CN203529996U - Cuprammouium complexing wastewater treatment device - Google Patents
Cuprammouium complexing wastewater treatment device Download PDFInfo
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- CN203529996U CN203529996U CN201320601995.8U CN201320601995U CN203529996U CN 203529996 U CN203529996 U CN 203529996U CN 201320601995 U CN201320601995 U CN 201320601995U CN 203529996 U CN203529996 U CN 203529996U
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- copper
- ammonia nitrogen
- tank
- hydrolytic
- settling pond
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Abstract
The utility model relates to a cuprammouium complexing wastewater treatment device, belonging to the technical field of wastewater treatment of environmental engineering. The device provided by the utility model is mainly characterized by comprising an MAP (Magnesium Ammonium Phosphate) reaction settling pond, a dephosphorization settling pond, a caustic soda flake mixer, a drier, a receiving pond, a hydrolytic pool and an electrolytic bath, wherein the MAP reaction settling pond is respectively connected with the dephosphorization settling pond and the caustic soda flake mixer through output pipelines, the output end of the caustic soda flake mixer is connected with the drier, the drier is respectively connected with the receiving pond and the hydrolytic pool through the output pipelines, the hydrolytic pool is connected with the electrolytic bath through the output pipeline, and the electrolytic bath is then communicated with the MAP reaction settling pond through the output pipeline. By means of a method matched with the device, the treatment effect of ammonia nitrogen and copper reaches the first level standard in GB18918-2002, and ammonia nitrogen and copper in wastewater are treated at the same time without independently treating copper or ammonia nitrogen. The problem that cuprammouium complexes are strong in stability and great in treatment difficulty is solved. Copper in wastewater is recovered in form of single substance copper, and phosphorus and magnesium sources can be further recycled, so that the agent is saved.
Description
Technical field
The utility model relates to a kind of cuprammonium complexing wastewater treatment equipment, belongs to environmental engineering technical field of waste water processing.
Background technology
The ammonia-containing water of commercial run discharge is polluted-water and causes the major cause that in water body, ammonia nitrogen concentration raises.Ammonia enters the large approach of waste water and mainly contains two kinds: first, in recourse processing process, the nitrogen in resource enters waste water with the form of ammonia, as industries such as chemical industry, coking; Secondly, ammonia closes leaching agent as a kind of acid neutralizing agent, precipitation agent, ammino cheap but excellent property, be widely used in the industries such as nonferrous metallurgy, chemical industry, but major part does not finally enter product, but enters waste water.Chemical industry is as the industrial trade of discharge ammonia nitrogen maximum, and within 2006, discharge ammonia nitrogen accounts for 45.8% of whole industry, and metallurgy industry (containing coloured, ferrous metallurgy, coking) discharge ammonia nitrogen in 2006 accounts for 10% of whole industry.The ammonia nitrogen waste water producing in the production process of metallurgy industry often also has certain density heavy metal ion, some heavy metals (as copper) can with ammonia nitrogen generation complex reaction, generate heavy metal ammonia nitrogen complex compound, because its stability is very strong, the difficulty of processing is also larger.And in the integrated wastewater discharge standard GB8978-1996 and GB18918-2002 of country's promulgation, the limit value of each heavy metal is had to clear and definite appointment, and so heavy metal complexing ammonia nitrogen waste water should be processed ammonia nitrogen, also to process heavy metal, the two all will reach emission standard.
