycling, when processing waste water, reclaim resource.
Summary of the invention
Main purpose of the present invention provides a kind of processing and recovery method of electrolytic manganese production tail end wastewater ammonia nitrogen in high density, utilize the inventive method finally can make ammonia nitrogen concentration in the Electrolytic Manganese Wastewater reach the emission standard requirement of national regulation, and the NH of the Separation and Recovery overwhelming majority therefrom
4 +Again be back to electrolytic manganese production, realize the combination of waste water treatment and resource recycling.
For achieving the above object, the present invention adopts following technical scheme:
A kind of processing of ammonia nitrogen in electrolytic manganese production end wastewater and recovery method, its step is as follows:
A. be 9 ~ 10 with regulating pH after the conventional dechromisation of electrolytic manganese production tail end wastewater process, demanganization, the filtration treatment, make NH
4 +Be converted into NH
3H
2O under 20 ℃ condition, adopts step by step fluidised form exchange adsorption mode, utilizes the NH in the transition metal ion absorption waste water of Zeo-karb load
3
B. when above-mentioned Zeo-karb after absorption reaches capacity, use H
2SO
4As regenerator, be under about 4 the condition, to carry out desorption and regeneration to adsorbing saturated exchange resin at pH.
Directly (GB8978-1996) up to standard discharging of water outlet through adsorbing among the above-mentioned steps a.
Aforesaid processing and recovery method, wherein, the Zeo-karb described in the step a is the homemade Zeo-karb that contains transition metal.
Aforesaid processing and recovery method, wherein, the Zeo-karb described in the step a is homemade cupric Zeo-karb.
Aforesaid processing and recovery method, wherein, the described Zeo-karb that contains cupric ion is the CuSO with 0.5 ~ 1.5mol/L
4Flow through the ion exchange column that a kind of weakly acidic cation-exchange resin is housed it is penetrated, thereby make it change into the cationic exchange resin of cupric;
Described weakly acidic cation-exchange resin refers to contain the Zeo-karb of slightly acidic cation exchange groups: carboxylic acid group-COOH.
Aforesaid processing and recovery method is characterized in that, described weakly acidic cation-exchange resin is the macroporous type weakly acidic cationic exchange resin of acrylic series.
Aforesaid processing and recovery method, wherein, the H of regenerator described in the above-mentioned steps b
2SO
4Concentration be 1 ~ 2mol/L.
Aforesaid processing and recovery method, wherein, the regenerated liquid that produces among the above-mentioned steps b is (NH
4)
2SO
4, it can be back to use in the production technique of electrolytic manganese, the regenerated liquid that ammonia nitrogen concentration is lower than 3000mg/L can overlap the regeneration step that is used for lower batch of cupric Zeo-karb with it.
Aforesaid processing and recovery method, wherein, cation exch ange adsorption preferably adopts " three grades of step by step exchange adsorption---synchronizing regeneration of fluidised form " technique among the present invention: described three grades of fluidised forms exchange step by step, be that the one-level absorption effluent is intake as secondary absorption, the secondary absorption water outlet is as three grades of absorption water inlets, and the modes such as employing mechanical stirring make resin fully adsorb NH
3Molecule, has adsorbed saturated Zeo-karb to other grades and has implemented synchronizing regeneration when a certain level is carried out exchange adsorption to saturated.So carry out, can guarantee the high-efficiency operation of whole device.
Aforesaid processing and recovery method, wherein, described three grades of fluidised forms step by step exchange process are the automatic mode that utilizes online ammonia nitrogen detector and all valves of Industrial Computer Control and flow.
Beneficial effect of the present invention is:
The present invention can make electrolytic manganese production tail end wastewater after above-mentioned processing, and the water outlet ammonia nitrogen concentration reaches the emission standard (GB8978-1996) of national regulation, i.e. ammonia nitrogen concentration≤15mg/L, clearance 〉=98%.Simultaneously can be with the ammonia nitrogen in high density Separation and Recovery in the waste water, its rate of recovery 〉=98%, thus realized effective improvement of waste water and the recycling of resource.Whole technical process can be adopted Industrial Computer Control, realizes automatic operating, has improved the stability of system's operation, has reduced human cost, has reduced labour intensity.
