CN109133486A - A kind of environment protection water closet urine high ammonia-nitrogen wastewater step recycling and qualified discharge method - Google Patents
A kind of environment protection water closet urine high ammonia-nitrogen wastewater step recycling and qualified discharge method Download PDFInfo
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- CN109133486A CN109133486A CN201710457365.0A CN201710457365A CN109133486A CN 109133486 A CN109133486 A CN 109133486A CN 201710457365 A CN201710457365 A CN 201710457365A CN 109133486 A CN109133486 A CN 109133486A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/341—Consortia of bacteria
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B17/00—Other phosphatic fertilisers, e.g. soft rock phosphates, bone meal
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/18—Alkaline earth metal compounds or magnesium compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/14—NH3-N
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/16—Total nitrogen (tkN-N)
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Microbiology (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Biodiversity & Conservation Biology (AREA)
- General Chemical & Material Sciences (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The purpose of a kind of environment protection water closet urine high ammonia-nitrogen wastewater step recycling and qualified discharge method is for nitrogen phosphorus magnesium ion concentration imbalance problem in high ammonia-nitrogen wastewater, by constructing single chamber electrolysis system, sacrificial magnesium anode, break electrolytic equilibrium in such a way that cathode produces hydrogen, pH value of solution is promoted to increase, and the hydrogen generated drives ammonia volatilization, realizes in a manner of resource reclaim of the high ammonia-nitrogen wastewater based on recovery ammonia；Electrolytic magnesium can provide magnesium source and form ammonium magnesium phosphate slow release fertilizer simultaneously, be used for based on high ammonia-nitrogen wastewater nitrogen resource reclaim to provide one kind, supplemented by magnesium ammonium phosphate slow release fertilizer, and the step method of resource generated with Hydrogen Energy.
Description
Technical field
The invention belongs to environmental sanitation fields, and in particular to a kind of environment protection water closet urine high ammonia-nitrogen wastewater step recycling and
Row up to standard
Put method.
Background technique
Currently, the technology of high ammonia-nitrogen wastewater Resource analysis comparative maturity is that ammonium magnesium phosphate chemical precipitation method forms guanite
Slow release fertilizer.However, the nitrogen, phosphorus and magnesium in waste water are not with the presence of equimolar ratio, such as biogas slurry, landfill leachate, people
The ammonia-nitrogen contents such as poultry urine will be significantly larger than phosphorus and magnesium, the urine after especially hydrolyzing, and ammonia-nitrogen content is up to 5000-
6000mg/L, significantly larger than phosphorus 300-400mg/L so additional a large amount of magnesium source and phosphorus is needed to adjust ion ratio, and are needed
Additional lye is wanted to promote guanite precipitating, this increases the use cost of this method, greatly limits its scale application.Though
So there is researcher to propose in such a way that magnesium ammonium phosphate thermal decomposition product recycles, reduces additional reagent cost, but magnesium ammonium phosphate
It is accompanied by the generation of magnesium pyrophosphate derivative during pyrolysis, greatly reduces the effect and medicament circulation time of ammonia precipitation
Number.
For the serious unbalanced high ammonia-nitrogen wastewater of nitrogen phosphorus magnesium ion, individually returning for ammonia nitrogen in high density should be carried out first
It receives, then considers further that the mode of chemical precipitation, simple deamination no thoroughness not only can be overcome, and can reduce subsequent
Additional a large amount of chemical reagent reduces operating cost；Resource reclaim efficiency can be greatly improved simultaneously.