Copper-removing method for cupric ammine complex mainly contains at present: sulphide precipitation is by adding S to complex copper waste water
2-(Na normally
2s) to form CuS precipitation, thereby remove the treatment process of copper, the subject matter of sulphide precipitation is S
2-add-on be difficult to accurate control, once S
2-excessively will produce stench, cause secondary pollution.The principle of oxidation style copper removal is to utilize strong oxidizer by the ligand oxygenolysis of complex copper, makes copper discharge and become free state from complex state, then by adding alkali, makes it produce Cu (OH)
2precipitate and remove.Oxidation style copper removal need be large with oxidant content, and medicament expense is with high, thereby practical engineering application is subject to certain restrictions.Reduction method is to utilize reductive agent that the cupric ion reduction of complex copper waste water is separated out to the copper removal treatment process of copper, therefore, selects suitable reductive agent and creates the key that favourable reduction reaction conditions is application reduction method copper removal.Conventional reductive agent has iron powder, hydrazine hydrate, hydrophosphate etc.Mostly iron powder reducing method sludge output is to cause it in engineering, to apply few major cause.The principle of ferrous sulfate method copper removal is based on Cu (NH
3)
4 2+and EDTA-Cu
2+with EDTA-Fe
3+the difference of stability constant, EDTA-Fe
3+stability constant maximum, therefore, to complex copper waste water, add Fe
3+can facilitate EDTA-Fe
3+combination and by Cu
2+cement out, make copper change free state into by complex state, then by heightening the pH value of waste water, just can obtain Cu (OH)
2, Fe (OH)
2, Fe (OH)
3precipitation and realize the removal of copper, iron, the main drawback of ferrous sulfate method is that chemical feeding quantity is large, sludge output is many.The chelating precipitator method are heavy metal improvement methods that development in recent years is got up, and it is the Cu utilizing in heavy metal chelating agent and waste water
2+, Hg
2+, Pb
2+etc. heavy metal ion generation chelatropic reaction, generate water-insoluble chelating salt, thereby realize, the trapping of heavy metal is removed.Absorption method refers to utilizes the huge specific surface area of sorbent material and the treatment process of a large amount of surface active groups adsorption cleaning complex copper waste water.In practical application, because complex copper waste water complex concentration is higher, for obtaining good treatment effect, absorption method needs frequent regeneration and novel sorbents more, causes operational management complicated, and working cost improves.Ion exchange method is a kind ofly by means of the exchangable ion on ion exchange resin, to carry out permutoid reaction with identical electrical ion in water and except anhydrating the treatment process of middle harmful ion.
Yet, aforesaid method all can not be processed the ammonia nitrogen in waste water, also i.e. explanation adopts current method to process cuprammonium complexing waste water and need to first process copper, and then processing ammonia nitrogen, not yet find both at home and abroad to adopt MAP method to process the report of cuprammonium complexing waste water, also find that the technique of employing precipitation-deamination-dissolving-galvanic deposit reclaims the example of elemental copper, more do not have the device supporting with the method to occur.
Utility model content
The purpose of this utility model is to provide the supporting device of a kind of efficient, easy method that copper in cuprammonium complexing waste water and ammonia nitrogen are removed simultaneously.
A cuprammonium complexing wastewater treatment equipment, comprises MAP reaction settling basin, dephosphorization settling tank, sheet alkali mixing tank, moisture eliminator, reception tank, hydrolytic tank and electrolyzer; MAP reaction settling basin is connected with sheet alkali mixing tank with dephosphorization settling tank respectively by output channel, output terminal and the moisture eliminator of sheet alkali mixing tank join, moisture eliminator is connected with hydrolytic tank with reception tank by output channel respectively, hydrolytic tank is connected with electrolyzer by output channel, and electrolyzer communicates with MAP reaction settling basin by output channel again.
Utility model effect:
The ammonia nitrogen waste water producing in the industries such as metallurgy, plating often has certain density heavy metal ion, some heavy metals (as copper) can with ammonia nitrogen generation complex reaction, generate heavy metal ammonia nitrogen complex compound, because its stability is very strong, the difficulty of processing is also larger.Can adopt at present the method decopper(ing)s such as sulphide precipitation, oxidation style, reduction method, the chelating precipitator method, absorption method, ion exchange method, and then adopt other method by ammonia nitrogen removal, just treating processes is divided into two steps, increased treatment process and cost, and the decopper(ing) link of back is very easily introduced secondary pollution.And adopt device of the present utility model and matching method can utilize MAP method, by ammonia nitrogen from cuprammonium complexing ion [Cu (NH
3)
4]
2+middle disengaging, generates MgNH
4pO
4thereby, realize in degradation of ammonia nitrogen, realize the contact break of cuprammonium and close, the copper in waste water is free out, and the alkaline environment providing can get off free copper ion precipitation, and precipitation MgNH
4pO
4can be Cu (OH)
2precipitation provides adheres to place, promotes its precipitation completely.Advantage of the present utility model is:
1. adopt the utility model device and matching method to make the treatment effect of ammonia nitrogen and copper reach the primary standard in GB18918-2002, Yu Tongliang is lower than 0.5mg/L, and remaining ammonia nitrogen amount is lower than 5mg/L.
2. process ammonia nitrogen and copper in waste water, without separately copper or ammonia nitrogen being processed simultaneously.
3. solved smoothly cupric ammine complex stability strong, the problem that intractability is large.
4. whole techniqueflow carries out according to rational optimized proportioning, is applicable to the waste water of different concns, particularly effective for the waste water below 2000mg/L.