Embodiment
The absorption principle of the inventive method is as follows:
(1) preparation of the Zeo-karb of copper ions:
(2) absorption ammonia nitrogen:
(3) resin regeneration:
Below by example to details are as follows according to embodiment provided by the invention.
Embodiment 1
The macroporous type weakly acidic cationic exchange resin of acrylic series that dispatches from the factory packed in the glass exchange column, and (Ф 28 * 350mm), make the CuSO of 1.5mol/L
4Solution stream is crossed this ion exchange column and it is penetrated, thereby makes it change into the cationic exchange resin of cupric, and color of resin becomes blueness.
Embodiment 2
The self-control cupric Zeo-karb of dry weight 20.002g is packed in the Erlenmeyer flask of 250mL.It is 10 that the 150mL Electrolytic Manganese Wastewater is regulated pH with NaOH, makes NH
4 +Be converted into NH
3H
2O, adopting magnetic stirring apparatus to stir fully adsorbs resin, adsorbing saturated aftertreatment water enters next stage and carries out exchange adsorption, ammonia nitrogen concentration is 1141.07mg/L in the raw wastewater, behind three grades of exchange adsorptions of homemade cupric Zeo-karb, ammonia nitrogen concentration reaches 11.17mg/L, is lower than the emission standard requirement of national regulation, and clearance can reach 99.02%.
Embodiment 3
Operate according to the operation steps described in the embodiment 2.The concentration of ammonia nitrogen is 1100.18mg/L in the raw wastewater, and the pH of will intaking is adjusted to 9, behind three grades of exchange adsorptions of homemade cupric Zeo-karb, ammonia nitrogen concentration reaches 12.88 mg/L, be lower than the emission standard requirement of national regulation, clearance can reach 98.83%, but the water outlet qualified discharge.
Embodiment 4
After cationic exchange resin adsorption is saturated, under the condition of pH=4, with the H of 1mol/L
2SO
4Carry out desorption and regeneration as regenerator, the ammonia nitrogen mean concns can reach more than the 630mg/L in the regenerated liquid; Use H
2SO
4Regulate regenerated liquid to pH=4, as regenerator saturated Zeo-karb is regenerated, secondary recycling liquefied ammonia average nitrogen concentration can reach more than the 1430mg/L; With same method circulation 5 times, regenerated liquid ammonia nitrogen mean concns can reach more than the 4000mg/L, can be back to use in the production technique such as chemical combination or electrolysis and go, and realizes the recycling to ammonia nitrogen, and the rate of recovery can reach more than 99%.
Embodiment 5
Operate according to the operation steps described in the embodiment 4.H with 1mol/L in the regenerative process
2SO
4Regenerator concentration changes 2mol/L into and carries out desorption and regeneration, the regenerated liquid ammonia nitrogen concentration can reach more than the 800mg/L, iterative loop regeneration 6 times, regenerated liquid ammonia nitrogen mean concns can reach more than the 5000mg/L, can be back to use in the production technique such as chemical combination or electrolysis and go, realization is to the recycling of ammonia nitrogen, and the rate of recovery can reach 99%.