Electrochemical method improves cathode chamber solution pH by electrolysis to promote recovery ammonia, and passes through sacrificial anode
Being added directly for chemical reagent is avoided, reaction process can be regulated and controled by external voltage or electrode potential.Currently, electrochemistry
Method is mainly to carry out nitrogen in urine, phosphorus and the recoverable money of hydrogen simultaneously for electrochemical process based on sacrificial anode recycling phosphor resource
Energy research in source is rarely reported.Number of patent application 201610259921.9 discloses dual chamber system electrolysis magnesium electrode and promotes pH
Increase, additional a large amount of chemical reagent, in a manner of the resource reclaim formed based on guanite, then for remaining ammonia using exposing
Air-blowing is de-, and this mode does not meet resource cascade utilization principle, and high proton exchange membrane is used in dual chamber system, also greatly
Engineer application is limited greatly.
Summary of the invention
The purpose of the present invention is pass through building single chamber electricity for nitrogen phosphorus magnesium ion concentration imbalance problem in high ammonia-nitrogen wastewater
Enzymatic hydrolysis system, sacrificial magnesium anode break electrolytic equilibrium in such a way that cathode produces hydrogen, the hydrogen for promoting pH value of solution to increase, and generating
Ammonia volatilization is driven, is realized in a manner of resource reclaim of the high ammonia-nitrogen wastewater based on recovery ammonia；Electrolytic magnesium can provide magnesium source shape simultaneously
At ammonium magnesium phosphate slow release fertilizer, it is used for based on high ammonia-nitrogen wastewater nitrogen resource reclaim to provide one kind, magnesium ammonium phosphate slow release
Supplemented by fertilizer, and the step method of resource generated with Hydrogen Energy.
For achieving the above object, the present invention provides a kind of environment protection water closet urine high ammonia-nitrogen wastewater step recycling and reaches
Mark row
Put method, which is characterized in that the method step specifically includes that urine hydrolysis → magnesium eletrolysis and magnesium ammonium phosphate recycling → ammonia
Stripping and absorption
(1) microbial hydrolytic urine discharges ammonia nitrogen
Since urine hydrolyzes excessive cycle naturally, the high-effective microorganism that the present invention selects screen this laboratory early period promotes urine water
Solution, wherein microorganism includes pseudomonad, one or more combinations in make pottery in distress Salmonella and bacillus.By adding bio-carrier
The mode of filler promotes microbe density, and wherein filler launches the 30%-50% that ratio is liquid volume.
(2) magnesium eletrolysis and ammonium magnesium phosphate (guanite) recycle
Anode selects the lower metal electrode of electrode potential, preferably metal magnesium plate, and cathode selects the materials such as stainless steel, graphite, sun
Pole is identical as cathodic surface area, and electrode spacing is 0.5cm~5cm.To ensure product magnesium ammonium phosphate purity, magnesium electrode contains magnesia amount
Score cannot be below 95%.
Urine after hydrolysis is introduced into electrolysis system, applied voltage >=0.1V, preferably applied voltage 0.2V~0.8V；Pass through
Applied voltage is controlled, the pH for adjusting electrolysis system maintains 8-10, while will form sediment in electrode base, wherein being mainly
Ammonium magnesium phosphate, reaction equation: Mg2++NH4 ++HnPO43-n+6H2O=MgNH4PO4·6H2O+nH+, recycled by way of the spoil disposal of bottom
Sediment, and be carried out dehydrating, it is used for slow release fertilizer.Wherein electrolysis reaction equation is as follows:
Magnesium oxidation reaction occurs for anode:
Mg=Mg++e-
Mg++H2O=Mg2+=0.5H2+OH-
Or Mg=Mg2++2e- ,
Evolving hydrogen reaction occurs in cathode:
2H++2e-=H2↑④
Voltage, which adjusts principle, should combine the purity of ammonia aeration efficiency and ammonium magnesium phosphate.It is blown although excessively high pH is conducive to ammonia
It is de-, but the purity of guanite can be reduced, reduce fertilizer efficiency.
(3) ammonia aeration and recycling
PH after above-mentioned electrolysis is increased to the urine of 8-10, is introduced into stripping system, by aeration stripping ammonia nitrogen, and using 2~
3% sour absorbing liquid carries out ammonia absorption, wherein sour absorbing liquid is hydrochloric acid or sulfuric acid etc..