5. with unique technique, realize resources circulation and utilization, adopt the utility model device and matching method not only can recycle phosphorus, magnesium source, thereby save medicament, and the copper in waste water is reclaimed with elemental copper form.
Accompanying drawing explanation
Fig. 1 is setting drawing of the present utility model.
1-MAP reaction settling basin, 2-dephosphorization settling tank, 3-sheet alkali mixing tank, 4-moisture eliminator, 5-reception tank, 6-hydrolytic tank, 7-electrolyzer.
Embodiment
Below in conjunction with the drawings and specific embodiments, the utility model is described in further detail, and unrestricted the utility model.
Device of the present utility model comprises MAP reaction settling basin 1, dephosphorization settling tank 2, sheet alkali mixing tank 3, moisture eliminator 4, reception tank 5, hydrolytic tank 6 and electrolyzer 7; MAP reaction settling basin 1 is connected with sheet alkali mixing tank 3 with dephosphorization settling tank 2 respectively by output channel, output terminal and the moisture eliminator 4 of sheet alkali mixing tank 3 join, moisture eliminator 4 is connected with hydrolytic tank 6 with reception tank 5 by output channel respectively, hydrolytic tank 6 is connected with electrolyzer 7 by output channel, and electrolyzer 7 communicates with MAP reaction settling basin 1 by output channel again.
Embodiment 1
The waste water of copper content 1000mg/L, ammonia-nitrogen content 2000mg/L is passed in MAP reaction settling basin, in MAP settling tank minute three sections add magnesium chloride and Sodium phosphate dibasic lysate, control each section and add ratio and be: n (NH
3-N): n (MgCl
2): n (Na
2hPO
4)=1:1:1, n (NH
3-N): n (MgCl
2): n (Na
2hPO
4)=1:0.2:0.17, n (NH
3-N): n (MgCl
2): n (Na
2hPO
4)=1:0.2:0.17, carries out pH regulator with NaOH, and by pH regulator 9.0, it is 3 minutes that each section of churning time all controlled, and it is 20 minutes that the reaction times is all controlled.After processing, supernatant liquor is passed into dephosphorization settling tank, and throw out is taken out stand-by.
After testing: the remaining ammonia nitrogen amount of water body is 4.8mg/L, remaining copper amount is 0.4mg/L, all lower than the primary standard value in GB18918-2002 (5mg/L, 0.5mg/L), remaining phosphorus amount is 253mg/L, in dephosphorization settling tank, add unslaked lime CaO, dosage is: n (CaO): n (P)=2.0:1(is m(CaO)=0.89g/L) the precipitin reaction time is controlled is 25 minutes, the residual quantity that finally detects P is 0.9mg/L, lower than the primary standard value 1mg/L in GB18918-2002, the operation after water can being entered.
In the throw out taking out at MAP reaction settling basin, add sheet alkali, at sheet alkali mixing tank, mix, the ratio that adds sheet alkali is n (NaOH): n (NH3-N)=0.5:1, add appropriate water to stir, make integral body be wet emulsus, putting into moisture eliminator, is 125 ℃ by Temperature Setting in moisture eliminator, and ammonia adopts clear water to receive at reception tank.After four hours, deamination product is taken out, at hydrolytic tank, add after diluted hydrochloric acid dissolution, adding water management pH is 2.5, and solution is passed into acid copper in electrolyzer, and control current density is 0.1A/cm
2, control flume voltage is 3.5V, solution temperature is 50 ℃ in groove, until solution be colourless after, discharge solution for later use, this solution recycles as the raw material of MAP method.The copper powder obtaining embathes through acidity, is placed in vacuum drying oven and dries, and the rate of recovery that records Cu in waste water is 99.5%.In above-mentioned solution, add part Sodium phosphate dibasic, quantity meets: n (Na again
2hPO
4): n (NH
3-N)=0.08:1, i.e. m(Na
2hPO
4)=1.63g/L, then by solution by volume 5:1:1 be divided into three parts, it is thrown one by one and is back in MAP reaction settling basins at different levels, each processing condition and deamination process are afterwards with above described identical, the remaining ammonia nitrogen amount recording after processing is 4.0mg/L, and remaining copper amount is 0.3mg/L; According to the same manner, have altogether after 6 circulations, recording remaining ammonia nitrogen amount is 4.5mg/L, and remaining copper amount is 0.3mg/L, all lower than the primary standard in GB18918-2002.