Claims (2)
1. the processing of an ammonia nitrogen in electrolytic manganese production end wastewater and recovery method is characterized in that, step is as follows:
A. be 10 with regulating pH after electrolytic manganese production tail end wastewater process dechromisation, demanganization, the filtration treatment, make NH
4 +Be converted into NH
3H
2O under 20 ℃ condition, adopts step by step fluidization exchange adsorption mode, with the NH in the cationic exchange resin adsorption waste water
3
B. as cationic exchange resin adsorption NH
3After reaching capacity, use H
2SO
4As regenerator, be under 4 the condition, to carry out desorption and regeneration to adsorbing saturated exchange resin at pH;
Described Zeo-karb is the CuSO with 0.5 ~ 1.5mol/L
4Flow through the ion exchange column that the macroporous type weakly acidic cationic exchange resin of acrylic series is housed it is penetrated, thereby make it change into the cationic exchange resin that contains cupric ion;
Regenerator H described in the step b
2SO
4Concentration be 1 ~ 2mol/L;
The regenerated liquid that produces among the step b is (NH
4)
2SO
4, it is back to use in the production technique of electrolytic manganese; Ammonia nitrogen concentration is lower than the regenerated liquid cover of 3000mg/L for the regeneration step of lower batch of cupric Zeo-karb;
Step by step fluidization exchange adsorption mode described in the step a is three grades of fluidization exchange adsorption techniques, and it is saturated to adopt the concussion stirring means that resin fully is adsorbed to, and the one-level absorption effluent is intake as secondary absorption, and the secondary absorption water outlet is as three grades of absorption water inlets.
2. processing according to claim 1 and recovery method is characterized in that, described three grades of fluidised forms are the automatic operation of the online ammonia nitrogen detector of exchange process utilization and all valves of Industrial Computer Control and flow step by step.
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| CN 201110033536 CN102120658B (en) | 2011-01-31 | 2011-01-31 | Treatment and recycling method of ammonia nitrogen in electrolytic manganese production end wastewater |
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| CN 201110033536 CN102120658B (en) | 2011-01-31 | 2011-01-31 | Treatment and recycling method of ammonia nitrogen in electrolytic manganese production end wastewater |
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| CN102120658B true CN102120658B (en) | 2013-02-27 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102839397B (en) * | 2012-08-17 | 2015-03-25 | 湖南振兴股份有限公司 | Manganese recycling process of electrolytic manganese slag |
| CN104030481A (en) * | 2013-03-08 | 2014-09-10 | 深圳中环科环保科技有限公司 | Electrolytic manganese waste water treatment and recycling method and system |
| CN103991927B (en) * | 2014-06-06 | 2015-07-29 | 四川恒达环境技术有限公司 | Bivalent manganese and ammonia nitrogen recovery method in electrolytic manganese production technique tail end wastewater |
| CN104005050B (en) * | 2014-06-06 | 2016-05-04 | 四川恒达环境技术有限公司 | In Electrolytic Manganese Wastewater, bivalent manganese is processed reuse method |
| CN106396056B (en) * | 2016-10-27 | 2019-08-27 | 长沙矿冶研究院有限责任公司 | Handle method magnesium eletrolysis containing manganese manganese waste water and recycle Manganese in Waste Water |
| CN108751325A (en) * | 2018-06-07 | 2018-11-06 | 成都恩承科技股份有限公司 | A kind of ammonia nitrogen waste water processing system and ammonia nitrogen waste water treatment method |
| CN110980876A (en) * | 2019-11-21 | 2020-04-10 | 武汉百富环保工程有限公司 | Treatment process for recovering copper and recycling chromium from passivation solution |
Citations (2)
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|---|---|---|---|---|
| CN101607769A (en) * | 2009-07-26 | 2009-12-23 | 江西理工大学 | A kind of treatment process of nitrogen-containing wastewater |
| CN101838061A (en) * | 2010-05-17 | 2010-09-22 | 赣州华兴钨制品有限公司 | Method for treating ammonia-nitrogen wastewater and recovering the same into ammonium salt |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101607769A (en) * | 2009-07-26 | 2009-12-23 | 江西理工大学 | A kind of treatment process of nitrogen-containing wastewater |
| CN101838061A (en) * | 2010-05-17 | 2010-09-22 | 赣州华兴钨制品有限公司 | Method for treating ammonia-nitrogen wastewater and recovering the same into ammonium salt |
Non-Patent Citations (1)
| Title |
|---|
| 彭佳乐.新型铜基离子交换树脂处理氨氮废水的研究.《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》.2010,第23页、28-33页、第56-58页. * |
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