The applied voltage can be applied by way of D.C. regulated power supply (DC-POWER), can also pass through constant potential
The mode of instrument control electrode potential applies.
The temperature of the reaction is not required to deliberately control, and under normal temperature condition, but the raising of temperature has rush to recovery ammonia
Into effect；
The plastic filler that volume ratio is 50%-70% is added in the sour absorbing liquid absorbed for gas, increases gas-liquid and connects
Contacting surface promotes gas adsorption effect.
The beneficial effects of the present invention are:
For high ammonia-nitrogen wastewater in ammonia recovering process, avoids additional a large amount of alkali and adjust pH raising, saved big quantization
Reagent is learned, the present invention breaks what the hydrogen that pH rises, and generates in ionization equilibrium promotion system was formed by anode magnesium eletrolysis
Air flotation effect promotes recovery ammonia.
Since magnesium electrode potential is lower, so only needing the voltage of additional 0.1V that can form cathode produces hydrogen, in phase
In same production hydrogen level, consumed electric energy is well below traditional electrolyte water, and low energy consumption.
High ammonia-nitrogen wastewater extremely unbalanced for nitrogen, phosphorus ratio, the present invention are dropped significantly by way of recycling ammonia first
Ammonia nitrogen concentration in low waste water reduces the gap between concentration of nitrogen and phosphorus, avoids the simple guanite precipitation process of high ammonia-nitrogen wastewater
Middle ammonia is superfluous or excessively adds external source chemical reagent；And magnesium source is provided in a manner of magnesium eletrolysis, does not need additionally to add chemistry
Reagent, it is easy to operate controllable.
Compared with existing recovery of nitrogen and phosphorus patent, the present invention reaches by step resource reclaim mode while recycling ammonia
Nitrogen, phosphorus and the comprehensive resources recovering effect for generating Hydrogen Energy, and effectively reduce nitrogen and phosphorus pollution in waste water.
This method treated urine water outlet, it is colourless, tasteless, and water outlet meets first discharge standard, can be used for recycling
It flushes the toilet use, saves water resource.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
Example 1
Now in conjunction with attached drawing, invention is further described in detail.
Assemble electrolysis system first, anode selects columnar magnesium bar magnesium alloy materials, and cathode selects graphite rod, anode with
Cathodic surface area is identical, and electrode spacing is set as 1.5cm, connects external circuit；Pass through the side of D.C. regulated power supply (DC-POWER)
The voltage of formula application 0.8V；It is process object with the biogas slurry after pig manure Anaerobic Treatment, temperature is 28 ± 3 DEG C, is powered on, cathode
A large amount of hydrogen are generated, and pH value of solution rises very rapidly up to 10.0, volatilize the mixed gas such as ammonia, hydrogen, inhaled by 3% sulfuric acid
It receives link and recycles ammonia nitrogen, then absorbed again by 10% lye, hydrogen is further purified, the content for finally obtaining hydrogen is up to
98%, effluent quality colorless and odorless, wherein ammonia nitrogen≤0.5mg/L, COD≤60mg/L, total nitrogen≤15mg/L, total phosphorus≤0.3mg/
L.The electrochemical reaction that anode and cathode occurs is as follows:
Magnesium oxidation reaction occurs for anode:
Mg=Mg++e-
Mg++H2O=Mg2+=0.5H2+OH-
Or Mg=Mg2++2e- ,
Evolving hydrogen reaction occurs in cathode:
2H++2e-=H2 ↑④
After a large amount of ammonia nitrogens are recovered, mole gap of ammonia nitrogen and phosphorus in solution is smaller and smaller, the offer in anode magnesium source
Under gradually form guanite precipitating, excluded by bottom, after dehydration and drying be used as slow release fertilizer.