Embodiment 2
Technological process is with embodiment 1, same Treatment of Copper amount is 500mg/L, ammonia-nitrogen content is the cuprammonium complexing waste water of 1000mg/L, control processing condition: pH value is 9.2, and churning time is 2 minutes, and the precipitin reaction time is each section 15 minutes, CaO dosage is: n (CaO): n (P)=3.0:1, finally detect: remaining ammonia nitrogen amount is 4.1mg/L, and remaining copper amount is 0.2mg/L, and remaining phosphorus amount is 0.4mg/L.After acidolysis, controlling pH value is 2.0, and control current density is 0.12A/cm
2, control flume voltage is 3.5V, and in groove, solution temperature is 40 ℃, and the rate of recovery that records Cu in waste water is 99.0%.By these processing condition, undertaken after 5 circulations, recording remaining ammonia nitrogen amount is 5.0mg/L, and remaining copper amount is 0.4mg/L, all meets the primary standard in GB18918-2002.
Embodiment 3
Technological process is with embodiment 1, and Treatment of Copper amount is 500mg/L, the waste water that ammonia-nitrogen content is 300mg/L, and control condition is: pH value is 9.2, and churning time is 3 minutes, and the precipitin reaction time is each section 20 minutes; CaO dosage is: n (CaO): n (P)=2.0:1, finally detects: remaining ammonia nitrogen amount is 3.5mg/L, and remaining copper amount is 0.1mg/L, and remaining phosphorus amount is 0.8mg/L.After acidolysis, controlling pH value is 3.0, and control current density is 0.12A/cm
2, control flume voltage is 3.0V, and in groove, solution temperature is 50 ℃, and the rate of recovery that records copper is 99.1%.By these processing condition, undertaken after 5 circulations, recording remaining ammonia nitrogen amount is 4.3mg/L, and remaining copper amount is 0.4mg/L, all lower than the primary standard in GB18918-2002.
Claims (1)
1. a cuprammonium complexing wastewater treatment equipment, is characterized in that, comprises MAP reaction settling basin, dephosphorization settling tank, sheet alkali mixing tank, moisture eliminator, reception tank, hydrolytic tank and electrolyzer; MAP reaction settling basin is connected with sheet alkali mixing tank with dephosphorization settling tank respectively by output channel, output terminal and the moisture eliminator of sheet alkali mixing tank join, moisture eliminator is connected with hydrolytic tank with reception tank by output channel respectively, hydrolytic tank is connected with electrolyzer by output channel, and electrolyzer communicates with MAP reaction settling basin by output channel again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201320601995.8U CN203529996U (en) | 2013-09-27 | 2013-09-27 | Cuprammouium complexing wastewater treatment device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201320601995.8U CN203529996U (en) | 2013-09-27 | 2013-09-27 | Cuprammouium complexing wastewater treatment device |
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| Publication Number | Publication Date |
|---|---|
| CN203529996U true CN203529996U (en) | 2014-04-09 |
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|---|---|---|---|
| CN201320601995.8U Expired - Lifetime CN203529996U (en) | 2013-09-27 | 2013-09-27 | Cuprammouium complexing wastewater treatment device |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106435192A (en) * | 2016-09-13 | 2017-02-22 | 南京大学 | Method for removing and recycling copper from magnesium ammonium phosphate sludge |
| CN110127918A (en) * | 2018-02-02 | 2019-08-16 | 中冶长天国际工程有限责任公司 | A kind of acidic flue gas washes Zero discharge treatment method and its device |
| CN110950499A (en) * | 2019-12-20 | 2020-04-03 | 中国电建集团江西省电力建设有限公司 | Copper ammonia complex wastewater treatment system and process |
-
2013
- 2013-09-27 CN CN201320601995.8U patent/CN203529996U/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106435192A (en) * | 2016-09-13 | 2017-02-22 | 南京大学 | Method for removing and recycling copper from magnesium ammonium phosphate sludge |
| CN106435192B (en) * | 2016-09-13 | 2018-06-26 | 南京大学 | Removal and the method for recycling copper in a kind of ammonium magnesium phosphate sludge |
| CN110127918A (en) * | 2018-02-02 | 2019-08-16 | 中冶长天国际工程有限责任公司 | A kind of acidic flue gas washes Zero discharge treatment method and its device |
| CN110127918B (en) * | 2018-02-02 | 2021-10-26 | 中冶长天国际工程有限责任公司 | Zero-discharge treatment method and device for acidic flue gas washing wastewater |
| CN110950499A (en) * | 2019-12-20 | 2020-04-03 | 中国电建集团江西省电力建设有限公司 | Copper ammonia complex wastewater treatment system and process |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20140409 |