When the ammonia nitrogen concentration variation in sour absorbing liquid is less obvious, when being lower than 10%, it is basically completed entire recycling ring
Liquid is discharged in section, refills waste water, carries out new round processing.Result of study shows that ammonia recovery reaches 80% in absorbing liquid,
The guanite purity of generation is up to 78%, and hydrogen purity reaches 98%.
Example 2
Contain higher nitrogen P elements in human urine, urine its ammonia-nitrogen content after especially hydrolyzing is up to 5000-6000mg/
L, significantly larger than phosphorus 300-400mg/L, example 2 are process object with the urine of hydrolysis, recycle nitrogen phosphorus, other operations and example 1
Unanimously, but its pH itself can rise to 9.0 or more after urine hydrolysis, be more advantageous to ammonia volatilization and guanite precipitates, grind
Study carefully the result shows that, ammonia recovery is up to 90%, but guanite purity only has 65%, and hydrogen purity reaches 98%, and effluent quality is colourless
It is tasteless, wherein ammonia nitrogen≤1mg/L, COD≤50mg/L, total nitrogen≤15mg/L, total phosphorus≤0.3mg/L.
Example 3
Contain higher nitrogen P elements in human urine, urine its ammonia-nitrogen content after especially hydrolyzing is up to 5000-6000mg/
L, significantly larger than phosphorus 300-400mg/L, example 3 are process object with unhydrolysed freshly voided urine, recycle nitrogen phosphorus.In urine biology
The mixed bacteria liquid that functional microorganism bacterial strain pseudomonad, make pottery Salmonella and bacillus in distress are added when hydrolysis, is rapidly completed urine water
Solution carries out nitrogen, phosphorus recycling then according to the mode of operation of example 1.Result of study shows that ammonia recovery is up to 90%, guanite
Purity 75%, hydrogen purity reach 98%, effluent quality colorless and odorless, wherein ammonia nitrogen≤0.5mg/L, COD≤50mg/L, and total nitrogen≤
15mg/L, total phosphorus≤0.5mg/L.
Of the invention a kind of environment protection water closet urine high ammonia-nitrogen wastewater step recycling and qualified discharge method have passed through tool
The example of body is described, and those skilled in the art can use for reference the content of present invention, the links such as appropriate feed change, process conditions
To realize that corresponding other purposes, correlation change all without departing from the contents of the present invention, all similar substitutions and modifications pair
It is it will be apparent that being considered as being included within the scope of the present invention for those skilled in the art.
Claims (5)
1. a kind of environment protection water closet urine high ammonia-nitrogen wastewater step recycling and qualified discharge method, it is characterised in that: the resource
Changing method flow is successively urine hydrolysis → magnesium eletrolysis and magnesium ammonium phosphate recycling → ammonia aeration and absorbs；
(1) microbial hydrolytic urine discharges ammonia nitrogen；
Since urine hydrolyzes excessive cycle naturally, the high-effective microorganism that the present invention selects screen this laboratory early period promotes urine water
Solution, wherein microorganism includes pseudomonad, one or more combinations in make pottery in distress Salmonella and bacillus；By adding bio-carrier
The mode of filler promotes microbe density, and wherein filler launches the 30%-50% that ratio is liquid volume；
(2) magnesium eletrolysis and ammonium magnesium phosphate (guanite) recycle；
Anode selects the lower metal electrode of electrode potential, preferably metal magnesium plate, and cathode selects the materials such as stainless steel, graphite, sun
Pole is identical as cathodic surface area, and electrode spacing is 0.5cm~5cm.
2. magnesium electrode mass fraction containing magnesium cannot be below 95% to ensure product magnesium ammonium phosphate purity；
Urine after hydrolysis introduces electrolysis system, applied voltage >=0.1V, preferably applied voltage 0.2V~0.8V；It is outer by controlling
Making alive, the pH for adjusting electrolysis system maintains 8-10, while will form sediment in electrode base, wherein mainly ammonium phosphate
Magnesium, reaction equation: Mg2++NH4 ++HnPO43-n+6H2O=MgNH4PO4·6H2O+nH+, precipitating is recycled by way of the spoil disposal of bottom
Object, and be carried out dehydrating, it is used for slow release fertilizer, wherein electrolysis reaction equation to be as follows:
Magnesium oxidation reaction occurs for anode:
Mg=Mg++e-
Mg++H2O=Mg2+=0.5H2+OH-
Or Mg=Mg2++2e- ,
Evolving hydrogen reaction occurs in cathode:
2H++2e-=H2↑④
Voltage, which adjusts principle, should combine the purity of ammonia aeration efficiency and ammonium magnesium phosphate, blow although excessively high pH is conducive to ammonia
It is de-, but the purity of guanite can be reduced, reduce fertilizer efficiency；
(3) ammonia aeration and recycling
PH after above-mentioned electrolysis is increased to the urine of 8-10, is introduced into stripping system, by aeration stripping ammonia nitrogen, and using 2~
3% sour absorbing liquid carries out ammonia absorption, wherein sour absorbing liquid is hydrochloric acid or sulfuric acid etc..
3. a kind of environment protection water closet urine high ammonia-nitrogen wastewater step recycling according to claim 1 and qualified discharge method,
It is characterized by: the applied voltage can apply by way of D.C. regulated power supply (DC-POWER), perseverance can also be passed through
The mode of potentiometer coordination electrode potential applies.
4. a kind of environment protection water closet urine high ammonia-nitrogen wastewater step recycling according to claim 1 and qualified discharge method,
It is characterized by: the temperature of the reaction is not required to deliberately control, under normal temperature condition, but the raising of temperature has recovery ammonia
Facilitation.
5. a kind of environment protection water closet urine high ammonia-nitrogen wastewater step recycling according to claim 1 and qualified discharge method,
It is characterized by: the plastic filler that volume ratio is 50%-70% is added in the sour absorbing liquid absorbed for gas, increase
Gas-liquid contact face promotes gas adsorption effect.
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| CN201710457365.0A CN109133486A (en) | 2017-06-16 | 2017-06-16 | A kind of environment protection water closet urine high ammonia-nitrogen wastewater step recycling and qualified discharge method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111584980A (en) * | 2020-05-27 | 2020-08-25 | 中国科学院重庆绿色智能技术研究院 | Method for recycling phosphorus resources and electric energy in urine based on magnesium air fuel cell |
| CN112499846A (en) * | 2020-09-29 | 2021-03-16 | 华航环境发展有限公司 | Method for concentrating and recovering nutrient substances in biogas slurry |
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| CN103482824A (en) * | 2013-09-18 | 2014-01-01 | 西安建筑科技大学 | Method and device for quickly recycling nitrogen and phosphorus nutrient substances in urine |
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| JP2004290862A (en) * | 2003-03-27 | 2004-10-21 | Ebara Corp | Method and apparatus for recovering nitrogen and phosphorus |
| CA2783519A1 (en) * | 2012-07-23 | 2014-01-23 | E2Metrix Inc. | Method for simultaneous elimination of orthophosphate and ammonium using electrolytic process |
| CN103482824A (en) * | 2013-09-18 | 2014-01-01 | 西安建筑科技大学 | Method and device for quickly recycling nitrogen and phosphorus nutrient substances in urine |
| CN105883982A (en) * | 2016-04-22 | 2016-08-24 | 浙江大学 | Device and method for recycling nitrogen and phosphorus of wastewater |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111584980A (en) * | 2020-05-27 | 2020-08-25 | 中国科学院重庆绿色智能技术研究院 | Method for recycling phosphorus resources and electric energy in urine based on magnesium air fuel cell |
| CN112499846A (en) * | 2020-09-29 | 2021-03-16 | 华航环境发展有限公司 | Method for concentrating and recovering nutrient substances in biogas slurry |
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